Professional Documents
Culture Documents
Geochemistry of Oil Field Waters
Geochemistry of Oil Field Waters
GEOCHEMISTRY OF OILFIELD
WATERS
A. GENE COLLINS
Bartlesville Energy Research Center
Bureau o f Mines
United States Department of the Interior
Bartlesville, Oklahoma, U.S.A.
Oxford
PREFACE
The purpose of this book is to provide information relevant to the analytical chemistry and geochemistry of oilfield waters. The book attempts to
recognize the importance of subsurface oilfield waters as they are related t o
origin, migration, accumulation, and maturation of oil and gas and thus their
relationship t o exploration for and production of oil and gas. One chapter
presents a simplistic introduction t o the origin of oilfield waters. Because oilfield waters can constitute an environmental pollution hazard, the book describes and comments on methods of their disposal or of recovering valuable
constituents from them.
The numerous references indicate that the book relies heavily upon the
work of others. The reader will vastly expand his knowledge of the subject
by consulting these references.
The writer appreciates the understanding and thoughtfulness of his Wife,
Barbara, and children, Sandy and Mike, during the preparation of part of this
book at our home. He acknowledges With appreciation the criticisms, opinions, and suggestions of various portions of the book by O.C. Baptist, W.H.
Caraway, P.H. Dickey, G.L. Gates, R.V. Huff, P.H. Jones, and C.C. Linville.
M.E. Crocker and Ms. C.A. Pearson, did an invaluable service of proof-reading
and index preparation. He extends appreciation t o Ms. D.J. Forbes, Ms. M.G.
Goff, and Ms. J. Haimson for typing the manuscript; t o D.W. Anderson, Ms.
E.S. Baldwin, J.A. Chidester, G.E. Fletcher, R.M. Horn, and W.A. McClung
for preparing the figures; and to authors, book publishers, companies, and
technical journals who granted permission t o use various illustrations.
Permission t o publish this manuscript was granted by the Director of the
United States Bureau of Mines. Bureau of Mines officials who generously
helped obtain this permission were: J.S. Ball, R.T. Johansen, and J.W.Watkins.
Finally inasmuch as it is the writers belief that this book is not perfect, he
takes this opportunity to solicit constructive criticism from its readers.
A. GENE COLLINS
Bartlesville Energy Research Center
U.S.Bureau of Mines
Bartlesville, Oklahoma
CONTENTS
Preface
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Chapter 1. Introduction
References . . . . .
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Chapter 3. Analysis of oilfield waters for some physical properties and inorganic
chemical constituents . . . . . . . . . . . . . . . .
Quality control . . . . . . . . . . . . . . . . . . . . . . .
Preliminary sample treatment . . . . . . . . . . . . . . . . . .
Reporting the analytical results . . . . . . . . . . . . . . . . .
Synthetic brine . . . . . . . . . . . . . . . . . . . . . . .
Determination of pH . . . . . . . . . . . . . . . . . . . . .
Determination of Eh . . . . . . . . . . . . . . . . . . . . .
Suspended solids . . . . . . . . . . . . . . . . . . . . . . .
Resistivity . . . . . . . . . . . . . . . . . . . . . . . . .
Specific gravity . . . . . . . . . . . . . . . . . . . . . . .
TITRIMETRIC METHODS . . . . . . . . . . . . . . . . . .
Acidity. alkalinity. and borate boron . . . . . . . . . . . . . . .
Calcium and magnesium . . . . . . . . . . . . . . . . . . .
Ammonium nitrogen . . . . . . . . . . . . . . . . . . . .
Chloride . . . . . . . . . . . . . . . . . . . . . . . . .
Bromide and iodide . . . . . . . . . . . . . . . . . . . . .
Oxygen . . . . . . . . . . . . . . . . . . . . . . . . .
Carbon dioxide . . . . . . . . . . . . . . . . . . . . . .
Sulfide . . . . . . . . . . . . . . . . . . . . . . . . .
Sulfur compounds . . . . . . . . . . . . . . . . . . . . .
FLAME SPECTROPHOTOMETRIC .METHODS . . . . . . . . . . .
Lithium . . . . . . . . . . . . . . . . . . . . . . . . .
Sodium . . . . . . . . . . . . . . . . . . . . . . . . .
Potassium . . . . . . . . . . . . . . . . . . . . . . . .
Rubidium and cesium . . . . . . . . . . . . . . . . . . . .
Manganese . . . . . . . . . . . . . . . . . . . . . . . .
Strontium . . . . . . . . . . . . . . . . . . . . . . . .
Barium . . . . . . . . . . . . . . . . . . . . . . . . .
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CONTENTS
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Chapter 5 . Significance of some inorganic constituents and physical properties of oilfield waters . . . . . . . . . . . . . . . . . . . . .
Lithium . . . . . . . . . . . . . . . . . . . . . . . . . .
Sodium . . . . . . . . . . . . . . . . . . . . . . . . . .
Potassium . . . . . . . . . . . . . . . . . . . . . . . . .
Rubidium . . . . . . . . . . . . . . . . . . . . . . . . .
Cesium . . . . . . . . . . . . . . . . . . . . . . . . . .
Beryllium . . . . . . . . . . . . . . . . . . . . . . . . .
Magnesium . . . . . . . . . . . . . . . . . . . . . . . . .
Calcium . . . . . . . . . . . . . . . . . . . . . . . . . .
Strontium . . . . . . . . . . . . . . . . . . . . . . . . .
Barium . . . . . . . . . . . . . . . . . . . . . . . . . .
Manganese . . . . . . . . . . . . . . . . . . . . . . . . .
Iron . . . . . . . . . . . . . . . . . . . . . . . . . . .
Copper . . . . . . . . . . . . . . . . . . . . . . . . . .
Zinc . . . . . . . . . . . . . . . . . . . . . . . . . . .
Mercury . . . . . . . . . . . . . . . . . . . . . . . . . .
Lead . . . . . . . . . . . . . . . . . . . . . . . . . . .
Cadmium . . . . . . . . . . . . . . . . . . . . . . . . .
Boron . . . . . . . . . . . . . . . . . . . . . . . . . .
Aluminum . . . . . . . . . . . . . . . . . . . . . . . . .
Silica . . . . . . . . . . . . . . . . . . . . . . . . . . .
Ammonium nitrogen . . . . . . . . . . . . . . . . . . . . .
Phosphorus . . . . . . . . . . . . . . . . . . . . . . . . .
Arsenic . . . . . . . . . . . . . . . . . . . . . . . . . .
Oxygen . . . . . . . . . . . . . . . . . . . . . . . . . .
Sulfur . . . . . . . . . . . . . . . . . . . . . . . . . .
Selenium . . . . . . . . . . . . . . . . . . . . . . . . .
Fluorine . . . . . . . . . . . . . . . . . . . . . . . . . .
Chlorine . . . . . . . . . . . . . . . . . . . . . . . . . .
Bromine . . . . . . . . . . . . . . . . . . . . . . . . . .
Iodine . . . . . . . . . . . . . . . . . . . . . . . . . .
Significance of some physical properties . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . .
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Chapter 7. Origin of oilfield waters . . . . . .
Definitions of some water terms . . . . . . .
Sedimentary rocks . . . . . . . . . . . .
Composition of oilfield waters . . . . . . .
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CONTENTS
Conclusions
References .
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Chapter 9. Some effects of water upon the generation. migration. accumulation. and
alteration of petroleum . . . . . . . . . . . . . . . . .
Compaction . . . . . . . . . . . . . . . . . . . . . . . .
Generation and migration . . . . . . . . . . . . . . . . . . . .
Accumulation . . . . . . . . . . . . . . . . . . . . . . . .
Alteration . . . . . . . . . . . . . . . . . . . . . . . . .
Conclusions . . . . . . . . . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . .
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Chapter 10. Geochemical methods of exploration for petroleum and natural gas . . 307
Introduction . . . . . . . . . . . . . . . . . . . . . . . .
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Hydrogeochemical research and methods . . . . . . . . . . . . . . . 313
Reviews . . . . . . . . . . . . . . . . . . . . . . . . . .
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Case history of the Delaware sand (Bell Canyon formation). Texas. by Visher (1961) 322
Formation water maps of others areas . . . . . . . . . . . . . . . . 330
Concluding remarks . . . . . . . . . . . . . . . . . . . . . .
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References . . . . . . . . . . . . . . . . . . . . . . . . .
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Chapter 11. Geopressured reservoirs . .
Geopressure . . . . . . . . . . .
Origin of abnormal pressures . . . . .
Abnormal pressures in the Gulf Coast area
Detection of abnormal pressures . . . .
References . . . . . . . . . . . .
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Chapter 12. Compatibility of oilfield waters . . . . . . .
Wellbore and formation damage . . . . . . . . . . .
Solubility of calciumcompounds invarioussaltsolutions . .
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Solubilities of the sulfates of barium and strontium in saline solutions . . . . . 372
Experimental determination of some solubilities of the sulfates of barium and
strontium . . . . . . . . . . . . . . . . . . . . . . . . .
372
Resultsand discussion of the experimental investigation . . . . . . . . . . 373
Brine stabilization . . . . . . . . . . . . . . . . . . . . . .
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Mixing of subsurface waters . . . . . . . . . . . . . . . . . . . 382
References . . . . . . . . . . . . . . . . . . . . . . . . .
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CONTENTS
XI
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Chapter 1.
INTRODUCTION
Petroleum, known to exist long before an oil well was drilled, first found
limited use as a medicine, lubricant, and waterproofing agent. The American
Indians knew of several oil and gas springs and gave this information t o the
early American settlers. Early settlements were commonly located close to
salt licks which supplied salt to the population. Often these salt springs were
contaminated with petroleum, and many of the early efforts to acquire more
salt by digging wells were rewarded by finding unwanted increased amounts
of oil and gas associated with the saline waters. In the Appalachians: many
saline water springs occurred along the crests of anticlines (Rogers and
Rogers, 1843).
In 1855 it was found that distillation of petroleum produced a light oil
similar to coal oil, which was better than whale oil as an illuminant (Howell,
1934, p.2). This knowledge spurred the search for saline waters which contained oil. Colonel Edward Drake, utilizing the methods of the salt producers, drilled a well on Oil Creek, near Titusville, Pennsylvania, in 1859. He
struck oil at a depth of 21 m, and this first oil well produced about 35 barrels
of oil per day (Dickey, 1959).
The early oil producers did not realize the significance of the oil and saline
waters occurring together. In fact, it was not until 1938 that the existence of
interstitial water in oil reservoirs was generally recognized (Schilthuis, 1938).
Torrey (1966) was convinced as early as 1928 that dispersed interstitial
water existed in oil reservoirs, but his belief was rejected by his colleagues
because most of the producing oil wells did not produce any water upon
completion. Occurrences of mixtures of oil and gas with water were recognized by Griswold and Munn (1907), but they believed that there was a
definite separation of the oil and water, and that oil, gas, and water mixtures
did not occur in the sand before a well tapped the reservoir.
It was not until 1928 that the first commercial laboratory for the analysis
of rock cores was established (Torrey, 1966); the first core tested was from
the Bradford Third Sand (from the Bradford field, McKean County, Pennsylvania). The percent saturation and percent porosity of this core were plotted
versus depth t o construct a graphic representation of the oil and water
saturation. The soluble mineral salts that were extracted from the core led
Torrey to suspect that water was indigenous t o the oil productive sand.
Shortly thereafter a test well was drilled near Custer City, Pennsylvania,
which encountered higher than average oil saturation in the lower part of the
Bradford Sand. This high oil saturation resulted from the action of an un-
INTRODUCTION
suspected flood, the existence of which was not known when the location
for the test well had been selected. The upper part of the sand was not
cored. Toward the end of the cutting of the first core with a Baker cable tool
core barrel, oil began t o come into the hole so fast that it was not necessary
t o add water for the cutting of the second section of the sand. The lower 1 m
of the Bradford Sand therefore was cut with oil in a hole free from water.
Two samples from this section were preserved in sealed containers for saturation tests, and both of them, when analyzed, had a water content of approximately 20% of pore volume. This well made about 10 barrels of oil per
day and no water after being shot with nitroglycerine. Thus, the evidence
developed by the core analysis and the productivity test after completion
provided a satisfactory indication of the existence of immobile water, indigenous t o the Bradford Sand oil reservoir, which was held in its pore
system and which could not be produced by conventional pumping methods
(Torrey, 1966).
Fettke (1938) was the first t o report the presence of water in an oilproducing sand. However, he thought that it might have been introduced by
the drilling process.
It was recognized by Munn (1920)that moving underground water might
be the primary cause of migration and accumulation of oil and gas. However,
this theory had little experimental data t o back it until Mills (1920)conducted several laboratory experiments on the effect of moving water and gas
on water-oil-as-sand
and water-oil-sand systems. Mills concluded that
the up-dip migration of oil and gas under the propulsive force of their
buoyancy in water, as well as the migration of oil, either up or down dip,
caused by hydraulic currents, are among the primary factors influencing
both the accumulation and the recovery of oil and gas. This theory was
seriously questioned and completely rejected by many of his contemporaries.
Rich (1923)postulated that hydraulic currents, rather than buoyancy,
are effective in causing accumulation of oil or its retention. He did not
believe that the hydraulic accumulation and flushing of oil required a rapid
movement of water, but rather that the oil was an integral constituent of the
rock fluids and that it could be carried along with them whether the movement was very slow or relatively rapid.
The effect of water displacing oil during production was not recognized in
the early days of the petroleum industry in Pennsylvania. Laws were passed,
however, to prevent operators from injecting water into the oil reservoir
sands through unplugged wells. In spite of these laws, some operators at
Bradford surreptitiously opened the well casing opposite shallow groundwater sands in order to start a waterflood in the oil sands. Effects of artificial
waterfloods were noted in the Bradford field, McKean County, Pennsylvania,
in 1907, and became evident about 5 years later in the nearby oilfields of
New York (Torrey, 1950). Volumetric calculations of the oil-reservoir
volume which were made for engineering studies of these waterflood opera-
INTRODUCTION
tions proved that interstitial water was generally present in the oil sands.
Publications by Garrison (1935) and Schilthuis (1938) give detailed information concerning the distribution of water and oil in porous rocks, and of the
origin and occurrence of connate water with information concerning the
relationship of water saturation to formation permeability.
The word connate was first used by Lane and Gordon (1908) to mean
interstitial water that was deposited with the sediments. The processes of
rock compaction and mineral diagenesis result in the expulsion of large
amounts of water from sediments and movement out of the deposit through
the more permeable rocks. It is therefore highly unlikely that the water
now in any pore is the same as that which was there when the particles that
surround it were deposited. White (1957) redefined connate water as fossil
water; it has been out of contact with the atmosphere for an appreciable part
of a geologic time period. Connate water is thus distinguished from meteoric
water which has entered the rocks in geologically recent times, and from
juvenile water which has come from deep in the earths crust and has never
been in contact with the atmosphere.
Meanwhile petroleum engineers and geologists had learned that waters
associated with petroleum could be identified with regard to the reservoir in
which they occurred by a knowledge of their chemical characteristics. Commonly the waters from different strata differ considerably in their dissolved
chemical constituents, making the identification of a water from a particular
strata easy. However, in some areas the concentrations of dissolved constituents in waters from different strata do not differ significantly, and the
identification of such waters is difficult or impossible.
The amount of water produced with the oil often increases as the amount
of oil produced decreases. If this is edge water, nothing can be done about it.
If it is bottom water, the well can be plugged back. However, it often is
intrusive water from a shallow sand gaining access t o the well from a leaky
casing or faulty completion and this can be repaired.
Enormous quantities of water are produced with the oil in some fields,
and it is necessary to separate the oil from the water. Most of the oil can be
removed by settling. Often, however, an oil-in-water emulsion forms which is
very difficult t o break. In such cases, the oil is heated and various surfaceactive chemicals are added to induce separation.
In the early days, the water was dumped on the ground where it seeped
below the land surface. Until about 1930, the oilfield waters were disposed
into local drainage, frequently killing fish and even surface vegetation. After
1930, it became common practice t o evaporate the water in earthen pits or
to inject it into the producing sand or another deep aquifer. The primary
concern in such disposal practice is to remove all oil and basic sediment from
the waters before pumping them into injection wells, to prevent clogging of
the pore spaces in the formation receiving the waste water. Chemical compatibility of waste water and host aquifer water must also be assured.
Waters produced with petroleum are growing in importance. In years past,
INTRODUCTION
REFERENCES
References
Dickey, P.A., 1959. The first oil well. J. Pet. Technol., 11:14-26.
Fettke, C.R., 1938. Bradford oil field, Pennsylvania, and New York. Pa. Geol. Surv.,
Fourth Ser., Bull., M21:l-454.
Garrison, A.D., 1935. Selective wetting of reservoir rock and its relation to oil production. In: Drilling and Production Practice. American Petroleum Institute, New York,
N.Y., pp.130-140.
Griswold, W.T. and Munn, M.J., 1907. Geology of oil and gas fields in Steubenville,
Burgettstown and Claysville Quadrangles, Ohio, West Virginia and Pennsylvania. U.S.
Geol. Sum. Bull., No.318, 196 pp.
Howell, J.V., 1934. Historical development of the structural theory of accumulation of
oil and gas. In: W.E. Wrather and F.H. Lahee (Editors), Problems of Petroleum
Geology. American Association of Petroleum Geologists, Tulsa, Okla., pp.1-23.
Lane, A.C. and Gordon, W.C., 1908. Mine waters and their field assay. Bull. Geol. SOC.
A m . , 19:501-512.
Mills, R. van A., 1920. Experimental studies of subsurface relationships in oil and gas
fields. Econ. Geol., 15:398-421.
Munn, M.J., 1920. The anticlinal and hydraulic theories of oil and gas accumulation.
Econ. Geol., 4:509-529.
Rich, J.L., 1923. Further notes on the hydraulic theory of oil migration and accumulation. Bull. Am. Assoc. Pet. Geol., 7:213-225.
Rogers, W.B. and Rogers H.D., 1843. On the connection of thermal springs in Virginia
with anticlinal axes and faults. A m . Geol. Rep., 1313.323-347.
Schilthuis, R.J., 1938. Connate water in oil and gas sands. In: Petroleum Development
and Technology, AIME, pp.199-214.
Torrey, P.D., 1950. A review of secondary recovery of oil in the United States. In:
Secondary Recovery of Oil in the United States. American Petroleum Institute, New
York, N.Y., pp.3-29.
Torrey, P.D., 1966. The discovery of interstitial water. Prod. Monthly, 30:8-12.
White, D.E., 1957. Magmatic, connate, and metamorphic water. Bull. Geol. SOC.A m . ,
68:1659-1682.
Chapter 2.
8
TABLE 2.1
Well 2
Well 1
Well 3
1947
1957
1947
1957
1956
1959
Sodium and
potassium
Magnesium
Calcium
Bicarbonate
Sulfate
Chloride
29,062
1,100
5,900
34
14
58,500
25,000
1,200
5,500
12
50
51,800
46,038
2,011
14,200
24
3
102,100
45,924
2,200
14,400
12
52
102,800
1,491
30
60
600
200
2,000
856
2
10
1,800
0
300
Total dissolved
solids
94,610
83,562
164,376
165,388
4,381
2,968
~-
_.
Drill-stem test
The drill-stem test, if properly made, can provide a reliable formation
water sample. Mud filtrate will be the first fluid to enter the drill-stem test
tool, and it will be found at the top of the fluid column immediately below
DRILL-STEM TEST
tester
Multiple closed i
pressure s a m p l e
Flow stream
pressure recorde
V e r t i c a l and rot
Locked down
Blanked o f f
pressure r e c o r d
RUNNING
IN HOLE
10
'
Rubber doughnut
Mud
Oroln
Floottnq p l s t o n
h
SAMPLE UNIT,'
for l o w p e r m o b i l i t i e s
Sample
v o l v e ( l o c k s open)
Dump chamber
"
MECHANICAL U N I T F I M - A
- J
SAMPLE U N I T
RECORDED TESTER
POSITION
m E
?
SP
SURFACE CONTROL
I N 0 ICATIDNS
S A M P L I N G PRESSURE
Pod set
Tool open
I n i t i a l shut-in
prss1ure
action
Sampling
pressure
F i n a l shul-in
pressure
Hydroltotic
head
RECORDED LOG
Fig. 2.2. Formation interval tester. (Courtesy of Schlumberger Well Services Company.)
DRILL-STEM TEST
11
12
TABLE 2.11
Concentration (mg/l)
top
Sodium
Calcium
Magnesium
Bicarbonate
Sulfate
Chloride
Total dissolved
solids
middle
-
bottom
29,600
8,100
600
500
2,000
59,900
43,500
13,100
900
500
1,300
91,800
71,800
22,400
1,400
400
500
154,000
101,000
151,000
251,000
sample is approximately half mud filtrate and half formation water. The
bottom sample is the most representative of Smackover water.
No single procedure is universally applicable for obtaining a sample of
oilfield water. For example, information may be desired concerning the
dissolved gas or hydrocarbons in the water, or the reduced species present such as ferrous or manganous compounds. Sampling procedures applicable to
the desired information must be used.
Sample containing dissolved gases
Knowledge of certain dissolved hydrocarbon gases is used in exploration.
Methane is quite soluble in water, but samples must be collected in a sampler
that keeps the subsurface pressure on the sample until it is opened in the
laboratory. The testing tool is kept open until the head of water in the drill
pipe is equalized with the formation pressure or until water flows at the
surface. The pressure equalization may require 4 or more hours. However, a
surface recording subsurface pressure gage can be lowered into the drill pipe
to determine when the pressure has equalized. After equalization of pressure,
formation-water samples can be obtained by lowering a subsurface sampler
into the drill pipe (Buckley et al.,1958). Zarrella et al. (1967) determined
the content of dissolved benzene. For this it is not necessary t o use a subsurface sampler; the samples are caught in buckets on opening the pipe
string, and immediately transferred from the buckets t o new narrow-necked
glass or metal containers.
A preferred method of obtaining a sample for subsequent gas analysis is t o
catch the aqueous sample in a metal container of about one-quart capacity.
This sample is immediately transferred to another metal sample container.
The second container should be filled completely t o the top, then the sides
of the can are lightly squeezed t o allow for fluid expansion, and the lid is
sealed tightly. A foil-lined (not plastic) lid should be used. If possible, the
13
-I
container
Valve
P i p e line
Valve
Rubber
tube
The device is connected to the flow line, and water is allowed t o flow into
and through the container, which is held above the flow line, until 10 or
more volumes of water have flowed through. The lower valve on the sample
container is closed and the container removed. If any bubbles are present in
the sample, the sample is discarded and a new one is obtained.
14
O i l and water
c03-*
+ HCO,-+
H+
H,CO,
15
Because the pH of the formation water sample will change, the pH should
be determined using a flowing sample. A pH/Eh flow sampling chamber
(Collins, 1964) is shown in Fig. 2.5. The Eh determination is difficult and
for corroboration it should be checked using a knowledge of the dissolved
Fig. 2.5. Flow chamber for use in determining pH and Eh at the wellhead.
16
--
Sample number
Field
Farm or lease
Well No.
in the
of Section
Township
Range __
County
State Operator
Operators address (main office)
-___
Date
Sample obtained by -_____
Address
Representing
Sample obtained from (lead line, separatory flow tank, etc.)
Elevation of well ___
Completion date of well
Name of productive zone from which sample is produced Sand -Shale
Lime
Other
Names of formations
Name of productive
formation
well passes through
Bottom of formation
Depths: Top of formation
Top of producing zone
Bottom of producing zone
Total depth drilled
Present depth
Bottom hole pressure and date of pressure
Bottom hole temperature
b e any chemicals
If yes,
Date of last workover
added to treat well? -what?
Well production
Initial
Present
Casing service record:
Oil, barrelslday
Water, barrels/day
_______
Gas, cubic feetlday
Method of production (primary or secondary)
__
Remarks: (such as casing leaks, communication, or other pays in same well, lease, or field)
17
The type of container selected is dependent upon the planned use of the
analytical'data. Probably the more satisfactory container, if the sample is to
be stored for some time before analysis, is the polyethylene bottle. All
polyethylenes are not satisfactory because some contain relatively high
amounts of metals contributed by catalysts in their manufacture. The
approximate metal content of the plastic can be determined using a qualitative emission spectrographic technique. If the sample is transported during
freezing temperatures, the plastic container is less likely to break than glass.
The practice of obtaining two samples and acidifying one sample so that
the heavy metals will stay in solution works better if the plastic container is
used. Some of the heavy metals are adsorbed by glass even if the sample is
acidified.
Tabulation of sample description
The sample is of little value if detailed information concerning it is not
available. Information such as that in Table 2.111 should be obtained for each
sample of petroleum-associated water, and for certain types of studies, additional information may be needed.
References
Bredehoeft, J.D., 1965. The drill-stem test: the petroleum industry's deep-well pumping
test. Ground Water, 3:15-23.
Buckley, S.E., Hocott, C.R. and Taggart, Jr., M.S., 1958.Distribution of dissolved hydrocarbons in subsurface waters. In: L.C. Weeks (Editor), Habitat of Oil. American
Association Petroleum Geologists, Tulsa, Okla., pp.850-882.
Collins, A.G., 1964. Eh and pH of oilfield waters. Prod. Monthly, 28:ll-12.
McAlister, J.A., Nutter, B.P. and Lebourg, M., 1965. A new system of tools for better
control and interpretation of drill-stem tests. J. Pet. Technol., 17 :207-214.
Noad, D.F., 1962. Water analysis data, interpretation and applications. J. Can. Pet.
TechnoL , 1 :82-89.
Wallace, W.E., 1969. Water production from abnormally pressured gas reservoirs in South
Louisiana, J. Pet. Technol., 21 :969-982.
Zarrella, W.M., Mousseau, R.J., Coggeshall, N.E., Norris, M.S. and Schrayer, G.T., 1967.
Analysis and significance of hydrocarbons in subsurface brines. Geochim. Cosmochim.
Acta, 31 :1155-1166.
20
Precision
Precision is the reproducibility among replicate observations, and in
quality control it is determined on actual water samples containing interfering constituents. Several methods to determine precision are available and
the following is representative:
(1) Study four separate concentration levels, including a low concentration near the sensitivity level of the method, two intermediate concentrations, and a concentration near the upper limit of application of the method.
(2) Make seven replicate determinations at each of the concentrations
tested.
(3) To allow for changes in conditions, the precision study should use at
least 2 hours of normal laboratory operation.
(4) To permit the maximum interferences in sequential operation, the
samples should be run in the following order: high, low, intermediate, intermediate. Repeat this series seven times to obtain the desired replication.
21
QTJALITY CONTROL
TABLE 3.1
Precision data on oilfield brine samples for boron
___
~~
Sample
Taylor
-
Eagle Ford
Average
Standard deviation
Paluxy
_ _ _ _-
Douglas
-
10.1
10.1
10.2
10.3
10.1
10.2
10.2
15.2
15.3
15.1
15.2
15.3
15.2
15.1
20.1
20.1
20.3
20.2
20.3
20.3
20.1
30.3
30.2
30.1
30.1
30.3
30.2
30.1
10.2
0.1
15.2
0.1
20.2
0.1
30.2
0.2
22
TABLE 3.11
Accuracy data on oilfield brine samples for boron
Sample
Paluxy
(added 15 mg/l boron)
20.2
20.2
20.1
20.1
20.3
20.3
20.4
35.5
35.4
35.2
35.2
35.3
35.2
35.1
Average
20.2
35.3
Percent recovery
20-2
] x 100 = 100.0
[ 10.2 + 10
[ 20.2 + 15
35.3
] x 100 = 100.3
The precision and accuracy data are valuable in determining that the
analyst and the method are capable of generating valid data. Once this is
proven, the data can be used to evaluate systematic performance. This can be
done by using spiked samples about 10% of the time to determine that the
accuracy is favorable, and evaluating replicate samples to determine that the
precision is favorable.
Preliminary sample treatment
The following determinations should be made in the field immediately
after sampling:
(1) temperature (in "C),(2) pH, (3) dissolved oxygen, (4) resistivity, ( 5 )
acidity, (6) alkalinity, (7) sulfide, and (8) carbon dioxide.
If possible, the oilfield water sample should be filtered immediately after
sampling in the field. A preferred method-is to use pressure filtration
through a 0.45-micrometer (pm) membrane filter. A liter of filtrate usually is
sufficient and the following determinations can be made on aliquots: (1)
iodide, (2) bromide, (3) chloride, (4) selenium, ( 5 ) sulfate, (6) nitrogen, (7)
phosphate, (8) silica, (9) boron, (10) potassium, (11) sodium, and (12)
lithium.
If a field-filtered sample cannot be provided, a laboratory-filtered sample
may be substituted with slightly less confidence in the reported data.
23
Standard solutions
Examples of standardization procedures are given for some of the
methods. The concentrations of standard solutions are indicated as the
weight of a given element equivalent to, or contained in, 1 ml of solution.
The strength of acids and bases are given in terms of molarities or normalities.
Accuracy of measurements
In the instructions for making the analysis and preparing the solutions,
significant figures are utilized to define the accuracy of weights and
measures.
Required accuracy for measurement of volume in the analysis and preparation of reagents is also shown. Standard solutions are prepared in and
measured from volumetric glassware.
Sampling
A field-filtered acidified sample also should be taken. It is pressured
filtered using a 0.45-pm membrane filter and then the filtrate is immediately
acidified to a pH of 3.0 or less with reagent-grade HCl. The acidified sample
is used for the following determinations: (1) aluminum, (2) arsenic, (3)
barium, (4) cadmium, (5) calcium, (6) copper, (7) iron, (8) lead, (9) magnesium, (10) manganese (11)nickel, (12) strontium, and (13) zinc.
24
TABLE 3.111
Units in which water analyses may be reported
milligrams per liter = mg/l
T o convert compounds expressed as parts per million t o ions expressed,as parts per
million (where compound is A, Bm):
ppm ion A = ppm compound A,
,(atomic weight A)
Bm molecular weight A, B,
,(atomic weight B)
Bm molecular weight A, ,
B
40.08
2
28.3 ppm Ca+ =
= 20.04; then:
28 3
20.04
milliequivalent weight
of determined ion
ml of sample used
106
Gravimetric analysis
(grams of preninitnta\
.,.F.U,
..._.
ml of sample used
%O
106
=.
me/l
.
.
_.- determined
~
element
Chlorinity (CZ)
Salinity (S)
sea water when all of the bromide and iodide have been replaced
by the equivalent amount of chloride, when all of the carbonate
is converted t o oxide and when all the organic matter is completely
oxidized
%o
S = 1.805 x
%o
Cl + 0.03
25
26
decimal point but preceding other digits are not significant. These zeros only
indicate the pbsition of the decimal point.
(d) Final zeros in a whole number may or may not be significant.
A good measure of the significance of one or more zeros before or after
another digit is to determine whether the zeros can be dropped by expressing
the number in exponential form. If they can, the zeros are not significant.
For example, no zeros can be dropped when expressing a weight of 100.08 g
in exponential form; therefore, the zeros are significant. However, a weight
of 0.0008 g can be expressed in exponential form as 8 x
g, and the
zeros are not significant. Significant figures reflect the limits of the particular
method of analysis. It must be decided beforehand whether this number of
significant digits is sufficient for interpretation purposes. If not, there is little
that can be done within the limits of normal laboratory operations t o improve these values. If more significant figures are needed, a further improvement in method or selection of another method will be required t o produce
an increase in significant figures.
Once the number of significant figures is established for a type of analysis,
data resulting from such analyses are reduced according t o set rules for
rounding off.
R o unding-of f numbers
Rounding off of numbers is a necessary operation in all analytical areas. It
is automatically applied by the limits of measurement of every instrument
and all glassware. However, it is often applied in chemical calculations incorrectly by blind rule or prematurely, and in these instances can seriously
affect the final results. Rounding off should normally be applied only as
follows.
SYNTHETIC BRINE
27
28
1I
solution of
known pH;
glass
membrane;
glass electrode
solution of
unknown pH
I 1 Hgo :HgC1
The voltage of the glass electrode is a logarithmic function of the difference in hydrogen-ion activity of the solutions on either side of the glass
membrane. To measure this voltage an electron-tube voltmeter is used because the resistance of the glass membrane is so great.
The pH should be determined at the time of sampling. A device similar to
that shown in Fig. 2.5, can be used, or the electrodes can be placed in a
container and then a stream of the sample allowed to flow from the oilwater separator (Fig. 2.4.) into the container while the pH is measured. If
accurate results are desired, at least two pH buffer solutions should be used
to calibrate the pH meter and electrodes before determining the pH. Because
TABLE 3.IV
pH buffer solutions (pH values of NBS standards from 0-30C)
Temperature 0.5M
potassium
("C)
tetroxalate
0
10
15
20
25
30
1.67
1.67
1.67
1.68
1.68
1.69
Potassium acid
tartrate (sat. at
25OC)
0.05M
potassium acid
phthalate
0.025M
potassium dihydrogen
phosphate + 0.025M
sodium dihydrogen
phosphate
0.01M
sodium
tetraborate
4.01
4.00
6.98
6.92
6.90
6.88
6.86
6.85
9.46
9.33
9.27
9.22
9.18
9.14
4.00
3.56
3.55
4.00
4.01
4.01
DETERMINATION O F Eh
29
TABLE 3.V
Performance characteristics of typical pH meters
Normal scale
Expanded scale
~~~
Range
Smallest scale division
Accuracy
Reproducibility
Temperature
compensation
Input impedance
-
1 pH (* 100 mV)
O - I O O ~ C(manual or
automatic)
1014
> 1013
>
the pH probably will fall between 5 and 7, the standard pH buffer solutions
used could be for pH 5 and pH 7.
Standard buffer solutions, covering a range of pH, may be purchased from
almost any chemical supply house and are satisfactory for routine use. Table
3.IV gives a list of NBS buffers (easily made in the laboratory) and the
resulting pH at several different temperatures.
An idea of the effect of temperature on pH may be obtained by observing
temperature versus pH of various buffers shown in Table 3.IV. Theoretically,
the potential response of the electrode system changes 0.20 mV per pH unit
per degree Celsius. Since all pH meters measure potential but read out in pH,
a variable compensation is used. A rough rule of thumb is that temperature
compensation is about 0.05 pH unit per 5' increase in temperature. Performance data of a conventional and an expanded scale pH meter are shown in
Table 3.V.
Determination of Eh
The Eh, called the oxidation-reduction potential or the redox potential,
is a measure of the relative intensity of oxidizing or reducing conditions in a
chemical system. It is expressed in volts, and at equilibrium it is related to
the proportions of oxidized and reduced species present. Standard equations
of chemical thermodynamics express the relationships (Collins, 1964).
Eo is the standard potential of a redox system when unit activities of
participating substances are present under standard conditions. Eo is related
to standard free energy change in a reaction by the equation:
A P
= -nfEo
30
When the system is not under standard conditions, the redox potential is
expressed by the Nernst equation:
R T log oxidized species)
Eh=Eo+ nf
(reduced species)
where R is the gas constant (1.987 calories per degree mole) and T is the
temperature in degrees Kelvin. Geochemical literature and biochemical literature such as that of Pourbaix (1949) use increasing positive potential values
to represent increasing oxidizing systems, and decreasing potential values to
represent reducing systems. The sign of Eh used in this manner is opposite to
standard American practice in electrochemistry.
Reagents. An Eh standard' which can be used is a solution of M/300
K3Fe(CN)6 and M/300 KqFe(CN), in M/10 KC1 (Zobell, 1946). The Eh of
this mixture is 0.430 V at 25'C.
Equipment. A pH meter equipped with a thermometer, a glass electrode, a
calomel electrode, a platinum electrode and a thermocompensating electrode.
Eh flowchamber, a design similar to Fig. 2.5 can be used.
Procedure. Buff the platinum electrode lightly with a fine abrasive cloth
and wipe it carefully with a dry soft tissue. Install the glass electrode, the
calomel electrode, the platinum electrode, the thermocompensator, and the
thermometer in the flowchamber. Standardize the instrument using the Eh
standard.
Connect a line t o the wellhead or waterline and install an oil-water
separator if oil and water both are present. Connect the flowchamber to the
waterline, allowing the water to flow into the bottom and out the top. Make
certain that all air bubbles are excluded at the top.
Take at least three readings of the Eh (in mV), and the temperature at
10-minute intervals. These readings should agree; if they do not, continue
making readings until three successive readings do agree. Make certain the
water is continually flowing, that there are no air bubbles in the flowchamber, and that the solution is being stirred. It may be necessary t o
remove and rebuff the platinum electrode.
Calculation. Because a thermocompensator is used in determining the pH, a
temperature correction need not be made. However, if a thermocompensator
is not used, a temperature correction should be made.
The Eh value is obtained by algebraically adding the measured voltage E
and the voltage of the constant voltage reference electrode, which in this
case is the saturated calomel electrode. The potential of the saturated
calomel electrode at 25OC is 0.242 V. Therefore, if the millivolt reading of
the sample is +300:
31
SUSPENDED SOLIDS
E = +0.242 - 7.6x
( t - 24)
Note: the calculations for Eh are correct only if the temperature of the
brine is 25OC at the time of measurement. If the temperature is not 25"C, a
correction should be made. For example, the potential of the saturated
calomel electrode is 0.246 V at 20C and 0.238 V at 30C. The following
formula can be used to obtain the correct potential:
= +0.242 - 7.6 x
( t - 24)
Turbidimeter
Instruments for the measurement of turbidity employ principles of design
related to transmission or reflectance of light. The lack of a primary standard
for turbidity, however, has resulted in a complete absence of uniformity
among the available instruments. Further, the Jackson candle turbidimeter,
which does not depend upon the use of a primary standard, is a primitive
instrument, subject to many interferences, and the measurements generally
are not reproducible.
Recently developed turbidimeters often use for calibration a suspension of
formazin permanently embedded in a cylinder of Lucite. These instruments
produce reproducible readings up t o 40 Jackson candle units (JCU), and
samples containing turbidities in excess of 40 JCU should be diluted to
32
values below this level and the results multiplied by the correct dilution
factor.
To obtain maximum accuracy and precision the following precautions
should be observed:
(a) Protect the Lucite standard from scratches, nicks, and fingerprints.
(b) While calibrating the instrument, use a constant orientation of the
Lucite standard.
(c) Use a homogeneous sample in the sample cuvette; do not take readings
until finely dispersed bubbles have disappeared.
(d) Dilute samples containing. excess tubidity to some value below 40
JCU; take reading, and multiply results by correct dilution factor.
Suspended solids analysis
RESISTIVITY
33
R E S I S T I V I T Y . .hm-n.ttrl
34
Cell preparation
To prepare the cell, clean it with chromic-sulfuric acid solution and rinse
thoroughly with water. Immerse the cell or fill it, depending upon whether a
dip or pipet cell is used, in the platinizing solution. Connect the electrodes of
the cell to three dry cells (1-1/2 V each) in parallel through a limiting
resistance of approximately 1,000 52. Reverse the direction of the current
once a minute for 6 minutes or until the shiny platinum surface is covered
with a dense black coating. Repeat the electrolytic process using 10%
sulfuric acid solution to remove chlorine. Remove the electrodes, rinse with
distilled water, and store in distilled water.
Note: new cells should be cleaned and platinized before use. They should
be cleaned and replatinized whenever the readings become erratic or when
the platinum black flakes off.
Cell resistance
To determine the cell resistance using the standard potassium chloride
solutions, adjust the temperature of each potassium chloride solution to
exactly 25OC and obtain a reading in ohms for each solution with the cell.
Calculate the cell constant using the following formula:
SPECIFIC GRAVITY
35
Method of determination
Procedure. To determine the resistivity of the petroleum-associated water,
filter the sample to remove oil and transfer the sample t o the cell or cell
container and place it in a water bath. Allow sample sufficient time to adjust
to bat!i temperature, and measure resistance of sample and record the
temperature to nearest 0.1Oc.
Calculation. The resistivity calculation is dependent upon the type of cell
and bridge used, but in general the following formula will apply:
R,
D2 V
=-
4LXT
R,
= KV
Calculated resistivity
The resistivity of petroleum-associated waters often is calculated using the
laboratory analysis (Dunlap and Hawthorne, 1951). The concentrations of
the ionic constituents are used in the calculation method.
Dunlap and Hawthorne (1951) caution users of their calculation method
that the sulfate factor 0.50 may give unreliable results if the water contains
appreciable concentrations. of sulfate. If the sulfate concentration exceeds
2,500 mg/l, a factor of 0.40 will give a better calculated resistivity value.
Specific gravity
Specific gravity is the ratio of the weight of a given volume of material to
the weight of an equal volume of some other material used as a standard
(Mellon, 1956, p.306), and pure water is the usual standard for liquids and
solids. Depending upon the accuracy desired, the specific gravity of a
petroleum-associated water can be determined with a pycnometer, specific
gravity balance, or hydrometer. Because any oil in or on the sample will
interfere with the specific gravity determination, the sample should be
filtered.
TABLE 3.W
Approximate relation of specific gravity (Sp. gr.) to mg/l of dissolved solids (DS)
Sp. gr.
DS
Sp.gr.
DS
Sp. gr.
DS
Sp.gr.
DS
Sp. gr.
DS
Sp.gr.
DS
1.ooo
0
1,400
2,800
4,200
5,600
7,000
8,300
9,700
11,100
12,400
13,700
15,200
16,600
17,800
19,100
20,500
21,900
23,200
24,500
25,900
27,300
28,500
29,800
31,000
32,400
33,900
35,100
36,400
37,700
39,100
40,400
41,700
43,000
44,300
45,600
46,900
48,300
49,500
1.038
1.039
1.040
1.041
1.042
1.043
1.044
1.045
1.046
1.047
1.048
1.049
1.050
1.051
1.052
1.053
1.054
1.055
1.056
1.057
1.058
1.059
1.060
1.061
1.062
1.063
1.064
1.065
1.066
1.067
1.068
1.069
1.070
1.07 1
1.072
1.073
1.074
1.075
'50,800
52,000
53,300
54,600
55,900
57,100
58,300
59,600
60,900
62,100
63,400
64,600
65,900
67,100
68,400
69,600
70,900
72,000
73,300
73,600
75,800
77,100
78,200
79,400
80,600
81.800
83,100
84,300
85,600
86,700
87,800
89,100
90,300
91,500
92,700
93,900
95,100
96,200
1.076
1.077
1.078
1.079
1.080
1.081
1.082
1.083
1.084
1.085
1.086
1.087
1.088
1.089
1.090
1.091
1.092
1.093
1.094
1.095
1.096
1.097
1.098
1.099
1.100
1.101
1.102
1.103
1.104
1.105
1.I06
1.107
1.108
1.109
1.110
1.111
1.112
1.113
97,400
98,700
99,800
101,000
102,200
103,400
104,600
105,800
106,900
108,100
109,300
110,400
111,600
112,800
114,000
115,100
116,200
117,400
118,600
119,600
120,800
122,000
123,100
124,400
125,500
126,700
127,800
128.800
130,000
131,100
132,300
133,400
134,500
135,600
136,800
137,900
139,100
140.1 00
1.114
1.115
1.116
1.117
1.118
1.119
1.120
1.121
1.122
1.123
1.124
1.125
1.126
1.127
1.128
1.129
1.130
1.131
1.132
1.133
1.134
1.135
1.136
1.137
1.138
1.139
1.140
1.141
1.142
1.183
1.144
1.145
1.146
1.147
1.148
1.149
1.150
1.151
141,200
142,300
143,400
144,500
145,600
146,700
147,900
148,900
150.00 0
151,100
152,100
153,200
154,400
155,500
156,600
157,700
158,800
159,900
161,000
162,000
163,100
164,100
165,200
166,200
167,300
168,400
169,400
170,400
171,500
172,500
173,600
174,700
175.7 00
176,800
177,900
178,900
180,000
181,100
1.152
1.153
1.154
1.155
1.156
1.157
1.158
1.159
1.160
1.161
1.162
1.163
1.164
1.165
1.166
1.167
1.168
1.169
1.170
1.171
1.172
1.173
1.174
1.175
1.176
1.177
1.178
1.179
1.180
1.181
1.182
1.183
1.184
1.185
1.186
1.187
1.188
1.189
182,100
183,200
184,200
185,300
186,300
187,400
188,400
189,500
190,500
191,600
192,600
193,600
194,700
195,700
196,700
197,800
198.800
199,800
200,900
201,900
202,900
203,900
204,900
206,000
207,000
208,000
209,000
210,000
211,000
212,000
213,000
214,000
215,000
216,000
217,000
218,000
219.000
22o;ooo
1.190
1.191
1.192
1.193
1.194
1.195
1.196
1.197
1.198
1.199
1.200
1.201
1.202
1.203
1.204
1.205
1.206
1.207
1.208
1.209
1.210
1.211
1.212
1.213
1.214
1.215
1.216
1.217
1.218
1.219
1.220
1.221
1.222
1.223
1.224
1.225
221,000
222,000
223,?00
224,000
225,000
226,000
227,000
228,000
229,000
1.001
1.002
1.003
1.004
1.005
1.006
1.007
1.008
1.009
1.010
1.011
1.012
1.013
1.014
1.015
1.016
1.017
1.018
1.019
1.020
1.021
1.022
1.023
1.024
1.025
1.026
1.027
1.028
1.029
1.030
1.031
1.032
1.033
1.034
1.035
1.036
1.037
230,000
230,800
231,800
232,800
233,700
234,700
235,700
236,700
237,600
238,600
239,500
240,500
241,500
242,400
243,400
244,300
245,300
246,200
247,700
248,100
249,100
250,000
250,900
251,900
252,800
253,800
254,700
3
m
TITRIMETRIC METHODS
37
TABLE 3.VII
Relationships for determining alkalinity after neutralization with a standard acid
Volume of standard acid used
P=O
P = 1/2T
P = 1/2T
P > 1/2T
P=T
<
OH
co3
HC03
0
0
0
2P-T
T
0
2P
2P
2(T-P)
0
T
T - 2P
0
0
0
38
HOOC ,
NaOH +
ChH,
+ H,O
-ChH,
KOOC
COOK
Normality calculation:
weight KHCs H, 0,
= 0.20422 x ml NaOH
N=
weight KI03
0.03567 x ml HC1
39
ml sample
40
Na
0 -CO
- CHI
CHI - C O - 0
\
, Na
N - (CH2) - N
\ 0 - CO - CH, /
CH,
- CO - 0
Its molecular weight is 372.254, and it forms 1:l complexes with most
cations according t o the following equations:
Me+ + H2Y-
Me+3 + H2Y-
Me+4 + H2Y-
* MeY-
* MeY* MeY
+ 2H+
+ 2H+
+ 2H+
* M-EDTA + In
where M-In = the metal indicator complex, M-EDTA = the metal-EDTA complex, and In = the indicator. The metal indicator complex must be weaker
than the metal-EDTA complex. The color change occurs because the metalindicator complex ionizes, and the free metal is completely complexed by
the EDTA, leaving a free indicator.
Sample size
Because many petroleum-associated waters contain high concentrations of
dissolved solids including calcium and magnesium, it usually is necessary t o
dilute them or to use a micropipet t o obtain a small sample before
performing a complexometric titration. The dilution and subsequent aliquot
TITRIMETRIC METHODS
41
TABLE 3.VIII
Aliquot size for total hardness, calcium, and magnesium determination
Specific gravity
Dilution
Aliquot (ml)
1.ooo--1.010
1.010-1.025
1.025-1 .O50
none
none
dilute 25 ml to
take 50 ml
dilute 25 ml to
take 25 ml
dilute 25 ml to
take 25 ml
dilute 25 ml to
take 25 ml
50
25
12.5
1.050-1.090
1.090-1.1 20
1.120-1.150
100 ml,
100 ml,
6.25
500 ml,
1.25
1,000 ml,
0.625
TABLE 3.IX
Comparison of errors in direct reading of sample size using a micropipet versus the
dilution technique
Direct-reading using micropipet
Dilution technique
sample size
error
(ml)
ml taken after
diluting 10 ml
to 100 ml
error
(ml)
f 0.004
2
5
10
10
20
50
f 0.01
~~
200 h
500 h
1,000 h
1ml
2 ml
5 ml
f 0.01
* 0.002
f 0.006
f 0.006
f 0.01
f 0.025
f 0.005
* 0.005
f 0.009
* 0.02
size usually can be determined by using data such as that illustrated in Table
3.VII1, which is applicable to most oilfield brines.
A more rapid method of obtaining a fraction of a milliliter of a liquid
sample is direct measurement using a micropipet. A micropipet in the hands
of a competent analyst can also yield a more accurate sample size than the
dilution technique illustrated in Table 3.VIII; e.g., two reading errors are
omitted because only one meniscus reading is necessary with the direct
measurement as compared to three using the dilution. Table 3.IX illustrates a
comparison of errors in sample sizes of the direct reading method versus the
dilution method.
Reagents: CDTA (disodium 1,2-cyclohexanediaminetet,raaceticacid) standard
solution, approximately 0.025M:dissolve 10.66 g CDTA in water and dilute
42
10.0 x 0.025
0.25
or V
V
Procedure. Filter the sample to remove undissolved solids and traces of oil
from the water. Transfer, by means of Lambda pipet or volumetric transfer pipet, an aliquot of sample containing not more than 10 mg of calcium
into an Erlenmeyer flask. Dilute t o approximately 50 ml with water. (No
more than 10 ml of standard CDTA are t o be used in a titration for either
calcium or magnesium.)
Add two to three drops of triethanolamine solution and approximately 4
ml of sodium hydroxide solution. The pH of the solution at this point
should be 12.0-12.5. Add six drops of calcon indicator and titrate with
standard CDTA solution until the indicator blue endpoint is reached. Record
the volume of CDTA titrant used t o titrate calcium.
Using the same pipet, pipet another aliquot into another Erlenmeyer flask
and dilute t o 50 ml with water. Add two to three drops of triethanolamine
solution, 3-5 ml of the ammonium chloride ammonium hydroxide buffer
solution, and three to four drops of Eriochrome Black T indicator. Refill the
buret with the same standard CDTA titrant and titrate the sample until the
color changes from wine to pure blue. This endpoint is sometimes delayed,
so proceed cautiously with the titration near the endpoint. Record the
volume of CDTA used t o titrate calcium and magnesium, or hardness (Ca +
Mg).
43
Calcula t ions :
B x M x 100,100
sample volume
A x M x 40,000
sample volume
= mg
(B-A) x M x 24,300
sample volume
Ca per liter
mg Mg per liter
44
Calculation:
(ml NaOH x N used for sample) -
Chloride
A modification of the Mohr method (Furman, 1962) is satisfactory for
the determination of chloride in petroleum-associated waters. Common
interferences are bromide, iodide, sulfide, and iron. Sulfide can be removed
by acidifying the sample with nitric acid and boiling. Iron can be removed by
ion exchange or precipitation with sodium hydroxide or sodium peroxide
followed by filtration.
Because most petroleum-associated waters contain high concentrations of
chloride, it usually is necessary to dilute the sample before titrating with
silver nitrate, because the voluminous precipitate masks the endpoint. About
50 mg of chloride is maximum for a satisfactory titration. The indicator
usually is potassium chromate or sodium chromate, and at the endpoint the
chromate ion combines with excess silver to form the slightly soluble red
silver chromate:
Ag+ + C1-
ZAg+ +
AgCl
--f
Ag2Cr04
The specific gravity of the sample can be used t o estimate the correct
aliquot size. Table 3.X indicates aliquot sizes that will contain less than 50
mg of chloride. The micropipet can be used as demonstrated in the
calcium-magnesium procedure and Table 3.IX.
TITRIMETRIC METHODS
45
TABLE 3.X
Aliquots that contain less than 50 mg of chloride as estimated from the specific gravity
Specific gravity
Dilution
Aliquot (ml)
1.000-1.002
1.003-1.004
1.005-1.012
1.01 3-1.019
1.020-1.032
1.033-1.064
1.065-1.087
1.088-1.162
1.163
none
none
dilute 10 ml to
dilute 10 ml to
dilute 10 ml to
dilute 25 ml to
dilute 20 ml to
dilute 10 ml to
dilute 10 ml to
100
50
5.0
2.0
1.0
0.5
0.4
0.2
0.1
>
46
Iron, manganese, and organic matter can interfere but are removed in the
procedure. Fluoride is added to mask interference from any remaining traces
of iron.
Reagents. The necessary reagents include a 2% ammonium molybdate solution; glacial acetic acid; calcium hydroxide; calcium carbonate; 0.05N
hydrochloric acid; 6N hydrochloric acid; potassium iodide; sodium fluoride;
starch indicator solution; 0 . O l N sodium thiosulfate (standardize prior t o
use); 3.8M sodium formate (prepare fresh daily); saturated bromine water;
and methyl red indicator solution.
Equipment. The necessary equipment includes a mechanical shaker, 200-ml
bottles, a hot-water bath, flasks, pipets, and microburets.
Procedure. To remove iron, manganese, and organic matter from the sample,
add exactly 100 ml of sample to a stoppered bottle. Add 1 g of calcium
hydroxide, and place the mixture in a shaker for 1 hour. Allow the mixture
to stand overnight and filter through a dry folded filter, discarding the first
20 ml that comes through. Brines with specific gravities of less than 1.009
may be filtered without standing overnight. Prepare a blank in the same
manner.
Transfer an aliquot of the filtrate containing 1-2 mg of iodide t o a
250-ml Erlenmeyer flask. Add sufficient water t o make the total volume 75
ml, and three drops of methyl red indicator. Add 0.05N hydrochloric acid
until the mixture is just slightly acid, add 10 ml of sodium acetate solution,
1 ml of glacial acetic acid, and 4 ml of bromine water, and allow to stand for
5 minutes. Next add 2 ml of sodium formate solution, blow out any bromine
vapor from the neck of the flask, and wash down the sides with water.
When the solution is completely colorless, add 0.2 g of sodium fluoride
and 0.5 g of potassium iodide. Mix until dissolved and add 15 ml of 6N
hydrochloric acid. Titrate with 0.01N sodium thiosulfate using starch indicator. Disregard any return of blue color after the endpoint. Record this titration volume for the iodide calculation.
Transfer another aliquot of the filtrate containing 1-2 mg of bromide t o a
250-ml Erlenmeyer flask and add sufficient water to make the total volume
75 ml. Add 10 ml sodium hypochlorite solution and approximately 0.4 g of
calcium carbonate (or enough so that approximately 0.1 g will remain after
the next step). Adjust the pH of the solution with 3N hydrochloric acid to
between 5.5 and 6.0 and heat in a water bath t o 90C for 10 minutes. (A
small amount of undissolved calcium carbonate should remain at this point.)
Remove the flask and cautiously add 10 ml of sodium formate solution,
return the flask to the water bath, and keep the contents hot for 5 minutes
more and observe the timing very closely. Rinse down the inside of the flask
with a few milliliters of distilled water and allow the solution to cool t o
room temperature. (Do not use a cold water bath.) To the ambient solution
TITRlMETRIC METHODS
47
add three drops of ammonium molybdate solution, 0.5 g sodium fluoride (if
iron is present), and 0.5 g potassium iodide, mix until dissolved, and acidify
with 15 ml of 6N hydrochloric acid. Titrate with 0 . O W sodium thiosulfate
using starch indicator. Disregard any return of blue color after the endpoint.
Record this titration for the bromide calculation.
Calculations. Iodide: ml of Na, S2O 3 for sample - ml of Na, S2O3 for blank
corrected ml of Na, S2O 3 :
MnO (OH),
48
On acidification in the presence of an iodide, the higher oxide of manganese liberates a quantity of iodine stoichiometrically equivalent t o the
quantity of dissolved oxygen present in the sample in the following manner:
MnO (OH), + 2H2 SO4 +. Mn(S04 )Z + 3H20
Mn(S04), + 2KI +. MnS04 + K2S04 + I2
The quantity of iodine liberated is determined by titrating an aliquot
portion of the sample with a standard solution of sodium thiosulfate
( N a 2 S 2 0 3 )using starch solution as an indicator, as shown by the equation:
2Na2S, O3 + I,
+. Na,
S40, + 2NaI
The iodine modification of the Winkler method depends upon the conversion of any hydrogen sulfide t o hydrogen iodide and free sulfur by reducing
the iodine added t o the brine. This reaction proceeds as follows:
H,S+I2 + 2 H I + S
Tests have shown that interfering substances other than hydrogen sulfide
that might be present in oilfield brines also are counteracted by the iodine
added.
TITRIMETRIC METHODS
49
50
added when the yellow color of free iodine has been almost eliminated by
the sodium thiosulfate titration, and the titration should be continued until
one drop changes the solution from a light blue to colorless. (Subsequent
blue recoloration should be disregarded.)
If no hydrogen sulfide or other interfering substances are present, the first
six steps of the determination may be eliminated, using only the part of the
procedure starting with the addition of the alkaline iodide solution.
Calculation. The dissolved oxygen content of the water is determined by the
following equations:
v = 200 x-(Y-1)
u=-200 w
V
Carbon dioxide
Petroleum-associated waters containing carbon dioxide and bicarbonate or
carbonate will contain a weak acid H2C03 or its salt, which buffers the
solution. This combination controls the pH of waters in the range of about
pH 4.5-8.0. Such buffering is caused by the presence of slightly dissociated
acids or bases, and when H+ or OH- ions are added they first convert the
undissociated acid or base to its salt or vice versa.
Loss of carbon dioxide will disturb the carbon dioxide-bicarbonatecarbonate buffer systems. For example, the pH probably will change and
precipitation of calcium carbonate or other compounds may occur. An increase in carbon dioxide will shift t h e . carbon dioxide-carbonatebicarbonate equilibria, allowing more material such as calcite t o go into
solution.
Bacterial reduction of sulfate can cause the amount of dissolved carbon
dioxide and hydrogen sulfide in petroleum-associated waters t o be quite
high. Several hundred milligrams per liter of C 0 2 can be present in such
waters. Knowledge of the amount of carbon dioxide in solution is useful in
carbonate equilibria studies (Garrels and Christ, 1965) and in water compatibility studies (Watkins, 1954).
51
Reagents. The necessary reagents are 0.05N sodium carbonate solution and
phenolphthalein indicator solution.
Procedure. Collect the water sample in the same manner used in taking the
sample t o be analyzed for dissolved oxygen. Pipet 100 ml of the water into a
flask and add five drops of phenolphthalein indicator. If the sample turns
red, no free carbon dioxide is present; if it remains colorless, titrate the
sample with the standard sodium carbonate solution to a red endpoint.
Calcula tion :
ml Na2CO, x N x 22,000
= mg/l C02
ml sample
Sulfide
+. Na2S4 O6 + 2NaI
52
Sulfur compounds
The redox potential of petroleum-associated waters indicates that sulfur
compounds other than sulfate and sulfide may exist in solution. When the
water is brought t o the land surface, the change in pressure and temperature
will affect the redox potential and, if the sample is allowed t o come into
contact with the atmosphere, the equilibria of the sample will start t o change
immediately. Better methods are needed t o determine the composition of a
water in situ. The following method can be used to gain a semiqualitative
estimation of the amomts of thiosulfate, sulfite, and sulfide in a water.
53
X ml
x N x 112,000
= mg/l S2 03-2
ml sample
Y ml x N x 40,000
= mg/l SO,-2
ml sample
Milliliters iodine used in C - milliliters iodine used in B = 2 ml
2 ml x N x 16,000
ml sample
= mg/l
S-
When a metal salt in solution is sprayed into a flame, the solvent evaporates and the salt decomposes and vaporizes, producing atoms. Some of these
atoms can be raised t o an excited state by the thermal energy of the flame,
although a major portion of the atoms present in the flame remain at the
grourid state. The return of the excited atoms to the ground state results in
the emission of radiant energy characteristic of the element atomized. The
quantitative measurement of this radiation is the basis of emission flame
spectrophotometry, and the essential difference between this form of
analysis and classical arc-emission spectrography is the temperature of the
source used to excite the atoms. Because the g a s a i r and gas-oxygen flames
54
are much cooler than the spark and arc sources used in spectrography, analysis by emission flame spectrophotometry is usually limited t o the more easily
excitable elements - lithium, sodium, and potassium.
Instrumentation requirements include:
(1) A method of introducing the sample into the flame for vaporization.
(2) A method of detecting and recording the radiation intensity emitted.
(3) A method of selecting the correct wavelength, ordinarily a variable
monochromator.
A more complete discussion of the theory and instrumentation can be
found in books by Burriel-Marti and Ramirez-Munoz (1957) and Dean
(1960), as well as in publications of commercial instrument manufacturers.
Lithium
Lithium usually is calculated as a part of the sodium content in reporting
the results of oilfield water analyses rather than being determined and
reported separately. One of the more accurate methods t o determine lithium
in petroleum-associated waters is the flame spectrophotometric method
(Collins, 1962).
Reagents. The reagents are lithium, standard solutions, 0.1 mg/ml and 0.01
mg/ml; and n-propanol.
Equipment. The necessary equipment includes a flame spectrophotometer,
10-ml'microburets, and volumetric flasks.
Preliminary calibration curves. Preliminary calibration curves are useful in
determining approximately how much lithium is in the sample and in determining the optimum amount of standard lithium solution t o use in the
analysis. Because n-propanol is easier t o work with, it usually is used; however, if additional sensitivity is needed, the acetone-n-amyl alcohol mixture
can be used (Collins, 1965).
To prepare the preliminary calibration curves, transfer t o 50-ml volumetric flasks aliquots of diluted standard lithium solution containing the following amounts of lithium: 0.01 mg, 0.05 mg, 0.1 mg, 0.15 mg, and 0.2 mg.
Add 20 ml of n-propanol to each flask and dilute to volume with distilled
water. Aspirate, burn, and record the emission intensity of each of these five
standards at 670.8 mp and their background at about 665 mp. Record
several peaks for each standard at various sensitivity levels and slit widths.
Plot the results on linear graph paper by plotting milligrams of lithium
versus intensity. Prepare a curve for each sensitivity level and slit width used,
as illustrated in Fig. 3.2. The sensitivity of the instrument will determine the
optimum concentrations of lithium and this will require some experimentation.
The analyst may find it convenient t o scan all the emission lines of
26 -
2
22-
-x 20180
0
'I
55
0.01
~ mm r l i t
1,620 volta to I T 1 F W 6836
tOppri 02
5 p s i C2H2
12.5 mm burner height
10-
mg L i / m l 5 0 % n - P R O P A N O L
Fig. 3.2. Preliminary calibration curves for use in selecting optimum standard additions:
Instrument: 0.01-mm slit, 1,620 V to ITT FW 6836, 1 0 psi 02,5 psi C2HZ,and 12.5-mm
burner height.
56
5
4
v)
13
2 3
W
a
c
a
.x2
I
u
1
L
I
COI
2s
4
5
6
tENTRATION OF STANDARD ADDITIONS
I
7
Fig. 3.3. Standard-addition calculation graph. In this ideal case the unknown would contain 2 x the dilution factor ( 2 could be 2 mg or 2 pg or whatever unit the analyst used).
57
Solution
Concentration
Reading
Unknown
c,
r,
Mixture
c,
= c, +
*C is a standard addition.
Sodium
The flame spectrophotometer offers an excellent instrumental technique
for determining sodium in a petroleum-associated water. The flames containing alkali metals give strong resonance lines of these metals plus some
additional continyous radiation. The strongest line for sodium results from a
transition between the lowest excited level and the ground state. The yellow
doublet of sodium at 589.0-589.6 mp results from such a transition.
Reagents. The necessary reagents are sodium standard solutions, 1 mglml
and 0.01 mg/ml; and n-propanol.
Preliminary Calibration curves. Preliminary calibration curves similar to those
shown in Fig. 3.2 should be used to determine the approximate amount of
sodium in the sample. These curves are prepared in the same manner as the
lithium curves, except that standard sodium solutions are used; the emission
intensity of the sodium at 589 mp is determined, minus a background at
about 582 mp.
Procedure. To analyze the petroleum-associated water, transfer an aliquot of
water t o a 50-ml volumetric flask, add 20 ml of n-propanol, and dilute to
volume with distilled water. (The size of the aliquot will vary with the
sample. The specific gravity can be used to help decide the aliquot size. For
a water with a specific gravity of 1.1,an aliquot of 1ml or less probably will
be sufficient.) Aspirate the sample into the flame and record the emission intensity of the background at 582 mp and sodium line at 589 mp. With these
readings, calculate approximately how much sodium is in the sample by using
the preliminary calibration curves.
Determine the aliquot size that will contain about 0.05 mg of sodium.
Transfer equal aliquots t o three 50-ml volumetric flasks. Add no sodium
58
standard to the first flask, 0.05 mg to the second flask, and 0.1 mg t o the
third flask. Add 20 ml of n-propanol to each flask and dilute to volume with
water. Aspirate and record the emission intensity of each sample at 589 mp
and its background at 582 mp.
Calculation. Use the graph or formula illustrated in the lithium method. The
value obtained in milligrams can be converted to milligrams per liter by the
following formula:
mg Na x 1,000
= mg/l Na'
ml sample
The precision and accuracy of the method are approximately 3%and 6%,
respectively, of the amount of sodium present. Some elements, when present
in the solution being analyzed, will cause a change in the emission intensity
of the sodium. The use of a standard addition technique largely compensates
for these interferences.
Potassium
Potassium usually is included with sodium without any differentiation in
reporting the results of brine analyses, although potassium is known to be
present in many oilfield brines. Potassium compounds often are dissolved
before sodium compounds; however, they do not remain dissolved as readily
because they are readily adsorbed and enriched in clays. In sea water and
oilfield brines, only a small part of the originally dissolved potassium remains
in solution. The fact that many oilfield brines are low in potassium with
respect to sodium, whereas surface waters and young volcanic waters are
enriched in potassium with respect to sodium, is an important criterion in
identifying the sources of brines.
The flame spectrophotometer provides a sensitive method for the determination of potassium. The strongest lines for potassium detection in a flame
are the doublet at 766.5 and 769.9 mp.
Reagents. The necessary reagents are potassium standard solution, 0.1
mg/ml; and n-propanol.
Preliminary calibration curves. Preliminary calibration curves are useful in
determining the approximate amount of potassium in the sample, so that the
optimum sample size for standard addition can be selected for the analysis.
These curves can be prepared in the same manner used in the preparation of
the lithium preliminary calibration curves (Fig.3.2) except that standard
potassium solutions are used. The emission intensity of the potassium line at
766.5 mp minus the background at about 750 mp can be used in preparing
the curves.
59
60
type 6911. Such tubes also are useful for lithium and potassium determinations.
Several elements can interfere in the determination of cesium and
rubidium. However, because a solvent extraction or standard-addition technique is used most interferences are either removed or compensated (Collins,
1965).
Reagents. The necessary reagents are cesium standard solution, 0.01 mg/ml;
rubidium standard solution, 0.01 mg/ml; buffer solution, pH 6.6 (adjust the
pH of a 1M sodium citrate solution to 6.6 with 0.5M nitric acid); sodium
tetraphenylboron, 0.05M (dissolve 0.855 g of sodium tetraphenylboron in
distilled water and dilute t o 50 ml - prepare a fresh solution daily);
nitroethane; hydrochloric acid, 0.1N; sodium hydroxide, 0.W;synthetic
brine solution.
Procedure. To determine the amount of rubidium and cesium in the
petroleum-associated water, transfer an aliquot of brine containing 0.005 to
0.05 mg of cesium and rubidium to a 100-ml beaker and add 25 ml of the
citrate buffer solution. Transfer the solution to a 125-ml Teflon-stoppered
separatory funnel and adjust to 100-ml volume. Add 2 ml of 0.05M sodium
tetraphenylboron aqueous solution and 1 0 ml of nitroethane, and shake the
mixture vigorously for 2 minutes. Allow the phases t o separate for 30
minutes, after which time withdraw the aqueous phase. Centrifuge the
nitroethane phase. Determine the cesium and rubidium emission intensities
by burning the nitroethane phase in the flame spectrophotometer and
automatically scanning the 780.0 mp, 794.8 mp, and 894.4 mp lines.
Calibration curves. Prepare calibration curves by using appropriate portions
of the standard cesium and rubidium solutions. Add 5 ml of synthetic brine
solution t o each standard sample before buffering and extraction. Plot the
resultant emission intensities versus milligrams of cesium or rubidium or
linear graph paper.
Calculation. Determine the milligrams of cesium or rubidium in the sample
by referring t o the calibration curves. The milligrams can be converted to
mg/l by the following formula:
mgx 1,000
= mg/l Cs+ or Rb'
ml sample
Fig.3.4 illustrates the relative emission intensities obtained with cesium
and rubidium in nitrobenzene, nitroethane, 1-nitropropane, and 2-nitropropane. 15 ml of each of these solvents.are used t o extract 0.1 mg each of
cesium and rubidium tetraphenylboron from aqueous solutions. The organic
phases then are aspirated directly into the flame, and the peaks scanned
automatically. Good resolution is obtained with a 0.01 mm slit width. Amy1
alcohol gives poorer results than nitrobenzene.
NITROETHANE
I- NITROPROPANE
63
2 - NITROPROPANE
Fig. 3.4. Relative intensities obtained by burning organic solvents containing tetraphenylboron salts of cesium and rubidium.
62
Procedure. Transfer an aliquot of brine containing up to 150 pg of manganese to a 100-ml beaker; add 1ml of hydrogen peroxide, 5 ml of ammonium
fluoride, and 10 ml of sodium potassium tartrate; and adjust the pH of the
mixture to 9.0 with ammonium hydroxide. Transfer the solution to a 125-ml
Teflon-stoppered separatory funnel, add 10 ml of 8-hydroxyquinoline
chloroform solution, and bring the mixture t o equilibrium by shaking it
vigorously for 1minute.
Draw the chloroform phase off into a 100-ml beaker and strip the aqueous
phase by an additional extraction with chloroform. Evaporate the combined
chloroform extracts to dryness over a hotplate, taking care t o prevent the
residue from charring. Dissolve the residue in n-propanol and make to 50 ml
volume with n-propanol. Aspirate the n-propanol solution directly into the
flame and determine the net emission by subtracting the background emission
at 400 mp.
Calculate the amount of manganese in the sample from a calibration curve
prepared by adding known amounts of manganese t o a synthetic brine solution. The calibration curve should be linear for up t o 150 pg of manganese
when the emission intensity is plotted versus micrograms of manganese on
linear graph paper.
Calculation :
pg Mn (from curve)
= mg/l Mn +*
ml sample
The intensity of the emission of manganese in a flame spectrophotometer
is enhanced by a factor of 16 by using n-propyl alcohol rather than water as
the solvent. With this increased intensity, the sensitivity of the method is
about 1 mg/l, although additional sensitivity is attainable by concentrating
the brine by evaporation. The precision of the method is about 3%,and the
accuracy is about 6% of the amount present.
Strontium
Several flame photometric methods are available for determining strontium in oilfield brines; a standard curie may be unreliable if there are
instrument changes, such as a slightly plugged burner, change of resistance in
the amplifying circuit, or other variables. Chemical precipitation of strontium as the sulfate does not satisfactorily separate strontium from barium
63
64
subject to few interferences except from calcium, but by using the chromate
precipitation, calcium is eliminated and barium is concentrated.
Reagents. The necessary reagents are barium standard solution, 1 mg/ml;
ammonium chromate solution (dissolve 10 g of ammonium chromate in
distilled water and dilute to 100 ml); 10%ammonium acetate aqueous solution; nitric acid ( 4 N ) ;n-propanol; acetic acid; and synthetic brine solution
(use carbon dioxide-saturated distilled water and dissolve the following
amounts of constituents in 1 liter of water: sodium bicarbonate, 0.4 g;
sodium chloride, 61 g; potassium. chloride, 5 g; calcium chloride, 19 g; magnesium chloride, 1 2 g; and strontium chloride, 5 g).
Procedure. Transfer an aliquot of the sample containing 0.5-15 mg of
barium t o a 100-ml beaker, add 1 ml of the ammonium acetate solution, 10
ml of the ammonium chromate solution, and adjust the pH t o 4.6 using
acetic acid. Cover the beaker with a watchglass; heat the solution t o near
boiling (90C), remove from the hotplate, and allow to stand for 1 hour.
Filter the solution through a 0.45-pm membrane filter using vacuum. Take
care to transfer all of the precipitate from the beaker to the filter funnel. Use
ammonium chromate solution rather than distilled water to aid in this transfer.
Wash the precipitate with 50 ml of ammonium chromate or until strontium and calcium are absent. Wash the precipitate with 50 ml of hot water to
remove excess chromate.
Add 5 ml of 4N nitric acid t o the filter and swirl the solution on the filter
gently to dissolve the precipitate. A clean test tube should be placed below
the filter to catch the dissolved precipitate. When all of the precipitate is
dissolved, turn on the vacuum and catch the solution in the test tube. Repeat
this procedure using an additional 5 ml of 4N nitric acid.
Transfer the solution from the test tube t o a 50-ml volumetric flask.
Carefully wash the test tube with two 5-ml portions of water. Add 25 ml of
n-propanol, dilute to 50 ml volume with water, and mix the solution
thoroughly. Burn the sample in the flame spectrophotometer and record the
emission intensity at 873 mp and the background at 900 mp.
Prepare calibration curves by adding up t o 25 mg of barium to 10 ml
portions of the synthetic brine followed by analysis according t o the foregoing procedure, and use in the calculation.
Calculation:
mg Ba x 1,000
= mg/l Ba+
ml sample
65
TABLE 3.XII
Approximate sensitivities for some metals to atomic absorption
Metal
Wavelength
--
Aluminum
Barium
Beryllium
Cadmium
Calcium
Chromium
Copper
Iron
Lead
Magnesium
Manganese
Mercury
Nickel
Silver
Sodium
Zinc
Sensitivity
(mg/l)
(A)
3093
5536
2348
2288
4226
3579
3247
2483
2833
2852
2794
2536
2320
3281
5890
21 38
1.o
0.2
0.1
0.04
0.08
0.15
0.2
0.3
0.5
0.02
0.15
0.01
0.15
0.1
0.03
0.04
nitrous oxide-acetylene
nitrous oxide-acetylene
nitrous oxide-acetylene
air-acetylene
air-acetylene
air-acetylene
air-acetylene
air-acetylene
air-acetylene
air-acetylene
air-acetylene
air-acetylene
air-acetylene
air-acetylene
air-acetylene
air-acetylene
.
-
66
Ionization
When a significant number of the atoms of the element being determined
are ionized in the flame, an error in the analysis can result. This ionization is
because of excessive flame temperature, which, however, can be changed to
control this interference. Another type of interference can be caused by the
presence in the sample of other, more easily ionizable elements than the one
sought. The resulting increase can be controlled by the addition of a sufficient amount of the interfering element t o both sample and standards t o
produce a plateau in the absorbance above which no further increase
occurs.
Che m ica 1
A chemical interference is caused by the formation, in the flame, of salts
of the element sought which are difficult to decompose, thus reducing the
amount of the element available for absorption. The formation of such
compounds may often be precluded by the addition of another element,
such as lanthanum, which forms a less-soluble salt with the interfering anion
than does the element desired. The interfering anion is thus removed from
the flame, and the interference is eliminated.
Phosphate combines with calcium and magnesium and produces an interference; however, the addition of lanthanum largely overcomes this interference. Addition of an excess of a cation having a similar or lower ionization potential usually reduces interference problems.
Matrix
Matrix interference is caused by unequal amounts of dissolved solids in
the standards and samples. This can cause error because of differences in
aspiration rates through the atomizer. Often this can be controlled by
matching the specific gravities of the standards and samples or by adding
salts t o the standards.
Burners and solvents
Various types of burners are used with atomic absorption spectrophotometers. For example, a Boling burner usually is used for aqueous solutions,
67
while a premix burner is used for organic solutions. A nitrous oxide burner
head with. a 2-inch slot is used for determining aluminium, barium, and
beryllium because overheating is often encountered wit,h a 3-inch slot
burner.
The use of concentration steps, such as solvent extraction of a chelated
compound, enables sensitivities lower than those shown in Table 3.XII to be
achieved. For example, aluminium and beryllium can be complexed with
8-quinolinol and extracted with chloroform; cadmium and lead can be complexed with ammonium pyrrolidine dithiocarbamate and extracted with
methyl isobutyl ketone. When burning the organic solvents, it usually is
necessary t o reduce the fuel air ratio because the burning organic solvent
contributes to the fuel supply producing an undesirable luminescent flame
and may also lift the flame off the burner. An optimum fuel/air ratio can be
found by noting the characteristics of the flame before burning the organic
solvent and then reducing the fuel flow, while burning the organic solvent
until the flame characteristics are similar t o those noted before the organic
solvent was burned. Ramirez-Munoz (1968) provides additional information.
Burner height is very important and adjustment often is necessary when
changing from one element t o another. Some instruments have a Vernier
adjustment for reproducing burner-height settings and some do not. Fig. 3.5
illustrates a device which can be used for reproducing exact burner height
(Ballinger et al., 1972).
0-m
Fig. 3.5. Device for reproducing burner height for emission and atomic absorption spectrometers.
68
Lithium
Lithium is determined at the 6707.8 A wavelength with an air-acetylene
flame.
Precision. In a single laboratory using oilfield water samples containing concentrations of 90 and 190 mg Li+/l, the standard deviations were k 3 and +5,
respectively. The recoveries were 100.6% and 92.996, respectively.
Sodium
Two wavelengths are used: the 5890-5896
69
70
Precision. In a single laboratory using oilfield water samples containing concentrations of 22,700 and 43,200 mg Na+/l, the standard deviations were
+485 and ?1,890, respectively. The recoveries were 100.8% and 100.9%,
respectively.
Potassium
Potassium is determined at the 7664.9 A wavelength with an air-acetylene
flame.
71
Precision. I n a single laboratory using oilfield water samples containing concentrations of 456 and 5,680 mg K+/1, the standard deviations were *25 and
+325, respectively. The recoveries were 93.7% and 97.8%, respectively.
Magnesium (1)
Magnesium is determined at the 2852.1
acetylene flame.
72
-L
4.000
1.00
1.05
1.10
1.15
1.20
I. 5
SPECIFIC G R A V I T Y
Fig. 3.6. Relationship of the concentration of magnesium to specific gravity for some
oilfield brines.
Calculations. See calculations under Lithium in the flame spectrophotometric section, Fig. 3.3, or Table 3.XI:
mgMgx 1,000
= mg/l Mg+2
rnl sample
Precision. In a single laboratory using oilfield water samples containing concentrations of 1,470 and 2,000 mg Mg+2/1, the standard deviations were
k36 and +128, respectively. The recoveries were 97.3%and 103.2% respectively.
Calcium (1)
Calcium is determined at the 4226.7 A wavelength with an air-acetylene
flame.
73
74
Add 5 ml of the lanthanum stock solution to each of the three flasks and
dilute to volume. Aspirate and record the absorbance readings for each
sample.
Calculations. See calculations under Lithium in the flame spectrophotometric section, Fig.3.3, or Table 3.XI:
mg Ca x 1,000
= mg/l Ca+
ml sample
Precision. In a single laboratory using oilfield water samples containing concentrations of 17,400 and 32,500 mg Cat /1, the standard deviations were
k430 and +1,090, respectively. The recoveries were 103.5% and 100.336,
respectively.
Magnesium (2)
The following method for the determination of magnesium in an oilfield
water was supplied through courtesy of the Halliburton Company (1970),
and can be used t o determine all concentrations of the magnesium ion in a
brine.
Procedure. Filter the sample with the micropore filter apparatus t o remove
solids and traces of hydrocarbons from the water. Transfer, by means of
Lambda pipet or volumetric transfer pipet, an aliquot of sample t o contain not more than 1.0 mg magnesium into a 100-ml volumetric flask. Add
5.0 ml hydrochloric acid, 1.0 ml lanthanum stock solution, and sufficient
water to dilute to exactly the 100-ml mark. Mix thoroughly. Aspirate the
5-mg/l standard through the burner, positioning the burner angle as necessary until the recorder indicates a stable reading of about 25% absorption
using a wavelength setting of 2852 a. Record the reading and aspirate distilled water through the burner until the recorder returns t o the original baseline. Next, aspirate the sample through the burner until a maximum stable
reading is obtained on the recorder. Record the reading and if the sample
75
reading on the recorder is greater than the 5-mg/l standard, aspirate the
9-mg/l standard through the burner until a maximum stable reading is obtained. Record the reading and if the sample reading on the recorder is less
than the 5-mg/l standard, aspirate the 1-mg/l standard through the burner
until a maximum, stable reading is obtained, and record the reading.
Calculations:
or :
Calcium (2)
The same apparatus used in determining magnesium by atomic absorption
can be used t o determine calcium.
76
with water. This yields standards of 1.0, 11.0, and 21.0 mg/l of calcium in
the first, second, and third flasks, respectively.
Procedure. Filter the sample through the micropore filter apparatus to remove
solids and traces of hydrocarbons from the water. Transfer, by means of
micropipet or volumetric transfer pipet, an aliquot of sample containing not
more than 2.0 mg calcium into a 100-ml volumetric flask. Add 5.0 ml hydrochloric acid, 1.0 ml lanthanum stock solution, and sufficient water t o dilute to exactly the 100-ml mark and mix thoroughly. Aspirate the ll mg/l
standard through the burner, positioning the burner angle as necessary until
the recorder reaches a maximum stable reading of about 22% absorption using
a wavelength setting of 4227 A. Record the reading and aspirate distilled water
through the burner until the recorder returns t o the original baseline. Remove and aspirate the sample through the burner until a maximum stable
reading is obtained on the recorder. Record the reading and aspirate distilled
water through the burner until the recorder returns t o the original baseline.
If the sample reading on the recorder is greater than the 11 mg/l standard,
aspirate the 21 mg/l standard through the burner until a maximum stable
reading is obtained. Record the reading and if the sample reading on the
recorder is less than the 11 mg/l standard, aspirate the 1 mg/l standard
through the burner until a maximum, stable reading is obtained. Record the
reading.
Calculations:
(%A,--%A 2 )
10 + mg/12 x DF = mg/l Ca+2
%A1 -76 2
where %A = percent absorption of high standard; %A2 = percent absorption
of low standard; %A, = percent absorption of sample; mg/ll = mg Ca+2/lof
high standard; mg/12 = mg Ca+2/l of low standard; mg/l, = mg Ca+?/l of
sample; and DF = dilution factor of sample (100/ml sample).
Strontium
Strontium is determined at the 4607 A wavelength with an air-acetylene
flame.
77
Precision. In a single laboratory using oilfield water samples containing concentrations of 840 and 2,250 mg Sr+2/1,the standard deviations were +48
and +110, respectively. The recoveries were 106.8%and 103.1%, respectively.
Barium
Barium is determined at the 5336
nitrous-oxide flame.
78
Precision. In a single laboratory using oilfield water samples containing concentrations of 7 and 8 mg Ba+/l, the standard deviations were k0.5 and
kO.9, respectively. The recoveries were 108.2% and 97.3% respectively.
Manganese
Manganese is determined at the 2794.8 8 wavelength with an air-acetylene
flame.
79
Calculations. See calculations under Lithium in the flame spectrophotometric section, Fig. 3.3, or Table 3.XI:
mg Mn x 1,000
= mg/l Mn+
ml sample
Precision. In a single laboratory using oilfield water samples containing concentrations of 20 and 97 mg Mn+2/1,the standard deviations were k 1 and
+3, respectively. The recoveries were 102.2% and 105.4% respectively.
Iron
Iron is determined at the 2483.2
flame.
Interferences. The sensitivity is reduced if nitric acid and nickel are present.
This effect can be controlled by using a very lean (hot) flame.
Reagents. The necessary reagent is a standard solution: obtain commercially
or dissolve 1.000 g of iron wire in 50 ml of (1+ 1)nitric acid and dilute to 1
liter with water. 1 ml of solution contains 1mg of iron.
Preliminary calibration. Prepare standard iron solutions containing 1-5 Mg/ml
using standard iron solution and 50-ml volumetric flasks. Aspirate these
standards and a blank as recommended in the calcium method and determine
the absorbance at a wavelength of 2483.2 A.
Procedure. Transfer an aliquot containing about 0.05 mg of iron to a 50-ml
volumetric flask. Dilute t o volume and aspirate. Calculate the approximate
sample concentration from the preliminary calibration readings and determine the aliquot size that will contain about 0.05 mg of iron.
Add no iron standard t o the first flask, 0.05 mg of the iron standard to
the second flask, and 0.10 mg to the third. Dilute to volume. Aspirate and
record the absorbance readings for each sample.
80
Calculations. See calculations under Lithium in the flame spectrophotometric section, Fig. 3.3, or Table 3.XI:
mg Fe x 1,000
= mg/l Fe+
ml sample
Precision. In a single laboratory using oilfield water samples containing concentrations of 6.3 and 6.8 mg Fe+2/1, the standard deviations were k0.5 and
k0.3, respectively. The recoveries were 115.6%and 97%,respectively.
copper
Copper is determined at the 3247.5 8 wavelength with an air-acetylene
flame.
Reagents. The necessary reagent is a standard copper solution: obtain commercially or dissolve 1.000 g of copper metal in a minimum volume of (1 +
1) nitric acid. Dilute 1 liter with 1% (v/v) nitric acid. 1 ml of solution
contains 1 mg of copper.
Preliminary calibration. Prepare standard copper solutions containing 1-5
pg/ml using the standard copper solution and 50-ml volumetric flasks.
Aspirate these standards and a blank as recommended in the calcium method
and determine the absorbance at a wavelength of 3247.5 8.
Procedure. Transfer an aliquot containing about 0.05 mg of copper t o a
50-ml volumetric flask. Dilute t o volume and aspirate. Calculate the approximate sample concentration from the preliminary calibration readings and
determine the aliquot size that will contain 0.05 mg of copper.
Transfer equal aliquots containing about 0.05 mg of copper to three 50-ml
volumetric flasks. Add no copper t o the first flask, 0.05 mg of the copper
standard to the second flask, and 0.10 mg t o the third. Dilute t o volume.
Aspirate and record the absorbance readings for each sample.
Calculations. See calculations under Lithium in the flame spectrophotometric section, Fig. 3.3, or Table 3.XI:
mgCux 1,000
= mg/l CU+
ml sample
zinc
Zinc 1- determined at the 2138.6
flame.
81
Reagents. The necessary reagent is a standard zinc solution: obtain commercially or dissolve 0.500 g of zinc metal in a minimum volume of ( 1 +1) HC1
and dilute to 1 liter with 1%(v/v) HCl. 1 ml of solution contains 500 pg of
zinc.
Preliminary calibration. Prepare standard zinc solutions containing 0.2-1.0
pg/ml using the standard zinc solution and 50-ml volumetric flasks. Aspirate
these standards and a blank as recommended in the calcium method and
determine the absorbance at a wavelength of 2138.6
a.
Precision. In a single laboratory using oilfield water samples containing concentrations of 27 and 120 mg Zn+2/1, the standard deviations were +1. The
recoveries were 103.5%and 102.3%,respectively.
Lead (1)
Lead is determined at the 2833.1 A wavelength with an air-acetylene
flame.
Reagents. The necessary reagent is a standard lead solution: obtain commercially or dissolve 1.598 g of lead nitrate, Pb(N03)2,in 1 liter of 1%(v/v)
HN03. 1 ml of solution contains 1,000 pg of lead.
Preliminary calibration. Prepare standard lead solutions containing 2-10
pg/ml using the standard lead solution and 50-ml volumetric flasks. Aspirate
these standards and a blank as recommended in the calcium method and
determine the absorbance at a wavelength of 2833.1 8.
Procedure. Transfer an aliquot containing 100 pg of lead t o a 50-ml volumetric flask. Dilute to volume and aspirate. Calculate the approximate
sample concentration from the preliminary calibration readings and determine the aliquot size that will contain 100 pg of lead.
82
Transfer equal aliquots containing about 100 pg of lead t o the three 50-ml
volumetric flasks. Add no lead standard t o the first flask, 100 pg of lead
standard to the second flask, and 200 pg t o the third. Dilute t o volume.
Aspirate and record the absorbance readings for each sample.
Calculations. See calculations under Lithium in the flame spectrophotometric section, and Fig. 3.3, or Table 3.XI:
mg Pb x 1,000
= mg/l Pb+
ml sample
Precision. In a single laboratory using an oilfield water sample containing a
concentration of 16 mg Pb+*/l,the standard deviation was k2.6. The recovery
was 74.8%.
Lead (2)
Lead is determined by chelating with ammonium pyrollidine dithiocarbamate (APDC) and extracting with methyl isobutyl ketone (MIBK) (Brooks
et al., 1967). The organic extract is analyzed by means of atomic-absorption
spectrophotometry. Interferences have not been observed in the airacetylene flame.
Reagents. The necessary reagents are methyl isobutyl ketone (MIBK); 0.3M
hydrochloric acid; ammonium pyrollidine dithiocarbamate (APDC) (dissolve
1.0 g of APDC in 100 ml of distilled water); bromphenol blue indicator
solution (dissolve 0.1 g bromphenol blue in 100 ml of 50% ethanol); 2.5M
sodium hydroxide; and lead standard solution. The latter can be bought
commercially or made from lead nitrate. The presence of 0.5% nitric acid in
the lead standards of low concentrations retards the plating of the lead on
the sides of the container.
Procedure. Pipet the sample into a 200-ml volumetric flask and adjust the
volume to approximately 100 ml with distilled water. Add two drops of the
bromphenol blue indicator solution. Adjust the pH by adding 2.5M NaOH
by drops until a blue color persists. Add 0.3M HC1 until the blue color
disappears. Add 2.0 ml of HC1 in excess. The pH should be 2.4. Add 2.5 ml
of the APDC solution and mix. Add 10 ml of MIBK and shake vigorously for
1 minute. Allow the layer to separate and add distilled water until the
ketone layer is in the neck of the flask. Aspirate the ketone layer for lead
content. Prepare a calibration curve by adding known amounts of lead t o a
synthetic brine solution.
Calculations:
mg Pb (from curve) - mg/l Pb
ml sample
EMISSION SPECTROMETRY
a3
EMISSION SPECTROSCOPY
7,700' C .
84
"'i
35 percent N-Amy1
65 percent acetone
90
Proplonlc Add,
Acetone
N-Proponoi
2 50
a
I-
430
2
0
3 4
5
6 7 8
CARBON, grams per SOml
101I
Fig. 3.7. Relative intensity of lanthanum versus grams of carbon in the solvent aspirated
into a plasma arc.
EMISSION SPECTROMETRY
85
86
8;B, I, 4995.46 8;Fe, 11, 5198.80 8;Mn, 11, 5152.20 8;Sr, 11,4215.52 8;
La, 11, 4086.62 8;and La, 11, 4429.90 8.
The background and intensity of the following lines can be read if some of
those above are too intense or if more than one line for a given element is
wanted: Ba, 11, 4934.09 8; B, I, 4993.56 8;Fe, 11, 4196.74 8; Mn, 11,
5187.46 8; La, 11, 4077.35 8; La, 11, 4123.23 8;Sr, 11, 4077.71 8;and Sr,
I, 4607.33 8.
98 = 0.2
96 = 0.2
1.585
Relative intensity
arbitrarily set at 0.2
0.317
100
0
FILTERED, percent
87
EMISSION SPECTROMETRY
20-
- 40-
v)
0
R E L A T I V E INTENSITY
A t 96 on the x-axis, find the curve intersection point on the y-axis; in this
case, it is 91.
%T
91 = 0.317 x 1.585
Relative intensity
0.502
88
I '
0.2
0.4
I
I 1
I
0.6 0.8 1.0
2.0
INTENSITY RATIO
4.0
t 0
To obtain data for calibration curves for barium, boron, iron, manganese,
and strontium, use size 50-ml volumetric flasks. To one flask add no standard solution; add 1.0 ml t o the second flask; and add 2.5 ml, 5.0 ml, 7.5 ml,
and 10.0 ml of standard solution to the third, fourth, fifth, and sixth flasks,
respectively. (These aliquots will vary with the sensitivity of your instrument.) Add 2 ml of concentrated hydrochloric acid, 2 ml of internal standard solution, 5 d of synthetic brine solution, 20 ml of n-propanol, and
sufficient distilled water t o adjust the final volume t o 50 ml at ambient
temperature. For optimum accuracy, prepare duplicate or triplicate samples.
Aspirate and burn the samples using the excitation conditions, the
development conditions, and the microphotometer conditions described
above; plot the curves using the above procedure.
The water sample should be adjusted t o a pH of about 1.5 at the time of
sampling t o prevent precipitation and adsorption. The sample should be
contained in a good quality plastic bottle that has been rinsed first with
dilute nitric acid and then with distilled water.
Transfer to a 50-ml volumetric flask an aliquot of the sample of sufficient
size to provide absolute quantities of the elements which will fall within the
calibration curves. The optimum aliquot size will vary from brine to brine;
however, equal-size aliquots often can be used for waters with similar
specific gravities from the same geologic formation. Add 2 ml of concentrated hydrochloric acid, 2 ml of internal standard solution, 5 ml of
synthetic brine solution (or try to approximate the ionic composition of the
EMISSION SPECTROMETRY
89
90
a,
Be 3130.42
Be 3131.07
and
3036.2
3036.3
Determine the concentration of beryllium using a calibration curve prepared by using 0.01-0.05 pg of beryllium standard. This concentration in
micrograms can be converted to milligrams per liter by this formula:
pg Be (from curve)
= mg/l Be+2
ml sample
Less than 1 ppb of beryllium can be detected with this method, the
precision and accuracy of the method are about 2%and 496, respectively, of
the amount present.
Aluminum,
Petroleum-associated water containing more than 5 mg/l of aluminum can
be analyzed using the same procedure and internal standard that are
91
described above for barium, boron, iron, manganese, and strontium; the
can be used. However, if the alumialuminum emission lines at 3082.5
num concentration is less than 5 mg/l, the aluminum should be separated
and concentrated from the aqueous phase. This can be done by adjusting the
pH of a sample containing up t o 100 pg of aluminum to pH 0.4 with
hydrochloric acid, adding 10 ml of a 6% aqueous solution of cupferron,
adjusting the pH t o 4.8 with sodium acetate, and extracting the aluminum
complex into chloroform. The chloroform phase then is aspirated into the
plasma arc using the same conditions and internal standard line that is
described above for beryllium.
92
T =-I 2
I1
COLORIMETRIC METHODS
93
94
Iron
The spectrochemical procedure will give values only for total iron and will
not differentiate ferrous iron from ferric iron. The following procedure can
be used t o determine F-+* and Fe+3 in a freshly sampled water (Collins et
al., 1961).
Reagents and apparatus. Standard iron solution: dissolve 1.00 g of
hydrogen-reduced iron in a minimum of hydrochloric acid and dilute to 1
liter with distilled water. This solution contains 1mg/ml of iron. Transfer 1 0
ml of this solution to a l-liter flask and dilute to volume with distilled water.
1ml of this solution contains 0.01 mg of iron.
Hydroquinone solution: dissolve 1 g of hydroquinone in 100 ml of distilled water.
IRON, m i l l i g r a m
Fig. 3.11. Plot of the optical density at 522 m p of the ferrous iron complex with 2,2'bipyridine.
COLORIMETRIC METHODS
95
Procedure. Prepare a calibration curve by transferring aliquots of the standard iron solution, containing from 0.02 mg t o 0.20 mg of iron, t o 100-ml
volumetric flasks. To separate aliquots, add 5 ml of the sodium citrate solution and determine how much sulfuric acid is necessary to adjust the pH t o
3.5. Add this amount to the aliquots in the volumetric flasks. Add reagents
in the following order: 5 ml of hydroquinone solution, 5 ml of
2,2-bipyridine or O-phenanthroline solution, and 5 ml of sodium citrate.
The citrate must always be added last. Convert t o volume with distilled
water, mix well, and let stand for 1hour. Prepare a reagent blank in the same
manner.
Determine the absorbance at 522 mp if 2,2-bipyridine is used or 508 mp
if O-phenanthroline is used. Plot the absorption versus iron concentration on
coordinate graph paper. The resulting curve should be linear, as shown in
Fig. 3.11.
Obtain a clean sample of brine, free of oil. Determine ferrous iron, by
following the above procedure, but omit the addition of hydroquinone. To
determine dissolved iron, filter the sample and follow the above procedure.
To determine total iron, do not filter the sample. The amount of ferric iron
can be calculated from the difference.
Calculations:
1,000 x mg iron from curve
= mg/l Fe+2 or Fe+
sample volume
Concentrating copper, iron, lead, and nickel by ion exchange
To determine accurately, using colorimetric methods, copper, nickel, lead,
zinc, and cadmium in oilfield brines, they should be separated from interfering ions. Many oilfield brines contain metals in such minute amounts that
they must be concentrated before analyses can be made. Concentration
methods investigated were ion exchange, electro-deposition, solvent extraction, and evaporation. An ion-exchange method proved t o be the most
practical for concentrating copper, nickel, and lead, because it is less time
consuming and requires less expensive equipment than any of the other
methods studied.
96
The compound 2,9-dimethyl-1,lo-phenanthroline, assigned the name neocuproine (Diehl and Smith, 1958, p.23), has the following structure:
COLORIMETRIC METHODS
97
This reagent is used t o determine copper because of its nearly specific reaction with cuprous copper. The combining ratio is 2 moles of neocuproine to
1 mole of copper. The increased selectivity of neocuproine for copper is
caused by a steric hindrance effect. The cuprous neocuproine compound is
formed over a pH range of 3-10 and is bright orange. The compound can be
extracted with n-amyl alcohol, isoamyl alcohol, n-hexyl alcohol, or chloroform. The maximum absorption of the compound in isoamyl alcohol occurs
at a wavelength of 454 mp.
Hydroxylamine hydrochloride can be used t o reduce the cupric ion t o
cuprous. Citrate will hold any iron present in solution when the pH is
adjusted to between 5 and 6. The chromate ion can cause low results; however, this effect does not occur when iron is present, which is almost always
the case with an oilfield brine. The anions such as sulfide, cyanide, periodate,
nitrate, t hiocyanate, and ferricyanide can interfere by reacting with
hydroxylamine; however, they are eliminated in the ion exchange separation.
Reagents. Neocuproine solution: dissolve 1 g of 2,9-dimethyl-l,1 O-phenanthroline in 1liter of ethyl alcohol.
Hydroxylamine hydrochloride solution : dissolve 10 g of hydroxylamine
hydrochloride in 100 ml of water.
Isoamyl alcohol, analytical reagent grade.
Sodium citrate solution: dissolve 300 g of sodium citrate in 1 liter of
water, add 2 ml of the hydroxylamine hydrochloride solution, add 1 ml of
neocuproine solution, and extract with 10-ml portions of chloroform until a
colorless chloroform extract is obtained.
Standard copper solution: dissolve 0.100 g of copper in 5 ml of nitric acid
and 5 ml of water by heating gently to dissolve the copper. Add 5 ml of
perchloric acid and evaporate to fumes of perchloric acid. Cool, dilute with
water, transfer t o a l-liter volumetric flask, and dilute t o volume. Pipet a
100-ml aliquot of this solution t o another l-liter volumetric flask. Dilute to
volume with water. This solution contains 10 mg/ml of copper.
Sodium acetate.
30
-.#
ml sample
mg/l C U + ~
Nickel
Nickel forms a wine-red or brown compound with dimethylglyoxime
(Sandell, 1959, p.555). The structure of the chelate on the basis of available
evidence is:
H3C - C-C
//
/I
H3C - C
/I
CH3
CH,
Dimethylglyoxime gives a nearly specific reaction with nickel that has been
oxidized t o its higher valences with an oxidizing agent such as bromine. The
wine-red compound is somewhat unstable; therefore, the absorbance measurements should be made within 10 minutes after formation of the nickel
dimethylglyoximate. Cobalt and copper also give colored compounds with
dimethylglyoxime, but they can be removed by washing the chloroform
extract of nickel dimethylglyoximate with dilute ammonium hydroxide.
Iron interference is removed by extracting the nickel dimethylglyoximate
with chloroform from a solution containing citrate. Palladium, platinum, and
gold also give colored compounds when nickel dimethylglyoximate is
extracted with chloroform; however, they are removed, if present, by the
ion-exchange separation.
COLORIMETRIC METHODS
99
Procedure. Add 10 ml of ammonium citrate solution, and 5 ml of hydroxylamine hydrochloride solution to a sample of effluent containing up to 100
pg of nickel, and adjust the pH t o 8 with ammonium hydroxide. Transfer the
mixture t o a 125-ml separatory funnel, add 10 ml of dimethylglyoxime
solution and 10 ml of chloroform, and shake the mixture vigorously for 1
minute. Let the phases separate and extract the chloroform phase into
another 125-ml separatory funnel. Make additional extractions of the sample
with 10-ml portions of chloroform until a colorless chloroform extract is
obtained. Add 10 ml of 4N ammonium hydroxide solution to the combined
chloroform extracts in the 125-ml separatory funnel, and shake the mixture
vigorously for 1 minute. Let the phases separate and discard the ammonium
hydroxide phase.
Acidify the chloroform phase with 1 ml of 6N hydrochloric acid, shake
the mixture vigorously for 2 minutes, let the phases separate, and discard the
chloroform phase. Add 10 ml of chloroform t o the acid phase, shake the
mixture vigorously for 1 minute, and discard the chloroform phase. Adjust
the pH of the acid phase to 6.9, transfer it t o a 100-ml volumetric flask, add
bromine water until a yellow color persists, swirl the mixture, and allow it to
stand for 10 minutes. Add 10 ml of 4N ammonium hydroxide and 10 ml of
dimethylglyoxime solution. Swirl to mix, cool to room temperature in an ice
water bath, and adjust t o 100-ml volume with water. After 5 minutes determine the absorbance at 445 mp using a 1-cm cell and a spectrophotometer.
Calculations. Calculate the nickel concentration in the water by using a
calibration curve prepared by using about 10-100 pg of nickel:
pg Ni (from curve)
= mg/l Ni+
ml sample
Lead
Dithizone (Sandell, 1959, p. 665) is an excellent reagent for the determination of traces of lead. Lead dithizonate probably has a formula similar to
the following:
r
C6HS
100
Reagents. Hydroxylamine hydrochloride solution : dissolve 10 g of hydroxylamine hydrochloride in water and dilute to 50 ml.
Standard lead solution: dissolve 0.100 g of lead in 10-15 ml of nitric
acid. Dilute to 1liter volume with water. Pipet a 100-ml aliquot of this stock
solution into another 1-liter volumetric flask, add 1 0 ml of nitric acid, and
dilute t o 1 liter volume with water. This solution contains 10 pg/ml of lead.
Ammonia-cyanide-sulfite
solution: add 350 ml of concentrated ammonium hydroxide, 30 ml of a 10%potassium cyanide solution, and 1.5 g of
sodium sulfite, t o a 1-liter volumetric flask and dilute to volume with water.
Dithizone solution: dissolve 0.01 g of dithizone in 200 ml of chloroform.
Chloroform.
COLORIMETRIC METHODS
101
pg Pb (from curve)
= mg/l Pb+2
ml sample
zinc
Extraction of zinc with dithizone from a weakly ammoniacal solution
containing a reducing agent and citrate prevents the precipitation of iron.
Extraction of zinc at a pH of 4.75 in the presence of sodium thiosulfate
largely eliminates interference from copper, mercury, lead, and cadmium.
The zinc dithizonate complex can be broken in 0.02N hydrochloric acid,
whereas cupric dithizonate cannot. Lead and cadmium dithizonates will dissociate in 0.02N hydrochloric acid, but only traces of them should be
present after the preliminary extractions.
More accurate results are obtained by applying a zincon (Platte and
Marcy, 1959) method t o the zinc which has been isolated by the dithizone
extractions than by making another dithizone extraction of the isolated zinc
and using it for absorption measurements. Therefore, the following method
is a combination of the dithizone and zincon methods. Traces of any remaining interferences can be complexed.
Zinc reacts with dithizone to form a compound similar to:
CsHS
102
COLORIMETRIC METHODS
103
Calculations. Prepare a calibration using aliquots of the standard zinc solution containing 10-80 pg of zinc, and use the curve t o calculate the amount
of zinc in the sample:
pg Zn (from curve)
= mg/l Zn+*
ml sample
Cadmium
Cadmium can be extracted from aqueous solutions as cadmium dithizonate into carbon tetrachloride or chloroform. Cadmium dithizonate is
extracted more readily into carbon tetrachloride than is zinc dithizonate, but
zinc dithizonate is extracted more readily into chloroform than the cadmium
compounds. Therefore, because many oilfield brines contain more zinc than
cadmium, the cadmium extraction should be made with carbon tetrachloride
to insure the best possible separation from zinc.
Although citrate and tartrate do not hinder the cadmium dithizonate
extraction, they do impede the extraction of lead and zinc. Cadmium
dithizonate can be extracted from an alkaline solution containing cyanide
and tartrate; the dithizonates of nickel, copper, silver, and tin are not extracted. Most of the interference from iron can be eliminated by oxidizing it
with peroxide and filtering.
Cadmium reacts with dithizone to form a compound of the type:
104
Procedure. Filter the brine through Whatman No.4 filter paper (double
thickness). Transfer 900 ml or less of the filtered brine to a 2-liter beaker,
add 5 ml of 30% hydrogen peroxide, and heat until complete decomposition
of the excess hydrogen peroxide is attained. Cool the solution and filter if
any precipitate is present. Add 100 ml of ammonium chloride solution, 10
ml of rochelle salt solution, 25 ml of sodium citrate solution, and adjust the
pH to between 8 and 8.5 with 5M ammonium hydroxide. Transfer the
solution to a liter separatory funnel, add 15 ml of the No.1 dithizone solution, and shake the mixture vigorously for 5 minutes. Let the phases separate
and extract the dithizone phase into a 50-ml separatory funnel. Reextract
the brine with another 15 ml of No.1 dithizone solution. Separate the
dithizone phase into the 50-ml separatory funnel and discard the brine
phase.
Add 10 ml of tartaric acid solution to the combined dithizone extractions
in the 50-ml separatory funnel and shake the mixture vigorously for 2
COLORIMETRIC METHODS
105
minutes. Discard the carbon tetrachloride phase and wash the tartaric acid
phase twice with a 3-ml portion of carbon tetrachloride. To the tartaric acid
phase add 1 ml of hydroxylamine hydrochloride solution, 5 ml of the 35%
sodium hydroxide-1% potassium cyanide solution, and 10 ml of the No. 2
dithizone solution Shake the mixture vigorously for 1minute. Let the phases
separate and extract the dithizone phase into another 50-ml separatory
funnel. Reextract the aqueous phase with 10 ml of No.2 dithizone solution,
and add the dithizone extraction of the previous separation. Wash the
aqueous phase with 5 ml of carbon tetrachloride, extract the carbon
tetrachloride, and combine it with the two dithizone extractions. Discard the
aqueous phase. Add 15 ml of 5% sodium hydroxide solution to the combined dithizone extractions, shake the mixture vigorously for 1 minute,
extract the carbon tetrachloride phase, and determine its absorbance at 620
mp in a l-cm cell with a spectrophotometer.
Calculations Run a blank and make appropriate corrections, using a calibration curve prepared by using aliquots of the standard cadmium solution
containing 1-7 pg of cadmium:
pg Cd (from curve)
= mg/l Cd+2
ml sample
Phosphate
Only orthophosphate will respond to the test. Polyphosphates must be
reverted to orthophosphates by boiling with acid (American Petroleum
Institute, 1968).
106
COLORIMETRIC METHODS
107
Nitrate nitrogen
Nitrate is the most highly oxidized form of nitrogen and is the most stable
form in an oxidizing environment. Many fertilizers contain nitrate, and
waters will leach the nitrate from soil or rock. Most rocks do not contain
much nitrate; therefore, it is unlikely that petroleum-associated waters contain appreciable quantities of nitrate. The nitrate in deep waters also may be
depleted through anion exchange (George and Hastings, 1951).
Chloride is a serious interference in many of the methods used to determine nitrate nitrogen. Oxidizing or reducing agents such as ferric or ferrous
iron also interfere. The Brucine method (Fisher et al., 1958)can be applied
to a petroleum-associated water. To determine the nitrate concentration,
transfer an aliquot of the sample containing up to 15 pg of nitrate into a
50-ml Erlenmeyer flask, add 15 ml of water, 1 ml of Brucine reagent (2%
108
COLORIMETRIC METHODS
109
Fluoride
Because of interferences from large amounts of chloride present in
petroleum-associated waters, a standard addition method was developed
which is accurate in the presence of large amounts of chloride and sulfate
and is more rapid than methods requiring distillation (Collins et al., 1961).
Up to 0.01 mg of phosphate in the aliquots taken for analysis can be tolerated. Larger amounts of phosphate than this decolorize the zirconium
110
A rapid, accurate method for the determination of iodide suitable for field
work utilizes the principle whereby iodide is oxidized to iodine with nitrous
acid and extracted into carbon tetrachloride. Hydrogen sulfide will interfere,
but it can be removed by acidifying the sample and boiling (Collins et al.,
1961).
COLORIMETRIC METHODS
111
Procedure. Pipet a sample containing less than 3 mg of iodide into a separatory funnel, and add three drops of the bromphenol blue solution and a few
drops of 9N sulfuric acid until the indicator turns yellow. Add 10 ml of carbon tetrachloride and 1 ml of a 10% aqueous potassium nitrite solution, and
vigorously mix the combined phases. Extract the carbon tetrachloride phase
into a glass-stoppered cylinder. A violet color in the carbon tetrachloride
indicates iodine. Repeat the extractions with 5-ml portions of carbon
tetrachloride until all of the iodine is extracted. Dilute the combined
extracts to 25 ml with carbon tetrachloride and measure the absorbance
using a spectrophotometer at a wavelength of 517 mp. Use a calibration
curve prepared with standard iodide solutions t o determine the milligrams of
iodide in the sample.
Calculation:
mg I (from curve) x 1,000
= mg/l
ml sample
Selenium
Selenium can be reduced t o the elemental form with sulfur dioxids
(Collins et al., 1964), hydrazine, hydroxylamine hydrochloride, hypophosphorous acid, ascorbic acid, and stannous chloride. From hydrochloric
acid solutions exceeding 8N,selenium is precipitated free of tellurium when
the reducing agent is sulfur dioxide. Both selenium and tellurium are precipitated by sulfur dioxide from 3 t o 5N hydrochloric acid solutions. Traces of
nitric acid should be removed before sulfur dioxide reduction. When precipitating selenium, it is important that the temperature of the solution be kept
below 30C because the volatile selenium monochloride easily can form and
be lost. A large excess of reducing agent helps to prevent loss of the monochloride.
Selenium can be determined semiquantitatively by comparing the color of
the red amorphous form, or it can be adjusted to the quadrivalent form,
reacted with 3,3-diaminobenzidine to form the monopiazselenol, and quantitatively determined spectrophotometrically. If sufficient selenium is
present, it also can be determined gravimetrically .
Selenate (VI) can be reduced to selenite (IV) by heating in concentrated
hydrochloric acid. Selenite is the only form that reacts with
3,3-diaminobenzidine; the reaction is :
%
N
H2 N
- NH2 + H, SeO,
NH2
N=
SeN
NH2 + 3Ha0
NH2
112
COLORIMETRIC METHODS
113
pulled through the precipitate until the entire filtration and washing process
is complete.
Transfer the filter and precipitate back t o the 150-ml beaker and add 5 ml
of a 1:l mixture of hydrochloric acid and nitric acid. Heat the mixture to
near boiling for a few minutes, taking care not t o let the mixture boil
violently or to dryness. Examine the mixture carefully t o make sure that all
of the selenium has dissolved. Place the beaker containing the mixture in a
vacuum desiccator over anhydrous magnesium perchlorate and sodium
hydroxide and let the mixture evaporate t o dryness. Dissolve the residue in 5
ml of concentrated hydrochloric acid and heat the mixture to near boiling
for a few minutes.
Cool the mixture, add 20 ml of water, and filter it through Whatman No.4
filter paper into a 100-ml volumetric flask. Adjust the volume to 100 ml and
pipet an aliquot containing 1-100 pg of selenium (IV) from the 100-ml flask
into a 100-ml beaker. Add 5 ml of 0.1M EDTA and 2 ml of 2.5M formic
acid and adjust the pH to 1.5 with hydrochloric acid. Adjust the volume to
about 50 ml with water, add 2 ml of 3,3'-diaminobenzidine solution, mix,
and let stand for 30 minutes. Adjust the pH to 8 and transfer the solution to
a 1 2 5 4 Teflon-stoppered separatory funnel containing 10.0 ml of toluene.
Shake this mixture vigorously for 2 minutes and let the phases separate.
Extract the toluene phase, which now contains the monopiazselenol, into a
centrifuge tube. Centrifuge briefly t o clear the toluene of water droplets. If a
centrifuge is not available, the organic phase can be filtered through a dry
filter paper to which has been added 100 mg of anhydrous sodium sulfate.
Determine the absorbance of the toluene phase at 420 mp versus a reagent
blank. 1-cm cells are used; however, longer path length cells will increase
sensitivity.
114
GRAVIMETRIC METHODS
GRAVIMETRIC METHODS
115
Barium
Interest in the knowledge of the barium concentration in most
petroleum-associated waters has spurred the development of several types of
methods to determine barium. Perhaps the most rapid but least accurate
method is the turbidimetric method, which measures the turbidity of the
sample caused by precipitated barium sulfate after addition of excess sulfate.
The gravimetric method also measures precipitated barium sulfate or more
preferably barium chromate. It is a more time-consuming method than the
turbidimetric method, but will yield more accurate results. The double
precipitation as chromate reduces the interference from calcium and strontium.
116
= mg/l Ba+
Precision and accuracy. The precision and accuracy of this method with
optimum conditions are 1%
and 2% respectively, of the amount of barium in
the sample.
OTHER METHODS
OTHER METHODS
117
Anions:
chloride
(50,000 mg/1)/(35.5 mg/me) = 1,410 me/l
sulfate
(1,290 mg/1)/(48.0 mg/me) =
27 me/l
bicarbonate (204 mg/1)/(61.0 mg/me)
=
3 me/l
Total anions
1,440 me/l
Cations: calcium
(5,900 mg/1)/(20.0 mg/me) =
magnesium (2,000 mg/1)/(12.1 mg/me) =
Total cations
295 me/l
164 me/l
459 me/l
Determination of sodium:
(1,440 - 459 me/l) x 23.0 mg/me = 22,600 mg/l
Dissolved solids
The dissolved solids determination can be used t o estimate the accuracy of
the resistivity determination. The specific gravity determination, and the
evaporation method can be used t o double check the calculated total dissolved solids. Theoretically, if all the dissolved solids are accurately determined, their sum will equal the weight of the residue left after evaporation
of the water. The dissolved solids include all the solid material in solution
which is ionized, or which is not ionized but does not include suspended
material, colloids, or gases.
The residue method involves evaporating a filtered sample t o dryness followed by drying the residue in an oven at 180C for 1 hour. The cooled
residue is weighed and the total dissolved solids are calculated; e.g., if 100 ml
of brine is evaporated and the residue weighs 3.0 g, then the dissolved solids
equal 30,000 mg/l. The evaporation method is subject to errors when
hygroscopic material such as calcium chloride is in the water, as is usually
the case in oilfield waters.
The calculation method simply involves adding the sum of all the analyzed
constituents as follows:
118
Constituent
Na+
K+
Li+
Ca+
Mg+
c1Br- HC03
S04-2
Concentration(mg/l)
13,500
400
10
2,000
1,200
23,500
500
1,200
1,200
43,500
Spent acid
Hydrochloric acid is the oldest and most common solution used in oil-well
acidizing (Halliburton Company, 1970)..Many additives and other acids may
be used in conjunction with HC1, for example HF and HAc. Normally, 15%
HCl is used; however, other strengths are quite common. These acid solutions are pumped into carbonate formations t o dissolve and remove a part of
the formation.
After reacting with carbonate rocks or being spent on the formation,
the solutions are returned t o the surface by various means. Often, they are
mixed with formation water, and an operator may want t o know when the
spent acid has been recovered, or if formation water or a mixture of solution
and water is being produced.
When 15% HC1 is completely spent on CaC03 or M g C 0 3 , the resulting
solution will contain 90,000 mg/l Ca or Ca equivalent. The normal formation
water contains only about 10,000 mg/l Ca or Ca equivalent. The procedure is
based on these differences.
Reagents and equipment. The necessary reagents and equipment include:
Calcium carbonate, 10-mesh.
NH4OH, reagent.
Whatman No.31 filter paper.
Plastic funnel.
150-ml beakers.
Graduated cylinder, 25 ml.
1-ml syringe or pipette, preferably plastic.
0.5% Eriochrome Black T indicator.
2N NaOH solution.
CDTA solution (disodium dihydrogen 1,2-cyclohexanediamine-tetraacetate): dissolve 100.0 g CDTA in 900 ml water and dilute to 1 liter. 1 ml
equals 9.0 mg Ca.
OTHER METHODS
119
100
Fig. 3.12. Graph for use in calculating the amount of spent mineral acid in a water
sample.
120
the blank titration (formation water) as 0% spent acid. Draw a straight line
from this point through the intersection of the 100% spent acid and the
10.0-ml CDTA lines as illustrated in Fig. 3.12. This procedure corrects for
any Ca+ or Mg+2 present in the dilution water.
In cases where it is impossible t o obtain formation water for the 0%spent
acid, a reasonable approximation can be made by titrating 100 ml of the
water used for washing and dilution. To this volume of CDTA, add 1.3 ml.
This value can then be used for the 0%spent acid point on the plot.
Free HCl
When free HC1 is indicated (pH below 4), and it is t o be determined, an
additional sample is required. Withdraw 1.0 ml of clear sample. Start with
step 3 and follow the procedure. The free HC1 is determined by the difference of the two titrations:
% free HC1= (A -B) x 1.5
ml, CDTA
Fig. 3.13. Graph for use in calculating the amount of spent mineral and organic acid in a
water sample.
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121
122
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Dean, J.A., 1960. Flame Photometry. McGraw-Hill, New York, N.Y., 354 pp.
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Mellon, M.G., 1950. Analytical Absorption Spectroscopy. John Wiley and Sons, New
York, N.Y., 618 pp.
Mellon, M.G.,. 1956. Quantitative Analyses. Thomas F. Crowell, New York, N.Y., 694 pp.
Platte, J.A. and Marcy, V.M., 1959. Photometric determination of zinc with zincon:
application to water containing heavy metals. Anal. Chem., 31 :1226-1228.
Potter, E.C., 1956. Electrochemistry. MacMillan, New York, N.Y., 418 pp.
REFERENCES
123
Chapter 4.
bicarbonate
sulfate
chloride
nitrate
126
TABLE 4.1
Reaction coefficients
Cation
Anion
Calcium
Magnesium
Iron
Sodium
0.0499
0.0823
0.0358
0.0435
bicarbonate
sulfate
chloride
Cation (mg/l)
RV
Anion (mg/l)
Ca 4,000x
Mg 3,000x
Fe 100 x
Na 9,400 x
199.6
246.8
3.6
408.9
HC03
0.0164
0.0208
0.0282
TABLE 4.11
Reacting values (RV)
0.0499 =
0.0823 =
0.0358 =
0.0435 =
so4
C1
RV
500 x 0.0164 =
8.2
200 x 0.0208 =
4.2
30,000 x 0.0282 = 846.3
858.9
858.7
TABLE 4.111
Reacting value distribution
Ca
Ca
Ca
Mg
Fe
Na
as
as
as
as
as
as
calcium bicarbonate
calcium sulfate
calcium chloride
magnesium chloride
iron chloride
sodium chloride
8.2
4.2
187.2
246.8
3.6
408.9
858.9
values (RV) or equivalents per million (epm) = mg/l of ion x valence of ion/
molecular weight of ion.
The term valence of ion/molecular weight of ion is called reaction coefficient and the positive and negative ions have values as shown in Table 4.1.
Table 4.11 indicates how the results of a water analysis are converted t o
reacting values.
The reacting values are a measure of the cations and anions dissolved in
the water. The 4,000 mg/l of calcium with a reacting value of 199.6 can
combine with all the bicarbonate, all the sulfate, and 187.2 epm of the
chloride. Magnesium will combine with 246.8,iron with 3.6, and sodium
with 408.9 epm of chloride. Thus the reacting values can be considered to be
distributed as shown in Table 4.111.
127
TABLE 4.IV
Combination factors
Reaction values given
Compound sought
Combination factor
Ca o r C 0 3
Ca or SO4
Ca or C1
Mg or C 0 3
Mg or SO4
Mg or C1
Fe or C03
Fe o r S 0 4
Fe orC1
Na or C03
Na or SO4
Na or C1
CaC03
CaS04
CaClz
MgCO3
MgS04
MgClz
FeC03
FeS04
Fa12
Na~C03
Naz SO4
NaCl
50.1
68.1
55.5
42.2
60.1
47.6
57.8
76.0
63.4
53.1
71.0
58.4
TABLE 4.V
Hypothetical combinations
Ca(HC03 ) to CaC03
CaS04
CaC12
MgCh
FeClz
NaCl
8.2 x 50.1
4 . 2 68.1
~
187.2 x 55.5
246.8 x 47.6
3.6 x 63.4
858.9 x 58.4
=
411 CaC03*
=
286CaS04
= 10,390 CaC12
= 11,748 MgClz
=
=
228 FeCIz
50,160 NaCl
*In mg/l.
128
Graphic plots
Graphic plots of the reacting values can be made to illustrate the relative
amount of each radical present. The graphical presentation is an aid t o rapid
identification of a water, and classification as t o its type, and there are
several methods that have been developed.
Tickell diagram
The Tickell (1921) diagram was developed using a 6-axis system or star
diagram. Percentage reaction values of the ions are plotted on the axes. The
percentage values are calculated by summing the epms of all the ions,
dividing the epm of a given ion by the sum of the total epms, and multiplying by 100.
Na
Ca+Mg
Na
ci
(a)
CI RV=49.92%
(b)
Ca+Mg
2-
So4
h 9 2 ma / I i tar
Fig. 4.1. Tickell (a) and modified Tickell (b) diagram for Gulf Coast water, sample No.1.
Na
(a)
Ca + Mg
Ca+Mg
CI ~ v = 4 9 . 2 9 %
(b)
Fig. 4.2. Tickell (a) and modified Tickell (b) diagram for Anadarko Basin water, sample
No. 2.
GRAPHIC PLOTS
129
so4
C I RV=49.92 %
(a)
so4
5,708 m e / l i t e r
(b)
Fig. 4.3. Tickell (a) and modified Tickell (b) diagram for Williston Basin water, sample
N0.3.
No
Ca+Ma
Co+Mg
c i\
(b)
so4
1.769 me / liter
Fig. 4.4. Tickell (a) and modified Tickell (b) diagram for Gulf Coast and Anadarko Basin
waters, mixed 1:l.
Na
Co+Mg
CI
so4
Na
Ca+Mg
7 $.
(b) C I
2870 me / i i t r r
Fig. 4.6. Tickell (a) and modified Tickell (b) diagram for Gulf Coast, Williston, and
Anadarko Basin waters, mixed 1 :1 :1.
130
REISTLE SYSTEM
GRAPHIC PLOTS
131
Reistle diagram
Reistle (1927) devised a method of plotting water analyses using the ion
concentrations as shown in Fig. 4.6. The data are plotted on a vertical
diagram, with the cations plotted above the central zero line and the anions
below. This type of diagram often is useful in making regional correlations or
studying lateral variations in the water of a single formation, because several
analyses can be plotted on a large sheet of paper.
St iff diagra m
Stiff (1951) plotted the reaction values of the ions on a system of rectangular coordinates as illustrated in Fig. 4.7. The cations are plotted to the left
and the anions to the right of a vertical zero line. The end points then are
connected by straight lines to form a closed diagram, sometimes called a
butterfly diagram. To emphasize a constituent that may be a key t o
interpretation, the scales may be varied by changing the denominator of the
Fig. 4.7. Water-analysis interpretation, Stiff method - sample numbers correspond to the
samples of Fig. 4.1-3.
132
Other methods
Several other water identification diagrams have been developed, primarily
for use with fresh waters, and they will not be discussed here. The Piper
(1953)diagram and the Stiff (1951)diagram were adapted to automatic data
processing by Morgan et al. (1966),and Morgan and McNellis (1969).The
Piper (1953)diagram uses a multiple trilinear plot t o depict the water analysis, and this quaternary diagram shows the chemical composition of the
water in terms of cations and anions. Angino and Morgan (1966)applied the
automated Stiff and Piper diagrams to some oilfield brines and obtained
good results.
References
Angino, E.E. and Morgan, C.O., 1966. Application of pattern analysis t o the classification
of oilfield brines. Kans. State Geol. Sum.,Comput. Contrib., No.7, pp.53-56.
Morgan, C.O. and McNellis, J.M., 1969. Stiff diagrams of water-quality data programmed
for the digital computer. Kuns. State Geol. Sum., Spec. Distrib. Publ., No.43, 27 pp.
Morgan, C.O., Dingman, R.J. and McNellis, J.M., 1966. Digital computer methods for
water-quality data. Ground Water, 4:35-42.
Piper, A.M., 1953. A graphic procedure in the geochemical interpretation of water analyses. US.Geol. Surv. Ground Water Note, No.12, 1 4 pp.
Reistle, C.E., 1927. Identification of oilfield waters by chemical analysis. U.S.Bur. Min.
Tech. Paper, No.404, 25 pp.
Stiff, H.A., 1951. The interpretation of chemical water analysis by means of patterns. J.
Pet. Technol., 3:15-17.
Tickell, F.G., 1921. A method for graphical interpretation of water analysis. Calif. State
Oil Gas Superv., 6:5-11.
Chapter 5.
Lithium
Lithium is the lightest alkali metal; it has a distinctly smaller radius,
0.60 8,than the other alkalies and is the smallest of all singly charged
cations. It is one of the less abundant elements, and its abundance in the
earths crust is about 6.5 x
wt.% (Fleischer, 1962). Here again, it is an
exception because in general, the lighter elements tend to be more abundant
than the heavier elements. It is lithophilic in that it tends t o be associated
with the silicate phase in rocks (Ahrens, 1965); however, because of its small
size, it supposedly cannot replace the abundant alkali metals in mica.
It and the other alkali metals exist in a uniform positive one state of
oxidation and are inherently ionic. Their chemical behavior depends almost
entirely upon electron loss, and their chemistry is simpler than that of any of
the other metallic elements (Moeller, 1954).
Lithium is potentially toxic to plants (Hem, 1970), yet it is regularly
found in plant ashes, which indicates that it normally is present in soil waters
(Goldschmidt, 1958). Coal ashes of Neurode, Silesia, contained up to 198
ppm lithium, whereas soils in northeast Scotland contain 30-5,000 ppm.
The content of lithium in sediments ranges up to 6 ppm in quartzites and
sandstones, up to 15 ppm in calcareous rocks, and up t o 120 ppm in clays
and shales.
134
TABLE 5.1
Lithium
Sodium
Potassium
Rubidium
Cesium
Atomic number
Nonhydrated
radius (A)
Hydrated
radius (A)
Outer
electronic
configuration
Atomic weight
Ionization
potential (V)
11
19
37
55
0.60
0.95
1.33
1.48
3.82
3.58
3.31
1s' 2s'
6.939
5.390
2s22p6 3s'
22.990
5.138
4s24p6 5s'
85.47
4.339
1.69
4.176
TABLE 5.11
Five relative concentration changes of some dissolved ions during evaporation of sea water
and brine*
Constituents
Concentrations (mg/l)
Sea water
Lithium
Sodium
Potassium
Rubidium
Magnesium
Calcium
Strontium
Boron
Chloride
Bromide
Iodide
CaSO4
0.2
2
11,000
98,000
350
3,600
0.1
1
1,300
13,000
400
1,700
60
7
5
40
19,000 178,000
65
600
0.05
2
NaCl
MgS04
11
12
140,000 70,000
23,000 37,000
6
8
74,000 80,000
100
10
1
10
300
310
275,000 277,000
4,000
4,300
5
7
KCI
27
13,000
26,000
14
130,000
0
0
750
360,000
8,600
8
MgC12
34
12,000
1,200
10
153,000
0
0
850
425,000
10,000
8
*Approximate mg/l. Columns headed sea water, CaS04, etc., represent stages in sea water
evaporation. For example, sea water contains 0.2 mg/l of lithium, after calcium sulfate
has precipitated the residual brine contains about 2 mg/l of lithium, after sodium chloride
has precipitated the residual brine contains about 11 mg/l of lithium, the residual brine
contains about 12 mg/l of lithium after magnesium sulfate precipitates, 27 mg/l of lithium
after potassium chloride precipitates, and 34 mg/l of lithium after magnesium chloride
precipitates.
LITHIUM
135
a,
LITHIUM, mgll
Fig. 5.1. Comparison of the lithium concentrations in some Tertiary (T),Cretaceous (C),
and Jurassic (J) age formation waters from Louisiana with an evaporating sea water.
136
u
10
20
LITHIUM, mg/l
Fig. 5.2. Comparison of the lithium concentrations in some Mississippian (M) and
Pennsylvanian (P) age formation waters from Oklahoma with an evaporating sea water.
Sodium
The most abundant member of the alkali-metal group is sodium, ranking
number 6 with respect t o all the metallic elements. The radius of the sodium
ion is 0.95 A, and its geochemistry is controlled to some extent by calcium
because of the similarity of their ionic radii. Its abundance in the earth's
crust is about 2.8 wt.% (Fleischer, 1962). Table 5.1 shows that its outer
electronic configuration is 2s' 2p6 3s' , with a first ionization potential of
5.138 V, indicating that its single outer electron is less firmly held than in
the lithium atom with a first ionization potential of 5.390 V. The ionization
potential is a measure of the chemical reactivity - the lower the potential,
the greater the reactivity. Table 5.1 (Moeller, 1954) also illustrates some qf
its other properties.
According t o Ahrens (1965),sodium is lithophilic, and many distinctly
lithophile elements have valence electrons outside a closed shell of eight
electrons. The ionic radius decreases as the charge on the cation increases.
Sodium does readily participate in solid solution relationships because its
radius is small, making replacement of cations with 30% larger radii difficult.
The amounts of sodium in argillaceous sediments and marine shales are
about 1,000ppm and 1,300ppm, respectively (Goldschmidt, 1958).
SODIUM
137
Sodium in solution tends to stay in solution; it does not readily precipitate with an anion, and it is less easily adsorbed by clay minerals than are
cesium, rubidium, potassium, lithium, barium, and magnesium. The major
source of sodium in sea water can be attributed t o the weathering of rocks.
Some sodium probably was derived through volcanic activity. The ocean and
evaporite sediments contain the bulk of the sodium. Igneous rocks contain
appreciably more sodium than sedimentary rocks with the exception of
evaporites.
Sea water contains about 11,000 mg/l of sodium, as illustrated in Table
5.11. The concentration of sodium increases in brine as it evaporates, t o
about 140,000 mg/l, when halite precipitates. Most oilfield waters contain
more sodium than any other cation, and most oilfield waters are believed to
be of marine origin. Fig.5.3 is a log-log plot of the chloride concentration
versus sodium of some subsurface brines taken from sediments of Tertiary,
Cretaceous, and Jurassic age. The straight line is a plot of chloride versus
sodium concentrations for some evaporite waters, and indicates the enrichment of sodium ions until halite (NaC1) precipitates - at a chloride concentration of about 140,000 mg/l (compared t o that of normal sea water,
19,000 mg/l). The plot of the concentrations of sodium versus chloride for
these subsurface brines falls very near the normal evaporite curve, indicating
that the concentration mechanism may be related to an evaporite process
(Collins, 1970). Fig. 5.4 is a similar plot for some subsurface brines taken from
sediments of Pennsylvanian and Mississippian age (Collins, 1969a). Several of
these samples are somewhat depleted in sodium which indicates that
SODIUM,
g/l
Fig. 5.3. Sodium versus chloride concentrations for some formation waters taken from
Tertiary (T), Cretaceous (C), and Jurassic (J) zge sediments and compared to evaporating
sea water.
138
500F --/
200t-
I-
/"
SODIUM, mg/l
Fig. 5.4. Sodium versus chloride concentrations for some formation waters taken from
Pennsylvanian (P) and Mississippian (M) age formation sediments and compared t o
evaporating sea water.
diagenetic processes, such as ion-exchange or ultra-filtration reactions involving clays and/or carbonates, may operate to deplete the sodium concentration in waters in older sediments.
Potassium
The second most abundant member of the alkali-metal group is potassium;
its abundance in the crust of the earth is about 2.55 wt.% (Fleischer, 1962).
Like the other alkali metals, it is lithophilic, and with its large ionic radius
(see Table 5.1) it participates in forming solid solutions and forms its own
minerals, such as feldspar and mica. The potassium feldspars are resistant to
leaching by water, which may account for the low potassium concentrations
in many natural waters. Clay minerals readily adsorb potassium, and in illite
it is incorporated into the crystal structure in such a manner that it cannot
be removed by ion-exchange reactions (Lyon and Buckman, 1960).
Potassium is less easily hydrated than sodium, and is more easily adsorbed
by colloids; therefore, it is retained in sediments and soils in greater abundance than sodium. It is an essential element t o plants and animals. According to Gol&chmidt (1958),potassium in pulverized potassium feldspars is
absolutely unavailable t o plants.
The concentrations of potassium in carbonates, sandstones, and shales is
about 2,700, 10,700,and 26,600 ppm, respectively (Mason, 1966). Potas-
139
POTASSIUM
~~
.lvv
200
- 100 -
1
POTASSIUM,
I I I IIll
g/ I
Fig. 5.5. Potassium versus chloride concentrations for some formation waters taken from
Tertiary (T), Cretaceous (C), and Jurassic (J) age sediments and compared to evaporating
sea water.
,'
-Nmal
evaporite curve
5--
m
POTASSIUM, mg/l
Fig. 5.6. Comparison of the potassium concentrations in some Pennsylvanian (P) and
Mississippian (M) age formation waters from Oklahoma with an evaporating sea water.
140
Rubidium
Rubidium, like the other alkali metals is lithophilic, and its abundance in
the earths crust is about 3.0 x
wt.%, which is greater than that of
lithium (Fleischer, 1962). It tends to be removed from solution more readily
than lithium, primarily because of its ability to replace potassium in mineral
structures. Table 5.11 indicates that it precipitates from an evaporite along
with sylvite to a greater extent than lithium, and it has a high chemical
reactivity. The radius of its ion, 1.48
is only about 10% larger than the
potassium ion, so it can be accommodated into the same crystal lattices.
Because of this, it forms no minerals of its own.
Rubidium and cesium occur sympathetically in nature; that is, both are
commonly found in amazonite, vorobyevite, and beryl (Goldschmidt, 1958).
Rubidium is a member of series NH4-K-Rb-Cs, and members of this series
are more similar in their chemical and physical properties than are the members of any other group, with the exception of the halogens. Rubidium
concentrates in the late crystallates, particularly those of granitic derivation,
and it has a greater tendency t o be adsorbed by clays than has potassium. It
is removed from igneous rocks by water leaching and then adsorbed by
hydrolysate sediments and soils.
Shales contain about 250 ppm of rubidium; deep-sea red clays, about 400
ppm; and some glauconites, about 500 ppm (Goldschmidt, 1958).Sea water
contains about 0.12 mg/l of rubidium; subsurface brines contain up t o 4
mg/l. Higher concentrations of rubidium probably can be found in brines
associated with rocks containing potassium minerals, such as microcline
feldspars, or lepidolite mica.
a,
141
CESIUM
Cesium
Cesium is the heaviest alkali metal and also the rarest, with an abundance
of about 7 x
wt.% in the earths crust (Fleischer, 1962). It has an ionic
radius of 1.69 8,which is distinctly larger than potassium, and it cannot
replace potassium in minerals as easily as rubidium; probably because of this,
it forms its own minerals. It is leached from igneous and metamorphic rocks
by water during weathering, and is adsorbed by hydrolysate sediments and
soils more readily than rubidium or potassium. Its low ionization potential
indicates that it has the greatest chemical reactivity of the alkali metals.
Cesium and rubidium were discovered in 1860 by Robert Bunsen by use of
spectral analysis, a method which he and Kirchhoff invented.
Cesium concentrates primarily like rubidium, in marine argillaceous sediments. Some shales contain about 15 ppm; deep-sea red clays, 20 ppm; and
glauconite, 15 ppm of cesium (Goldschmidt, 1958). Sea water contains
5x
mg/l of cesium, and some subsurface brines contain up to 1mg/l.
Beryllium
Beryllium is a member of the alkaline earth group in the periodic chart of
the elements, but few of its properties are similar t o the more abundant
members, such as magnesium, calcium, and strontium. Beryllium, like
lithium, is a light element with an atomic weight of 9.012 (Table 5.111; see
also Moeller, 1954), and like lithium, it is an exception t o the rule that light
elements are more abundant than heavy elements. The earths crust contains
about 6 x
wt.% of beryllium (Fleischer, 1962).
In sedimentary rocks, beryllium is restricted primarily to hydrolysates and
especially to bauxites enriched in aluminum (Goldschmidt, 1958). Shales
contain about 6 ppm, and some coal ashes contain up to 8,000 ppm, although generally only about 4 ppm. The concentration of beryllium in sea
TABLE 5.111
Properties of the alkaline earth metals
Property
Beryllium Magnesium
Atomic number 4
Ionic radius
(A 1
0.31
Outer electronic
configuration
1s 2s
Atomic weight 9.012
Ionization
9.320
potential (V)
12
0.65
2s 2p6 3s
24.31
7.644
Calcium
Strontium
Barium
20
38
56
0.99
3s2 3p6 4s2
40.08
6.111
1.13
4s 4p6 5s2
87.62
5.692
1.35
5s2 5p66s
137.34
5.210
142
water is about 5 x lo-' mg/l, and some subsurface brines contain 0.02-4.2
mg/l. Since beryllium is highly toxic, waters containing it should be handled
with caution.
Magnesium
One of the more abundant members of the alkaline earth group of metals,
magnesium makes up about 2.1 wt.% (Fleischer, 1962) of the crust of the
earth.
Magnesium is dissolved during chemical weathering, mainly as the chloride
and sulfate. Ferromagnesian minerals in igneous rocks and magnesium carbonate in carbonate rocks are generally considered t o be the principal
sources of magnesium in natural waters. Carbon dioxide plays an important
role in the dissolution of magnesium from silicate and carbonate minerals.
Waters associated with either granite or siliceous sand may contain less than
5 mg/l of magnesium, whereas those associated with either dolomite or
limestone may contain over 2,000 mg/l of magnesium.
Elements commonly found in oilfield waters have the following ionic
potentials: sodium, 0.95; calcium, 0.50; magnesium, 0.33; chlorine, 1.81;
bromine, 1.95; and iodine, 2.16. Apparently the cation (magnesium) and the
anion (chlorine) would be the most likely to remain in true ionic solution;
however, several other variables occur during diagenesis which lead to depletion of magnesium in waters.
Depletion of magnesium in some waters probably is a result of the replacement reaction t o form dolomite, CaMg(C0, ) 2 . Whole mountain masses are
made of dolomite, which is formed by the regular substitution in the calcite
2oo
C
J
?$
'so0
500
rpoo
2,000
5ooO
lop00
2
0
m
,
5Q(
MAGNESIUM, mg I I
Fig. 5.7. Comparison of the magnesium concentrations in some Tertiary (T), Cretaceous
(C), and Jurassic (J) age formation waters from Louisiana with an evaporating sea water.
143
CALCIUM
c
Normal evaporite curve
500
M
M
P
r
20
10
1,000
I 0,000
lO0,OoO
MAGNESIUM, mg/l
Fig. 5.8. Comparison of the magnesium concentrations of some Pennsylvanian (P) and
Mississippian (M) age formation waters from Oklahoma with an evaporating sea water.
crystal lattice of alternate ions of calcium and magnesium. The large differences in the ionic radii of Ca (0.99A) and Mg (0.65A) are the reason for this
diadochy.
Magnesium ions in aqueous solution have a large attraction for water
molecules and probably are surrounded by six water molecules in octahedral
arrangement. This may account for the paucity of magnesium in soils,
because the small cation becomes large by hydration. Sodium has a similar
reaction, but potassium, which does not, is readily adsorbed by soil colloids.
Shales, sandstones, and carbonates contain 15,000,7,000,and 47,000
ppm of magnesium, respectively (Mason, 1966). Subsurface brines contain
from less than 100 mg/l t o more than 30,000 mg/l; however, many subsurface brines are depleted in magnesium if compared to a sea water evaporite
sequence, (Table 5.11). Sea water contains about 1,300 mg/l. Fig. 5.7 is a
plot of chloride versus magnesium for some subsurface brines taken from
Tertiary, Cretaceous, and Jurassic age sediments. The position of the normal
evaporite curve indicates that all of these waters were depleted in magnesium
with respect to this curve (Collins, 1970). Fig. 5.8 is a plot showing similar
depletion of some subsurface brines taken from some sediments of Pennsylvanian and Mississippian age.
Calcium
The abundance of calcium in the crust of the earth is about 3.55 wt.%
(Fleischer, 1962),making it the most abundant of the alkaline earth metals,
144
but only in the crust; in the earth as a whole, magnesium is much more
abundant. Calcium is dissolved as bicarbonate as a result of chemical
weathering of calcium-bearing minerals. Waters associated with limestone,
dolomite, gypsum, or gypsiferous shale usually contain an abundance of
calcium, but waters associated with granite or silicious sand may contain less
than 10 mg/l of calcium. Slight changes in the pH of waters containing
calcium bicarbonate will cause calcium carbonate to precipitate, and calcium
carbonate is one of the most common deposits found in plugged oilfield
lines, equipment, and reservoirs.
Precipitation of calcium carbonate in the sea is the prime mode of the
origin of limestone. The solubility of calcium carbonate in sea water increases with salinity and increasing partial pressure of carbon dioxide, but it
decreases with increasing pH, calcium content, and temperature. The
solubility of calcium sulfate decreases with increasing temperature.
Shales, sandstones, and carbonate rocks contain about 22,100, 39,100,
and 302,300ppm of calcium, respectively (Mason, 1966).Sea water contains
400 mg/l and subsurface brines often contain 2,000-3,000 mg/l, with some
as high as 30,000 mg/l. Fig. 5.9 is a plot of chloride versus calcium concentrations for some subsurface waters taken from Tertiary, Cretaceous, and
Jurassic age sediments. The amount of calcium in these waters increases with
increasing salinity, and the waters from the older sediments appear to contain more calcium. Fig. 5.10 is a similar plot for some subsurface brines
taken from sediments of Pennsylvanian and Mississippian age. These samples
all appear to be enriched in calcium relative t o the evaporite curve, and the
concentration of calcium appears to increase with increasing salinity.
200
\
0
100-
I 1 I I I111
1
500
1 , m
5poo
lop00
29ooo
CALCIUM, mg/l
Fig. 5.9. Comparison of the calcium concentrations of some Tertiary (T), Cretaceous (C),
and Jurassic (J) age formation waters from Louisiana with an evaporating sea water.
STRONTIUM
145
&-\-
P
P
Ii
201
M
M
1
00
CALCIUM, mg/ I
Fig. 5.10. Comparison of the calcium concentrations of some Pennsylvanian (P) and
MEsissippian (M) age formation waters from Oklahoma with an evaporating sea water.
Strontium
Strontium, a minor element compared t o calcium and magnesium comprises about 0.03 wt.% of the earth's crust (Fleischer, 1962). Table 5.111
illustrates some of its properties, and it resembles calcium chemically. Strontium has a tendency to work upward during fractional crystallizaticn because of its relatively large radius (Goldschmidt, 1958).It occurs abundantly
with potassium in volcanic rocks, alkali rocks, and pegmatites.
Dissolved strontium results from water leaching of rocks, and it has been
postulated that the strontium in petroleum-associated waters also may be a
byproduct of the organic decay processes which originally formed
petroleum. Strontium is only a microconstituent in most terrestrial animals,
but several species of marine animals contain considerable quantities of
strontium in their skeletons (Odum, 1951).
Table 5.11 indicates that strontium may reach a concentration of 60 mg/l
during sea-water evaporation, and then most of it precipitates with calcium
sulfate. The amount of sulfate in the water influences the amount of strontium that remains in solution. Data by Sillhn and Martell (1964)indicate
that if the sulfate activity in a water is 100 mg/l, the strontium activity can
be about 28 mg/l. Davis and Collins (1971)studied the solubility of strontium sulfate in strong electrolyte solutions and found that 958 mg/l of
strontium is soluble in a synthetic brine solution of ionic strength 3.05,
146
I
C -Cretaceous
J -Jurassic
C
c cc 2,000
C
cC
20
1
0
50
I IIII
100
2 a
I IIL
STRONTIUM, mgll
200 -
Ill
50
100
ZOO
STRONTIUM, mg/l
500
1,000
Fig. 5.12. Comparison of the strontium concentrations of some Pennsylvanian (P) and
Mississippian (M) age formation waters from Oklahoma with an evaporating sea water.
BARIUM
147
TABLE 5.IV
Properties of aluminum. copper. iron, lead, manganese, and zinc
property
Aluminum
Copper
Iron
Lead
Manganese
Zinc
Atomic number
Ionic radius (A)
13
0.50
26
0.76(+2)
0.64(+3)
. .
82
1.20(+2)
0.84(+4)
. .
25
0.80(+2)
0.46c+7 1..
30
0.74
Outer electronic
configuration
Atomic weight
Ionization potential (V)
27
0.96(+1)
0.691+21
. ,
2s22p63s23p1
26.98
5.984
3s23p63d'04s'
63.54
1.723
3s23p63d64s'
55.54
1.165
3s2'3p63d" 4s'
65.37
9.391
4d'05s'5p64f'5d106s'6p'
207.19
7.415
MANGANESE
149
150
Iron, cobalt, and nickel possess atomic radii that differ only about 2% or
less, so that the crystal chemistry of the three are related. The divalent ions
of nickel, magnesium, cobalt, and iron have similar ionic radii; consequently,
their chemistries in the sequence of isomorphous crystallization of mixtures
are similar. The trivalent ions of iron and cobalt are similar in size, but the
high oxidation potential of cobalt prevents much replacement (Goldschmidt,
1958).
The solubility of iron compounds in ground waters is a function of the
type of iron compound involved, the amounts and types of other ions in
solution, the pH, and the Eh. According t o Larson and King (1954), 100
ppm of ferrous iron can stay in solution at pH 8 and pH 7; the theoretical
maximum is about 10,000 ppm. The effects of many other ions, plus temperature and pressure differentials, such as those common to oilfield waters,
have not been thoroughly studied. When a ground water in which ferrous
iron is dissolved contacts the atmosphere, the following reaction can occur:
2Fe2++ 4HCO3- + H20 + 1 / 2 0
+ 2Fe(OH), + 4C02
Sandstone contains iron oxide, iron carbonate, and iron hydroxide, and
shales and carbonate rocks contain oxides, carbonates, and sulfides of iron.
Oilfield waters with characteristic low redox potentials dissolve some iron
from the surrounding rock. The iron occurs in such waters at two levels of
oxidation, ferrous or ferric.
Knowledge of the amount and type of iron compounds in oilfield waters
is used to estimate the amount of corrosion that is occurring in the production system, and t o determine the type of treatment required if the water is
t o be used for waterflooding. This knowledge also enables determination of
the Eh of the in situ water, because the Eh can be calculated from the Fe+2
and Fe+ values.
Shales, sandstones, and carbonates contain about 47,200, 9,800, and
3,800 ppm, respectively, of iron (Mason, 1966). Sea water contains about
0.01 mg/l, and subsurface brines contain from traces to over 1,000 mg/l of
iron.
Copper
Copper is a member of the VIII group of elements, and it is characteristically thiophile; the largest concentrations of it are found in various sulfur
compounds. The earths crust contains about 0.01 wt.% of copper (Fleischer,
1962). Its compounds are dissolved easily during weathering, if the pH of the
solution is less than 4.5. Many of the water-soluble copper compounds are
salts of organic acids such as acetic, citric, and naphthenic. Much of the
copper that is dissolved is precipitated afterward as sulfide. Traces of copper
remain in the oceans, but its content is kept low because of the adsorption
on, or combination with, marine organisms. Miholic (1947) presented an age
ZINC
151
division for mineral waters based on the presence of heavy metals in waters
associated with joints and faults caused by tectonic movements of different
geological ages. He placed copper as the predominant heavy metal in the
Caledonian Group of the Orogenic Epoch (post-Silurian). Biochemical processes are known to be responsible for enriching a deposit in metals such as
uranium, copper, and vanadium; therefore, this classification is restricted to
waters of igneous origin.
Most shales and carbonates contain about 45 and 4 ppm, respectively, of
copper, with sandstones containing less than 1 ppm (Mason, 1966). Sea
water contains about 0.003 mg/l, and most subsurface brines analyzed in this
laboratory contained from less than 0.5 mg/l up to about 3 mg/l. The solubility of copper generally decreases with decreasing redox potential and
increases with increasing redox potential if reduced sulfur is present. Most
subsurface oilfield brines have relatively low redox potentials.
zinc
Zinc is a member of the I1 B group of elements and is predominantly
thiophile. Its abundance in the crust of the earth is about 0.013 wt.%
(Fleischer, 1962). Its geochemistry results from the similarity of its divalent
ionic radius and the radii of Mg+, Ni+?, Co+, Fe+, and Mn+
(Goldschmidt, 1958).
Zinc is dissolved readily as sulfate or chloride from acid rocks, such as
granite, during weathering. Conversely, zinc is not dissolved easily from
limestone with which it is deposited. Most alkaline waters do not extract
zinc; however, a solution of NH,, NH,NO,, and NaC10, can extract and
hold small quantities of zinc; the more acidic the water, the greater the
amount of zinc extracted. Zinc is precipitated as the sulfide, oxide, carbonate, or silicate. Traces of zinc are found in sea water, but eventually zinc is
deposited in carbonated sediments or in bottom muds or sapropels as sulfide.
Shales, sandstones, and carbonates contain about 95, 16, and 20 ppm,
respectively, of zinc (Mason, 1966). Sea water contains about 0.01 mg/l, and
subsurface brines contain traces to more than 500 mg/l of zinc.
Mercury
Mercury is a member of the I1 B group of elements, which also includes
zinc and cadmium. It is relatively abundant for a heavy element, but still
must be considered scarce, with an abundance of about 4 x lo- wt.% of
the crust of the earth (Fleischer, 1962). Most commercial deposits of
mercury are of hydrothermal origin and are related to magmatic rocks; the
commercial ore is cinnabar, HgS, or the liquid metal itself (Goldschmidt,
1958). Mercury is predominantly thiophile, and its geochemistry is controlled by the fact that it is volatile, with a boiling point of 357C, and can be
reduced to the metal by ferrous iron. Therefore, in a magmatic environment
152
the temperature and the redox potential control its occurrence. It is transported in hot springs (White et al., 1963).
Shales, sandstones, and carbonates contain about 0.4, 0.03, and 0.04 ppm,
respectively, of mercury. Sea water contains 3 x lo- mg/l, and subsurface
oilfield brines contain 0-0.15 mg/l. The samples containing 0.15 mg/l of
mercury were found in relatively dilute brines taken from the Cymric and
the Rio Bravo oilfields in California. Free mercury is found in the oils
produced from these fields, and the ages of the producing formations range
from Eocene t o Pleistocene.
The mercury content of natural waters has been used t o locate cinnabar
deposits (DallAglio, 1968). The amounts of mercury in waters appear t o
increase with increasing bicarbonate concentration. Karasik et al. (1965)
found that saline waters containing 200,000 mg/l of chloride contain very
small amounts of mercury, which suggests that anionic complexes such as
HgC14-* may not be important transporters of mercury. Brackish waters containing up t o 3,000 mg/l dissolved solids, up to 400 mg/l of bicarbonate, and
the iodide ion sometimes contain up to 10 ppb of mercury, while stronger
brines contain <0.1 ppb of mercury, which suggests that mercury may be
transported as Hg14-* in brackish waters.
Lead
Lead is a member of the IV A group of elements; it is ubiquitous in the
earth, but its abundance in the crust is only about 0.002 wt.% (Fleischer,
1962). It is extracted from its minerals during weathering and migrates in the
form of soluble-stable compounds. It is particularly soluble in acetic and
other acids. Because the bicarbonate form is more soluble than the carbonate, lead can be transported as the bicarbonate. Most of the lead is
precipitated from waters before they reach the sea. Hemley (1953) studied
lead sulfide solubility related to ore deposition from saline waters. He concluded that lead-complex concentrations increase with increasing concentrations of bivalent sulfur and decrease at pH values above 7. The solubility
of lead is limited primarily by the solubility restrictions of its sulfide and
sulfate in reducing and oxidizing systems. How its solubility is influenced by
many other ions, such as those found in a brine, has not been sufficiently
studied.
Shales, sandstones, and carbonates contain about 20, 7, and 9 ppm of
lead, respectively. Sea water contains about 0.003 mg/l, and subsurface
brines contain trace amounts to more than 100 mg/l of lead.
Cadmium
Cadmium is a member of the I1 B group of elements and may be considered one of the rarer elements; its abundance is about 3 x lo- wt.% of the
earths crust (Fleischer, 1962). It is strongly thiophile, but its chemistry
BORON
153
differs from that of zinc in that it will precipitate from a strong acid solution, whereas zinc will not. There are few independent cadmium minerals,
and its distribution is mainly that of a guest atom or ion in minerals. It
frequently is present in lead-zinc deposits and occurs in solid solution in
hypogene sulfides. A main carrier of cadmium is sphalerite, and oxidation of
sphalerite or other sulfides containing cadmium will release the soluble
cadmium sulfate.
Shales and carbonates contain about 0.3 and 0.035 ppm of cadmium,
respectively, and sandstones contain less than 0.01 ppm (Mason, 1966). Sea
water contains about 0.0001 mg/l, and the subsurface oilfield brines may
contain from 0 to about 0.001 mg/l of cadmium. Subsurface brines of the
sulfate type in contact with lead-zinc deposits probably contain higher
concentrations of cadmium.
Boron
Boron is a member of the I11 A group of elements, and it is an oxyphile
and lithophile element. Its abundance in the crust of the earth is about 0.001
wt.% (Fleischer, 1962). It has small atomic and ionic radii.
Knowledge of the presence of boron compounds in oilfield waters is important for several reasons. Boron is useful in identifying the sources of
brines intrusive t o oil wells, or in fresh-water lakes or streams. In concentrations exceeding 100 mg/l, it affects electric log deflections. Boron is
present in oilfield brines as boric acid, inorganic borates, and organic borates.
When it is present as undissociated boric acid, it is an important buffer
mechanism, being second only to the carbonate system. It may be precipitated as the relatively insoluble calcium and magnesium borates.
Kazmina (1951) calculated the borate-chloride coefficient of some
Russian oilfield waters. With a plot of the borate-chloride coefficient in
logarithmic coordinates as a function of chloride content, he distinguished
genetic groups of natural waters found in oil-bearing regions.
Mitgarts (1956) studied the significance of boron and other elements in
petroleum prospecting. In general, boron, together with bromine and iodine,
is always associated with waters accompanying petroleum. Like chlorine, it
can be considered an element of marine origin. The solubility of most boron
compounds, the hydrolytic cleavage of boron salts, and their ability t o be
occluded and coprecipitated with other compounds account for the extensive migration of boron. Soluble-complex boron compounds in brines and
connate waters probably are there as a result of the decay of the same plants
and animals that were the source of petroleum.
Shales, sandstones, and carbonates contain about 100, 35, and 20 ppm,
respectively, of boron. Sea water contains about 4.8 mg/l, and subsurface
oilfield water contains from trace amounts to more than 100 mg/l. Fig. 5.13
is a plot of chloride versus boron concentrations of some oilfield brines taken
from some sediments of Tertiary, Cretaceous, and Jurassic age. The plot
154
---I200
T T
a
50
0
"
30
"k/~ /
C "
T
c
BORON,mg/I
Fig. 5.13.Comparison of the boron concentrations of some Tertiary (T), Cretaceous (C),
and Jurassic (J) age formation waters from Louisiana with an evaporating sea water.
BORON, m g / l
Fig. 5.14. Comparison of the boron concentrations of some waters from Pennsylvanian
(P) and Mississippian (M) age sediments with an evaporating sea water.
indicates that the majority of these brines are enriched in boron relative to a
normal evaporite-formed brine, and that the samples that were depleted in
boron may have contained dissolved halite. Fig. 5.14 is a similar plot for some
samples taken from some Pennsylvanian and Mississippian age sediments.
Boron is one of the elements whose concentration in the aqueous phase
increases as a brine is evaporated, as illustrated in Table 5.11.
ALUMINUM
155
Aluminum
Aluminum is the third most abundant element in the earths crust, but its
concentration in natural waters usually is less than 1 mg/l. The ionic radius
of trivalent aluminum is 0.57 (Goldschmidt, 1958),and it usually behaves
as a cation when 6-coordinated with oxygen compounds. However, when
4-coordinated, it usually acts like the central atom of an anion. The
4-coordination usually, but not exclusively, is associated with minerals
formed at high temperatures, but the 6-coordination is associated with
minerals formed at low temperatures, which includes most sediments in the
petroleum environment.
The clay minerals illite, kaolinite, and montmorillonite often contain
about 13.5, 21, and 11%aluminum, respectively. Quartzites, sandstones,
limestones, and shales contain about 0.7, 3.0, 0.6, and 10% aluminum,
respectively. During weathering silica will leach out and leave aluminum
hydroxide behind (Pirsson and Knopf, 1947), and sedimentation processes
leave only about 0.4 mg/l aluminum in sea water.
According t o Hem (1970), the cation A P 3 predominates in solutions with
a pH of 4.0 or less. Above pH 4.5, polymerization gives rise to an aluminum
species with a gibbsite (aluminum hydroxide) structural pattern. Above pH
7.0, the dissolved form is the anion A1 (OH),-.
The pH of the water is the main control of the amount of alumium that is
likely to be present in natural waters. A water with a pH less than 4.0 may
contain 1%or more of aluminum; for example, waters associated with acid
mine drainage. Oilfield waters contain trace amounts t o more than 100 mg/l
of aluminum.
A 1ha 1inity
Alkalinity is defined as the capacity of a solution to neutralize an acid,
usually t o a pH of 4.5. A solution with a neutral pH of 7.0 may have a
considerable amount of alkalinity; therefore, alkalinity is a capacity function,
in contrast to pH, which is an intensity function. The alkalinity-pH ranges
originally coincided with methyl orange and phenolphthalein color end
points. The potentiometric titration produces more accurate alkalinity
results, and it utilizes an end point where the most abrupt pH change occurs
while specific increments of a standard acid are added.
Alkalinity usually is caused by the presence of bicarbonate, carbonate, or
hydroxyl ions in a water; however, the weak acids such as silicic, phosphoric,
and boric can contribute titratable alkalinity species. Carbon dioxide, which
is dissolved in circulating waters as bicarbonate or carbonate as a result of
the carbon cycle, is the prime source of alkalinity in shallow ground waters.
However, in deep subsurface brines, additional carbon dioxide probably is
dissolved as a result of diagenesis of inorganic and organic compounds.
Most oilfield waters contain no hydroxyl ions, and most of them contain
156
Acidity
The basis of acidity is the solvated hydrogen ion H 3 0 + ,which is found in
nature. Volcanic emanations produce HF, HCl, and H2SO4, probably formed by reactions between water and constituents associated with the
magma. Waters associated with peat may contain organic acids, rain waters
may contain carbonic acid, and waters associated with reducing conditions
and anaerobic bacteria may contain H2 S.
Acidity, as contrasted to alkalinity, is the capacity of a solution to
neutralize a base, usually from below pH 4.5 t o pH 7.0. Most oilfield brines
normally do not contain acidity. New wells or reworked wells often are
acidified or "acidized" with a strong mineral acid or a combination of
mineral and organic acids. This treatment causes the produced water to
contain a certain amount of acidity until all of the acid is neutralized or
diluted. Because of the large quantities of acids used in some treatments, it
m a y take 6 months or more for the water produced from a treated well t o
return to normal. Organic acids and organic acid salts commonly are found
in oilfield waters, and the concentration ranges from trace amounts to more
than 3,000 mg/l.
Silica
Silicon is the second most abundant element in the earth's crust, which
contains about 27 wt.% of it (Fleischer, 1962). It always occurs in a combined form. Most of the silicon compounds involve structures with oxygen,
and there are about a thousand silicate minerals in the earth's crust; however,
those which are predominant are relatively few in number.
The solubility of silica in water is a function of temperature, pressure, pH,
and other ions in solution. Most silica in natural water probably is in the
form of monomolecular silicic acid, H4 Si04 or Si(OH)4. Collins (196913)
studied the solubility of a serpentine in solutions of calcium chloride and
sodium chloride a t temperatures from 30" to 200C and pressures from 176
t o 1,055 kg/cm2. The solubility calculated as silicon molarity in solution
increased with increasing concentrations of sodium chloride, increasing pressure, and increasing temperature up to about 125C. Between about 125"
and 2OO0C, the solubility decreased with increasing temperature. The solu-
157
AMMONIUM NITROGEN
State
Formation
1
2
3
4
5
6
7
8
9
10
Utah
Utah
Utah
Okla.
Okla.
Utah
Utah
Okla.
Okla.
Okla.
Navaho
Green River
Lower Green River
Morrow
Rue
Uinta Surface, Green River
Green River
Hunton
Oswego
Chester
30-143
0
852-1,719
71
91
914-1,737
2,713-2,715
0
116
1,958-1,963
717-1,111 2,069
5
68 1-1,5 5 6
2,696-2,77 1
434
1,928-1,951
233
23
2,408-2.437
The NH4N content of several oilfield brines was determined and a wide
variation in concentration was found. Table 5.V illustrates the amounts of
NH4N found in 10 samples taken from subsurface rocks in Oklahoma and
Utah.
158
Phosphorus
SULFUR
159
the free form. Most combined oxygen is ionic; however, it forms a covalent
molecule with hydrogen, namely water. It also forms complex oxy-salts with
various metals. The oxygen content of rocks decreases with depth.
The solubility of oxygen in water is primarily a function of temperature
and pressure, and surface waters at ambient conditions may contain 7.63
mg/l a t 3OoC and 11.33 mg/l at 10C (Hem, 1970). The amounts of
dissolved oxygen in subsurface petroleum-associated waters is usually low,
and in most in situ conditions it is undetectable because of the low redox
potential of the environment. It can cause corrosion problems in the well
pipes, but in most cases it is atmospheric oxygen that mixes with the produced brine during production operations that causes oxygen corrosion.
Sulfur
Sulfur is a member of the VI A group of elements and is widely dispersed
in sedimentary and igneous rocks as metallic sulfides. The crust of the earth
contains about 0.05 wt.% of sulfur (Fleischer, 1962). Free sulfur often is
related to volcanic activity and can be deposited directly as a sublimate.
Many commercial deposits, however, are associated with sedimentary
gypsum, and probably result from biogenic activity such as that. of anaerobic
bacteria. Large deposits of sulfur are found in caprocks of anhydrite overlying some salt domes.
Hydrogen sulfide, often found in oilfield waters, is formed by anaerobic
bacteria. One such species of bacteria is the Desulphouibrio,which obtains
its oxygen from sulfate ions, causing them to be reduced to hydrogen
sulfide.
complexed
)
with
Sulfur in surface water usually occurs in the form ( S 6
oxygen as the sulfate anion S04-2. As previously mentioned, the conversion
of oxidized sulfur t o a reduced form commonly involves a biogenic process,
and such a reduction may not occur unless these bacteria are present. The Eh
of subsurface oilfield brines usually is somewhat reducing, and the sulfur
species in such environments can include hydrogen sulfide (H2 S), sulfite
and thionates (S406-). Detailed studies of the sulfur species in
subsurface brines have not been made, and it is likely that other forms of
sulfur are present in some brines. The temperature, pressure, Eh, pH, and
other constituents in solution all influence the types of dissolved sulfur that
occur in oilfield brines.
Shales, sandstones, and carbonates contain about 2,400, 240, and 1,200
ppm, respectively, of sulfur (Mason, 1966). Sea water contains 900 mg/l of
sulfur as sulfate, and subsurface oilfield brines contain from none up to
several thousand milligrams per liter. The amount of sulfate in the brine is
influenced by bacterial activity and by how much calcium, strontium, and
barium is present. If these three cations are present in relatively high concentrations, the amount of sulfate present will be low. However, some brines
containing high concentrations of magnesium and low concentrations of the
other alkaline earth metals may contain high concentrations of sulfate.
160
Selenium
Selenium is a member of the VI A group of elements and occurs in -2,0,
+4,and +6 valence states, respectively. It is a scarce element with an abundance of about 9 x 10" wt.% of the crust of the earth (Fleischer, 1962).
Large areas of North America are underlain by seleniferous rocks and soils.
These seleniferous rocks are of sedimentary origin and range in age from
Late Paleozoic to Holocene. Selenium is the only known element that can be
absorbed by plants in sufficient amounts to make them lethal when eaten by
animals (Trelease, 1945).Fig. 5.15 illustrates the distribution of seleniferous
vegetation.
Sandstones, shales, and carbonates contain about 0.6, 0.05,and 0.08 ppm,
respectively, of selenium. Sea water contains about 0.004 mg/l of selenium.
A few subsurface oilfield brines from areas where selenium is present in soils
were analyzed at this laboratory, but no selenium was detected in the brines
analyzed. Most brines are present in a petroleum environment under
reducing conditions, and in such an environment, selenium likely is reduced
to the element and precipitated. However, in areas where outcrop water
flows through petroleum-bearing formations, it is possible that selenium in
the form of t)e anion Se03-2 may be present.
1
Fig. 5.15. Distribution of seleniferous vegetation in the United States.
FLUORINE
161
Fluorine
Fluorine is a member of the VII A group of elements and is the most
electronegative of all the elements. Its ionic radius is 1.33 A, which is about
the size of OH- and O-*;therefore, it enters a variety of minerals. The
earths crust contains about 0.03 wt.% of fluorine (Fleischer, 1962). In
solutions, fluorine usually forms the fluoride F- ion; at a low pH, the HFo
form might occur. It also can form strong complexes with aluminum, beryllium, and ferric iron.
Fluorine occurs in several minerals, but the only common industrial
source is fluorspar (CaF2). It occurs as HF or SiF in volcanic emanations,
and even as the free element in (stinkfluss) stinking fluorspar of Wolssendorf, Bavaria. The solubility of calcium fluoride (fluorite) in water at 25OC is
about 8.7 ppm of fluoride (Aumeras, 1927);this solubility could be affected
by other dissolved constituents. Sodium fluoride is very soluble, and magnesium fluoride is more soluble than calcium fluoride; therefore, a petroleumassociated water that is deficient in calcium and has been in contact with
rocks containing fluoride minerals will contain appreciable quantities of
fluoride.
Shales, sandstones, and carbonates contain about 740, 270 and 330 ppm
of fluorine, respectively (Mason, 1966). Sea water contains about 1.3 mg/l,
and natural waters with a dissolved solids concentration of less than 1,000
mg/l usually contain less than 1 mg/l of fluoride. However, concentrations
up t o 50 mg/l have been reported (Hem, 1970). Not many subsurface
petroleum-associated brines have been analyzed for fluoride, but a few are
known t o contain up t o 5 mg/l.
Chlorine
Chlorine is a member of the VII A group of elements and is the most
important member of the group with respect to water. The crust of the earth
contains about 0.19 wt.% of chlorine (Fleischer, 1962);some estimates place
the fluorine abundance above the chlorine abundance. Volcanic activity
produces the gas hydrogen chloride and sometimes chlorine, but much less
frequently. The caliche evaporite deposits in Chile contain the perchlorate
ion C104-; however, the mechanism by which it formed is not clear. Several
minerals contain the chloride ion.
The chloride ion does not form low-solubility salts. I t is not easily
adsorbed on clays or other mineral surfaces. It is not significant in oxidation
and reduction reactions, and it forms no important solute complexes.
Chloride is very mobile in the hydrosphere, yet it is relatively scarce in the
earths crust. It is the predominant anion in sea water and in most
petroleum-associated waters. It is found in all natural waters, and its average
concentration in rainwater is about 3 mg/l (Hem, 1970). Chloride salts are
162
very soluble; therefore, chloride is usually not removed from solution except
during freezing or evaporation processes and in hyperfiltration, as water
moves through some types of clay beds (White, 1965).
Shales, sandstones, and carbonates contain about 180, 10, and 150 ppm,
respectively, of chloride. Sea water contains about 19,000 mg/l of chloride,
the principal anion in the sea. The chloride content of the hydrosphere is
much greater than can be accounted for by weathering of rocks, and it has
been postulated that the primordial atmosphere may have been rich in
chlorine compounds. The volcanic emission of chlorine gases appears a more
plausible explanation, however.
Oilfield brines usually contain relatively high concentrations of chloride;
in some brines the concentration may be 200,000 mg/l or more. Chloride
usually is the predominant anion in oilfield brines. Table 5.1 illustrates how
its concentration can increase in an evaporite-associated brine. Evaporation
probably is the only geochemical process which appreciably affects the
chloride content of the seas.
Bromine
Bromine is a member of the VII A group of elements and it behaves
somewhat similarly t o chlorine. The crust of the earth contains about 0.0005
wt.% of bromine (Fleischer, 1962). It usually occurs as the ion bromide Br-,
and it does not form its own minerals when sea water evaporates (Valyashko,
1956). It forms an isomorphous admixture with chloride in the solid phases.
The order of crystallization (see Table 5.1) is halite (NaCl), sylvite (KCl),
carnallite (MgC12-KC1*6H20), and/or kainite (MgS04 *KC1=3H2
0), and at
the eutectic point, bischofite (MgCl? -6H2 0). Each of these chlorides
entrains bromide in the solid phase. This distribution accounts for the relative enrichment of bromide in the liquid phase because with each crystallization more bromide is left in solution than is entrained in the solid phase.
Mun and Bazilevich (1962) reported that, in fresh-water lakes, bromide
accumulates in the muds, that its concentration is proportional t o the
organic-matter concentration in the sediments, and that it is not influenced
by the pelitic fraction. In muds of salt lakes, the higher the bromide concentrations in the brine, the higher it is in the muds. In general, the bromide
content in the pore solutions increased with depth, but the bromide content
in muds decreased with depth, owing to more complete decomposition of
organic bromine compounds.
Bromide is two t o three times more concentrated in carnallite than in
sylvite and five to ten times more than in halite (Myagkov and Burmistrov,
1964). Apparently, concentration and dilution are responsible for the complex distribution of bromide in rocks of a carnallite zone. The determining
factor in the replacement of chloride by bromide is the mineral composition
rather than the bromide concentration in the brine.
BROMINE
163
Braitsch and Herrmann (1963) found that the absolute bromide content of
rocks can be used to determine primary and secondary paragenesis. Distribution of bromide between solution and crystals of halite, sylvite, carnallite,
and bischofite, and the effects of other ions plus temperatures between 25"
and 83OC, confirm this. This method was also applied to determine the
temperature of primary potash deposits. An investigation of the bromide/
sodium chloride relation in salt deposits revealed that bromide can be used
to determine the stratigraphy of evaporite-salt deposits (Baar, 1963).
Derivation of theoretical profiles of bromide thickness versus salt
thickness indicated that, with constant inflow, evaporation, and reflux, the
thickness profiles were all monotomic logarithmic functions. The irregular
and high bromide concentrations of some salt deposits were attributed to
inflow of bromide-rich bitterns from an adjacent potash basin (Holser,
1966).
Shales, sandstones, and carbonates contain about 4,1,and 6 ppm, respectively, of bromide (Mason, 1966). Sea water contains about 65 mg/l of
bromide, and subsurface petroleum-associated brines contain from less than
50 to more than 6,000 mg/l of bromide. Fig. 5.16 illustrates the bromide
concentration plotted versus the chloride concentration for some subsurface
brines taken from Tertiary, Cretaceous, and Jurassic age sediments. This plot
indicates that the waters from these Tertiary age sediments are depleted in
bromide relative to a normal evaporite brine, whereas those from the
Cretaceous and Jurassic age sediments are enriched'in bromide.
BROMIDE, mg / I
Fig. 5.16. Comparison of the bromide concentrations in some formation waters from
Tertiary (T), Cretaceous (C), and Jurassic (J) age sediments from Louisiana with an
evaporating sea water.
164
P
M
PI
300
1,000
BROMIDE, m g l l
3000
10
Fig. 5.17. Comparison of the bromide concentrations in some formation waters from
Pennsylvanian (P) and Mississippian (M) age sediments from Oklahoma with an evaporating sea water.
Fig. 5.17 is a similar plot for some brines taken from some Pennsylvanian
and Mississippian age sediments. The bromide concentrations in these brines
do not appear t o be significantly different.
Brines containing 1,500 to 8,000 mg/l of bromide, with calcium and
magnesium chloride as the major constituents, are formed by evaporation of
sea water and associated sedimentation rather than by dissolution of salts.
Increase in temperature causes a phase shift in the solid and brine phases,
resulting in an increase of bromide in solution.
Iodine
Iodine is a member of the VII A group of elements, and of the four
members discussed in this chapter, it is the least abundant, since it comprises
only about 3 x lo-' wt.% of the earth's crust (Fleischer, 1962). I t forms
three minerals of its own; namely, iodoargyrite (AgI), iodoembolite
[Ag(Cl,Br,I)], and miersite [(Ag,Cu)I]. Marine plants, such as kelp and plankton algae, concentrate iodine.
The distribution of iodide in marine and oceanic silts and interstitial
waters indicates that near-shore ocean Sediments contain more iodide than
deep-sea sediments. Red clays and calcareous sediments contain less iodide
than organic-bearing argillaceous sediments. The iodide concentration in the
marine and oceanic sediments decreases with depth, but the iodide concen-
IODINE
165
tration in the interstitial waters increases with depth (Shishkina and Pavolva,
1965).
The iodide in bottom water layers and in the interstitial water of muds in
some Japanese lakes was found t o be selectively captured by flocculated
iron, manganese, and aluminum hydroxides which sank to anaerobic layers
(Sugawara et al., 1956). Reduction of the hydroxides releases iodide to the
bottom waters. However, the release of iodide is incomplete, and the
flocculates reach the bottom muds where the Eh is even more negative,
resulting in high accumulation of iodide in interstitial water of muds.
The primary source of organic matter in marine and oceanic basins is
photosynthesis by plankton algae. Algae are directly or indirectly the food
resource of all the remaining life in the basins, and the proliferation rate
differential and the types of feeding organisms influence the sediment deposition rate as well as the amount of iodide and bromide in the sediment
(Bordovskii, 1965).
Shales, sandstones, and carbonates contain about 2.2, 1.7, and 1.2 ppm,
respectively, of iodide (Mason, 1966). Sea water contains about 0.05 mg/l,
and most subsurface petroleum-associated brines contain less than 10 mg/l;
however, some have been found to contain up t o 1,400 mg/l.
Fig. 5.18 is a plot of the chloride concentrations versus the iodide concentrations for some brines taken from some Pennsylvanian and Mississippian
age sediments. Iodide is tremendously enriched in all of these brines compared to the normal evaporite-associated brine. Some mechanisms such as
leaching or solubilization of iodine, iodate, or iodide compounds, ion filtration, anion exchange, and desorption had t o occur, t o account for this
enrichment of iodide in the aqueous phase. A similar plot for some waters
taken from Tertiary, Cretaceous, and Jurassic age sediments gave similar
results except that these particular brines were not as heavily enriched in
iodide.
The iodide concentration of some subsurface waters is dependent on the
proximity of argillaceous deposits containing organic matter, rather than on
dissolved mineralization. Gas may play an important part in the accumulation of iodide in subsurface waters. Some gas structures are bounded by
iodide-rich waters, and the iodide content is depleted at a distance from the
gas structure (Ovchinnikov, 1960).
Studies of some reservoirs, Holocene to Miocene in age, in lagoonal sedimentary basins of thick sediments with wide areal extent, indicate that a
genetic relation exists between iodide in the formation waters and the
accompanying natural gas (Marsden and Kawai, 1965). Possibly the high
concentrations of iodide are the result of concentration by algae and other
marine organisms from ancient sea waters; their remains became part of the
sediments, and later the iodide was solubilized. However, because the iodide
usually is strongly incorporated in the sediment, such sediments must contain large quantities of iodide, and other mechanisms must operate to solub i k e the iodide in associated waters.
166
1
0
/
~ w mevaporite
i
I#OOO
cn
500
200
loot
CUM
/1
/
w'
2
sI
'
1,200
,
,
/-
P
MM
50E
20
vs
M
M F P
M
MhP
IODIDE, mg/l
Fig. 5.18. Comparison of the iodide concentrations of some formation waters from
Pennsylvanian (P) and Mississippian (M) age sediments from Oklahoma with an evaporating sea water.
Redox potential
The redox potential often is abbreviated as Eh, and may also be referred
to as oxidation potential, oxidation-reduction potential, or pE. It is expressed in volts, and at equilibrium it is related to the proportions of oxidized
and reduced species present. Standard equations of chemical thermodynamics express the relationships.
Eo is the standard potential of a redox system when unit activities of
participating substances are present under standard conditions. Eo is related
to standard free energy change in a reaction by the equation:
PHYSICAL PROPERTIES
167
redox reaction and f is the Faraday constant in units that give a potential in
volts (94,484 absolute coulombs). Standard free energy values are given in
texts such as that of Latimer (1952).
When the system is not under standard conditions, the redox potential is
expressed by the Nernst equation:
Eh = E o
T
(oxidized species)
+R
log
nf
(reduced species)
where R is the gas content (1.987 cal. degree mole), and T is the temperature
in degrees Kelvin. Geochemical literature and biochemical literature, such as
that of Pourbaix (1950), present increasing positive potential values to represent increasing oxidizing systems and decreasing potential values to represent
reducing systems. The sign of Eh used in this manner is opposite to standard
American practice in electrochemistry.
Zobell (1946) established basic procedures for measuring the Eh of
geologic-related materials. The Zobell solution containing 0.003M potassium
ferrocyanide and 0.003M potassium ferricyanide in a 0.1M potassium chloride solution has an Eh of 0.428 V at 25OC. Minor temperature variations can
be calculated using the equation:
Eh = 0.428+).0022 ( t - 25)
where t = temperature of the sample in degrees Celsius.
Garrels and Christ (1965) describe procedures for determining Eh
equilibria of mineral substances. Particularly useful are the procedures described for constructing diagrams showing fields of stability for various
mineral substances as functions of pH and Eh. Fig. 5.19 is an Eh/pH
diagram. Such stability field diagrams might be constructed for the substances comprising petroleum and should be of considerable help in understanding the mechanisms of origin, accumulation, and chemical stability of
petroleum. Unfortunately, this approach does not yield simple results
because most oxidation reactions involving hydrocarbons and other
petroleum constituents are not reversible in the usual sense. Furthermore,
thermodynamic data are available for only a small fraction of the large
number of reactions and products that are possible.
Attempts t o obtain useful results from Eh measurements in natural media
involve numerous difficulties. In a natural medium, such as petroleumassociated water, there are many variables, none of which is controlled,
which individually or collectively may have little or great influence on Eh
measurements made on the water. Many chemical substances, such as ferric
or ferrous ions, various organic oxidation-reduction systems, sulfides, and
sulfates, may be present in the water in large or small amounts. Even controlled systems in the laboratory often produce unaccounted-for variances.
In the field, the lack of knowledge of actual participating species may seriously impair proper interpretation of Eh readings. Eh measurements made
168
1,200 -
H2O
000 600
<
400-
200
/Modern
sea water
Acid
Fa++
I
I
Alkaline
on poorly poised media (media with poor Eh stability), such as some oilfield
waters, involve additional uncertainties. Response of electrodes in such solutions is sluggish, and electrodes are easily contaminated with trace amounts
of substances which will produce invalid readings.
In the natural environment, reactions occur that involve protons and electrons, such as:
FeS04 + 2H20
* S04-2
+ FeO-OH + 3H+ + e-
Such reactions depend upon both the pH and the Eh of the system, and
the equilibrium line of such reactions is Eh = E o - 59 a/n pH mV, where a is
the number of protons.
Knowledge of the redox potential is useful in studies of how compounds
such as uranium (Naumor, 1959), iron, sulfur (Hem, 1960), and other minerals (Cloke, 1966; Pirson, 1968) are transported in aqueous systems. The
solubility of some elements and compounds is dependent upon the redox
potential and the pH of their environment. The Eh/pH diagram shown in
PHYSICAL PROPERTIES
169
Fig. 5.19 can be used to predict that ferrous ions are the more common form
of dissolved iron and that ferric ions will precipitate in an oxidizing environment if the pH is above 1. Similar diagrams can be drawn for other constituents.
Some water associated with petroleum is connate water, and Fig. 5.19
indicates that such water has a negative Eh; this has been proven in various
field studies (Buckley et al., 1958). The Eh of some petroleum-associated
waters in the Anadarko Basin ranged from -270 mV to -300 mV (Collins,
1969a).
Knowledge of the Eh is useful in determining how t o treat a water before
it is injected into a subsurface formation (Ostroff, 1965). For example, the
Eh of the water will be oxidizing if the water is open to the atmosphere, but
if it is kept in a closed system in an oil-production operation, the Eh should
not change appreciably as it is brought to the surface and then reinjected. In
such a situation, the Eh value is useful in determining how much iron will
stay in solution and not deposit in the well bore.
Organisms that consume oxygen cause a lowering of the redox potential.
In buried sediments, it is the aerobic bacteria that attract organic constituents which remove the free oxygen from the interstitial water. Sediments laid down in a shoreline environment will differ in degree of oxidation
as compared t o those laid down in a deep-sea environment (Pirson, 1968).
For example, the Eh of the shoreline sediments may range from -50 t o 0
mV, but the Eh of deep-sea sediments may range from -150 to -100 mV.
The aerobic bacteria die when the free oxygen is totally consumed; the
anaerobic bacteria attack the sulfate ion, which is the second most important
anion in the sea water. During this attack, the sulfate reduces t o sulfite and
then t o sulfide; the Eh drops to -600 mV; H2S is liberated, and CaC03
precipitates as the pH rises above 8.5 (Dapples, 1959).
170
* HzCO, * HC03-
+ H+
* 2H+ + C03-
Fig. 5.20. Changes in pH as a result of the addition of carbonate ions to distilled water
and water solutions containing sodium and chloride ions.
The pH of concentrated brines usually is less than 7.0, and the pH will rise
during laboratory storage, indicating that the pH of the water in the reservoir
probably is appreciably lower than many published values. Addition of the
carbonate ion to sodium chloride solutions will raise the pH, as illustrated in
Fig. 5.20. If calcium were present, calcium carbonate would precipitate. The
reason why the pH of most oilfield waters rises during storage in the laboratory is because of the formation of carbonate ions as a result of bicarbonate
decomposition.
PHYSICAL PROPERTIES
171
Ionic radii
Table 5.VI contains data concerning the radii of the nonhydrated ions, the
hydrated ions, the ionic potential, and the polarization. The size of the ions
is of interest concerning the mobilities or the relative transport coefficient of
a given ion through a clayshale membrane system or the replacement
coefficient in a clay ion-exchange system. The ionic potential is of interest
because elements with low ionic potentials are the most likely to remain in
true solution. The polarization, which is equivalent to the valency divided by
the ion radius, is of interest because the larger the polarization, the lower the
replacing power in an exchange system (Collins, 1970).
The ionic potentials of the constituents involved in the diagenesis are
important (Hem, 1960). Those that stay in true ionic solution to rather high
pH levels include Na+, K+, Mg+, Fe+, Mn+, Ca+, Sr+*,and Ba+ ;they
are the soluble cations, and their ionic potentials range from 0.3 to 1.3,
where the ionic potential is the ratio between the ionic charge and the ionic
radius. Constituents that are precipitated by hydrolysis are those with ionic
potentials of 3-12 and include such ions as A P 3 , Fe+3, S P 4 , and M r P 4 .
Constituents which form soluble complex ions and usually go into true ionic
solution include B+3, C 4 ,N + 5 , P+, S 6 ,and Mn+ ;their ionic potentials
are over 12. In general, the hydroxides of the soluble cations possess ionic
bonds; therefore, they are soluble. The hydrolysates, or those ions precipitated by hydrolysis from hydroxyl bonds, and the soluble complex ions both
have hydrogen bonds.
TABLE 5.VI
Radii, valence, ionic potentials, and polarization
Constituents
Nonhydrated
radius (A)
Valence
Hydrated Ionic
radius (A) potential
Polarization
Lithium
Sodium
Potassium
Calcium
Magnesium
Strontium
Barium
Boron
Chloride
Bromide
Iodide
Sulfate
0.60
0.95
1.33
0.99
0.65
1.13
1.35
0.23
1.81
1.95
2.16
2.90
+1
+1
+1
+2
+2
+2
+2
+3
-1
-1
-1
-2
3.82
3.58
3.31
4.12
4.28
4.12
4.04
1.67
1.05
.75
2.02
3.08
1.77
1.48
3.32
3.30
3.31
3.79
0.60
0.95
1.33
0.50
0.33
0.57
0.68
0.08
1.81
1.95
2.16
1.45
0.55
0.51
0.46
0.69
172
Density
Equations that were developed for sea water can be applied to oilfield
waters to obtain approximate values for engineering studies. The density
values (ao) at OC and atmospheric pressure are related to the chlorinity (CZ)
as follows:
Vapor pressure
The relative lowering of the vapor pressure of oilfield water can be calculated with the following equation:
Ap/po = 0.538 x
1968).
Boiling point
A first approximation of the boiling point elevation can be calculated
from:
At = 0.0158S
where S = the salinity.
Freezing point
An empirical equation which can be used t o estimate the freezing points
is :
- 0.0001055 ( 0 0 ) ~
PHYSICAL PROPERTIES
173
Viscosity
The viscosity will increase with decreasing temperature and with increasing salinity. The viscosities of sodium chloride solutions of the same ionic
strength can be used to estimate oilfield water vicosities.
Osmotic pressure
Po
(1+ 0.00367t)
Specific heat
The values for the specific heat, c p , of oilfield waters can be approximated from the values of an equivalent sodium chloride solution.
Thermal conductivity
The thermal conductivity coefficient, A, can be calculated from thermal
capacities because the ratio of thermal conductivities of two materials is the
same as that of the thermal capacities of equal volumes. The values for X at
various temperatures are available in a Saline Water Conversion Technical
Data Book (Kellog and Company, 1956,1966,1968).
Surface tension
The surface tension of an oilfield water increases with decreasing temperature and with increasing salinity. An empirical formula which can be used t o
calculate it is:
174
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Chapter 6.
178
tained minute quantities of hydrocarbon, to be squeezed out of the consolidating sediments, and subsequently the oil was accumulated in sands and
left behind in structural traps (Kidwell and Hunt, 1958). Obviously, the
waters associated with petroleum play a very important part in the origin,
migration, accumulation, and subsequent production of petroleum - the
accumulation and production of petroleum being totally dependent upon
hydraulic flow in response to geostatic and hydrostatic pressures.
Consider briefly that 99% of the oil found and produced typically occurs
within the pore spaces of sedimentary rocks (Hedberg, 1964).About 59% of
the production comes from sandstone reservoirs, 40% from carbonates, and
1% from other types of rock. Petroleum in igneous and metamorphic rocks
occurs primarily in fracture pore spaces and probably has migrated to these
rocks from its place of origin.
The solubilities of petroleum hydrocarbons in water increase with
temperature and decrease as the salinity of the water increases. A temperature drop from 150 t o 25C reduces the solubility of petroleum in water by
a factor of 4.5-20.5. Such a mechanism can account for the accumulation
of petroleum because as upward moving subsurface waters containing
dissolved hydrocarbons decrease in temperature and pressure and meet more
saline waters, they will release dissolved hydrocarbons (Price, 1973).
Information concerning dissolved organic matter in sea water was
published as early as 1892 (Duursma, 1965). Palmitic acid, stearic acid,
acrolein, and organic nitrogen were tentatively identified. The dissolved
organic matter was found t o be about 2 mg/l in the open sea, increasing to
about 15 mg/l in water taken near the coast of Greece, all of which was
attributed t o saponification of the fats of dead organic organisms. Phytoplankton organisms comprise most living marine organic matter, 10% of
which eventually becomes animal matter. The bulk of the organic particulate
matter in the sea results from dead animal matter, but the dissolved organic
constituents appear to be derived from dead phytoplankton and detritus
rather than excretions from living cells.
Decomposition of organic matter results primarily from the activities of
heterotrophic bacteria. Organic matter decomposes more rapidly in a nearshore environment, where there is an abundance of such matter and bacteria,
than in a deep-sea environment, where both the matter and bacteria are
diluted. The dissolved organic matter can be classified into groups as follows:
(1)nitrogen-free (for example, carbohydrates); (2)nitrogen-containing (for
example, proteins); (3)lipids (for example, esters of fatty acids); and (4)
complexes comprised of mixtures of the preceding three groups (for
example, humic acids).
Nitrogen-free organic compounds
179
180
siderably among the electrolytes (McDevit and Long, 1952). A limiting law
for determining the influence of electrolytes on the activity of nonpolar
solutes was developed, which related the magnitude of the salt effect t o the
volume changes associated with salt and water mixing.
Molecular hydrogen was found in oilfield waters in the Lower Volga region
(Zinger, 1962). Up to 43%of the dissolved gas in these waters was hydrogen;
other gases dissolved in the waters were methane, ethane, butane, pentane,
carbon dioxide, nitrogen, helium, and argon. The pH of these waters was as
low as 3.4, and the iron content was as high as 1,100 ppm.
The solubility of methane increases with pressure and decreases with increased salt concentration at ambient temperature in NaC1-H2 0 and
CaC12-H20 systems (Duffy et al., 1961). From the experimental data, it
was estimated that 1 cubic foot of sedimentary rock with 20% porosity
buried 300 m deep and saturated with a brine containing 50,000 ppm of
NaCl could accommodate 0.3 mole of methane in solution.
A gas-liquid partition chromatographic technique was used t o determine
the solubilities of C1-C9 paraffin and branched-chain paraffins, four
cycloparaffins, and five aromatic hydrocarbons in water (McAuliffe, 1963).
Later this study was extended to seventeen paraffins, seventeen olefins, nine
acetylenes, seven cycloparaffins, seven cycloolefins, and six aromatic hydrocarbons (McAuliffe, 1966). The data indicated that the solubilities of the
hydrocarbons in water increased as unsaturate bonds were added t o the
molecule, with ring closure, with addition of unsaturate bonds in the ring,
and with addition of bonds which decreased the hydrocarbon molar volume.
Branching increased the solubility in water for paraffin, olefin, and acetylene
hydrocarbons but not for the cycloparaffin, cycloolefin, and aromatic hydrocarbons. Plots of the log of the solubility in water were a linear function of
hydrocarbon molar volume for each homologous series of hydrocarbons.
A capillary-cell method was used to measure the diffusion of methane,
ethane, propane, and n-butane in water (Witherspoon and Saraf, 1964). At
25OC, the results indicated that the diffusion coefficients times los cm2/sec
were 1.88, 1.52, 1.21, and 0.96, respectively, for methane, ethane, propane,
and n-butane. The coefficients increased with higher temperatures.
Near the critical solution temperature and about 300 atm, the solubility
versus pressure curves for some hydrocarbon-water systems show a sharp
maximum. However, pressure has a negative effect on solubility beyond this
maximum, and a second two-phase region appears. The five binary
hydrocarbon-water systems studied were benzene, n-heptane, n-pentane,
2-methyl-pentane, and toluene (Connolly, 1967).
The accommodation of CI2-C& n-alkanes in distilled water was determined as a function of hydrocarbon supply, settling time, filtration poresize, and mode of introduction (Peake and Hodgson, 1967). Apparently it is
possible to accommodate hydrocarbons in water at levels higher than solubil-
181
ity levels, and such accommodation systems are stable for several days.
Preferential accommodation of alkanes in the C16-C20range was found at
the expense of other 'alkanes with lower and higher carbon numbers.
A gas chromatographic method for the determination of petrol in water
was developed whereby the petrol was extracted from the water into
nitrobenzene and the extract was analyzed using a column polyethylene
glycol 1,500 on silanized Chromosorb W (Jeltes-and Veldink, 1967). The
methods were sensitive t o 0.1 mg/l, and for concentrations > 0.5 mg/l the
precision was about 5% for the major components.
Low-molecular-weight hydrocarbons in the C1-C4range were detected in
sea water. Generally the concentration tended to decrease with depth
(Swinnerton and Linnenbom, 1967). Methane was the most abundant
hydrocarbon found, but smaller amounts of ethane, ethylene, propane,
propylene, n-butane, isobutane, and some butenes also were detected and
measured.
Hundreds of drill-stem samples of brine from water-bearing subsurface
formations in the Gulf coastal area of the United States were analyzed to
determine their amounts and kinds of hydrocarbons (Buckley et al., 1958).
The chief constituent of the dissolved gases usually was methane, with measurable amounts of ethane, propane, and butane present. The concentration
of the dissolved hydrocarbons generally increased with depth in a given
formation and also increased basinward with regional and local variations. In
close proximity t o some oilfields, the waters were enriched in dissolved
hydrocarbons, and up to 14 standard cubic feet of dissolved gas per barrel of
water was observed in some locations.
The ratio of toluene t o benzene in 27 crude oils from various sources
ranged from 2.0 t o 11.3. Toluene is less soluble than benzene in distilled
water, where the ratio is about 0.3 (McAuliffe, 1966). A method of
prospecting for petroleum, utilizing information concerning the amount of
benzene dissolved in subsurface waters, was patented (Coggeshall and
Hanson, 1956). Gas chromatographic methods proved t o be good for determining the amount of benzene and other hydrocarbons in the petroleumassociated waters (Zarrella et al., 1967). Collected information indicates that
the concentration of benzene in petroleum-associated water varies with
different types of hydrocarbon accumulations, that the benzene concentration decreases with increasing distance from the hydrocarbon accumulation, and that benzene is specific for detecting the occurrence of petroleum
hydrocarbon accumulation in a given geologic horizon. A brine sample taken
from a horizon separated by 27 m of shale from an oil pool contained 0.02
ppm of benzene, indicating that low-permeability shale prevents movement
of hydrocarbons.
Chromatographic techniques were developed for the determination of
sugars and phenols in sea waters and in sediments (Degens and Reuter,
1964). Biogeochemical differences were observed between the sugars in the
sea and in the sediments.
182
FATTY ACIDS
183
184
185
186
in soils. Later, Page and Dutoit (1930) modified the name humus acid to
humic acid. Sestini (1898) demonstrated that the humic acids are of complex composition and contain ethereal and anhydride components in
addition to alkyl, hydroxyl, and ketonic groups.
Burges (1960) suggested that humic acid is a single chemical substance or
a group of similar substances, and that primarily it is nonnitrogenous.
Steelink et al. (1960) fused soil humic acids and found the following degradation products: catechol, profocatechuic acid, and resorcinol. Steelink and
Tollin (1962) determined the presence of two free-radical species in humic
acid using an electron paramagnetic-resonance spectrometer. They believed
that one could be a semiquinone radical and the other a quinhydrone radical.
Fulvic acids, humic acids, and hymatomelanic acids have been found in
natural waters (Wilson, 1959; Black and Christman, 1963; Packman, 1964).
The brown color, characteristic of many natural waters, is attributed to
complex organic compounds which probably are derived from water-soluble
peptizable components of soil humus.
A method that can be used t o determine the organic acids in petroleumassociated waters was published by the Natural Gasoline Association of
America (1953). The water is treated with lime water to convert the organic
acids to their calcium. salts, which are titrated with a standard mineral acid.
Determination of oil in water
The following method was developed by Nalco Chemical Company (1971)
and is applicable t o waters and brines where the oily matter is hydrocarbons
or hydrocarbon derivatives and all liquid or unctuous substances that have a
boiling point above 90C and are extractable from waters or brines at pH 5.0
or lower using benzene, chloroform, or carbon tetrachloride.
The sample is extracted with a fluorocarbon solvent which is evaporated
off in a specially designed vessel and the residual oil measured volumetrically
in a microsyringe.
Pear-shoped l o p , capacity opprox.17 m l ,
o f f s e t odditionol opening so th0t"popped"
somple w i l l be r e t o i n e d
Fig. 6.1.Microsyringe-evaporatingflask.
187
188
Calculation :
1-11measured = mg/l oily matter
mi sampIe
Reagents and apparatus. Acetone; NaOH, 0.02N; HC1, 0.05N; acetic acid, 10
mg/l; a hotplate; and a standard pH meter.
Procedure. Pipet 25 ml of filtered brine into a 250-ml beaker; add 25 ml of
acetone and adjust the pH t o precisely 6. Titrate the sample to a pH of 3.5,
and record the amount of 0.05N HC1, used in the adjustment from pH 6 to
3.5. Boil the solution for 5 minutes. Cool and titrate back to pH 6 with
0.02N NaOH. Make a blank determination for NaOH and HC1. To calculate,
subtract blank from NaOH and HC1 titrations.
Calculation:
(ml HC1 x HC1 N ) - (ml NaOH x NaOH N )
x 60,030 = mg/l organic acids
ml sample
as acetic acids.
References
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Bohon, R.L. and Claussen, W.F., 1951. The solubility of aromatic hydrocarbons in water.
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191
The five spheres of the earth are the lithosphere (rocks), the pedosphere
(soils, till, and other surficial materials), the hydrosphere (natural waters),
the atmosphere (gases), and the biosphere (living organisms). Oilfield waters
are a part of the hydrosphere, and petroleum is a product of the biosphere.
The total volume of water in the hydrosphere is about 1,338 x 10'' liters,
and about 8.4 x 10" liters is ground water (Skinner, 1969). Most of the
water, 1,300 x 10" liters, is in the oceans. Less than 50% of the total
ground water is in strata below 1 km. The total amount of water in sedimentary rocks and associated with liquid and gaseous hydrocarbons is less than
1.3 x 1 O I 8 liters.
All of the petroleum recovered t o date has been taken from oil wells
drilled into the upper 8 km of the earth's crust. The average thickness of the
0 km
I 7 km
400km
1,000 k m
2.900km
5,000km
6,371 k m
194
earths crust is about 1 7 km, ranging from 5 km under the oceans t o about
35 km under the continents (Clark and Ringwood, 1964). Fig. 7.1 illustrates
the various regions of the interior of the earth, with the distance from the
surface of the crust to the center of the inner core being 6,731 km. In this
discussion we are concerned only with the crust to a distance of 0.08% of
the depth to the center of the earth.
Hydrocarbons are believed t o have originated from organic material in
sedimentary material which was produced by weathering and erosion of the
earths surface. This eroded material is carried away by water, ice, or wind
and redeposited, ultimately forming sedimentary rocks. The major sedimentary, minerals are clays, quartz, calcite, gypsum, anhydrite, dolomite, and
haiite. Most of the large bodies of sedimentary rocks were formed in marine
environments; smaller sedimentary deposits formed in lakebeds and river
floodplains.
Definitions of some water terms
Meteoric water. White (1957) defined it as water that was recently involved
in atmosphere circulation and further that the age of meteoric groundwater
is slight when compared with the age of the enclosing rocks and is not more
than a small part of a geologic period.
Sea water. The composition of sea water may vary somewhat, but in general
will have a composition relative t o the following (in mg/l): chloride 19,375, bromide - 67, sulfate - 2,712, potassium - 387, sodium - 10,760,
magnesium - 1,294, calcium - 413, and strontium - 8.
Table 7.1 (Anonymous, 1964) gives a more comprehensive picture of the
constituents found in sea water. The analyses given in Table 7.1. are in parts
per million.
Interstitial water. Interstitial water is the water contained in the small pores
of spaces between the minute grains or units of rock. Interstitial waters are:
(1) syngenetic (formed at the same time as the enclosing rocks); or (2)
epigenetic (originated by subsequent infiltration into rocks).
SEDIMENTARY ROCKS
195
TABLE 7.1
Average composition of sea water
Element
Amount
(PPm)
Element
Amount
(PPm 1
Element
Amount
(PPm)
Chlorine
Sodium
Magnesium
Sulfur
Calcium
Potassium
Bromine
Carbon
Oxygen
Strontium
18,980
10,560
1,270
880
400
380
65
28
8
8
Zinc
Molybdenium
Selenium
Copper
Arsenic
Tin
Lead
Uranium
Vanadium
Manganese
Titanium
Thorium
Cobalt
Nickel
Gallium
Cesium
Antimony
Cerium
Yttrium
Neon
Krypton
Lanthanum
Silver
Bismuth
Cadmium
0.01
0.01
0.004
0.003
0.003
0.003
0.003
0.003
0.002
0.002
0.001
0.0007
0.0005
0.0005
0.0005
0.0005
0.0005
0.0004
0.0003
0.0003
0.0003
0.0003
0.0003
0.0002
0.0001
Tungsten
Germanium
Xenon
Chromium
Beryllium
Scandium
Mercury
Niobium
Thallium
Helium
Gold
Praseodymium
Gadolinium
Dysprosium
Erbium
Ytterbium
Samarium
Holmium
E uro pi um
Thulium
Lutetium
Radium
Protactinium
Radon
1
1
1
5x
5
4x
3x
1
1
5x
4x
Boron
Silicon
Fluorine
Nitrogen
Argon
Lithium
4.8
3.0
1.3
0.8
0.6
0.2
Rubidium
Phosphorus
Iodine
Barium
Indium
Aluminum
Iron
0.12
0.07
0.05
0.03
0.02
0.01
0.01
lo4
lo4
lo4
1010-~
1010-~
10"
lod
2x
2
2
2
2
2
8x
4x
4x
4x
3 x lo-"
2 x lo-'*
9
196
TABLE 7.11
Si
A1
Fe
Ca
Na
K
Mg
Ti
P
Mn
F
S
C
c1
Rb
Sr
Ba
Cr
Zn
Ni
cu
Li
N
Sn
co
Pb
Th
cs
Be
As
U
B
Br
I
Cd
Se
Hg
Ra
Evaporites
(halite)
hydrolyzates precipitates
277,200
367,500
272,800
24,200
90
81,300
25,300
81,900
4,300
20
11
50,000
9,900
47,300
4,000
36,300
39,500
22,300
304,500
930
28,300
3,300
9,700
370
325,000
25,900
11,000
27,000
2,700
800
20,900
7,100
14,800
47,700
460
4,300
4,400
960
0.8
1,180
350
740
175
trace
620
385
1
1,000
600-900
510
250
20
520
2,800
2,600
1,100
770
320
13,800
15,300
113,500
70
trace
314
200
586,000
0
310
273
300
300
< 26
170
425-765
250
170
460
120
2
200
68-200
410-680
2
132
< 20
200-1,000 < 50
1
80
2-8
24
0
0
70
3
192
20.2
65
17
46
< 26
46
40
40
0
8
0
23
16
20
20
5-1 0
2
11.5 (? )
6.1
10.1
1.1
<
0.2
7
12
<4
0
6 (3
5
- 5
4
1.2
1.2
1.3
0.01
3
9-31
310
3
<2
1.62
< 0.2
60
0.07-0.55 < 2
0.3
0.15
0
0.3
0.09
0.6
< 0.1
< 0.5
0.08-0.5
0.1
0.3
0.03
1.3 x
0.7 x
1.08 x lod
0.42 x lod
-
SEDIMENTARY ROCKS
197
The volume of the earth is about 1,100 billion km3 and the volume of the
oceans is about 1.3 .billion km3; however, the oceans with an area of 360
million km2 cover 70% of the surface of the earth. The average composition
of some of the igneous and sedimentary rocks of the earths crust is shown in
Table 7.11, which was taken from Clarke and Washington (1924) and
Rankama and Sahama (1950). The resistate rocks referred to in Table 7.11
are composed of residues not chemically decomposed in the weathering of
the parent rocks. Hydrolyzate rocks are the insoluble products formed by
chemical reactions during weathering of parent rocks. Precipitate rocks are
those formed by chemical precipitation of minerals from aqueous solution.
Evaporite rocks are marine evaporites which were produced when the water
in which they were dissolved was evaporated.
Sedimentary rocks comprise about 5% of the lithosphere, while the
igneous rocks form 95%. The three main types of sedimentary rocks are
shale, sandstone, and iimestone, and their relative abundance determined
from geochemical data ranges from 70 t o 83% shale, from 8 to 16%sandstone; and from 5 t o 14% limestone (Pettijohn, 1957). Levorsen (1966)
noted that oil and gas are found in reservoir rocks consisting primarily of
sandstones, limestones, and dolomites.
Weathering
Weathering is a most important factor in producing the source material for
the creation of sedimentary rocks. Processes that cause weathering are
chemical, physical, and biological (Ross, 1943).
The weathering of rock by physical methods includes temperature changes
brought about by climate changes. Examples are the breaking of rock by
thermal expansion (heat), the breaking of rock by the expansion of freezing
water in the pores or cracks, or the mechanical breaking of rock as a glacier
moves over it. Breaking the rock causes the surface area to become larger
without significantly changing the chemical composition.
Biological weathering includes the cracking of rock as a result of plant
roots and the action of acids derived from plants, animals, and bacteria. The
biotic factor includes bacteria, algae, protista, protozoa, higher animals and
plants, during both life and subsequent necrotic decomposition which
furnish Ht ions, colloids, complexing agents, and dispersants.
Chemical weathering involves the action of water upon the parent rock
and upon the products of physical and biological weathering. In chemical
weathering the composition of the source rock is changed by solution,
hydrolysis, oxidation, and reduction reactions. The Ht ion when concentrated in aqueous solution is a very important energy factor because it will
cause rapid chemical reactions with parent rocks. The redox potential influences the rate of removal of elements, such as iron and manganese from
the parent rock, and if it is a reducing potential, these elements are more
likely to remain in solution after solubilization.
198
Erosion
Erosion is the opposite of deposition (the processes are reversible), but
erosion must occur before deposition can proceed. The products of weathering are eroded and transported to a new location by the action of water
and wind. The water serves to transport the majority of these products, and
it can transport them by dissolution, suspension, or pushing of larger
particles.
*A
=+
H2C03
HC03-+H+
2H++C03-2
7PH 5)
(PH 6-31
(pH 10.3)
SEDIMENTARY ROCKS
199
600 -
I
I
400r
W
200
Acid
Fe++
-400
-600
-eooo
/M,odern
sea water
I
Alkaline
10
H2,
12
14
PH
200
Geosynclinal trough
For eland
(stable)
Borderland
r
Shelf area
SEDIMENTARY ROCKS
201
erosion and redeposition of sediment deposits. The salinity of the sea may
change somewhat during transgression but probably not much.
Deltaic deposits result from a combination of environmental factors and
are related t o both fluvial and regressive marine processes. During flood
times the rivers transport tremendous volumes. of material, both clastic and
organic, into delta areas. Deltaic deposition is a very important factor in the
formation of petroleum because of the tremendous amount of organic material deposited.
Bathyal-abyssal deposits are formed in deep-water areas in the sea, and
turbidity currents are responsible for most of the clastic deposition (Emery,
1960). Lacustrine deposits are those that are formed in lakes. If the lake is a
fresh-water lake, the dissolved solids may be less than 1,000 mg/l; in a
salt-water lake, the dissolved solids may be greater than 35,000 mg/l.
Consider a simplistic sedimentation area where the borderland area is the
prime source of sediments. The coarse- t o fine-grained clastics which are
weathering products of the high-mountains borderland are deposited near
their source. The clastics are detritus transported mechanically to the point
of sedimentation and are not solubilized by the water before deposition.
Primarily they are the sandstones and shales (clays). They will not be found
on the for.eland side of a depositional basin. Clay deposition can be detrital
or authigenic; illite often is detrital. There are at least two dozen clay
minerals, many of which occur in very minute grains and most of which
cannot be resolved by high-power petrographic microscopes. The electron
microscope, X-ray diffraction, and differential thermal analysis are used to
determine the type of clay.
The clays are very important in relation t o petroleum and gas because
they are the major component in the shales from which petroleum and gas
are generated. The clays also possess base exchange properties which will
react with constituents in water and petroleum. The detrital clays settle in
low-energy waters and they settle more rapidly from a saline water than from
a fresh water.
202
and consists of calcite with up to 50% detrital quartz. Types I11 and IV are
similar in percentage of minerals; however, they are further differentiated
according t o grain size, sorting, roundness, and fossils, as are the other types.
Type V is deposited in strongly agitated (high-energy) water and it consists of
calcite, < 5% clay, and < 25% detrital quartz.
The calcium in the carbonates is released during rock weathering and goes
into solution as bicarbonate. The solubility of calcium carbonate in water is
also dependent upon the amount of carbon dioxide in solution. If the
amount of dissolve carbon dioxide decreases, calcium carbonate is precipitated; therefore, the amount of calcium carbonate precipitation increases in
warm water because the amount of carbon dioxide in solution is less than in
cold water. Considerable amounts of carbonate precipitation occur in warm
environments (Illing, 1954). Aquatic plants also absorb carbon dioxide and
cause carbonate precipitation. The deposited carbonates can be pure or
mixed with sand, clay, iron, manganese, and organic matter.
Modern carbonate deposition occurs as deep-water oozes, and reefs, and
on shallow shelves. The deepwater oozes form along the flanks of ocean
basins at depths of less than 6,000 m. They do not form at depths greater
than 6,000 m because the calcium carbonate solubility increases with the
increased pressure. On the flanks of the basins, terrigenous material mixes
with the calcium carbonate. Often the mixture is 65--89% percent calcium
carbonate with silt making up the remainder (Gevirtz and Friedman, 1966).
Reef carbonates develop in open oceans on shallow platforms forming
atolls, as isolated patches on the ocean shelves, or along the margins of shelf
areas as fringing reefs. Fringing reefs generally occur in tropical regions on
the western side of the ocean basin. Reefs form as a result of living organisms
which form the framework of the sediment (Ginsburg and Lowenstam,
1958).
Present-day shelf carbonates are developing in Florida Bay, on the Bahama
Banks, on the Australian shelf, and on shelves off British Honduras, Yucatan,
and India. The precipitation often occurs as shallow carbonate mud banks.
The sediment in the shallow shelf areas often consists of about 10%skeletal
material mixed with oolites, mud aggregates, grapestone, aragonite needles,
calcareous algae, etc. The average rate of carbonate accumulation on the
Bahama Banks is 50 mg cm-2 yr-I (Broecker and Takahashi, 1966). The
salinity of the water ranges from 36,000 mg/l of dissolved solids t o 46,500
mg/l. The more saline waters occur in lagoonal areas. The pH ranges from
about 8.0 to 8.2 and is lowest at the end of the day because of C02
extraction from the water by marine plants.
In the simplistic depositional basin shown in Fig. 7.3 (Moore, 1969),
limestones and reef limestones will be deposited on the foreland side, formed
from water soluble constituents that precipitated from the saline solutions.
SEDIMENTARY ROCKS
203
204
TABLE 7.111
Concentration changes during evaporation of sea water and brine
Element
Sea water
Lithium
Sodium
Potassium
Rubidium
Magnesium
Calcium
Strontium
Boron
Chloride
Bromide
Iodide
2
0.2
11,000
98,000
350
3,600
1
0.1
13,000
1,300
1,700
400
60
7
40
5
178,000
19,000
600
65
2
0.05
295,000
Total
CaS04.l
NaCl
MgS04.l
KCI
MgClz.1
11
140,000
23,000
6
74,000
100
10
300
275,000
4,000
5
12
70,000
37,000
8
80,000
10
1
310
277,000
4,300
7
27
13,000
26,000
14
130,000
0
0
750
360,000
8,600
8
34
12,000
1,200
10
153,000
0
0
850
425,000
10,000
8
517,000
469,000
538,000
602,000
SEDIMENTARY ROCKS
205
salts; or if they did, these salts were later removed by leaching so that their
occurrence is relatively rare.
Holser (1963) analyzed some brine inclusions in halite from Permian age
evaporites. He found that the Br/Cl and Mg/Cl ratios in many of the brine
inclusions are similar to those found in the late stages of halite deposition.
He concluded that some of the inclusions were connate bitterns with few
diagenetic changes, and that the Br/Mg ratio of sea water has remained
relatively constant since Permian time. Some diagenetic changes were evident
in a few of the inclusions in which a large ratio of Ca/C1 and a low ratio of
SO4/Cl compared t o sea water were found.
Sediments commonly associated with evaporites are red beds, quartzose
sandstones, subgraywacke sandstones, carbonate rocks, and marine shales
(Krumbein, 1951). Normal marine evaporite successions are found in intercratonic basins such as the Michigan and Williston Basins. Euxinic black
shales sometimes are associated with evaporites. Low redox potentials have
been found in modern evaporite (Morris and Dickey, 1957; Quaide, 1958).
Examples of modern depositional evaporites are the Karaboghaz Gulf on the
eastern side of the Caspian Sea, the Great Bitter Lake of Suez, the Rann of
Cutch in northwest India (Grabau, 1920), and the Persian Gulf sabkhas
(Evans et al., 1963; Butler, 1969).
Deposition of organic matter
The organic matter can be biogenic (produced by living systems) or
abiogenic (not produced by living systems). The source of biogenic matter
can be both terrestrial and marine; for example, considerable plant and
animal debris is collected from the land by streams and rivers and carried to
the sea, while in the sea large quantities of plant and animal matter live and
die.
The organic matter that is deposited with sediment usually decomposes if
the conditions are right; however, if the environment is reducing some of it
may be preserved. The preserved organic matter is transformed into other
organic compounds (Kvenvolden, 1964). During sediment diagenesis the
organic matter is transformqd to insoluble organic matter (kerogen) and
soluble petroleum hydrocarbon (Hunt and Jamieson, 1958). Chemical,
bacterial, and catalytic reactions are involved in these conversions. Temperature and pressure affect the reaction rates. Some of the chemical reactions
are as follows:
(1)Oxidation :
(2) Reduction:
(3) Elimination:
(4) Polymerization:
(5) Cracking:
C2Hm + 0 2
R'OH + H2
R'COOH
(small units)
nC02 + '/znH,O
+H20
+ R'H + co2
+ big molecule
-+
+ R'H
c-c-c-c-c-c~oc-c-c-
c-c
206
Deposition of silica
Most of the silica in sediments is of the detrital variety but some is
authigenic. Silica is dissolved by waters with high pH potentials and precipitated from water with a low pH. The precipitated silica often acts as a
cement.
SEDIMENTARY ROCKS
207
minute for 10,000 years. Compaction water is further considered in a subsequent chapter concerned with the accumulation of petroleum.
The resistance t o flow of bound interstitial water is greater than the
resistance to deformation of the sediment framework during the first stages
of compaction. As pressure is increased and sediment compacts, the sediment framework increases resistance to deformation, which also governs the
deformation rate of the bound-water films and the outflow of the interstitial
water. Rosenqvist (1962)found that bound water has a higher viscosity than
unbound insterstitial water. Permeability decreases with compaction, and
this together with the increased water viscosity leads to additional resistance
to expulsion of bound interstitial water during subsequent compaction.
Porosity decreases during compaction, and at infinite depth it would
become infinitely small. Porosity and permeability are two important factors
in determining the amount of petroleum and/or water that can be recovered
from a given reservoir or aquifer (Pollard and Reichertz, 1952;Caraway and
Gates, 1959). The porosity of an aquifer indicates how much fluid the
aquifer can hold, and the permeability indicates how fluid can move through
the aquifer. If the porosity is high but the permeability is low, the reservoir
may contain large amounts of oil, gas, or water, but they cannot be
recovered unless special techniques are used to increase the permeability.
Sediment diagenesis
Mineralogical and chemical changes occur in the sediments as they compact. The mineralogic composition of recent marine sediments and ancient
marine sedimentary rocks are different, as is the composition of the interstitial water in the recent sediments compared with the waters in ancient
stratigraphic units. Chemical reactions occur between the sediments and
their interstitial water (Chave, 1960). It has been shown that chemical
changes can be measured in recent sediments, e.g., below the sedimentwater interface, changes in pH and Eh result from degradation of sulfate ions
by bacteria (Emery and Rittenberg, 1952).
Numerous chemical inhomogeneities occur within a single core sample of
recent sediments (Degens and Chilingar, 1967). The magnesium concentration in the interstitial w&er decreases slightly with depth, while the concentrations of calcium and potassium increase (Siever et al., 1965). The
interstitial waters from continental shelf sediments have higher chloride concentrations and higher ratios of Ca/C1, K/Cl, and Rb/C1 than the overlying sea
water; the ratios of Li/Cl and Mg/Cl are about the same as in the overlying
sea water except that the Li/C1 ratios are higher in the innershelf samples
than in the outershelf samples. The Sr/Cl ratio is higher in the overlying sea
water, while the pH and Eh values are lower in the sediments than in the
overlying sea water (Friedman et al., 1968).
A detailed study indicates that virtually no environment exists on or near
the earths surface where the pH/Eh conditions are incompatible with
208
organic life (Baas Becking et al., 1960). Because COz is the main byproduct
of organic oxidation and the building material of plant and much bacterial
life, it plays a dominant role. Carbon dioxide dissolves in water, producing
the bicarbonate ion and a free hydrogen ion. The concentration of the
hydrogen ion is lo- equiv./l (pH 7) at 2OoC in pure water, but when
saturated with COz it rises t o lo- (pH 5). This reaction moves to the right
with increasing temperature in a closed system. In the presence of organic
constituents, the equilibrium is modified, and the pH range can extend from
2 to 12.
The ionic potentials of the constituents involved in diagenesis are important (Cloke, 1966). Those that stay in true ionic solution up t o rather high
pH levels are Na+, K+, Mg+, Fe+, Mn+2,Ca+, Sr+, Ba+, etc.; they are
the soluble cations, and their ionic potentials range from 0 t o 3, where the
ionic potential is the ratio between the ionic charge and the ionic radius.
Constituents that are precipitated by hydrolysis are those with ionic potentials from 3 t o 12 and include such ions as A P 3 , Fe+3, S P 4 , and
Constituents that form soluble complex ions and usually go into true ionic
and Mn+ ; their ionic potentials
solution include B+3 , V 4 , N+ P+ , S6,
are over 12. In general, the hydroxides of the soluble cations possess ionic
bonds; therefore, they are soluble, the hydrolysates or those precipitated by
hydrolysis form hydroxyl bonds, and the soluble complex ions have hydrogen bonds.
Organisms that consume oxygen cause a lowering of the redox potential,
and in buried sediments it is the aerobic bacteria that attract the organic
constituents and remove the free oxygen from the interstitial water. Sediments laid down in a shoreline environment often differ in degree of oxidation from those laid down in a deep-sea environment (Pirson, 1968). For
example, the Eh of the shoreline sediments may range from -50 t o 0 mV
while the Eh of deep-sea sediments may range from -150 to -100 mV. The
aerobic bacteria die when the free oxygen is totally consumed, and the
anaerobic bacteria attack the sulfate ion which is the second most important
anion in the sea water. During this attack, the sulfate is reduced to sulfite
and then t o sulfide. Also the Eh drops t o -600 mV (Fig.7.2). Sulfide is
liberated and CaC03 precipitates as the pH rises above 8.5 (Dapples, 1959).
Sulfur has two stable isotopes, * S and
S, with a mass differential of 6%.
The isotopes are fractionated during the change of S04-2 to Sv2, and SZ
is enriched in the more energetic 32S isotope. The average ratio of 3zS/34S
in normal sea water sulfate is about 21.76 (Ault, 1959). The sulfate isotopes
are useful in interpreting ancient diagenetic stages.
Reactions occur during sediment diagenesis and affect the composition of
the interstitial water. Calcite is precipitated if the pH is high, or it is dissolved if the pH is low. Dolomitization occurs as follows:
2CaC03 + MgClz
* CaMg(C03)2 + CaClz
SEDIMENTARY ROCKS
209
2Si02
2H20 + Mg(OH)2
+ 2 H 2 0 + CaSO,
2H20
210
SEDIMENTARY ROCKS
21 1
212
occurs if the equilibria in the aqueous phase remain constant while the water
moves through the sedimentary rocks. Deposition or accumulation of
hydrocarbons occurs if the equilibria in the aqueous phase shifted, causing
desolubilization or precipitation of the hydrocarbons.
Temperature gradients in sedimentary basins usually are about 1C per 46
m of depth, and the rate of heat flow to the surface is approximately
1.2 x loV6 cal cmV2 sec-I (Birch, 1954). Temperature is believed to be a
primary cause in the conversion of organic matter in rocks t o petroleum
(Philippi, 1965), it is also believed that lipids are the major precursors of
petroleum and that most petroleum is generated by chemical reactions occurring at temperatures above 115C.
Nonmarine sources are recognized for many crude oils, in contrast to the
once general belief that such sources are unfavorable for the generation of
petroleum. Perhaps the best known examples in the United States are the
nonmarine sequences in the Eocene of the Uinta Basin in Utah. Other
examples of oil and gas with continental source sediments are basins such as
the Dzungaria, Tsaidam, Tarim, Turfan, Ordos, Pre-Nan Shan, and Sungliao
of China (Meyerhoff, 1970). There is considerable nonmarine Tertiary age
strata in the Cook Inlet-Kena Basin in coastal Alaska.
TABLE 7.IV
Tertiary system - highest concentration of a constituent found, average concentration.
and number of samples analyzed
Constituent
Concentration (mg/l)
highest
Lithium
Sodium
Potassium
Rubidium
Cesium
Calcium
Magnesium
Strontium
Barium
Boron
Copper
Chloride
Bromide
Iodide
Bicarbonate
Carbonate
Sulfate
Organic acid
as acetic
Ammonium
Number of samples
average
27
103,000
1,200
0.6
0.4
38,800
5,800
420
240
450
1
201,300
1,300
35
3,600
300
8,400
4
39,000
2 20
0.24
0.20
2,530
530
130
60
36
0.63
64,600
85
28
560
75
3 20
169
379
176
11
9
37 6
368
142
140
170
3
380
323
322
3 64
8
139
1,900
2,700
140
230
53
64
213
TABLE 7.V
Cretaceous system - highest concentration of a constituent found, average concentration,
and number of samples analyzed
Constituent
Concentration (mg/l)
highest
Lithium
Sodium
Potassium
Rubidium
Cesium
Calcium
Magnesium
Strontium
Barium
Boron
Chloride
Bromide
Iodide
Bicarbonate
Sulfate
Ammonium
13
88,600
580
0.10
0.10
37,400
8,000
980
67 0
70
187,000
1,760
190
1,660
7,100
35
Number of samples
average
4
31,000
130
0.10
0.10
7,000
900
200
40
20
62,OOb
550
25
260
280
23
26
987
38
1
1
987
987
39
34
38
987
173
172
864
776
2
214
TABLE 7.VI
Number of samples
Concentration (mg/l)
highest
average
-
Lithium
Sodium
Potassium
Rubidium
Cesium
Calcium
Magnesium
Strontium
Barium
Boron
Chloride
Bromide
Iodide
Bicarbonate
Sulfate
Organic acid
as acetic
400
120,000
900
0.10
0.10
56,300
5,200
2,080
50
50
210,000
6,000
40
2,640
1,480
10
57,300
140
0.10
0.10
25,800
2,500
320
10
13
141,000
1,200
16
140
21 0
12
12
80
85
9
1
1
85
84
9
7
9
85
80
8
72
78
1
TABLE 7.VII
Permian system - highest concentration of a constituent found, average concentration,
and number of samples analyzed
Constituent
Concentration (mg/l)
Number of samples
highest
Lithium
Sodium
Potassium
Rubidium
Cesium
Calcium
Magnesium
Strontium
Boron
Copper
Chloride
Bromide
Iodide
Bicarbonate
Carbonate
Sulfate
Organic acid
as acetic
Ammonium
average
6
109,000
40 5
2
0.20
22,800
5,800
10
20
0.88
177,000
68
3
281
36
3,400
3
47,000
170
0.80
0.13
8,600
2,000
7
8
0.88
92,700
46
3
77
36
7 30
2 20
24
170
24
3
54
3
3
3
54
53
3
3
1
64
3
1
49
1
41
2
3
21 5
TABLE 7.VIII
Pennsylvanian system - highest concentration of a constituent found, average concentration, and number of samples analyzed
Constituent
Concentration (mg/l)
highest
Lithium
Sodium
Potassium
Rubidium
Cesium
Calcium
Magnesium
Strontium
Barium
Boron
Manganese
Chloride
Bromide
Iodide
Bicarbonate
Carbonate
Sulfate
Organic acid
as acetic
Ammonium
Number of samples
average
35
101,000
710
2.30
8.50
205,000
15,000
4,500
640
70
105
270,000
3,900
1,410
1,200
70
5,400
7
43,000
170
0.55
0.15
9,100
1,900
600
30
15
60
87,600
490
210
130
40
430
45
951
57
25
19
9 50
947
70
41
54
2
950
57
52
897
2
7 56
2,300
3,300
430
300
44
51
Table 7.V indicates that oilfield water samples taken from Cretaceous age
strata were enriched in lithium with respect to sea-water. The highest lithium
concentration found in 26 samples was 13 mg/l.
Table 7.VI indicates that oilfield waters taken from Jurassic age strata
contain up t o 400 mg/l of lithium, which, compared with sea water (Table
7.1), represents a concentration factor of 2,000. Compared t o the hydrolyzates in sedimentary rocks (Table 7.11), the concentration factor is about
9.
The lithium concentration in oilfield waters taken from Permian age strata
averaged 3 mg/l (Table 7.VII). Only three samples were available for use in
determining this average.
Table 7.VIII indicates that the lithium concentration averaged 7 mg/l in
45 samples taken from Pennsylvanian age strata. This represents a concentration factor of 35 compared with sea water (Table 7.1).
Table 7.IX indicates that the lithium concentration in oilfield waters
taken from Mississippian age strata is enriched by a factor of 45 compared
with sea water. Table 7.X indicates a similar enrichment factor of 250 for
oilfield waters taken from Devonian age strata. For waters from Silurian age
strata (Table 7.XI) the enrichment factor found was 185; for the Ordovician
216
TABLE 7.IX
Mississippian system - highest concentration of a constituent found, average concentration, and number of samples analyzed
Constituent
Concentration (mg/l)
highest
Lithium
Sodium
Potassium
Rubidium
Cesium
Calcium
Magnesium
Strontium
Barium
Boron
Copper
Manganese
Chloride
Bromide
Iodide
Bicarbonate
Carbonate
Sulfate
Organic acid
as acetic
Ammonium
55
115,800
5,000
5
2
37,800
11,200
3,390
20
240
3
36
206,000
1,800
620
1,590
450
3,500
3,070
700
Number of samples
average
9
41,500
430
1
0.40
8,900
1,600
630
5
40
3
12
85,000
410
110
185
450
540
81
210
80
47
37
209
202
52
44
86
2
5
210
88
89
198
1
191
370
210
84
83
age (Table 7.XII), it w a s 100; and for the Cambrian age (Table 7.X111), it was
85.
The data in Tables 7.VI-XI11 indicate that waters taken from sediments
that formed during the various geologic ages do not all have the same chemical composition and that the waters have evolved considerably in comparison
to modern sea water composition (Table 7.1). The manner whereby this
evolution occurred is not completely understood; however, recent studies
have shed some light on the problem. Note the amount of organic acid as
acetic found in waters taken from the sedimentary rocks (Tables 7.VI-XIII).
The organic acids are present in the oilfield waters as organic acid salts.
These organic compounds possibly are a precursor of petroleum and serve as
a transportation mechanism for migration. The exact composition of each
organic acid salt has not been determined. Knowledge of the composition of
these organic acid salts would aid in geochemical studies of petroleum.
Rittenhouse et al. (1969) studied the minor elements in 823 oilfield-water
samples taken from subsurface formations in the United States and Canada.
The data that they found are shown in Table 7.XIV as 25% quartiles, median
concentrations, and 75% quartiles. The dissolved solids are given in grams per
217
Concentration (mg/l)
highest
Number of samples
average
~~
Lithi um
Sodium
Potassium
Rubidium
Cesium
Calcium
Magnesium
Strontium
Barium
Boron
Copper
Manganese
Chloride
Bromide
Iodide
Bicarbonate
Carbonate
Sulfate
Organic acid
as acetic
Ammonium
170
101,000
11,600
11
1.4
129,000
26,000
2,300
120
90
2
200
259,000
3,500
120
1,000
60
1,700
67 0
560
50
48,000
3,100
4
0.5
18,000
2,900
1,000
40
30
2
175
115,000
1,060
30
155
30
450
130
110
29
85
30
12
11
85
82
8
7
30
1
2
85
32
32
67
2
74
27
32
liter, the data followed by p are given in parts per billion (ppb), and the
other data are given in parts per million. They analyzed samples from several
basins as illustrated in Table 7.XIV, and the elements analyzed included
lithium, magnesium, manganese, nickel, cobalt, chromium, copper, potassium, tin, strontium, titanium, vanadium, and zirconium.
Rittenhouse et al. (1969) concluded that elements in oilfield waters commonly are present in the following concentrations:
5%
5% or ppm
> 100 ppm
1-100 ppm
ppb (most oilfield waters)
ppb (some oilfield waters)
Na, C1
Ca, SO4
K, Sr
Al, B, Ba, Fe, Li
Cr, Cu, Mn, Ni, Sn, Ti, Zr
Be, Co, Ga, Ge, Pb, V, W, Zn
They found no relationship between the constituents in the brine and the
minerals in the aquifer rocks except for potassium. They postulated that
exchange reactions occurred between the clays in the rocks and potassium in
the water to control the dissolved potasssium.
218
TABLE 7.XI
Silurian system - highest concentration of a constituent found, average concentration,
and number of samples analyzed
Constituent
highest
Lithium
Sodium
Potassium
Rubidium
Cesium
Calcium
Magnesium
Strontium
Barium
Boron
Chloride
Bromide
Iodide
Bicarbonate
Sulfate
Organic acid
as acetic
Ammonium
Number of samples
Concentration (mg/l)
-
90
89,000
8,400
8
0.4
41,000
12,000
880
15
90
195,000
1,700
30
27 0
3,500
average
37
49,100
1,900
4
0.4
21,000
4,300
7 30
15
30
122,000
520
17
115
830
220
20 0
90
80
8
14
11
2
2
14
12
2
1
10
14
11
10
11
13
9
10
TABLE 7.XII
Ordovician system - highest concentration of a constituent found, average concentration,
and number of samples analyzed
Constituent
Concentration (mg/l)
highest
Lithium
Sodium
Potassium
Rubidium
Cesium
Calcium
Magnesium
Strontium
Barium
Boron
Manganese
Chloride
Bromide
Iodide
Bicarbonate
Carbonate
Sulfate
Organic acid
as acetic
Ammonium
Number of samples
average
70
89,100
2,890
6
0.5
39,000
10,900
900
10
80
56
205,600
7 20
70
2,260
60
7,600
20
31,000
990
2
0.2
6,100
1,300
340
6
20
56
62,000
300
25
270
25
1,070
598
26
583
3,300
630
5 20
140
14
16
15
609
15
11
9
609
607
12
10
18
1
609
19
16
RESEARCH STUDIES
21 9
TABLE 7.XIII
Cambrian system - highest concentration of a constituent round, average concentration,
and number of samples analyzed
_______--__
~-
Constituent
highest
._____
Lithium
Sodium
Potassium
Rubidium
Cesium
Calcium
Magnesium
Strontium
Boron
Chloride
Bromide
Iodide
Bicarbonate
Sulfate
Organic acid
as acetic
Ammonium
__
Number of samples
Concentration (mg/l)
~
40
43,000
2,000
3.3
0.6
14,500
8,800
360
13
95,000
1,170
40
790
2,600
50
120
average
_
17
23,400
440
3.3
0.6
4,000
1,300
125
7
46,100
520
18
260
1,170
30
60
8
23
10
1
1
23
22
7
5
23
5
3
23
22
3
3
Compared with sea water the 823 brines were enriched in manganese,
lithium, chromium, and strontium, and depleted in tin, nickel, magnesium,
and potassium. Generally the silicon content varied inversely with the dissolved solids content. This agrees with a study of the solubilities of silicate
minerals where Collins (1969b) found that in general the silicon solubilities
decreased with increasing concentrations of dissolved salts at ambient conditions.
Research studies related to the origin of oilfield brines
Tables 7.IV-XIV indicate that the compositions of oilfield brines are not
consistent, and that they are not formed by the simple evaporation or dilution of sea water. Oilfield brines are found in deep formations that sometimes contain fresher water nearer surface outcrop areas, in formations containing evaporites or in close proximity to soluble minerals, and in formations close to surface saline waters.
The amounts and ratios of the constituents dissolved in oilfield waters are
dependent upon the origin of the water and what has occurred t o the water
since entering the subsurface environment. For example, some subsurface
waters found in deep sediments were trapped during sedimentation, while
other subsurface waters have infiltrated from the surface through outcrops.
N
ES
TABLE 7.XIV
Minor elements in 823 oilfield brine samples in United States and Canada*'
Number
of
samples
Illinois Basin
22
Louisiana and Texas
Gulf Coast
79
East Texas
88
North Texas
24
West Texas and New
Mexico
148
Permian only
74
Pennsylvanian only
34
Silurian and Devonian
only
15
Ordovician and Cambrian
only
21
Anadarko Basin*'
118
Williston Basin, postPaleozoic
25
Williston Basin,
Paleozoic
55
Powder River Basin
22
Other Wyoming
28
Colorado
18
California
116
Sea Water
Estimated detection
limit
Lithium
q25 md
Magnesium
q75 q25
Manganese
md
q75
q25
Nickel
md
q75
q25
10
15
25
3,000
6,000
8,000
8Op 175p
750p
ND
ND
ND
ND
ND
ND
4
ND
15
15
150
3,000
250
250
5,000
550
800
6,000
3.5
8OOp
1 , 8 0 0 ~ 3.3
25
45
>5,OOOp
>5,OOOp
90
3
2
3
15
10
10
25
25
20
500
500
500
1,000
1,000
1,000
1,650
2,000
1,500
2OOp
18Op
500p
10
25
200
400
560
30p
10
ND
15
10
25
35
500
900
800
1,550
1,000
3,000
150p 400p
600p
5.6
>5,OOOp
>5,OOOp
ND
ND
10
10
250
2,000
9Op 300p
450p
18
ND
ND
ND
ND
35
ND
ND
ND
ND
0.1
50
2
45
ND
ND
300
10
20
10
35
600
40
100
30
90
1,272
2,000
225
200
300
175
<
10
2OOp
300p
60p
9Op
300p
1.8
1.7
2.8
>5,OOOp
>5,OOOp
>5,OOOp
300p >5,OOOp
660p
450p
300p
300p
950p
lp-lop
1P
1,200~
2,000~
1,000~
750p
2,800~
Tin
md
q75
q25
md
ND
ND
ND
< 1P
< 1P
< lp <
< 1P
3p ND
3p ND
150p ND
15p
< lp
< 1P
< lp
< lp
< lp
<
<
<
<
6p
< 3p <
<
ND
< 3p <
ND
< 3p <
lop
5.4p
_ 1P_
q75
5P
3P
12p
1P
1lP
25p
l p ND
3p ND
l p <Ip
< 1P
< 1P
< 1P
3P
3P
3P
l p ND
IP
5P
l p <1
15p ND
IP
2P
4P
4P
3p ND
< lp
< lp
< lp
< lp
< lp
< lp
< lp
< lp
3p
3p
3p
3p
35p
ND
ND
ND
ND
ND
<lop
<lop
2.5~ 4.5~
3P
1P
___
*' Medium (md - Rittenhouse et al., 1969)and quartile (9) concentrations in each area; ND = below detection limits; p = concentration in ppb, otherwise ppm.
** No data, less sensitive methods of analysis used.
*3
md
md
q75
_ _
*'
*'
*3
.-.
ND
ND
180
300
400
<25p
< 1
150p
<25p
< 1
450p
160
ND
ND
300
<50
300
400
300
1,000
1P
2P
1P
10P
10P
5P
200
350
400
300
500
750
400
1P
4~
1 5 ~ 170
300
450
3P N 4
2 5 ~ < 1P
4~
lop
1 5 ~ 200
20
25p
400
250
650
500
30
27
173
69
66
222
131
116
241
ND
ND
<5P
ND*~ ND*~ ND*~
ND
ND
ND
80
111
143
115
173
215
168
ND
ND
ND
ND
ND
ND
ND
ND
ND
4P
4P
4P
ND
ND
ND
42
55
72
ND
ND
ND
4P
<
53
51
67
137
128
203
ND
ND
ND
ND
<5P
59
88
ND
<5P
<5P
115
3
4
3
5
173
5
5
5
18
35
296
11
11
15
30
3P
< 2P
2P
35P
ND
ND
ND
ND
<5P
<5P
<5P
ND
ND
ND
ND
ND
<5P
<5P
2P
1P
q75
75p
ND
0.27~
md
lop
<lop
119
ND
q25
98
q75
md
q75
q75
70
61
70
Potassium
22
Illinois Basin
Louisiana and Texas Gulf
79
Coast
88
East Texas
24
North Texas
West Texas and New
148
Mexico
74
Permian only
Pennsylvanian only
34
Silurian and Devonian
15
only
Ordovician and
21
Cambrian only
Anadarko Basin*3
118
Williston Basin, postPaleozoic
25
Williston Basin,
Paleozoic
55
22
Powder River Basin
Other Wyoming
28
Colorado
18
California
116
Sea water
Estimated detection
limit
Copper
Chromium
Cobalt
< 2P
<25p
2Op
200
300
400
1 5 ~ ND
<25p
3P
<25p
5P
70p
30
<25p
2Op
.400
800
200
ND
300
300
300
45
380
<5,000
400
700
400
70
5p
15p
0.04~-0.07~
IP
<
120
160
<25p
< 6~
20
< 6;
ND
<25p
< 1P
25P
ND
ND
<25p
2p
<25p
5p
lp-15p
1P
200
ND
50
~~
Medium (md - Rittenhouse et al., 1969)and quartile (4)concentrations in each area; ND = below detection 1imits;p = concentration in ppb,otherwise ppm.
No data, less sensitive methods of analysis used.
Includes Oklahoma Platform and Ardmore Basin.
to
to
to
Number
of
samples
Strontium
q25 md
Titanium
q75 q25
__.
Illinois Basin
Louisiana and Texas
Gulf Coast
East Texas
North Texas
West Texas and New
Mexico
Permian only
Pennsylvanian only
Silurian and Devonian
only
Ordovician and
Cambrian only
Anadarko Basin
Williston Basin,
postPaleozoic
Williston Basin,
Paleozoic
Powder River Basin
Other Wyoming
Colorado
California
Sea water
Estimated detection
limit
~
md
~
Vanadium
Zirconium
q75
q25
q25
md
q75
md
_____.
-
22
140 300
400 < l o p
<1 op
<lop
ND
ND
<lop
<lop
79
88
24
85 200 ND
45
75 350 750 ND
150 450 700 < l o p
<lop
<lop
1P
<lop
<lop
<lop
ND
ND
ND
ND
<lop
148
74
34
15
21
118
25
55
22
28
18
116
1 5 200
65
90
180 300
75
90
7P
2OP
ND
ND
ND
400 ND
300 ND
450 ND
<lop
<lop
<lop
<lop
<lop
<lop
ND
ND
ND
ND
ND
ND
ND
ND
ND
<lop
300 < l o p
<lop
<lop
ND
ND
ND
ND
<lop
<lop
<lop
<lop
ND
ND
ND
ND
ND
ND
<lop
ND
<lop
ND
ND
ND
ND
<lop
25P
<lop
<lop
<I op
<lop
<lop
<1 op
<lop
7P
present
ND
ND
ND
ND
ND
<lop
<lop
ND
10
7
ND
ND
95 450 < l o p
25
50 < l o p
45 ND
20
20
60 < l o p
1 0 22 < l o p
13
ND
16
10P
<
lop
ND
ND
2Op
ND
ND
<lop
<lop
ND
ND
ND
ND
ND
<lop
<lop
ND
ND
ND
1OP
-.
*' Medium (md; from Rittenhouse e t al., 1969) and quartile ( 4 ) concentrations in each area; ND = below detection limits; p = concentration
in ppb, otherwise ppm.
RESEARCH STUDIES
223
Some waters are mixtures of the infiltration water and trapped ancient sea
water.. Also, the rocks containing the waters often contain soluble constituents which dissolve in the waters or contain chemicals which will
exchange with chemicals dissolved in the waters causing alterations of the
dissolved constituents.
The amounts of dissolved constituents found in oilfield waters range from
less than 10,000 mg/l t o more than 350,000 mg/l. This salinity distribution
is dependent upon several factors including hydraulic gradients, depth of
occurrence, distance from outcrops, mobility of the dissolved chemical
elements, soluble material in the associated rocks, ion exchange reactions,
and clay membrane filtration.
Concentration of sea water can occur by surface evaporation, and there
are at least three independent processes that can cause major changes in
buried, isolated sea water:
(1) Dilution with meteoric or fresher waters which have entered outcrops.
(2) Reactions with minerals in the sediments and sedimentary rocks (the
reactions are often temperature and pressure dependent).
(3) Membrane filtration through clays and shales as a result of pressure
and osmosis.
Playa deposits
Jones et al. (1969) studied the composition of brines in shallow, finegrained playa deposits in the Great Basin. The concentrations of dissolved
solids in the water in these sediments often were as much as five times
greater than in the water in the associated lakes. They attributed the concentration processes t o capillary evaporation and entrapment of fossil brines
when the salinity of the lake water was greater (lake nearly dry).
224
mation water exist in the Western Canada Sedimentary Basin, that the flow
systems affected accumulations of hydrocarbons in the basin, and further
that pressure and salinity variations might be explained by membrane
properties of the shales. He saw a need for studies of the hydrodynamics of
the basin.
Hydrodynamics and geochemistry of the Paradox Basin were studied by
Hanshaw and Hill (1969). The ground-water movement in the basin is
generally southwestward from the high outcrop areas in western Colorado,
flowing toward the Colorado River discharge areas. Hydrodynamic conditions exist in lower Paleozoic strata which are favorable to accumulations
of petroleum in stratigraphic traps. Paleozoic aquifers in northwestern New
Mexico have very high potentiometric surfaces and these aquifers may be the
outflow receptors of an osmotic membrane system operating within the San
Juan Basin. This regional study was excellent and of value in exploration for
petroleum and gas.
Parker (1969) studied brines and waters in five aquifers of Cretaceous age
in the East Texas Basin. He found that the composition of the waters in the
older, more deeply buried aquifers were modified more than waters in
younger, less deeply buried aquifers. Most of the modifications were made
by exchange reactions, dilution by meteoric waters, and loss of sulfate because of bacterial reduction. Hydrodynamic movement of the waters in the
Woodbine formation contributed t o the giant oil accumulation in the East
Texas Basin. Much of the stratigraphic trapped oil probably was trapped in
part because of this type of flow.
Sabkha sediments and transport of valuable ores
Bush (1970) discussed the origin of chloride-rich brines from Sabkha sediments and how they are related t o inclusion brines and lead-zinc deposits of
the type found in the Mississippi Valley. He noted that Helgeson (1964) and
Barnes and Czamanske (1967) have shown that chloride-rich scrlutions can
transport lead and zinc as chloride complexes. According t o Bush (1970),
Sabkha brines free of sulfur are expelled by sediment compaction, migrate,
and become enriched in base metals until they contact a zone of higher
temperature and pressure. In this zone, sulfides are present as a result either
of inorganic reduction of sulfate, anaerobic reduction, or hydrocarbon
reduction of anhydrite. The sulfides cause the base metals to precipitate.
Formation brines are the medium in which several metals, in addition to
hydrocarbons, migrate prior to deposition in ore deposits. A current theory
is that the metals travel primarily as chloride complexes in solutions that are
depleted in reduced sulfur species (Dunham, 1970). The metals subsequently
are precipitated when a source of reduced sulfur is met. An example of a
source of reduced sulfur is an area where anaerobic bacteria are reducing
sulfate. This occurs in waters near petroleum-bearing formations, and such
waters in carbonate reservoirs often contain considerable amounts of sulfide.
RESEARCH STUDIES
225
Brine classification
A study of the evolution of subsurface brines in Israel by Bentor (1969)
led him to classify brines into four groups. The first group consists of brines
similar t o sea water except for an increased concentration of calcium and a
decreased concentration of magnesium, which he attributed to dolomitization. The second group was similar t o sea water but contained two to three
times higher concentrations of dissolved salts, deficient in sulfate and
magnesium, and enriched in bromide and iodide. The sulfates were lost by
organic reduction, the magnesium was lost by exchange reactions with clays,
and bromide and iodide were added by organic sources. The third group was
a high-salinity calcium chloride-type brine formed by surface evaporation
and later modified in the subsurface by differential ultrafiltration, The
fourth group was a highly saline, calcium chloride type with Ca/Na ratios
greater than one. This group was divided into two subgroups where the first
subgroup is a highly saline and highly differentiated Early Paleozoic brine,
while in the second subgroup they are old Paleozoic brines which were
submitted t o an additional cycle of surface concentration by evaporation.
Ion association
Truesdell and Jones (1969) studied ion association in brines and found
that, except for the chloride ion, the major simple ions form ion pairs, while
the minor and trace metals in brines form coordination complexes. Selective
ion electrodes can be used to determine directly the ionic activities of
sodium, potassium, chloride, fluoride, and sulfide in brines. Experimental
data were used t o calculate chemical models for ion association and coordination complexes in brines. These models are useful in explaining the
chemical behavior of brines.
Relation t o lithology
Kramer (1969) used factor analysis to study the relationships of the brines
to the type of rock from which they were taken. His results indicated that
the major ions in most brines are sodium, calcium, and chloride; brines are
enriched in calcium and bicarbonate and are deficient in magnesium and
sulfate relative t o sea water. The factor groupings did not reflect the lithology of the rocks from which the brines were taken, indicating that such a
relationship does not exist or is difficult to detect. The brine analyses used in
the study were primarily macro analyses and did not include pH, minor, or
trace constituents. A study of this type would benefit significantly if the
following conditions were met: (1) use only the best available sampling
methods; (2) use field analysis techniques; (3)use positive lithology identification; and (4) use only the best available laboratory methods of analysis.
226
Kramer (1969) did not have these controls because he used only the
published data of various laboratories.
Carpenter and Miller (1969) used statistical and thermodynamic methods
in an effort t o determine the origin of the dissolved chemical constituents in
saline subsurface waters in north-central and northwestern Missouri. Statistical analysis of scatter diagrams indicated that the concentrations of lithium,
sodium, potassium, and bromide and the ion activity ratios of K+/H+,
Ca+/Mg+*, and Sr+ /Ba+ in the waters are influenced by reactions with
constituents in the aquifer rocks. They concluded that the ion ratios are of
little value in determining the origin of the waters because the concentrations of the dissolved constituents in the waters had reacted with minerals
in the aquifer rocks. This study was excellent because it did show that the
concentrations of constituents in the water are controlled to some extent by
reactions with the aquifer rocks. Additional work of this kind is needed in
the study of deep brines.
A study of brines from the Sylvania formation in the Michigan Basin
indicated that evaporation and dolomitization were two dominant controls
for their dissolved concentrations of calcium, magnesium, sodium, strontium, and bromide (Egleson and Querio, 1969). Mechanisms responsible for
concentrations of elements such as potassium, lithium, rubidium, ammonia,
boron, and iodide were believed t o be reactions with sedimentary rocks,
leaching of organic constituents, and bioconcentration.
227
RESEARCH STUDIES
trations of bromide in many of these brines are lower than the iodide which
is unusual. Localized sedimantary rock deposits enriched in organic iodine
are the source of the high iodide concentrations in these brines (Collins et
al., 1971).
Hot brines
Hot brines containing minor and trace amounts of several metallic
elements in addition to macro concentrations of some alkalies, alkaline
earths, and chloride are found in drill holes in southern California, in the
Caspian Sea, and in deeps in the Red Sea. These brines were formed from
evaporites dissolved by meteoric water, and the metallic elements were
leached from country rocks by the hot brines (Tooms, 1970). Laboratory
reactions of 2M and 4M sodium chloride with andesite and shale at
300"-500C have produced solutions containing metallic elements in concentrations similar to the hot brines (Ellis, 1968).
Comparison of oilfield brines with evaporated sea water
Bromide does not form its own minerals when sea water evaporates. It
forms an isomorphous admixture with chloride in the precipitates
(Valyashko, 1956; Braitsch and Herrmann, 1963). As sea water evaporates,
the carbonates precipitate first, followed by the sulfates. Little or no
bromide precipitates, or if it does, it is occluded with these.
Halite (NaCl) begins t o precipitate when the chloride concentration is
about 275,000 mg/l (Table 7.111) compared with that of normal sea water,
19,000 mg/l. Some bromide is entrained with chloride in the precipitate.
300
2oo
.c
Fig. 7.4. Use of the bromide ion to differentiate some Tertiary (T), Cretaceous (C), and
Jurassic (J) age brines.
228
TABLE 7 .XV
Bioconcentrated bromide and iodide in seaweeds and corals
Bromide (ppm)
Seaweed
Laminaria digitata (dry matter)
Laminaria saccharina (dry matter)
Desmaresta (ash)
Corals*
Gorgonia uerrucosa
Gorgonellidae
Isididae
1,380
340
6,800
16,200
19,800
7,400
Iodide (ppm)
5 10-8,000
2,000
5,200
69,200
22,100
20,300
RESEARCH STUDIES
229
from the bottom t o the top of the depositional strata. These variations can
be attributed t o inflow of fresh sea water during the deposition or subsequent
leaching after deposition. Rittenhouse (1967) developed a method to classify
oilfield waters based upon the bromide concentrations.
Fig. 7.4 is a log-log plot of chloride versus bromide concentrations for
some Louisiana oilfield waters. The T, C, and J on the figure refer t o Tertiary, Cretaceous, and Jurassic, indicating the ages of the rocks from which the
waters were taken. The normal evaporite curve was plotted by using data
from Table 7.111. The data in the figure indicate that most of the Tertiary
waters are deficient in bromide when compared to an evaporite water,
whereas the Cretaceous and Jurassic waters are enriched in bromide (Collins,
1967).
The Tertiary waters contain dissolved halite, which accounts for their low
bromide concentration, while the waters that are enriched in bromide contain bitterns or have leached bromide from sediments that were enriched in
bioconcentrated bromide.
The bromide content of oilfield brines can be used t o distinguish between
brines that originated because of evaporation of sea water and those formed
by the dissolution of evaporite minerals. This can be done by using Fig. 7.4.
If the bromide concentration falls to the right of the normal evaporite curve,
the brine contains evaporated sea water, while if it falls t o the left of the
curve, it contains dissolved evaporite minerals.
Fig.7.5 illustrates how closely the concentration of sodium of some
Louisiana oilfield waters taken from Tertiary, Cretaceous, and Jurassic age
rocks follow the sodium concentration of a brine associated with normal
evaporation (Collins, 1970).
300
0 ,
200
- 100
Normal evaporite curve
50
0
20
lo
5,000
10,000
20,000
'
&bob I llob!OOO
'
1
500 300
SODIUM, m g / l
23 0
Ion exchange
Ion exchange reactions on clay minerals are reversible and they follow the
law of mass action. The number of exchange sites governs the reaction, and
other important factors include temperature, pressure, solution concentrations, and bonding strength of exchangeable ions. Ion exchange between
clay minerals and a brine will stop when equilibrium is attained.
As the waters move in their subsurface environment, their dissolved ions
have a tendency to exchange with those in the rocks. There are two extreme
types of adsorption in addition to intermediate types of adsorption. The
extreme types are: (1) a physical adsorption or Van der Waals adsorption
with weak bonding between the adsorbent and the constituent adsorbed; and
(2) a chemical adsorption with strong valence bonds.
Cations can be fixed at the surface and in the interior of minerals. These
fixed cations can exchange with cations in the water. Under the right
physical conditions of the adsorbent, similar exchange can occur with the
anions. Some of the constituents in formations that are capable of exchange
and adsorption are argillaceous minerals, zeolites, ferric hydroxide, and certain organic compounds.
Particle size influences the exchange rates and capacities if the solids are
clays such as illite and kaolinite. The rate increases with decreasing particle
size. However, if a larger mineral has a lattice, the exchange can easily occur
on the plates. The concentration of exchangeable ions in the adsorbent and
in the water is important. More exchange usually occurs when the solution is
highly concentrated.
According t o Grim (1952), the replacing power of some ions in clays is:
These two clays often are present in sedimentary rocks and the replacing
order indicates that lithium and sodium are more likely to be left in solution,
while cesium and rubidium are more likely t o be removed from solution.
Fig. 7.6 is a plot of the chloride content versus the lithium content of
some oilfield waters taken from the Smackover formation. The .lithium
enrichment results at least in part from exchange reactions on clays. Lithium
has a small radius, a low atomic number, a larger hydrated radius than
sodium, and a larger polarization than sodium. Because of these, its replacing
power in the lattices of clay minerals is low (Kelley, 1948). Other ions such
as barium, strontium, calcium, magnesium, cesium, rubidium, potassium, and
sodium will preferentially replace lithium in clay minerals, thus releasing
lithium t o solutions. Furthermore, the solubility products of most lithium
23 1
RESEARCH STUDIES
1,000
000 -
400 -
600
Louisiana
Mississippi
Alabama
Arkansas
Texas
0 0
V
0
40 -
20-
10
O I , I
300
200
- 100
50
30
20
C- J
T
,I
19
100
1 I II,]
200
500
1,000
2,000
POTASSIUM, m g / I
1 1 1 I I I L
5,000
10 100
compounds are higher than those of other alkalies and alkaline earths. Therefore lithium tends to stay in solution.
Fig. 7.7 compares the potassium concentration of some Louisiana oilfield
waters with those of waters subjected to evaporation. All of these waters are
depleted in potassium with respect to a brine subjected t o evaporation,
indicating that potassium was lost to the associated sediments during
23 2
Fig. 7.8. Relationships of the concentrations of chloride t o calcium in an evaporiteformed brine to oilfield brines taken from the Smackover formation in five states of the
United states.
RESEARCH STUDIES
1,000
000 600 -
Louisiana
Mississippi
Alabama
Arkansas
Texas
400 -
A
0
0
- 200 -
233
\
0
0 100,
80
60
40
20
101I<I
100
200
' I
' I ' l ' ' ' 1 '
1,000 2,000 4,000
10,000
I 1 1 1 1 1 1
400
'
40,000
BROMIDE, mg/l
Fig. 7.9. Relationships o f the concentrations of chloride t o bromide in an evaporiteformed brine t o oilfield brines taken from the Smackover formation in five states of the
United States.
234
1,000 -
000 600 -
400-
A
0
-w 200
Louisiana
Mississippi
Alabama
Arkansas
Texas
100:
LL
006040 20 -
BORON, mg/l
Fig. 7.10. Relationships of the concentrations of chloride to boron in an evaporiteformed brine to oilfield brines taken from the Smackover formation in five states of the
United States.
Mineral formation
A study of some brines taken from Devonian age reservoir rocks indicated
that dolomitization probably is the most important mechanism in determining the calcium, strontium, and magnesium content of these brines
(Egleson and Querio, 1969). It also was concluded that the relative amounts
of ammonium, iodide, and lithium in these brines were too high to be
derived directly from sea water, and the ammonium and iodide probably
were enriched in the brines as a result of bioconcentration and subsequent
leaching of organic debris.
Dolostone deposits owe their origin t o hypersaline brines (Friedman and
Sanders, 1967). Some dolomite, including diagenetic and epigenetic forms,
originates from subsurface brines. In the geologic columns in several oil-
TABLE 7.XVI
Approximate sea-water composition before and after gypsum precipitation (mg/l)
Ion
Before precipitation
After precipitation
Calcium
Magnesium
Bromide
Sulfate
390
1,300
65
2,580
0
1,300
65
2,580
RESEARCH STUDIES
23 5
TABLE 7.XVII
Approximate sea-water composition after dolomitization or bacterial reduction (mg/l)
Ion
After dolomitization
Calcium
Magnesium
Bromide
Sulfate
0
883
65
0
0
1,300
65
0
productive basins, mixtures of dolomite and anhydrite occur, which indicates that sulfate may have been removed from the associated waters by
dolomitization as well as by bacterial reduction.
Table 7.XVI illustrates the approximate amounts of calcium, magnesium,
bromide, and sulfate that could exist in a waterbefore and after precipitation of gypsum.
Assuming that the residual sulfate (1,644 mg/l) was removed by the
dolomitization reaction:
MgC12 + 2CaC0, += CaC12 + CaMg(C0,- )*CaC12- + MgS04- += CaS04 + MgCi2
MgSO, + 2CaC03 + CaS04 + CaMg(C0, ) 2
then the Mg/Br ratio would be about 883/65 = 13.6, as illustrated by the
data in Table 7.XVII. However, if the residual sulfate was removed by bacterial reduction :
C,H,
+ Na2 SO4
Na2C03 + H 2 S + C 0 2 + H 2 0
236
TABLE 7.XVIII
Concentration ratios and excess factor ratios for some constituents in Smackover brines
Constituent
Lithium
Sodium
Potassium
Calcium
Magnesium
Strontium
Barium
Boron
Copper
Iron
Manganese
Chloride
Bromide
Iodide
Sulfate
Mg'*
Smackover
brines
0.2
10,600
380
400
1,300
8
0.03
4.8
0.003
0.01
0.002
19,000
65
0.05
2,690
1,543
17 4
66,975
2,841
34,534
3,465
1,924
23
134
1.1
41
30
171,686
3,126
25
446
24,362
Concentration
ratio*'
870
6
8
86
3
241
767
28
359
4,049
14,957
9
48
501
0.2
16
Excess
factor*'
18.1
0.1
0.2
1.8
0.1
5
16
0.6
7.5
84.2
31 1
0.2
1
10.4
0.003
0.3
Number of
Smackover
samples
71
283
82
284
280
85
73
71
64
90
69
284
74
73
27 1
284
sandstone (Table 7.XIX) had an average ratio of 2.8, while brines from some
Cretaceous age rocks had an average ratio of 6.0 (Table 7.XX).
Bromide does not form its own minerals when sea water evaporates. Some
of it is lost from solution because it forms an isomorphous admixture with
chloride with the halite precipitate. However, more bromide is left in solution than is entrained in the precipitate. Therefore, relative t o chloride, the
bromide concentration in the brine increases exponentially. Bemuse of this,
the bromide concentration in the brine is a good indicator of the degree of
sea water concentration, assuming that appreciable quantities of biogenic
bromide have not been introduced.
Table 7.XVIII presents data that were obtained by comparing the average
composition of some Smackover brines with that of sea water. The concentration ratio was calculated by taking the mean average for a given constituent in the Smackover brines and dividing it by the amount of the constituent found in normal sea water. The excess factor was determined by
dividing the concentration ratio of a constituent by the concentration ratio
of bromide. The calculation for Mg' or total equivalent magnesium was
previously explained, and the number of Smackover samples indicates how
237
RESEARCH STUDIES
TABLE 7.XIX
Concentration ratios of some constituents in some brines taken from Tertiary age rocks
Constituent
Lithium
Sodium
Potassium
Calcium
Magnesium
Strontium
Barium
Boron
Chloride
Bromide
Iodide
Sulfate
Mg'
sea water
Tertiary brines
0.2
10,600
380
400
1,300
8
0.03
4.8
19,000
65
0.05
2,690
1,543
3
37,539
226
2,077
686
148
73
20
63,992
79
21
104
1,947
Concentration
ratio*'
Excess
factor *
15
3.5
0.6
5.2
0.5
18.6
2,439
4.1
3.4
1.2
426
0.03
1.3
12.5
2.9
0.5
4.3
0.4
15.5
2,033
3.4
2.8
'
355
0.03
1.1
*'
*3
TABLE 7.XX
Concentration ratios of some constituents in some brines taken from Cretaceous age rocks
Constituent
Lithium
Sodium
Potassium
Calcium
Magnesium
Strontium
Barium
Boron
Chloride
Bromide
Iodide
Sulfate
Mg'*3
sea water
Cretaceous brines
0.2
10,600
380
400
1,300
8
0.03
4.8
19,000
65
0.05
2,690
1,543
4
28,462
193
4,999
606
346
48.3
27.5
54,910
287
37
206
3,643
Concentration
ratio*'
Excess
factor*'
20
2.7
0.5
12.5
0.5
43.3
1,608
5.7
2.9
4.4
737
0.1
2.4
4.5
0.6
0.1
2.8
0.1
9.8
365
1.3
0.7
1
168
0.02
0.5
*'
23 8
8 Si02
- 2 H 2 0 + 9.2 MgO + 6 H 2 0
1.7 A1203 6.4 Si02
10.1 MgO
+=
8 H 2 0 + 1.6 Si02
1,000 -
-cn
Louisiana
Mississippi
Alabama
Arkansas
Texas
200 -
*/
W*
g
5
I
0
100:
8060 40 -
Normal
curve
evaporite
20 10 I I I
1 1 6 1
1 1 8 1
00
Fig. 7.11. Relationships of the concentrations of chloride to magnesium in an evaporiteformed brine to oilfield brines taken from the Smackover formation in five states of the
United States.
RESEARCH STUDIES
23 9
1,000
000
600
Louisiana
Mississippi
Alabama
Arkansas
Texas
400
2 00
\
0
0 0 0 4, 0
: 00
100
60
40
20
00
24 0
RESEARCH STUDIES
241
> HC03-2
+ SO4-
> C1->
Assuming that this mechanism operates in a shale filtration system, the order
of ion concentration on the high brine concentration side would be the
same. The ion concentrations on the fresher water side would be the reverse
or :
NO3-
+ HC03-*
Other investigators have obtained similar results. For example, Loeb and
Manjikian (1965) found a rejection order of SO4- > Mg+ > Ca+ > Na+
> HC03- > C1- > NO3-. Michaels et al. (1965) found a rejection order of
Ca+2 > Li+ > Na+ > K+ for the pressure independent portion of salt
transport in cellulose acetate reverse osmosis desalination membranes. This
correlates with the size of the hydrated ion radii because calcium is the
largest and potassium the smallest. Further, this indicates that the pore size
of the membrane is a controlling factor.
The data of Larson (1967) showed that sulfate and carbonate scale
formed on the high-pressure side of the membrane and if not removed would
cause flow to decrease or stop. The pH on the output or fresh-water side of
the membrane decreased.
242
Russell (1933)considered several processes which could produce subsurface brines more concentrated than sea water. He concluded that evaporation of the water by natural gas generally is not important, water evaporation in coarse-grained rocks generally is not important, gravitational settling
of dissolved solids is not greatly important, rocks containing considerable
amounts of feldspars and other unstable minerals take up large quantities of
hydration water, clays adsorb bases and later expel them into solution
causing concentration, and osmosis may occur through semipermeable membranes.
DeSitter (1947)noted that oilfield waters are altered as a result of two
prominent diagenetic phases. During the first phase magnesium, calcium,
sulfate, and carbonate precipitate from the original sea water. During the
second phase the concentration of magnesium and calcium ions increases
along with the concentration of other dissolved solids. He reasoned that the
second phase occurred because of filtration through semipermeable shales.
The filtration results because of sediment compaction until a semipermeable membrane develops which allows water molecules t o pass through
but retards salt ions. Thus, the more concentrated brines are found where
sediment compaction and water flow distance were the greatest. This usually
occurs in the deepest portion of a basin.
McKelvey et al. (1957) forced aqueous saline solutions through ionexchange resins and found that the effluent solutions contained less dissolved salts than the influent solutions. Effluents from cation-exchange
resins were found to contain Na/K ratios similar t o those in the influent;
however, the Mg/Ca ratios were at first higher than in the influent but with
additional squeezing the ratio decreased t o much lower values. They
postulated that similar reactions occur during the compaction of sediments
to change the concentrations of constituents dissolved in waters.
Pressures of 7 kg/cm2 to 105 kg/cm2 were applied t o force sodium
chloride solutions through cation-exchange membranes. The results indicated
that the membranes desalted the saline solutions, producing a filtrate containing less salt than the influent. This salt filtering effect was attributed t o
the electrical properties of the membrane.
Milne et al. (1964)determined the filtering efficiencies of sodium chloride
solutions by bentonite membranes. The filtration efficiencies were 94% at
140 kg/cm2 and 88% at 703 kg/cm2 with 0.5N sodium chloride. Increased
salinity caused less efficient filtration because filtration efficiencies of 94%
for 0.W sodium chloride and 66% for 4N sodium chloride at a pressure of
352 kg/cm2 were obtained. A similar mechanism could operate in the subsurface to create concentrated brines.
Young and Low (1965)performed an experiment using natural rock and
demonstrated that osmotic flow of water through shale and siltstone occurs.
The osmotic pressures produced were less than theoretical and they were
attributed to microcracks in the natural rock which caused them t o be less
effective than a perfect membrane.
RESEARCH STUDIES
243
244
recent times, before pumpage, the differences in vertical head in the deep
aquifers were insufficient t o cause upward flow through shale, resulting in
ultrafiltration (Bond, 1972). In fact the head differentials were barely sufficient to enable upward flow through an open conduit.
Berry (1969) outlined the relative factors that influence membrane filtration in geologic environments. The membrane properties of shales are caused
by the electrfcal properties of their clays and organic materials. Clays
predominantly are cation exchangers with singly charged SiO- and
AlOSi-% sites and minor anion exchanges with replaceable OH- ions.
Divalent cations are adsorbed in preference to monovalent cations and
sodium is hyperfiltratcd with respect t o lithium and strontium with respect
to calcium, because of preferential adsorption of ions with ionic potentials
most similar t o the ionic potential of the exchange site. The selectivity of
hyperfiltration for the halogens is C1 > Br > I > F because of their substitution for O H in the clays. Thus, in waters concentrated by this process the
Ca/Na, Na/Li, Sr/Ca, Cl/Br, Br/I, and I/F ratios should increase. These ratio
increases have been found in some brine systems, but by no means in all
systems.
Billings et al. (1969) found five types of formation waters in the Western
Canada Sedimentary Basin and postulated the origin of two of the types.
One type of water was formed by selective membrane filtration which produced waters containing high concentrations of dissolved solids. A second
type was a mixture of membrane-concentrated formation water and bitterns
formed after the precipitation of halite but before the precipitation of
sylvite. They theorized that the alkalies were filtered selectively by clayshale membranes, producing a concentrated brine, and that the relative concentration pattern is Rb > K > Na > Li. This pattern is the reverse of what
occurs by ion exchange but is similar to the surface mobilities of cations
along clay surfaces.
A detailed study of the Western Canada Sedimentary Basin, including a
determination of the rock volume and pore volume (Hitchon, 1968), the
effect of topography upon the fluid flow (Hitchon, 1969a), and the effect of
geology upon the fluid flow (Hitchon, 1969b), strongly suggested that
thermal, electro-osmotic, and chemico-osmotic forces are operating within
the basin to affect the fluid energy gradients. Pressure differentials of about
98 kg/cm*along with salinity differences of 200,000 mg/l between formations in close proximity were found which suggest that chemico-osmotic
forces are occurring.
Hitchon and Friedman (1969) used chemical analyses and stable-isotope
analyses for hydrogen and oxygen for surface waters, shallow ground waters,
and deep ground waters in a study of the origin of formation waters in the
Western Canada Sedimentary Basin. They postulated that surface waters have
mixed with diagenetically altered sea water to form the formation waters.
Using mass balance data for the deuterium and dissolved solid contents of
the formation waters, they calculated not only how much fresh water is
CONCLUSIONS
245
present in the modified sea water but also observed how it redistributed the
dissolved solids t o prQduce salinity variations.
They concluded that formation waters result from mixing of surface
waters with modified marine or nonmarine water in the subsurface rocks,
that exchange of oxygen isotopes between the water and rock caused different water types in different basins, and that formation waters that have
passed through shale ultrafilters are more depleted in deuterium.
A study of the Surat Basin showed that most of its hydrocarbon accumulations are associated with quasi-stagnant waters. The salinities of these
quasi-stagnant waters were higher than were the salinities of the waters in the
more dynamic recharge areas. The investigators postulated that these high
salinity waters were formed by membrane filtration because of crossformational flow and also that the hydrocarbon accumulations in these
quasi-stagnant areas resulted from release of hydrocarbons mobilized by a
moving water. The hydrocarbons were released because of the higher
salinities of the waters in the quasi-stagnant areas (Hitchon and Hays, 1971).
A study of waters in sedimentary rocks of Neogene age in the northern
Gulf of Mexico Basin was made by Jones (1969). The hydrologic conditions
currently found in these sediments are similar to conditions that previously
occurred in older sedimentary basins. Osmotic flow has a dominant influence
upon the hydrology of normally and abnormally pressured aquifer systems
in the northern Gulf Basin.
Jones (1969) found that many forces such as gravity, sediment diagenesis,
different water salinities, ionic and molecular diffusion, different electrical
potentials of sediments, thermal potentials, pressure, and osmotic membrane
filtration affect the hydrology in this basin.
Fowler (1970) found that salinity variations within the Frio sands in the
Chocolate Bayou field, Brazoria County, Texas, are the result of selective
concentration of ions by shales acting as membranes. In this field, pressures
seem to reflect the flow paths of the waters, and the greatest changes in
pressures are found across shaly sections. Analyses of water samples from
this field over a 28-year period indicate decreasing salinity with production
time caused by dilution of the original brines by waters squeezed from the
shales adjacent to the aquifers.
Chilingarian and Rieke (1969) reviewed the processes which can alter the
chemical composition of formation waters. They concluded that most of the
original water was sea water, and that the concentration process in many
cases results from compaction and membrane filtration rather than evaporation. Their experimental results indicated that solutions squeezed out of
rocks during compaction progressively decrease in dissolved solids concentrations with increasing depth.
Conclusions
The origin of oilfield waters is related to many natural processes. Initially,
246
meteoric water reacted with weathered rock, soil, and organic matter. The
excess waters that did not penetrate the rock or soil caused the rock and soil
to erode and channels formed through which the water could move more
easily. Forces of gravity caused the water to move from areas of high potential to areas of low potential, and as the waters moved, the concentrations of
dissolved solids in them increased. Some of these waters found their way to
lakes and the sea. As they entered the lakes or seas their movement slowed,
causing some of the suspended particles in them t o deposit. Mixing of the
waters with the more saline waters in the sea caused dissolved carbonate and
organic compounds to precipitate.
Evaporation of the sea and lake waters caused other compounds such as
sulfates t o precipitate. The pH of the waters changed slightly because of
reactions with the atmosphere, the sediments, and other waters. Each pH
change caused precipitation of compounds or dissolution of new compounds.
Some of the waters became highly concentrated in dissolved solids in the
more shallow marine environments. Evaporites formed in these lagoons,
pans, and exposed supratidal sabkhas. Evaporites also formed in deep-water
basins when the salinity of the water at the bottom of the basin became
sufficiently high.
The sediments were buried as additional sediments were deposited on
them, and water surrounding the sediment particles also was buried. As the
depth of burial increased, the sediments compacted and some of the water
was squeezed out. Both the squeezed-out water and the remaining interstitial
water reacted with minerals in the sediments t o change the composition of
the dissolved solids in the water and the composition of the sediments.
Mechanisms that cause the oilfield waters t o differ in composition from
water originally deposited with the sediments include ion exchange, infiltrating waters, sediment leaching, mineral formation, sulfate reduction, and
ultrafiltration through clay-shale membranes.
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254
PALMERS CLASSIFICATION
25 5
ties of the water; e.g., the principal soluble decomposition products of the
oldest rock formations are the alkalies (primary), while more recent rock
formations are the principal source of the alkaline earths (secondary), This
theory of Palmers that the terms primary and secondary are associated with
the age of the rock should not necessarily be considered undisputably true,
because primary salinity certainly can be acquired from other soluble
material than that derived directly from decomposition products of the
oldest rock formations.
The five special properties of water are:
(1) Primary salinity (alkali salinity); that is, salinity not t o exceed twice
the sum of the reacting values of the radicles of the alkalies.
(2) Secondary salinity (permanent hardness); that is, the excess (if any) of
salinity over primary salinity, not t o exceed twice the sum of the reacting
values of the radicles of the alkaline earths group.
(3) Tertiary salinity (acidity); that is, the excess (if any) of salinity over
primary and secondary salinity.
(4) Primary alkalinity (permanent alkalinity); that is, the excess (if any) of
twice the sum of the reacting values of the alkalies over salinity.
(5) Secondary alkalinity (temporary alkalinity); that is, the excess (if any)
of twice the sum of the reacting values of the radicles of the alkaline earths
group over secondary salinity.
Reacting values in percent are used in this system. The percentage values
are determined by summing the milliequivalents of all the ions, dividing the
milliequivalents of a given ion by the sum of the total milliequivalents, and
multiplying by 100. Waters are classified by numerical values of the relationships of anions to the cations, where a , b , and d represent the percentage
values of the alkali cations, alkaline earth cations, and strong acid anions,
respectively. Any one of the following five conditions may exist: d may be
equal t o or less than a , greater than a and less than a + b y equal to a + b y or
greater than a + b . Using these conditions, waters are classified into five
classes:
Classl: d < a
2d = primary salinity
2(a - d ) = primary alkalinity
2b = secondary alkalinity
Class 2: d = a
2u or 2d = primary salinity
2b = secondary alkalinity
Class 3 : d > a ; d < (a + b )
2a = primary salinity
2(d - a ) = secondary salinity
2(a + b - d ) = secondary alkalinity
256
Class 4: d = (a + b )
2a = primary salinity
2b = secondary salinity
Class 5: d > ( a + b )
2u = primary salinity
2b = secondary salinity
2(d - a - b ) = tertiary salinity (acidity)
These five classes of water are found in nature. Examples of the first three
classes are various surface waters, sea water and brines represent class 4,
while mine drainage waters and waters of volcanic origin fall in class 5
(Palmer, 1911).
Rogers (1917, 1919) studied oilfield waters of the San Joaquin Valley,
California, and used the classification system of Palmer (1911). He found
that generally the surface waters of the San Joaquin Valley possess secondary salinity rather than primary alkalinity, contain more sulfate than
chloride, and contain low amounts of bicarbonate. With increasing depth,
the subsurface waters decrease in secondary salinity until primary alkalinity
becomes evident. Waters above an oil zone often contained hydrogen sulfide,
which was attributed t o reduction of sulfates by hydrocarbons, thus decreasing the amounts of sulfate and increasing the bicarbonate in the water,
which Rogers called an altered water. Further he found that, in these altered
waters in close proximity to hydrocarbon accumulations, chloride becomes
relatively and absolutely important because of the residual chloride from the
original (ancient) sea water chlorides as compared to waters above the oil
zone which often are freshened because of a more hydrodynamic situation.
Altered waters, according t o his definition, can have either primary alkalinity
or secondary salinity depending upon their amounts of carbonate and chloride, but normal waters have only secondary salinity.
Elliott (1953) used the Palmer system t o determine the chemical characteristics of some Paleozoic age formation waters in Texas. He found that all
of the waters in the group that he studied (about 70) contained predominant, primary salinity. Many of these waters contained appreciable concentrations of sulfate; one contained 5,800 mg/l sulfate, and many contained
more than 2,000 mg/l. The calcium concentration ranged up to 13,000 mg/l
while the bicarbonate concentrations ranged up t o 800 mg/l.
Ostroff (1967) used the Palmer classification to classify waters from
several basins and t o compare this classification system with two other
systems. He found that the Palmer system groups some of the constituents
together that are not closely related chemically. Furthermore the system
does not consider ionic concentrations or saturation conditions related t o
sulfate or bicarbonate.
SULINS CLASSIFICATION
257
Sulins classification
Sulin (1946), a Russian geochemist, proposed a classification system based
upon various combinations of dissolved salts in the waters. The waters are
described according to chemical type, subdivided into group, subgroup, and
class. He found four basic environments of natural water distribution:
(1) Continental (terrestrial) conditions which promote the formation of
sulfate waters. Such conditions supply soluble sulfate constituents t o the
water and the genetic type of such a water is sulfate-sodium.
(2) Continental conditions which promote the formation of sodium bicarbonate waters. The genetic type is bicarbonate-sodium.
( 3 ) Marine conditions and the formation of a chloride-magnesium type
of water.
(4) Deep subsurface conditions within the earths crust and the formation
of a chloride-calcium type of water.
The first two types are characteristic of meteoric and/or artesian waters,
the third of marine environments and evaporite sequences, and the fourth of
deep stagnant conditions.
Water classes
Subdivision of the groups of waters were made by Sulin (1946) using the
Palmer (1911) characteristics, because these characteristics express the dissolved constituents in the waters in a generalized format. For example, the
sum of the alkali chlorides and sulfates corresponds t o primary salinity, and
the sum of the alkaline earth chlorides and sulfates corresponds to secondary
258
SULINS CLASSIFICATION
25 9
TABLE 8.1
Sulins method of water characterization
_____
Na/Cl
>1
Sulfate-sodium type:
(Na+ - C1-)
so,,-2
Bicarbonate group
class A2
calcium subgroup
magnesium subgroup
Sulfate group
class S1
calcium subgroup
magnesium subgroup
sodium subgroup
class Sp
calcium subgroup
magnesium subgroup
Chloride group
class S 1
calcium subgroup
magnesium subgroup
sodium subgroup
Na/Cl
<1
Bicarbonate-sodium type:
(Na+ - C1-)
so4-2
Bicarbonate group
class A1
sodium subgroup
class A2
calcium subgroup
magnesium subgroup
sodium subgroup
class S 1
sodium subgroup
Sulfate group
class S1
sodium subgroup
Chloride group
class S1
sodium subgroup
<1
Chloride-magnesium type:
Bicarbonate group
class Aq
calcium subgroup
magnesium subgroup
Sulfate group
class s1
calcium subgroup
magnesium subgroup
class S2
calcium subgroup
magnesium subgroup
Chloride group
class S1
calcium subgroup
magnesium subgroup
sodium subgroup
class S2
calcium subgroup
magnesium subgroup
(C1-- Na+)
- Na+) >
< 1 Chloride-calcium type: (Cl-Mg+2
Mg+
Bicarbonate group
class A 2
calcium subgroup
magnesium subgroup
Sulfate group
class S1
calcium subgroup
magnesium subgroup
class s 2
calcium subgroup
magnesium subgroup
Chloride group
class S1
calcium subgroup
magnesium subgroup
sodium subgroup
class s 2
calcium subgroup
magnesium subgroup
>
26 0
TABLE 8.11
Coefficients characterizing the genetic types of waters
~~
Type of water
Na+/Cl-
(Na - Cl-)/S04-2
(Cl--
Chloride-calcium
Chloride-magnesium
Bicarbonate-sodium
Sulfate-sodium
<1
<1
>1
>1
<O
<O
>1
<1
>1
<1
<O
<O
Na+)/Mg+
>
26 1
262
TABLE 8.111
Cycles and types of products of weathering (after Chebotarev, 1955)
Cycles of
weathering:
b
rn
residual products
accumulative products
residual products
accumulative products
residual products
(1) chloride-sulphate
(chiefly alluvial)
(2) calcareous
(chiefly colluvial
and proluvial)
(3)siallitic
(1) detrital
(1) chloride-sulphate
Types of
(1) coarse detrital
products
of weathering (2) calcareous
(under vegetation
cover)
(3)siallitic
(2) siallitic
(supra-calcareous
(3) allitic (?)
accumulative products
(4) a l l i t i ~ * ~
(lateritic crust of
weathering)
* A large quantity of silica and much of its calcium and sodium compounds are removed; the aluminosilicates pass gradually into residual aluminosilicic acids,
*
*3
zrrl
is
b
=iJ
TABLE 8.IV
Geochemical classification of subsurface waters (after Chebotarev, 1955)
( A ) Relationship of the products of weathering to the genetic types of water
Presumable phase of weathering
Products of weathering
Fourth phase
bicarbonate (alkaline)
siallitic drift
bicarbonate-chloride (alkaline-saline)
chloride-bicarbonate (saline-alkaline)
calcareous accumulation
First phase
chloride-sulphate accumulation
chloride-sulfate (saline)
chloride (saline)
Class
Genetic types of
water
H C 0 3 - + COB- ClBicarbonate
Sulphate
Chloride
SO4-
Cl-
SO4-
H C 0 , - + CI-
HC03-
bicarbonate
>40
<lo
I1
bicarbonate-chloride
40-30
10-20
111
chloride-bicarbonate
30-15
20-35
IV
sulphate-chloride
15-5
<25
>25
sulphate
>40
111
chloride-bicarbonate
30-15
>20
IV
chloride-sulphate
15-
>20
<2 5
ch 1or ide
< 5
>40
<10
SOq-
26 5
CHEBOTAREVS CLASSIFICATION
geochemical groups of waters. The three major groups of waters are divided
into genetic types, which are determined from the absolute concentrations
of the dissolved constituents expressed in reacting values in percent. The
bicarbonate group contains three genetic types of water, namely: (1)bicarbonate; (2) bicarbonate-chloride; and (3)chloride-bicarbonate. The amounts
of bicarbonate plus carbonate and chloride plus sulfate determines the
genetic type. The sulfate group is subdivided into two genetic types: (1)
sulfate-chloride; and (2) sulfate. The chloride group is divided into three
genetic types: (1)chloride-bicarbonate; (2) chloride-sulfate; and (3) chloride.
Chebotarev relates the genetic types to the products of weathering because
he believes that although the concentration of dissolved solids in subsurface
waters may vary substantially, the types of soluble salts remain largely
unchangeable .
The water classes are related to the products of weathering, rainfall, and
drainage conditions. Class I corresponds t o soluble products from the weathering of orthoeluvium or igneous and highly metamorphosed rocks and their
silicate compounds. Class I1 waters are related t o products of weathering
from the same silicates and calcareous accumulations. Class I11 waters
primarily are related to weathered products from calcareous accumulations.
Class IV waters are related to weathering of alluvial, detrital, and gypsum
deposits. Class V waters are related to marine deposits plus weathering of the
products that derived the Class IV waters.
Table 8.IV shows the approximate reacting values in percent for waters
found in some oilfields (Chebotarev, 1955). For example, in such waters in
the bicarbonate group, the major cations are sodium plus potassium with the
reacting value percentage for calcium and magnesium less than 2.5 if the
saline facies are high. (The divisions between his saline facies are shown in
Table 8.V.)
Table 8.V shows the relationships of hydrodynamic zones t o the geochemistry of the water and the geological environment. The zones are: (1)
recharge with active water exchange; (2) pressure with delayed water
exchange; and (3)accumulation with stagnant conditions.
The equilibrium of the chemical systems (those typical of the major geochemical group of waters) is a criterion called the coefficient of water
exchange ( K e ) and is computed as:
Na(K)HC03 + (Ca,M&)(HC03)2
Ke =
Na(K)Cl + (Ca,Mg)C12 + Naz SO4 + (Ca,Mg)S04
The absolute and relative coefficients of water exchange for the three major
groups of waters are as follows:
Bicarbonate waters
Sulfate waters
Chloride waters
Ke (absolute)
Ke (relative)
1.55
0.11
0.016
96.9
6.9
1.o
TABLE 8.V
Relationships of hydrodynamic zones to the geochemistry of water and the geological evironment (after Chebotarev, 1955)
Hydrodynamic zone
Geochemistry of water
rechargedischarge
cycle
waterexchange
class
hydro-chemical
facies
Zone of
recharge
active
exchange
delayed
exchange
stagnant
Zone of
accumulation condition
approximate
salinity
(ppm)
common
terms for
water
structures
relation to water
depth
(ft)
examples
180-2,400
fresh
different
intensive flush
usually less
than 500
everywhere
sometimes
(some
times
111)
transitional
(typical) facies
Zone of
pressure
Geological environment
111 and
2,400--11,400 brackish
11,400-37.800 saline
400-2,500
fresh
different
inadequate flush
usually less
than 1,000
everywhere
trazs. Lional
(typical) facks
2.500-7.400
brackish
deeper portions
of structures,
folded zones
circulation and
drainage limited
sometimes
precaucasian Basin,
different
salt accumulation
prevails upon
leaching
hampered flush
IV
7,400--19,300 saline
1.500-20,000
transitional
(typical) facies
90,000-300,000 brines
fresh and
saline
brines
different
sometimes
deeper portions
of structures,
highly folded
zones
8,000-1 3,000
water exchange
manifests on geoloeical scale time
SCHOELLERS SYSTEM
26 7
The absolute and relative coefficients were derived from assumed chemical
compositions of typical waters of the major geochemical groups. The absolute value can be not lower for the group, but it can be relatively higher.
Several thousand analyses of waters associated with oil pools in the world
were used to formulate the typical waters. As the water-exchange conditions
deteriorate, the type of water changes, and the changes are related to alteration or diagenesis of the waters (metamorphism). The data in Table 8.V give
hydrochemical facies, common names of various waters as related to
dissolved solids concentrations, geological structures, flush or water circulation, depths, and examples where some of the water types are found.
The highly concentrated chloride waters are primarily associated with oil
occurrences; however, this is not always true. A prime determinant of the
chemical composition of oilfield waters is the hydrodynamic situation and
the type of trap. For example, an intensively flushed zone will contain a
different type of water from a zone with limited circulation. The type of
basin strongly influences the type of water that.is likely t o be found. For
example, an open basin probably will contain artesian waters of the bicarbonate group, a partly closed basin may contain artesian or subartesian
waters of the bicarbonate or sulfate groups, while a closed basin is more
likely t o contain bicarbonate waters on the flanks of the basin with sulfate
and chloride waters in the deeper areas.
Chebotarev (1955) applied his classification t o 917 subsurface waters in
oilfields in the world. The classification indicated that 73.7% of the waters
were of the chloride genetic type, 23.0% of the bicarbonate type, and 3.3%
of the sulfate type. Most of the sulfate and bicarbonate types were found in
the Rocky Mountain areas of the United States and probably were mixtures
containing infiltrating meteoric water.
Schoellers system
26 8
TABLE 8.VI
Schoellers scheme for classifying petroleum reservoir waters*
>
Very high if
700
Marine if 420 - 700
High if 140 - 420
Average if 40 - 140
Low if 10 - 40
N o r m a l i f < 10
>
-
Very high if
58
High if 24 - 58
Average if 6 24
Normalif< 6
Near saturation when J(S04-)
(Ca+)
> 70
c03-
>
<
High if
7
Normal if 2 7
Low if
2
However, he recommends using q ( H C 0 3 - + CO3- )(Ca+ ) rather
than HC03- + C03-
If Cl-
> Na+ then IBE = (Cl- - Na+)/Cl> Cl- then IBE = ( C T - Na+)/(S04-
If Na+
Na+
Na+
+ HCO3- + C03-2)
SCHOELLERS SYSTEM
26 9
Also, in very high chloride waters only the sequence Na+ > Ca+ > Mg+2
is found. As the C1- decreases, the sequence Na+ > Mg+ > Ca+ becomes
more frequent. In very high chloride waters SO4- > Ca+, but in less
concentrated waters the opposite may occur. The sequence HC03-< Ca+
always is found in very high chloride waters. In less concentrated chloride
waters, either HCO,- < Ca+ or HC03- > Ca+ may be found, while in
low chloride waters HC03- > Ca+ is predominant.
x Ca+ to indicate
Schoeller used an arbitrary value of 70 for JSO4that a water is saturated with CaS04. (This is not necessarily true because
some waters, depending upon their other dissolved constituents, can contain
smaller or larger amounts.) He divided waters into four additional types
depending upon their amounts of sulfate.
Saturation with CaS04 was found to occur only in very high chloride
waters. The calcium concentration always is very high - ranging from 150 to
1,100 epm - in high chloride waters which have SO4- > 58 epm and
usually is less than 150 epm in high chloride waters where SO4- < 58 epm.
All petroleum waters even if saturated in CaS04 have a low S04/C1 ratio
which is attributed t o reduction of sulfates and high concentrations of
chloride. The ratio never exceeds one except in low or normal chloride
waters.
The third subgroup contains three additional types depending upon the
amounts of bicarbonate and carbonate in the waters. The preferred formula
for this calculation is Y(HCO,- + C03- ) (Ca+ ) which is proportional to
the gaseous pressure of C 0 2 in equilibrium with CaCO, in the water. As the
Cl- increases, the tendency is for Ca+ t o increase and HC03- to decrease;
however, because the Ca+ increases, the product of y(HCO,- + C03- )
(Ca+ ) does not vary greatly.
As the waters move in their subsurface environment their dissolved ions
have a tendency to exchange with those in the rocks. Two extreme types of
adsorption can be noted in addition to intermediate types of adsorption. The
extreme types are a physical adsorption or the Van der Waals adsorption with
weak bonding between the adsorbent and the constituent adsorbed and a
chemical adsorption with strong valence bonds. Both of these adsorptions
can act simultaneously.
Cations can be fixed at the surface and in the interior of the associated
minerals. These fixed cations can exchange with the cations in the water.
When the exchange occurs, there is an exchange of bases. With the right
physical conditions of the adsorbent, similar exchange can occur with the
anions. Some of the formation constituents that are capable of exchange and
adsorption are argillaceous minerals, zeolites, ferric hydroxide, and certain
organic compounds.
Particle size influences rates and capacities, if the solids are clays such as
illite and kaolinite. The.rate increases with decreasing particle size. However,
if a larger mineral has a lattice, the exchange can easily occur on the plates.
27 0
(a-x)=K
( a E x ) IP
The IBE is used to indicate the ratio between the exchanged ions and the
same ions as they originally existed. For example, assume that in the original
'
)
, and that when
water there were as many equivalents of C1- as (Na+ + K
the Na+ and K+ of the water exchanged with the alkaline earths in the rocks
alkaline exchange occurred, then:
IBE =
C1-
- (Na+ + K+)
c1-
and this value is positive if the equivalents are Cl- > (Na' + K
'
)
. Theoretically all the halides should be included as C1- and all the alkalies as Na+ or
(Na+ + K
'
)
.
However, when the alkaline earth ions in the water exchange for alkali
metal ions on the rocks then:
Cl- - (Na+ + K + )
IBE =
SO4- + HC03- + NO3and this value is negative if the equivalents are Cl- < (Na+ + K+).The lack
of equilibrium between the halides and the alkalies is not always a characteristic of base exchange because sea water has a positive value without the
occurrence of base exchange. Negative values usually are observed for water
coming from altered crystalline rocks. Waters with an IBE equal t o or greater
than 0.129 can be true connate petroleum reservoir waters. Waters with a
negative IBE are waters of meteoric origin that have infiltrated into marine
sediments.
Comparison of petroleum-reservoir waters with other types of subsurface
waters revealed that the other waters have most of the same characteristics
a much higher SO4- concentration and a lower
or Kr. Waters that are in contact with organic matter
SCHOELLERS SYSTEM
271
(other than petroleum), such as bitumens, lignites, and coals, resemble petroleum reservoir water, but the frequency of a Kr above normal is greater in
petroleum associated waters. Waters related
- to magmatic reactions commonly possess high concentrations of HC03 .
Schoellers (1955) study of petroleum reservoir waters indicated that a
positive IBE is more frequent as the C1- increases. A negative IBE is more
frequent as the C1- decreases, and a negative value is predominant in low
and normal chloride waters associated with petroleum. In fact, this characteristic appears specific for petroleum reservoir waters since in other subsurface waters a positive index occurs as frequently as a negative index.
Ancient sea water (connate water) deposited with the sediments usually
has an IBE > 0.129 and a Cl/Na > 1.17. Intruding meteoric water in sedimentary marine rock has an IBE < 0.129 and Cl/Na < 1.17. Petroleumreservoir waters with an IBE greater than sea water 0.129 also have the
characteristics Cl/Na > 1.17, Cl/Ca < 26.8, Cl/Mg > 5.13, Mg/Ca < 5.24; a
very high value for $(HCO,-) (Ca+*) indicating sulfate reduction; low concentrations of HC03-; and frequent high concentrations of NH4 +.
Petroleum-reservoir waters containing infiltrating meteoric water mixed
with ancient sea water have an IBE less than sea water, 0.129, and the
characteristics Cl/Na < 1.17, the ratio Mg/Ca increases and approaches but
never equals 5.24, and the ratios Na/Ca and Na/Mg decrease as the dissolved
solids increase.
27 2
273
between the reacting values of the assumed total anions and cations until
about 1960, after which time it was determined by flame photometry or
atomic absorption.
Several other analyses for dissolved constituents in oilfield brines are now
made by the Bureau of Mines. For example, potassium, lithium, rubidium,
and cesium are determined by atomic absorption or flame photometry;
strontium and barium by atomic absorption; manganese, iron, and boron by
atomic absorption or titrimetric methods; and bromide and iodide by
titrimetric methods.
The precision of the methods is as follows: alkalinity, 2-3% of the
amount present; sodium, 2--5% of the amount present; calcium and magnesium, 4--5% of the amount present; sulfate, 1-2% of the amount present;
chloride, 1% of the amount present. If sodium is calculated, the precision
value reflects the sum of the precision data for the data from which it is
calculated plus the undetermined dissolved constituents. The significant
figures for the analytical data are all the certain digits and only the first
doubtful digit. This number usually is limited to three significant figures
except for specific gravity, where four or five are common.
It often is recognized that the sampling method is as important as the
analytical method. This certainly is true of oilfield brines.
Field sampling methods
Most of the 4,000 samples were obtained only from wells where reasonable assurance was evident that the formation brine was not contaminated
by drilling fluids or by intrusion of water from other formations. Wells were
selected on the basis of age, type of completion, and production of fluids.
Samples were not taken from some gasfields because of the likelihood of
dilution by water condensed from vapor carried up the hole with the gas.
Some samples were taken from gas-condensate wells that produced large
volumes of brine.
In many cases the electrical resistivity measurement was made on the
sample at the time the sample was taken, and resulting values were compared
with measurements from other samples from the same formation within that
field or nearby fields. Obvious discrepancies were eliminated by sampling
additional wells.
Nearly all samples were withdrawn at production wellheads, and the water
was separated from the oil in portable separators. A few samples were taken
of brines from formations that did not produce enough water t o permit
taking samples at individual wellheads. Such samples were taken from gunbarrels or oil-water separators.
Samples were taken in clean, 1-gallon glass jugs that were first rinsed
several times with the water sampled and then filled, capped, and labeled. In
a few instances samples were obtained by the producer from comparatively
isolated small pools or fields and shipped t o the laboratory in 1-gallon polyethylene jugs.
274
Calculations
The analyses of most oilfield waters are reported in units of milligrams per
liter (mg/l). The conversion of mg/l to equivalents per million (epm) is done
using the following formula:
mg/l of ion
= epm ion
atomic weight of ion
specific gravity of brine x
valence of ion
Table 8.VII provides formulas for calculating the epm for many of the
common constituents found in oilfield brines. If the constituent is reported
in parts per million (ppm), it is not necessary t o divide by the specific gravity
of the brine.
The sum of the epms (Z epm) shown in Table 8.VII are converted to
Zr/100 g of water for the Sulin calculations by moving the decimal to the
left in the Z epm and calling this Zr. The term s is used t o indicate the
percent of equivalent of a given constituent. The percentage equivalent (s) of
each ion is determined by dividing the equivalents per 100 g of water by the
total equivalent in 100 g of water. For example, if the r for sodium equals
27 5
TABLE 8.VII
Formulas for converting milligrams per liter to equivalents per million for constituents
commonly found in oilfield waters
Lithium
Potassium
Sodium
Magnesium
Calcium
Strontium
Barium
Carbonate
Bicarbonate
Sulfate
Chloride
Bromide
Iodide
mg/l Li+
mg/l K+
mg/l Na+
mg/l Mg+
mg/l Ca+
mg/l Sr+
mg/l Ba+
mg/l co3-
mg/l HC03mg/l SO^+
mg/l C1mg/l Brmg/l I-
x
x
x
x
x
x
x
x
x
x
x
x
x
0.1442/sp. gr.* =
O.O256/sp. gr. =
O.O435/sp. gr. =
O.O823/sp. gr. =
O.O499/sp. gr. =
O.O228/sp. gr. =
O.O146/sp. gr. =
O.O333/sp. gr. =
O.O164/sp. gr. =
0.0208/sp.gr. =
O.O282/sp. gr. =
O.O125/sp. gr. =
O.O079/sp. gr. =
Zepm
epm Li+
epm K+
epm Na+
epm Mg+
epm Ca+
epm Sr+
epm Ba+
epm c03-
epm HC03eprnS04-
epm C1epm Brepm I-
* Specific gravity.
200.6 and the Zr for the total equivalents equals 518.8, then
200.6/518.8 x 100 = 38.7, or 38.7 percentage equivalents for sodium.
The Sulin classification considers only the macro constituents; if ions such
as potassium, lithium, strontium, barium, bromide, and iodide are determined, they should be added t o their associated macro constituents t o be
properly considered in the analysis report. For example, when sodium,
potassium, and lithium are determined by atomic absorption the total mg/l
of each is reported. Therefore, the epm Na + epm K + epm Li should be
added to obtain the correct r value for sodium:
rNa=
rCa=
rC1 =
epm Na
epmCa
epm C1
epm K
10
epm Li
10
e p m S r + epmBa
10
10
epm Br
10
epm I
10
The r values then are divided by the Zr and multipIied by 100 to obtain
the s value or percentage equivalents. The s values are used to determine the
type, class, and other Sulin values of the water as illustrated in Table 8.1,
where a = sNa, b = sCa + sMg, and d = sC1+ s S 0 , . The epm values are used
to determine the Schoeller characteristics such as the degree of chloridization, the degree of sulfation, IBE, etc., illustrated in Table 8.VI.
27 6
TABLE 8.VIII
Classification of some oilfield waters from 1 0 formations in eight sedimentary basins
No.
State
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
Kans.
Kans.
Kans.
Kans.
Kans.
Kans.
Kans.
Kans.
Kans.
Kans.
Kans.
Kans.
Kans.
Kans.
Kans.
Kans.
Kans.
Kans.
Kans.
Kans.
Okla.
Okla.
Okla.
Okla.
Okla.
Okla.
Okla.
Okla.
Okla.
Okla.
Ark.
Ark.
Ark.
Texas
Texas
Texas
Texas
Texas
Texas
Texas
31
32
33
34
35
36
37
38
39
40
Formation Basin
Depth
Arbuckle
Arbuckle
Arbuckle
Arbuckle
Arbuckle
Arbuckle
Arbuckle
Arb u ck le
Arbuckle
Arbuckle
Lansing
Lansing
Lansing
Lansing
Lansing
Lansing
Lansing
Lansing
Lansing
Lansing
Wilcox
Wilcox
Wilcox
Wilcox
Wilcox
Wilcox
Wilcox
Wilcox
Wilcox
Wilcox
Cent .Kans.
Cent .Kans.
Cent.Kans.
Cent.Kans.
Cent.Kans.
Cant.Kans.
Cent.Kans.
Cent.Kans.
Cent .Kans.
Cent .Kans.
Cent. Kans.
Cent.Kans.
Cent.Kans.
Cent .Kans.
Cent. Kans.
Cent. Kans.
Cent .Kans.
Cent.Kans.
Cent.Kans.
Cent .Kans.
Cherokee
Cherokee
Cherokee
Cherokee
Cherokee
Cherokee
Cherokee
Cherokee
Cherokee
Cherokee
1,050
1,091
1,023
1,102
992
1,152
1,174
949
1,195
1,104
928
1,075
966
999
902
1,009
1,063
1,148
1,172
853
1,228
1,731
904
1,539
1,106
1,020
582
1,432
1,97 2
1,865
Nacatoch
E.Texas
360
233.4
9.0
22.4
Nacatoch
Nacatoch
Nacatoch
Nacatoch
Nacatoch
Nacatoch
Nacatoch
Nacatoch
Nacatoch
E.Texas
E.Texas
E.Texas
E.Texas
E.Texas
E.Texas
E.Texas
E.Texas
E.Texas
465
373
905
70 1
242
650
283
191
181
463.4
300.4
788.2
481.8
274.0
492.7
295.4
451.5
490.6
39.5
25.9
9.4
7.8
8.1
10.4
8.1
17.6
3.6
59.5
36.8
28.7
17.3
14.7
16.5
14.7
44.7
7.8
>
Concentration (e pm)
634.6
581.6
282.0
639.9
430.3
458.7
473.2
356.4
446.4
577.4
1,759.6
570.4
1,899.9
1,728.2
1,903.8
2,514.8
1,854.7
2,087.2
2,414.5
1,898.4
2,366.5
2,188.4
2,161.5
2,365.3
1,997.1
1,990.0
1,587.2
2,459.0
2,701.4
2,635.5
<
60.6
58.4
24.8
56.6
38.8
34.4
53.1
57.4
35.4
49.4
266.6
117.4
266.4
232.0
274.5
309.3
225.2
223.6
251.0
210.8
193.3
209.5
163.2
200.8
140.4
161.3
151.2
174.5
153.1
180.6
133.0
121.8
40.2
13.0
65.4
81.3
119.4
100.4
71.2
112.1
373.9
174.6
442.1
512.4
478.8
532.7
449.8
384.8
519.0
416.7
810.1
529.4
530.3
445.6
457.3
513.7
287.5
511.6
606.0
629.6
7.7
6.5
9.5
2.2
8.5
3.4
5.1
12.8
9.0
35.9
1.8
2.4
0.3
1.7
1.1
0.4
0.5
1.4
0.7
0.8
1.1
0.3
0.4
1.1
0.9
0.7
1.8
1.1
0.7
1.1
3.7
1.4
4.3
3.1
3.3
2.5
18.9
2.4
7.1
2.8
49.0
22.7
22.1
46.6
17.5
45.9
36.0
39.9
30.0
45.5
0.0
34.9
0.8
2.5
0.0
1.5
1.1
1.o
2.4
0.7
7.7
9.8
7.3
15.9
7.8
13.3
1.4
6.0
8.4
8.6
0.0
0.0
1.0
0.0
0.0
0.8
0.1
0.9
0.4
0.6
> 58, ( H )
773.8
732.3
313.9
827.0
510.9
523.2
705.0
456.7
512.7
685.8
2,398.9
826.6
2,605.0
2,469.4
2,655.6
3,353.6
2,529.6
2,706.1
3,17 9.9
2,515.5
3,360.6
2,917.2
2,847.4
2,992.0
2,584.3
2,650.8
2,021.6
3,138.8
3,449.1
3,436.6
261.1
559.5
357.7
824.6
503.5
294.2
498.4
313.6
506.2
498,4
Sulin
Zepm
type
1,659.0 Cl-Ca
1,523.6 Cl-Ca
692.6 Cl-Ca
1,585.4 C l - C a
1,071.6 C1-Ca
1,147.2 Cl-Ca
1,492.0 CI-Ca
1,024.0 Cl-Ca
1,105.0 CI-Ca
1,506.4 C1-Ca
4,800.9 CI-Ca
1,726.6 Cl-Ca
5,214.7 Cl-Ca
4,946.5 Cl-Ca
5,314.0 CI-Ca
6,712.5 Cl-Ca
5,061.1 Cl-Ca
5,404.4 Cl-Ca
6,367.7 Cl-Ca
5,043.1 Cl-Ca
6,739.4 Cl-Ca
5,854.9 Cl-Ca
5,710.4 Cl-Ca
6,021.0 Cl-Ca
5,188.0 C l - C a
5,330.0 Cl-Ca
4,051.1 Cl-Ca
6,291.3 C l - C a
6,918.8 Cl-Ca
6,892.3 Cl-Ca
529.8 CI-Ca
1,123.5 C l - C a
726.2 Cl-Ca
1,654.2 C k C a
1.013.8 Cl-Ca
594.5 Cl-Ca
1,037.4 Cl-Mg
635.2 C l - C a
1.027.8 Cl-Ca
1,004.0 C l - C a
277
Schoeller*
class
CT
so4-
80.7
52.6
29.8
77.8
33.8
61.1
65.6
62.3
46.2
71.4
0.0
78.0
19.4
36.0
0.0
28.7
22.5
20.4
35.9
17.8
79.1
72.3
62.3
84.3
59.9
82.7
20.5
55.7
71.4
73.6
0.6
0.0
6.0
0.0
0.0
3.6
1.6
3.6
4.5
2.2
20.0
17.4
15.4
8.7
16.8
9.9
14.6
25.2
17.9
52.5
10.7
10.2
3.5
11.6
8.5
4.4
5.1
9.1
6.3
6.6
9.9
3.6
4.7
8.5
7.1
6.4
9.9
8.7
7.1
9.4
6.8
4.9
8.8
6.5
5.7
4.6
18.1
4.4
13.2
4.0
0.18
0.21
0.10
0.23
0.16
0.12
0.19
0.22
0.1 3
0.16
0.27
0.31
0.27
0.30
0.28
0.25
0.27
0.23
0.24
0.25
0.30
0.25
0.24
0.21
0.23
0.25
0.21
0.22
0.22
0.23
0.11
0.17
0.16
0.04
0.04
0.07
0.01
0.06
0.1 1
0.02
278
TABLE 8.VIII (continued)
No. State
Formation Basin
Depth
(m)
Concentration (epm)
Na+
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
61
62
63
64
65
66
67
68
69
70
71
72
73
74
75
76
77
78
79
80
Ark.
Ark.
Ark.
Ark.
Ark.
Texas
Texas
Texas
Texas
Texas
Ark.
Ark.
Ark.
Ark.
Texas
Texas
Texas
Texas
Texas
Texas
Texas
Texas
Texas
Texas
Texas
Texas
Texas
Texas
Texas
Texas
Ala.
Ala.
Ala.
Miss.
Miss.
Miss.
Miss.
Miss.
Miss.
Miss.
Paluxy
Paluxy
Paluxy
Paluxy
Paluxy
Paluxy
Paluxy
Paluxy
Paluxy
Paluxy
Rodessa
Rodessa
Rodessa
Rodessa
Rodessa
Rodessa
Rodessa
Rodessa
Rodessa
Rodessa
Woodbine
Woodbine
Woodbine
Woodbine
Woodbine
Woodbine
Woodbine
Woodbine
Woodbine
Woodbrine
Eutaw
Eutaw
Eutaw
Eutaw
Eutaw
Eutaw
Eutaw
Eutaw
Eutaw
Eutaw
E.Texas
E.Texas
E.Texas
E.Texas
E.Texas
E.Texas
E.Texas
E.Texas
E.Texas
E.Texas
E.Texas
E.Texas
E.Texas
E.Texas
E.Texas
E.Texas
E.Texas
E.Texas
E.Texas
E.Texas
E.Texas
E.Texas
E.Texas
E.Texas
E.Texas
E.Texas
E.Texas
E.Texas
E.Texas
E.Texas
Interior Sal.
Interior Sal.
Interior Sal.
Interior Sal.
Interior Sal.
Interior Sal.
InteriorSal.
Interior Sal.
Interior Sal.
InteriorSal.
=->
1,115
737
1,297
884
1,417
2,340
2,174
1,943
1,512
1,943
1,897
1,241
1,033
711
2,844
2,519
2,722
2,115
2,289
3,062
1,047
1,750
898
841
1,809
1,144
925
1,442
1,596
1,332
1,061
972
1,060
1,444
2,263
1,312
2,443
1,690
1,315
2,469
Mg+
1,246.8 90.6
586.0 32.2
1,310.3 107.1
934.9 64.8
1,507.2 138.6
1,642.1 22.5
1,515.1
51.1
1,495.4 89.0
205.3
6.4
1,522.8 90.2
1,971.8 157.2
1,943.8 185.1
1,060.3 108.2
538.6 35.9
1,772.1 127.3
1,861.9 217.4
2,068.5 148.5
1,950.3 139.9
2,020.0 141.2
1,877.5 92.7
1,507.0 44.3
1,263.0 33.4
341.8
4.4
1,060.5 32.4
1,271.9 59.6
809.1 12.7
478.8 12.4
1,451.3 26.7
1,447.3 38.3
1,268.0 30.2
1,124.4 45.0
1,102.9 25.6
1,186.7 59.6
1,733.6 82.7
2,009.8 75.9
1,572.7 88.9
1,721.3 256.7
1,925.9 61.6
1,579.6 60.6
2,153.7 87.7
Ca+
254.1
86.7
278.5
197.6
504.4
378.5
205.9
448.9
10.0
448.1
669.7
563.6
289.8
75.0
878.8
1,084.7
900.9
726.1
741.8
610.0
161.4
56.3
9.3
58.9
154.9
61.1
23.6
213.3
144.1
81.9
164.7
160.5
164.3
287.3
306.8
224.9
458.0
359.9
252.9
518.9
HCOJ- S04-*
Cl-
0.4
2.8
2.7
1.5
0.5
0.0
4.7
2.7
14.9
1.8
0.0
0.9
0.0
3.0
1.5
1.1
0.6
1.8
0.8
1.0
4.2
8.2
11.3
0.0
1.0
7.3
7.0
3.9
1.6
8.3
2.7
2.0
2.9
0.9
5.2
0.9
0.0
3.9
2.3
0.0
1,594.4
699.0
1,692.0
1,194.9
2,208.7
2,033.8
1,763.1
2,022.2
202.4
2,050.3
2,789.9
2,679.0
1,436.5
643.4
2,773.2
3,165.1
3,111.6
2,802.4
2,909.8
2,576.9
1,705.0
1,342.2
343.5
1,161.4
1,478.2
873.3
507.7
1,685.1
1,629.4
1,367.4
1,330.1
1,288.9
1,411.8
2,108.5
2,358.5
1,890.2
2,433.4
2,352.4
1,893.5
2,765.6
0.0
3.3
.7
1.1
3.3
9.3
3.7
8.2
6.0
8.3
8.0
11.7
21.4
2.9
2.8
2.7
4.8
8.5
4.2
5.4
3.5
1.8
0.6
0.2
4.9
3.7
0.1
0.0
0.1
4.0
0.0
0.0
0.0
0.0
33.6
0.0
0.0
0.0
0.0
1.0
<
Sulin
Zepm
type
3,186.6 CI-Ca
1,410.3 CI-Ca
3,391.5 Cl-Ca
2,395.0 CI-Ca
4,363.0 CI-Ca
4,086.4 Cl-Ca
3,543.9 Cl-Ca
4,066.7 Cl-Ca
445.2 SO4-N
4,121.6 CI-Ca
5,596.8 Cl-Ca
5,384.3 Cl-Ca
2,916.3 CI-Ca
1,299.0 CI-Ca
5,556.0 Cl-Ca
6,333.1 Cl-Ca
6,235.2 Cl-Ca
5,622.2 CI-Ca
5,818.1 CI-Ca
5,163.7 CI-Ca
3,425.6 Cl-Ca
2,705.0 CI-Ca
711.0 CI-Mg
2,313.7 Cl-Ca
2,970.7 CI-Ca
1,767.3 C1-Ca
1,029.9 Cl-Ca
3,379.5 Cl-Ca
3,261.0 Cl-Ca
2,760.0 Cl-Ca
2,667.1 Cl-Ca
2,580.1 Cl-Ca
2,825.4 CI-Ca
4,213.1 Cl-Ca
4,789.9 Cl-Ca
3,777.7 Cl-Ca
4,869.6 Cl-Ca
4,704.8 Cl-Ca
3,789.1 Cl-Ca
5,527.1 Cl-Ca
Schoeller*
class
CT
d c a + ' + so4-'
279
_-
SO^-'
3.1
17.1
14.1
15.0
41.0
59.5
27.9
60.9
7.7
61.0
73.3
81.3
78.7
14.8
50.1
54.4
66.2
79.0
55.9
57.4
23.9
10.0
2.4
4.0
27.6
15.1
1.5
0.0
3.7
18.1
0.1
0.1
0.1
0.1
101.6
0.0
0.0
0.0
0.0
22.7
3.8
8.8
12.8
7.6
5.4
0.0
16.6
13.6
13.1
11.1
0.5
8.0
0.4
8.8
12.9
11.1
7.3
13.5
7.7
8.4
14.2
15.6
10.6
0.0
5.4
14.8
10.5
14.8
7.4
17.8
10.6
8.8
11.1
6.2
20.3
5.7
0.0
17.8
11.0
0.0
0.22
0.16
0.23
0.22
0.29
0.19
0.14
0.26
0.0
0.26
0.29
0.27
0.26
0.16
0.36
0.41
0.34
0.30
0.31
0.27
0.12
0.06
0.oo
0.09
0.14
0.07
0.06
0.14
0.11
0.07
0.15
0.14
0.16
0.18
0.15
0.1 7
0.29
0.18
0.17
0.22
280
State
Formation Basin
Depth
(m)
-___
81
82
83
84
85
86
87
88
89
90
91
92
93
94
95
96
97
98
99
100
101
102
103
204
105
106
107
108
109
110
111
Miss.
Miss.
Miss.
Miss,
Miss.
Miss.
Miss.
Miss.
Miss.
Miss.
La.
Ark.
Ark.
Ark.
Ark.
Ark.
Ark.
La.
La.
La.
La.
La.
La.
La.
La.
La.
La.
La.
La.
La.
N.D.
Concentration
Na+
Mg+2
Ca+2
c1-
Wilcox
Wilcox
Wilcox
Wilcox
Miocene
Miocene
Miocene
Miocene
1,975
1,748
1,412
1,871
2,031.8
1,847.9
1,362.9
2,157.3
36.8
48.4
15.0
54.1
100.3
94.9
82.5
89.9
4.5
3.8
4.4
6.8
0.0
0.0
0.0
0.0
2,163.3
1,985.9
1,455.8
2,114.0
Wilcox
Wilcox
Wilcox
Wilcox
Wilcox
Wilcox
Smackover
Smackover
Smackover
Smackover
Smackover
Smackover
Smackover
Smackover
Smackover
Smackover
Wilcox
Wilcox
Wilcox
Wilcox
Wilcox
Wilcox
Wilcox
Wilcox
Wilcox
Wilcox
Silurian
Miocene
Miocene
Miocene
Miocene
Miocene
Miocene
N .Louisiana
N.Louisiana
N.Louisiana
N.Louisiana
N.Louisiana
N. Louisiana
N.Louisiana
N.Louisiana
N.Louisiana
N.Louisiana
W. Gulf
W. Gulf
W. Gulf
W. Gulf
W. Gulf
W. Gulf
W. Gulf
W. Gulf
W. Gulf
W. Gulf
Williston
2,330
1,646
2,162
2,268
1,552
1,327
3,109
2,103
2,399
2,509
2,240
2,526
2,615
2,949
3,271
701
1,399
1,814
747
1,561
1,722
666
1,124
2,441
2,158
471
3,633
1,972.2
1,992.4
2,043.7
2,198.7
1,280.8
1,318.9
1,589.7
2,444.9
2,518.1
2,790.1
2,418.0
2,729.0
4,277.5
2,225.4
1,971.2
681.8
1,718.5
2,035.8
1,206.3
1,874.2
2,138.9
1,057.5
1,379.4
2,119.4
2,132.3
840.1
3,431.2
65.8
38.0
25.5
83.8
36.7
20.9
86.7
275.9
280.4
222.2
279.5
218.6
10.0
149.7
173.5
35.2
44.9
46.5
43.6
40.9
41.9
26.6
41.8
43.7
15.3
26.8
100.6
95.7
81.9
132.2
90.7
56.3
99.6
1,256.8
1,392.8
1,622.1
1,641.6
1,470.8
1,598.2
34.9
2,282.1
1,668.9
63.6
90.1
124.7
47.2
91.0
96.2
51.0
60.0
100.2
115.2
24.1
993.7
3.9
3.0
7.2
3.9
9.4
3.9
0.0
2.0
1.8
2.3
0.0
2.4
2.4
0.0
0.0
5.1
1.4
5.6
4.6
0.7
1.4
0.0
2.5
6.1
4.0
7.0
1.5
7.2
0.0
0.0
0.3
0.0
0.0
8.8
4.6
3.7
1.7
4.1
1.7
0.0
1.4
1.8
2.1
0.2
0.8
0.6
0.8
1.4
0.0
0.6
0.0
8.0
0.0
8.4
2,122.3
2,108.5
2,194.5
2,369.8
1,364.3
1,434.8
2,940.8
4,105.9
4,413.8
4,648.6
4,163.0
4,540.4
4,312.9
4,654.9
3,810.9
778.6
1,851.2
2,199.9
1,291.2
2,003.8
2,273.4
1,058.4
1,477.6
2,263.4
2,256.4
888.4
4,305.3
>
* Chloride (epm): (VH)C = 700, (MC) = 420-700, (H)C = 140-420, (A)C = 4040,
(L)C = 10-40, (N)C = < 10. Sulfate (epm): (VH) = 58, (H) = 24-58, (A) = 6-24, (N)
=<6.
>
Cepm
type
4,336.9
3,981.1
2,920.8
4,422.4
Cl-Ca
Cl-Ca
Cl-Ca
HCO,
-Na
Cl-Ca
Cl-Ca
Cl-Ca
Cl-Ca
Cl-Ca
Cl-Ca
Cl-Ca
Cl-Ca
Cl-Ca
Cl-Ca
Cl-Ca
Cl-Ca
Cl-Ca
Cl-Ca
Cl-Ca
Cl-Ca
Cl-Ca
Cl-Ca
C1-Ca
Cl-Ca
Cl-Ca
Cl-Mg
Cl-Ca
Cl-Ca
Cl-Ca
Cl-Ca
Cl-Ca
class
~ 1 -
281
SO^-^
~
4,267.3
4,223.9
4,403.4
4,747.3
2,747.7
2,878.2
5,883.0
8,226.2
8,840.1
9,306.8
8,335.6
4,454.9
8,637.9
9,313.8
7,626.5
1,566.7
3,706.6
4,413.6
2,593.7
4,011.7
4,55 3.5
2,193.6
2,962.2
4,533.4
4,531.3
1,786.7
8,840.7
0.0
0.0
0.0
12.7
11.2
11.8
16.1
0.06
0.07
0.06
0.0
26.2
0.0
0.1
5.4
0.0
0.0
103.6
80.0
78.0
53.5
78.0
53.4
0.0
57.5
55.5
11.4
5.1
10.2
5.6
8.8
11.7
0.0
6.1
0.0
29.9
0.0
90.6
11.4
9.0
18.9
11.1
17.0
11.5
0.0
17.7
17.9
21.1
0.6
21.3
5.9
0.7
0.6
11.6
5.6
15.8
10.1
3.6
5.9
0.0
7.3
15.2
12.1
9.9
13.0
0.7
0.06
0.07
0.07
0.06
0.08
0.46
0.40
0.43
0.40
0.42
0.40
0.01
0.52
0.48
0.12
0.07
0.07
0.07
0.06
0.06
0.0
0.07
0.06
0.05
0.05
0.20
Q.0
282
283
exchanged with metal ions on the clays. (Schoeller made the arbitrary assumption that the concentrations of sodium and chloride originally present
in the water were equal.) If the IBE is a positive number the exchange was
alkali metals in the water for alkaline earth metals on the clays, and if the
IBE is negative the exchange was alkaline earth metals in the water for alkali
metals on the clays. Very few negative numbers were evident when the IBE
was determined on the 4,000 oilfield water analyses. This indicates that most
of the formation waters associated with hydrocarbons had exchanged dissolved alkali metals for alkaline earth metals on the clays. The few samples
that yielded the negative IBE numbers were sulfate-sodium and bicarbonatesodium type waters which, according to Sulin, is indicative of terrestrial
derived waters.
Ratios
The ratios Na/(Ca + Mg) and Ca/Mg were calculated from the analytical
data for the 4,000 oilfield water samples. Fig.8.1 illustrates a plot of the
Na/(Ca + Mg) ratio versus dissolved solids for samples from the East Texas
Basin. The ratio tends to decrease with increasing dissolved solids concentration. The depletion of sodium with respect to calcium + magnesium can
be attributed to diagenesis of the waters. This correlates with Schoeller's
IBE, indicating that the alkali metals in the water exchange with alkaline
KEY
Tertiary
6
Upper Cretaceous
Lower Cretaceous
Jurassic
x Pennsylvanian
0
DISSOLVED SOLIDS, g / l
Fig. 8.1. Plot of the Na/(Ca + Mg) ratio versus the concentration of dissolved solids in
some formation waters taken from sedimentary rocks in the East Texas Basin.
284
7-
Fig. 8.2. Plot of the Na/(Ca + Mg) ratio versus the concentration of dissolved solids in
some formation waters taken from the Rodessa formation in the East Texas Basin. The
line is a least squares fit (y = a + bx + ex2 ) for the scattered data.
earth metals on the clays, decreasing the dissolved alkali metals and increasing the dissolved alkaline earth metals.
Fig.8.2 shows the scattered data for the brines taken from the Rodessa
formation in the East Texas Basin. The scattered data were submitted t o
least squares analysis to determine with more certainty how the ratios varied
with depth and with dissolved solids concentrations. The least squares
formula used was y = a + bx + cx2or the approximation to a parabola. If the
best fit is a straight line, the solution will regress to it, and this occurred for
the data shown in Fig. 8.2. Also, if this occurs, the value for c i n the formula
is very small. The curve shown in Fig. 8.2 represents a fit of about 88%of
the sum of the mean, a fit of 100%would be ideal.
Preliminary plots of the scattered data indicated that a better fit could be
obtained with the parabolic least squares approximation than with the least
squares approximation for a straight line. A computer was used t o obtain the
fit.
The least squares curve indicates that the concentration of sodium
decreased with respect t o calcium plus magnesium until the dissolved solids
were about 210,000 mg/l and then increased. This could be attributed to
exchange of sodium in the water for alkaline earths on the minerals until the
concentration of dissolved solids reached 210,000 mg/l, at which point the
solubility products of the alkaline earths are such that they are unable to
stay in solution. This would correlate with Schoellers IBE. However, the
IBE does not consider the effect of other ions in solution upon the solubility
product of an ion.
30 0
285
Tertiary
Upper Cretaceous
Lower Cretaceous
Jurassic
x Pennsylvanian-
-=2
0
20-
:Is
10-
.n
n&
n
0
0
0
315
7b
105
I40
I'l5
2;O
245
DISSOLVED SOLIDS, g / l
280
3;5
50
Fig. 8.3. Plot of the Ca/Mg ratio versus the concentration of dissolved solids in some
formation waters taken from sedimentary rocks in the East Texas Basin.
Fig. 8.3 illustrates a plot of. the Ca/Mg ratio versus dissolved solids. Here
the trends appear t o be that the Ca/Mg ratio increases as the dissolved solids
increase. This trend also is related to diagenesis of the waters. The calcium
increases as the magnesium decreases, and this may be related to the formation of dolomite and chlorite, or to reactions with argillaceous minerals.
Fig. 8.4 is a plot of Ca/Mg versus dissolved solids. The Ca/Mg ratios for
some brines from the Rodessa formation in the East Texas Basin were submitted t o least squares analysis, and the results were used to plot Fig. 8.4.
The scattered data in Fig. 8.4 did not yield as good a fit to the formula
y = a + bx + cx2 as did the data in Fig. 8.2, because the fit is about 35%of
the mean where 100% is ideal. The line indicates that the ratio increased as
the dissolved solids increased. This is the result of magnesium lost from the
brine by reactions t o form minerals, ion exchange, or shale membrane filtration. It is not a result of solubility product because most magnesium compounds are more soluble than calcium compounds.
Fig. 8.5 is a plot of Na/(Ca + Mg) against depth from which the samples
were taken. The trend does not indicate a definite relationship for these
samples.
Fig. 8.6 is a plot of the least squares analysis data for Na/(Ca + Mg) versus
depth for some brines from the Rodessa formation in the East Texas Basin.
The plot indicates that the sodium concentration decreases with respect to
286
calcium plus magnesium until the depth is about 2,350 m and then it increases. The curve in Fig. 8.6 represents a 45% mean fit of the scattered data
where an ideal fit is 100%.
Fig. 8.7 is a plot of Ca/Mg versus depth, and there appears to be an
increase of this ratio with depth which would indicate that magnesium is
depleted more with respect t o calcium in brines taken from deeper strata.
7t
21i
I1
20
80
I40
200
DISSOLVED SOLIDS, g/l
3 10
260
Fig. 8.4. Plot of the Ca/Mg ratio versus dissolved solids for some formation waters taken
from the Rodessa formation in the East Texas Basin. The line is a least squares fit
(y = a + bx + cx') for the scattered data.
I
"
6C -
o
A
50 -
o
x
KEY
Cretaceous gulf
Cretaceous Comanche
Jurassic
Pennsylvanian
Tertiary
2c -
..
IC
500
1,000
1,500
2,000
2,500
3,000
DEPTH, meters
Fig. 8.5. Plot of the Na/Ca + Mg) ratio versus depth for some formation waters taken
from sedimentary rocks in the East Texas Basin
287
500
I
1.000
1,500
2,000
2,500
100
DEPTH, meters
Fig. 8.6. Plot of the Na/(Ca + Mg) ratio versus depth for some formation waters taken
from the Rodessa formation in the East Texas Basin. The line is a least squares fit
(y = a + bx + cx2 ) for the scattered data.
3c -
o
A
x
0
2c
'F
I:
KEY
Cretaceous gulf
Cretaceous Comanche
Jurassic
Pennsylvanian
Tertiary
r"
A
0
10
0
A
500
. ..
If300
I
1,500
2,000
DEPTH, meters
**
2,500
3,( 30
Fig. 8.7. Plot of the Ca/Mg ratio versus depth for some formation waters taken from
sedimentary rocks in the East Texas Basin.
This would indicate that magnesium is taken from the brine by reactions to
form minerals or absorbed by clays.
Fig. 8.8 is a plot of the least squares analysis data for Ca/Mg versus depth
for some brines from the Rodessa formation in the East Texas Basin. The
plot indicates that the concentration of calcium increases with depth with
288
500
I.000
1.500
2POO
10
2.500
L
3pOO
DEPTH, meters
Fig. 8.8. Plot of the Ca/Mg ratio versus depth for some formation waters taken from the
Rodessa formation in the East Texas Basin. The line is a least squares fit (y = a
+ bx + cxz ) for the scattered data.
Ternary diagram
Ternary or triangular diagrams are useful in studying the distribution of
the cations and anions in subsurface waters. The ions which often are used in
these diagrams are sodium, calcium, and magnesium or chloride, sulfate, and
bicarbonate. To plot these constituents, the equivalent weights of three
cation constituents or three anion constituents are determined and summed
t o equal 100%.The percentage of the three then are plotted. Dickey (1966)
used these types of plots fo study the composition of some deep subsurface
waters.
Fig. 8.9 is a ternary plot of the normalized values for sodium, calcium,
and magnesium concentrations of some brines taken from oil-productive
sedimentary basins. This diagram indicates that all of these brines contain
more calcium than magnesium. For these particular samples the diagram
seems to indicate that the calcium equivalents tend to increase with the age
of the rocks from which the brines were taken; this does not, however, apply
to all brines.
DISCUSSION
289
Fig. 8.9. Relative concentrations of sodium, calcium, and magnesium in some formation
waters taken from sedimentary rocks in oil-productive basins.
Discussion
Chebotarev (1955) postulated that most subsurface waters are altered by
meteoric water. The three hydrodynamic zones that he considers are: (1)
active exchange, where water is influenced by a relatively high degree of
hydrodynamic movement with flushing-out of most of the salt thus producing a low salinity water; (2) delayed exchange, where the hydrodynamic
flow is less rapid, thus leaving a higher salinity water; and (3) stagnant
conditions, where there is little hydrodynamic movement, so that the
salinity accumulates and is higher.
This system was not applied to the 4,000 waters because it evaluates in a
rather complex manner the types and classes of waters from the constituent
compositions in reacting values in percent. The method appears useful in
certain general types of studies.
Palmers system does not consider ionic concentrations or possible conditions of saturation of calcium carbonate or calcium sulfate. Some constituents such as the alkaline earths and chloride and sulfate are lumped togeth-
290
er. Calcium and magnesium should not be lumped together because even
though they are in the same chemical group in the Periodic Table, they often
behave quite differently in chemical reactions. For example, the solubilities
of many of their salts are considerably different. The same often is true of
the chlorides and sulfates.
The portion of the Palmer system applied t o the 4,000 brines was used
only because it is incorporated in Sulins system. The Palmer system by itself
appears to have little value in studying subsurface brines related t o hydrocarbon accumulations.
Schoeller separates the waters into six types solely on the basis of the
concentration of the chloride ion and into four additional types using the
concentration of the sulfate ion. Because of this, his classification of oilfield
waters gives considerably more variation in types than the Sulin system, and
thus it is more confusing in interpretation. Schoellers formula for determining relative saturations of sulfates and carbonates in the waters has value
in production problems. For example, knowledge that the sulfates or carbonates may precipitate from a water under certain conditions is useful so that
correct treatment can be applied t o prevent well and/or formation damage.
The index of base exchange also is useful in evaluating diagenetic reactions
that may have occurred to change the water.
Sulins system considers some of the ions in determining the type of
water, and the class indicates the predominance of the anion groups. These
two characteristics of waters appear useful in studying waters that are likely
to be associated with hydrocarbon accumulations. For example, several investigators have determined that the chloride-calcium type in the S1 S2 A2
class of water is the most likely type to be associated with a hydrostatic
environment that promotes the accumulation of hydrocarbons. The next
most likely type is bicarbonate-sodium in the S1 A l A2 class and the least
likely types are chloride-magnesium and sulfate-sodium.
Knowledge of the type and class plus what Sulin describes as the significant indicators (direct and indirect) appears useful in hydrocarbon exploration studies. The Sulin system does not consider the degree of saturation of
the water with respect to sulfates and carbonates, which is a disadvantage in
production problems. Also, the system makes no provision for determining
the degree of base exchange which is useful in certain interpretations of
diagenesis.
Bojarskis modification of the Sulin system appears t o have little value in
evaluating a water that is likely to be associated with petroleum. Many of the
values that were found for the Na/Cl ratio in the 4,000 samples were greater
than 0.85. This value in a chloride-calcium type water according to Bojarski
is not likely t o be found in a water associated with petroleum. It is possible
that the waters that Bojarski evaluated were consistently very concentrated
waters with respect to dissolved solids.
CONCLUSIONS
291
Conclusions
Classification of the subsurface waters aids in interpreting the type of
water that is more likely t o be associated with a hydrocarbon accumulation.
Application of water classification techniques t o 4,000 oilfield brine samples
revealed that the majority of the samples were chloride-calcium type of the
S1 S2 A2 class, had positive IBE values, had a predominant cation sequence
of Na > Ca > Mg, and were very highly concentrated with dissolved chloride.
Many of the 4,000 samples had values greater than 7 for
C 0 3) (Ca), and some had values greater than 70 for d
m , indicating
that many of the waters were saturated or nearly saturated with respect to
carbonate and sulfate.
The Bojarski modification of the Sulin system appears to be of little value.
The ratio Na/(Ca + Mg) generally decreased with increasing dissolved solids
and depth. The ratio Ca/Mg generally increased with increasing dissolved
solids and depth.
Studies of the water characteristics and mapping of the more important
water properties in conjunction with other geological and geophysical data
appear useful in exploration. Maps of certain water characteristics such as
the JCa+ x SO,,- and d ( H C 0 3 - + C03- ) (Ca+ ) are useful in solving
production problems.
References
Ambrose, A.W., 1921. Underground conditions in oilfields. US.Bur. Min. Bull., 195, 238
PP.
American Petroleum Institute, 1968. API Recommended Practice for Analysis o f Oilfield
waters. Subcommittee on Analysis of Oilfield Waters, API RP 45, 2nd ed., 49 pp.
Bojarski, L., 1970. Die Anwendung der hydrochemischen Klassifikation bei Sucharbeiten
auf Erdol. 2.Angew. Geol., 16:123-125.
Chebotarev, I.I., 1955. Metamorphism of natural waters in the crust of weathering.
Geochim. Cosmochim. Acta, 8:22-48, 137-170,198-212.
Collom, R.E., 1922. Prospecting and testing for oil and gas. U.S. Bur. Min. Bull., 201, 170
PP.
Dickey, P.A., 1966. Patterns of chemical composition in deep surface waters. Bull. A m .
Assoc. Pet. Geol., 50:2472-2478.
Elliott, Jr., W.C., 1953. Chemical characteristics of waters from Canyon, Strawn, and
Wolfcamp formations in Scurry, Kent, Borden, and Howard Counties, Texas. Pet.
Eng., 25 :B7 7-BB9.
Mills, R. van A., 1925. Protection of oil and gas field equipment against corrosion. U.S.
Bur. Min. Bull., 233, 127 pp.
Ostroff, A.G., 1967. Comparison of some formation water classification systems. Bull.
A m . Assoc. Pet. Geol., 51:404-416.
Palmer, C., 1911. The geochemical interpretation of water analyses. U.S. Geol. Sum.
Bull., 749~5-31.
Reistle, Jr., C.E., 1927. Identification of oilfield waters by chemical analysis. U.S.Bur.
Min. Tech. Paper, No.404, 24 pp.
Reistle, Jr., C.E. and Lane, E.C., 1928. A system of analysis of oilfield waters. U.S.Bur.
M i a Tech. Paper, No.432, 14 pp.
292
Rogers, G.S., 1917. Chemical relations of the oilfield waters in San Joaquin Valley,
California. U.S. Geol. Sum. Bull., 653:5-116.
Rogers, G.S., 1919. Sunset-Midway oil field, California, 11. Geochemical relations of oil,
gas, and water. U.S. Geol. Sum. Prof. Paper, No.117, 103 pp.
Schoeller, H.,1955. Geochemie des eaux souterraines. Rev. Znst. Fr. Pet., 10:181-213,
219-246, 507-552.
Sulin, V.A., 1946. Waters of Petroleum Formations in the System of Nature Waters.
Gostoptekhizdat, Moscow, 96 pp. (in Russian).
Swigart, T.E. and Schwanenbek, F.X., 1921. Petroleum engineering in the Hewitt
Oilfield, Oklahoma. Cooperative Bulletin published by the US. Bureau of Mines, the
State of Oklahoma, and the Ardmore, Oklahoma, Chamber of Commerce, 61 pp.
U.S.Bureau of Mines, 1965.Analyses of Oilfield Waters. Open-file Report.
Chupter9.
Both water and hydrocarbons are ubiquitous in the crust of the earth and
water is in contact with most if not all chemical and physical reactions. The
water cycle is comprised of mechanisms whereby it precipitates from the
atmosphere t o the crust of the earth and there enters various environments e.g., surface and subsurface, chemical and physical, and biogenic and
abiogenic - until it ultimately returns t o the atmosphere. The carbon cycle
comprises the reaction of water, minerals, carbon dioxide, and a catalyst
(chlorophyll) t o form organic plant material composed of carbohydrates,
fats, lignins, proteins, and some hydrocarbons such as alkanes. Production of
additional types of organic material results from the consumption of plants
by animals.
Organic matter from land and marine plants and animals is deposited with
inorganic sediments t o form a biomass from which petroleum and natural gas
originate. Most of the organic matter that will later produce the hydrocarbons is deposited in an aqueous environment; therefore, it is evident that
water profoundly influences not only the hydrocarbon precursors but (as
will be demonstrated later) also the generation, migration, accumulation, and
alteration of hydrocarbons.
The environment controls where and how inorganic and organic matter is
deposited. Most of the petroleum source material is marine (autochthonous);
however, Corbett (1955) noted that considerable terrestrial (allochthonous)
derived organic matter is carried by streams and rivers until the bulk of it
often is deposited in deltas. In the marine depositional environment, the
sediment characteristics are controlled by hydraulics and by grain size of the
detrital material. Most coarse-grained sediment will deposit on beaches, bank
tops, and shelves, or where water turbulence is maximum. Finer grained
sediments are deposited in shelf areas, while the finest grained are deposited
in the deep basin (Emery, 1960).
Reducing conditions which aid in preserving organic matter are prevalent in
sediments and bottom waters in many marine environments and in general
tend t o become more reducing with depth below the water-ediment interface. Therefore, most of the oxidation of organic detritus occurs as it falls t o
the sea bottom where the reducing environment will inhibit further
oxidation. Rapid deposition will aid in the preservation of more organic
matter as well as more of the easily oxidized organic compounds.
294
Compaction
Recently deposited sediments have water-filled pore spaces which comprise 8Wo or more of their volume, and deposition of a few more hundred
meters of sediments causes this porosity to be reduced to 30% accompanied by
the expulsion of water (Hedberg, 1964). Considerable time is necessary for
water t o be expelled from low-permeability fine clays (Terzaghi and Peck,
1948). In some cases, pressures approaching geostatic are created because
with increasing compaction, the pore water, which cannot easily escape,
carries the full load. The pressure will drop to hydrostatic as the water is
squeezed out, then the water bears the weight of the overlying water column
and the sediments carry the weight of the overlying sediment column minus
the buoyancy factor of the water.
Compaction occurs in most sediments, but it is greater as muds form
shales than when sands form sandstones, and likewise the expulsion of water
from muds is greater. Also carbonate compaction will halt before argillaceous mud compaction because carbonate recrystallization causes formation of a rigid, difficult t o compact, structure.
The clay, montmorillonite, expands when interlayer water is added and
contracts when it is removed. The removal of water from montmorillonite is
a function of pressure and temperature (Burst, 1969). Schmidt (1971) found
that the temperature is about 93-104OC when clay starts releasing intracrystalline water and that rate of release increases with higher temperatures.
Powers (1967) also suggested that it is a function of the amount of potassium which is necessary for the transformation of montmorillonite t o illite.
Removal of water from montmorillonite with compaction resulting from
deep burial yields large amounts of free water which can migrate. The
amount of freed interlayer water depends upon the amount of montmorillonite or other clays in an expanded state in the sediment. The conversion of
montmorillonite to chlorite does not require any volume change (Weaver and
Beck, 1969), but the conversion of montmorillonite t o illite reduces the clay
volume about 5096, so it is apparent that this freed water can be equivalent
to 50% of the amount of montmorillonite in the sediment. The dehydration
of montmorillonite occurs in three stages and probably a t three different
depths of burial since the dehydration is a function of depth. Therefore, the
second and third dehydration stages could release water at about 1,500 m
and perhaps below 3,000 m thus allowing new supplies of water t o migrate.
In the Gulf Coast area, the last water is not removed from montmorillonite until the depth is about 4,500 m. The clays in this area are composed
of 50--80% montmorillonite, and the last water out comprises about 20% of
the volume of montmorillonite present so it is evident that considerable
freed water also is available at depths to 4,500 m.
Von Engelhardt and Gaida (1963) noted that compaction of clays appears
to proceed more rapidly if the pore solution is enriched in dissolved electrolytes. This may influence the compaction rate as, for example, a nonmarine
295
clay may compact more slowly than a marine clay. This could relate t o a
nonmarine source evolving a different type of hydrocarbon.
Generation and migration
Most petroleum and natural gas hydrocarbons are generated from sediment organic matter by low-temperature chemical reactions (Philippi, 1965).
Philippi also concluded that lipids probably are the major petroleum
precursor and that most petroleum is generated by chemical reactions occurring at temperatures above 115C. A catalytic effect of the surrounding
sediment, and in particular the shales, influences the rate and type of
hydrocarbon formation.
According t o McIver (1963)the maturation of hydrocarbon is influenced
by depth, and the heavy hydrocarbons in the liquid crude oil decrease with
depth while the lighter hydrocarbons increase with depth. Fig. 9.1 illustrates
how an aromatic type oil might generate and mature to graphite with depth,
and how a paraffinic type crude oil might generate and maturate t o methane
with depth. In reality many crude oils contain both aromatics and paraffins
and the ultimate end product with increasing burial depth would be graphite.
It has been postulated that oil migrates from the fine-grained source rock
to a trap as a discrete oil phase. However, calculations indicate the migration
of oil globules in reservoirs required forces several thousand times greater
than those produced by hydrodynamic gradients in most reservoirs
(Levorsen, 1954).
Because water is present in all sediments that contain organic matter
which transforms to petroleum and natural gas hydrocarbons, it is reasonable
t o assume that water is closely related to petroleum-generation processes. In
essence, water controls the depositional environment of the petroleum
S t a r t i n g material
Starting material
1
P a r a f f i n i c crude oil
1
L i g h t e r hydrocarbons
plus N, S, and 0
compounds
1
CH 4
Fig.9.1. Schematic of how an aromatic crude oil can maturate to graphite with increasing
temperatures associated with increasing depth, and how a paraffinic crude oil can
maturate t o dry methane gas. (After McIver, 1963.)
296
297
Welte (1965) extracted some bituminous rock samples with oilfield brines
which had been cleaned of traces of hydrocarbons. The extracted n-paraffins
had an approximately equal carbon number distribution.
Cooper and Bray (1963) postulated a mechanism whereby the carbon
number distribution may change when fatty acids are dissolved in water.
Each fatty acid can lose COz to form an intermediate product which reacts
to produce an n-paraffin and a fatty acid. The products have one less carbon
atom than the original fatty acids. The oilfield waters that they investigated
contained fatty acids with 14-30 carbon atoms with a balanced distribution
between even and odd carbon numbers.
Kartsev et al. (1959) reported that some oilfield waters contain up t o
5,000 mg/l of sodium naphthenate. Gullikson et al. (1961) found 5,000 t o
8,000 mg/l of organic acid salts in oilfield waters from the Ventura Basin.
Collins (1969) reported that some waters from the Anadarko Basin contain
up t o 3,000 mg/l of organic acid salts. The presence of 50 mg/l of organic
acid salts in waters could transport significant amounts of hydrocarbons out
of source rocks.
It is apparent that petroleum hydrocarbons are generated from organic
matter in sediments, that hydrocarbons are formed primarily at temperatures
above 115'C through abiogenic reactions, and that water serves to transport
the hydrocarbons from the sediments. It is possible that the water also may
transport. petroleum precursors from the sediment. These precursors might
be released from the water phase when the environment is right and then be
transformed into petroleum hydrocarbons.
Fluids in subsurface strata will move from regions of high potential t o a
low-energy region. The permeabilities of the strata influence how quickly
equilibrium can be attained between high-energy and low-energy fluid potentials. The fluids will move toward the strata offering the least resistance and
that have the greatest permeability. Generally the lower energy environment
is straight up, but it may also be straight down or lateral. The source sediments may overlie a sand structure, in which case the migration is likely t o
be down into the sand structure which may serve as a reservoir.
Energy gradients which cause fluids to move are caused by potentials
resulting from temperature, pressure, elevation, and osmotic forces which
have not been completely described mathematically (Hitchon, 1969). Rapid
tectonic uplift can alter the steady-state equilibrium in a basin.
Primary transit of hydrocarbon or precursors is this migration from the
source sediment and usually is only for a short distance or far enough t o
reach a coarse-grained sediment. After they reach the coarse-grained
sediment, they may or may not be trapped. Secondary migration occurs
after the hydrocarbons or precursors move into the coarser grained sediment,
and it may result in long or short-distance migration. The forces suggested
above affect the migration. Once the petroleum and gas have separated from
the aqueous phase they tend t o move t o higher zones because of gravity
segregation.
298
Accumulation
Compaction of sediments containing organic matter and water results in
the expulsion of water and solubilized organic matter. Conceivably, the
organic matter and gases can be solubilized or combined with the water
phase as organic acid salts or as other soluble, colloidal, or suspended forms
as a result of increased pressure. Meinschein (1959) outlined a method
whereby ptroleum hydrocarbons may dissolve in compaction-expelled
water, migrate, and later be unloaded to form an accumulation.
Cartmill and Dickey (1970) formed a crude oil in water emulsion and
found that it freely passed through coarse sand. However, it tended t o
coalesce with decreasing grain size. They attributed this to electrochemical
and capillary phenomena. Such a process could operate in a subsurface
environment and form a hydrocarbon accumulation. Related t o this
phenomenon, Kidwell and Hunt (1958) studied the hydrocarbon content
produced from sands. They decided, that in the lenticular sands hydrocarbons are being filtered out of the moving stream of water by capillary
action.
Jones (1968) gives some data illlustrating the relation of pressure differentials to salinity differences in waters attributed to osmotic flow of water
through a clay-shale membrane. He found that the salinity differential may
exceed 100,000 mg/l between two aquifers separated by a 10-to 50-m layer
of clay-shale. Waters carrying dissolved or solubilized hydrocarbons could
release them because of salting out when contacting highly saline brines
because water will accommodate less hydrocarbon as its dissolved salt concentration increases (Baker, 1967). I t also has been speculated that the solubilized or dissolved hydrocarbons may be unloaded from the aqueous phase
because of temperature or presssure changes, filtration, salinity changes, or
the attraction of the organic constituents in the water for a hydrocarbon
accumulation.
According to Baker (1962), the nature of the oil, whether paraffinic,
naphthenic, or aromatic, probably depends less on the nature of the
hydrocarbons originally available in the sediments for collection than on the
proportions of neutral and ionic micelles that were able t o release crude oil
droplets for subsequent pooling in the reservoir rock. It appears that the
frequency distribution of hydrocarbons in crude oil reflects variations in the
kind and size of the micelles in which the sediment hydrocarbons selectively
dissolve. The subsequent release of solubilized hydrocarbons from aqueous
solution results in the accumulation of oil. The hydrocarbons, after undergoing this solution and release process, would exist in the proportion characteristic of hydrocarbon occurrence in crude oil.
Welte (1965), in discussing the micelle theory, noted that Neumann
distilled several crude oils and observed that the surface tension of the
distillate decreased and the dielectric constants increased with increasing
boiling point. This means that the polar surfaceactive molecules which are
ALTERATION
299
necessary for the formation of micelles are enriched in the high molecularweight fraction. The surface-active components were phenols, and it was
found that the interfacial tension between oils and a buffered solution was
strongly pH dependent, suggesting that pH variations in pore solutions are
important for stability of micelles.
Hodgson and Hitchon (1966) theorized that surfactants aid in the mobilization of hydrocarbons in water, allowing them to migrate. During
migration, the surfactants may decompose, leaving the hydrocarbons in an
unstable state in the water phase. If the water is moving, the hydrocarbons
will have a tendency not to agglomerate, but in a hydrostatic quasi-stagnant
area the hydrocarbons will tend to separate by gravity t o form an accumulation.
Hydrocarbons accumulate in areas called traps, and these traps sometimes
are structural traps such as an anticline or stratigraphic traps such as
permeability barrier. Accumulations of hydrocarbons in oil pools apparently
form by the release of hydrocarbons from a water system. The hydrocarbons
accumulate subsequent t o their migration, and the volume of water associated with their migration is large; however, tremendous volumes of water
are available in the subsurface, and large amounts of water are freed by diagenesis or alteration of clays.
Baker (1967) postulated that the tar mats that form near the edges of
sedimentary basins can be attributed t o organic solutes moving in a water
phase. The water merely evaporates at the sediment-air interface with complete release of the heavy oil solute containing compounds of carbon,
hydrogen, nitrogen, oxygen, and sulfur.
Because the solubilities of petroleum hydrocarbons increase with temperature and decrease with increasing salinity, a mechanism for petroleum
accumulation can be formulated. Upward moving subsurface waters will
decrease in temperature, and as they move upward, the pressure will be
lower, and they may meet more saline waters. Because of these changing
conditions they will release dissolved hydrocarbons.
Alteration
Hydrocarbons are subject t o alteration as soon as they are formed. The
long-chain alkanes may react with other chemicals associated with the water
phase, resulting in bond breaking and the formation of a shorter chain
alkane. Organic acid salts may form which are relatively soluble in water and
they may be further altered if the redox potential or pH of the water
changes. The pH may change because of release of carbon dioxide associated
with a hydrocarbon reaction. The hydrogen proton in the low pH water will
react with dissolved organic acid salts, causing a reversion to the less soluble
organic acid, which will disaccommodate from the aqueous phase.
A positive change in the redox potential of the water could cause oxidation of dissolved or associated hydrocarbons. A negative change in the redox
300
potential will aid in preserving the hydrocarbon, but if the redox should
become extremely reducing, it could cause hydrogenation of the hydrocarbons, this is, however, very unlikely. Reservoired oil becomes lighter with
depth in all productive sedimentary basins; this usually is attributed to increased cracking of the larger hydrocarbon molecules into smaller ones, and
is associated with increased temperatures (Philippi, 1965). This process
requires more hydrogen for the smaller molecules, which may result in condensation and polymerization of large molecules. Ultimately, with deeper
burial and higher temperature, the hydrocarbons would be converted t o
methane and graphite (Fig.9.1).
Water washing
Water washing is a simple dissolving of light hydrocarbons by water
moving past a reservoir. The water washing causes the hydrocarbon accumu-
O i l m i g r a t e d l o here
ALTERATION
301
Bacterial
Biological degradation of a hydrocarbon accumulation is more complex
than water washing. I t results from the introduction of bacteria into the
reservoir or the reactivation of dormant species.
Alteration of petroleum by bacteria cannot be directly termed alteration
because of water, but water indirectly aids the alteration because water must
be present so that the bacteria can live. Aerobic bacteria can exist and thrive
at the surface or in the subsurface only if several conditions are met, and
these requirements as listed by Beerstecher (1954)and Davis (1967)include
the following:
(1) Water: water must be present t o serve as a medium in which the
bacteria can live.
(2) Bacteria: the bacteria themselves must be present.
(3) Nutrients: certain inorganic trace nutrients must be present.
(4)Temperature: bacteria can exist at temperatures up t o about 90C but
thrive at temperatures of less than 60C.
(5)Food: a supply of food such as organic matter or petroleum must be
present.
(6) Toxics: bacterial poisons such as hydrogen sulfide must not be present
in excessive concentrations.
(7)Oxygen: aerobic bacteria require free oxygen dissolved in the water
medium in which they live.
Obviously all of these conditions are most easily met at the surface and
the heavy oils and tars common t o oil seeps are products of fractionation
and aerobic degradation of crude petroleum. Bacterial alteration of petroleum can also occur below the surface of the earth if the prerequisite conditions are met. These conditions, especially the presence of dissolved
oxygen, occur only where subsurface waters are in hydrodynamic connection with the surface and are actively receiving surface-recharge waters. The
presence of free oxygen is critical although it generally exists in very small
concentrations, Kuznetsov (1957)measured the dissolved oxygen content in.
302
waters from wells in the Groznyv oil district and found up t o 10.6 mg/l at a
depth of 249 m. In general, dissolved oxygen was found only in the zone of
active water circulation (surface recharge) and was lacking in the zone of
stagnate water.
Dissolved oxygen in smaller concentrations (less than 1 ppm) sustains
aerobic bacteria and controls the rate at which they consume food (organic
matter and petroleum). Since the oxygen content of subsurface waters
usually is low, alteration and consumption of petroleum in reservoirs may
require thousands or even millions of years to achieve a significant degree of
change.
Kuznetsov (1957) made bacterial counts in produced subsurface waters
and found that the number of bacteria varied directly with the rate of
exchange of water (recharge). The amount of dissolved oxygen varied
directly with the rate of recharge, and the size of the bacterial population is
dependent upon the amount of oxygen available. Aerobic bacteria in
outcropping rocks were carried into the subsurface by recharge waters and
were sustained by dissolved atmospheric oxygen in such waters.
Apparently the rate at which bacteria are able t o move depends only on
the amount of available oxygen and food. All digestible organic matter in the
carrier bed along the recharge path would have t o be removed before the
bacteria could proceed. Biodegradable organic matter in the carrier bed
would be depleted as the oxygen front advanced and would permit free
oxygen to reach great distances into the subsurface. The ultimate advance of
bacterial alteration depends principally on time and temperature. If favorable conditions are present for sufficient time, bacterial alteration can reach
great distances if the temperature remains below about 6OoC. Although some
forms of bacteria can exist at temperatures up to about 90C, they apparently are in a dormant state above about 6OoC (Davis, 1967).
Zobell (1949, 1950, 1952) found that all kinds of hydrocarbons appear to
be susceptible t o bacterial action, even though the process is selective. In
general, aliphatic hydrocarbons and aliphatic side chains on cyclic compounds are most susceptible t o attack while naphthenes and aromatics are
least affected. Bacteria prefer the normal alkanes over the branched alkanes
and concentrate on the heavier molecules, rarely touching hydrocarbons as
light as C 3 .
Bacteria consume alkanes at a hydrocarbon fermentation plant at Grangemouth, England (Anonymous, 1971). The nearly pure mixture of paraffins is
prepared from crude oil by molecular sieving. The microorganisms assimilated the material with little waste and produced microbial protein which is
used in animal feed.
After consumption of the normal alkanes, branched chain alkanes are
attacked (Winters and Williams, 1971), as are long chains attached t o
aromatic and naphthenic rings (Davis, 1967). Bacteria usually reject ring
compounds and many aromatics are toxic t o bacteria. However, with ideal
conditions, bacteria can break naphthenic rings and consume them. Because
ALTERATION
303
304
voir sand. Evidence of aerobic organisms was found in waters produced with
altered Bell Creek oils; oils in the Hackberry field, Louisiana, were bacterially altered by loss of n-paraffins and singly branched isoparaffins, and in
North Africa an oil was depleted in n-paraffins.'
Conclusions
A suitable mechanism for removing water and organics from source sediments is compaction and squeezing of the fluids into adjacent beds either
vertically, laterally, or below. Accommodation of hydrocarbons or hydrocarbon precursors in the aqueous phase appears t o be a probable means of
primary migration. Variations in salinity, pressure, temperature, pH, redox
potential, capillarity, hydrodynamics, or lithology may cause dissolution of
mobilized hydrocarbons and serve t o begin an accumulation. Finally, the
moving waters can serve t o alter an accumulation.
Alteration of crude oils in the reservoir by water washing and biodegradation is common t o many producing areas and affects a significant portion of
the world's reserves. Biodegradation is most prevalent in shallow-basin flank
environments where fresh meteoric water reaches into the subsurface and
carries with it aerobic bacteria and the oxygen necessary t o sustain them.
Bacterial alteration selectively removes n-alkanes first, followed by isoalkanes and aliphatic side chains on cyclic compounds, leaving an oil relatively
enriched in naphthenes, aromatics, asphaltenes, and sulfur compounds. The
API gravity is lowered, and the nitrogen content and optical activity are
increased. Asphaltic base oils may be reduced t o an immobile tarry residue
that can block porosity and form a seal which may trap oil. Alteration of
paraffinic based crudes produces the so-called naphthenic oils, which,
because of their relatively small asphaltene content, remain mobile even
under advanced alteration conditions.
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Int. Geol. Congr., Prague, 1968, 17:113-125.
Kartsev, A.A., Tabasaranskii, Z.A., Subbotta, M.I. and Mogilevskii, G.A., 1959. Geochemical Methods of Prospecting and Exploration for Petroleum and Natural Gas.
University of California Press, Berkeley, Calif., 349 pp.
Kidwell, A.L. and Hunt, J.M., 1958. Migration of oil in recent sediments in Pedernales,
Venezuela. In: L.C. Weeks (Editor), Habitat o f Oil. American Association of Petroleum Geologists, Tulsa, Okla., pp.790-817.
Kuznetsov, S.I., 1957. A review of fundamental research on the microflora of petroleum
deposits. Mikrobiologiya, 26 (6):651-658.
Levorsen, A.I., 1954. Geology of Petroleum. W.H. Freeman, San Francisco, Calif., 703
PP.
"McIver, R.D., 1963. Maturation of oil, an important natural process. Geol. SOC. A m .
Annual Meet., 1963 Paper, 15 pp.
Mehschein, W.G., 1959. Origin of petroleum. Bull. A m . Assoc. Pet. Geol., 43:925-943.
Peake, E. and Hodgson, G.W., 1966.Alkanes in aqueous systems, I. Exploratory investigations on the accommodation of Czo-C33 n-alkanes in distilled water and occurrence
in natural water systems. J. A m . Oil Chem. SOC.,43 (4):215-222.
Peake, E. and Hodgson, G.W., 1967.Alkanes in aqueous systems, 11. The accommodation
of C, *-C36 'n-alkanes in distilled water. J. A m . Oil Chem. SOC.,44 (12):696-702.
Philippi, G.T., 1965. On the depth, time, and mechanisms of petroleum generation.
Geochim. Cosmochim. Acta, 29:1021-1049.
306
Powers, M.C., 1967. Fluid-release mechanisms in compacting marine mudrocks and their
importance in oil exploration. Bull. Am. Assoc. Pet. Geol., 51:(7)1240-1254.
Price, L.C., 1973. Solubility of petroleum in water as function of temperature and
salinity and its significance in primary migration. Bull. Am. Assoc. Pet. Geol., 57:801.
Rubio, F.E., 1959. The conditions of the accumulation of petroleum of the Costaueros
Fields, in the Bolevar District, Lake Maracaibo. Tercer Congr. Geol. Venezolana,
Mem., 3:1009-1023 (in Spanish).
Schmidt, G.W., 1971. Interstitial Water Composition and Geochemistry o f Deep Gulf
Coast Shales and Sands. M.S. Thesis, University of Tulsa, Tulsa, Okla., 121 pp.
Smith, H.M., 1940. Correlation index to aid in interpreting crude-oil analyses. U.S.Bur.
Min. Tech. Rep., No.610, 34pp.
Terzaghi, K. and Peck, R.B., 1948. Soil Mechanics in Engineering. John Wiley and Sons,
New York, N.Y., 566 p9.
Von Engelhardt, W. and Gaida, K.H., 1963. Concentration changes of pore solution
during the compaction of clay sediments. J. Sediment. Petrol., 33 (4):919-930.
Weaver, C.E. and Beck, K.C., 1969. Changes in the clay-water system with depth,
temperature, and time. O f f Water Resour. Res. Project N0.A-008-GA WRC-0769,
Georgia Inst. Technol., Completion Rep., 95 pp.
Welte, D.H., 1965. Relation between petroleum and source rock. Bull. Am. Assoc. Pet.
Geol., 49 (12):2246--2268.
Winters, J.C. and Williams, J.A., 1969. Microbiological alteration of crude oil in the
reservoir (preprints). Am. Chem. SOC.,14(4):E22-E31.
Winters, J.C. and Williams, J.A., 1971. Microbiologic alteration of crude oil in muddy
sandstone and other reservoirs. Bull. Am. Assoc. Pet. Geol., 55:369.
Zobell, C.E., 1949.Action of microorganisms on hydrocarbon. Am. Pet. Inst. Rep. Progr.
1946-1947, pp. 107-132.
Zobell, C.E., 1950. Assimilation of hydrocarbons by microorganisms. Adu. Enzymol.,
10:443--468.
Zobell, C.E., 1952. Part played by bacteria in petroleum formation. J. Sediment. Petrol.,
22:42-49.
Chapter 10. GEOCHEMICAL METHODS OF EXPLORATION FOR PETROLEUM AND NATURAL GAS
The current worldwide concern for energy resources results from the fact
that man eases his burdens and accomplishes enormous amounts of work by
harnessing mineral energy. His material progress is reflected by the amount
of energy his machines consume, and the continued upward thrust of such
progress is dependent upon the supply of mineral fuels. In the United States
this energy has eased the burdens of man t o the extent that every person in
the U.S.A. has available the energy equivalent of the output of 260 men.
About 33% of the total mineral energy demand is supplied by natural gas
and about 42% by crude oil. In 1967 the U S . demand for natural gas was
17.7 trillion cubic feet and the demand for crude oil was 4.5 billion barrels.
The demand for both is expected t o double by the year 2000.
Improved methods of finding petroleum and gas are needed. Many investigators believe that the application of geochemical methods in conjunction
with geological and geophysical methods can markedly improve the
discovery ratio. Data presented in this chapter primarily are in the form of
an annotated survey of the available literature and many of these data were
taken from Petroleum Abstracts with permission of H.O. McLeod (1971).
Introduction
Type of methods
Geochemical methods of exploring for petroleum and gas can be termed
direct and indirect. The direct methods are as follows:
(1) Analysis of soil samples t o determine the amounts of hydrocarbon
gases adsorbed by the soil.
(2) Analysis of free hydrocarbons in soils.
(3) Analysis of soils to determine the amounts of soil wax, paraffin dirt,
and other bitumens.
(4)Analyses of waters t o determine their amounts of dissolved hydrocarbons.
These methods are classified as direct because the determined constituents
are present in accumulations of petroleum and gas or derived from them.
The indirect methods are as follows:
(1)Measure the oxidation-reduction potential of soils, rocks, and waters.
(2) Analyze soil samples for various salts such as bromides, chlorides,
carbonates, and sulfates.
308
INTRODUCTION
309
Source rocks
There are three basic elements relevant t o hydrocarbon accumulations: (1)
source rock; (2) trap; and (3)reservoir. Before any hydrocarbons can accumulate in commercial quantitites, a source rock must be present. Concepts
of hydrocarbon generation from source rocks have been reviewed by
Hedberg (1964), Erdman (1965), Philippi (1965), Welte (1965), Landes
(1967), Tissot et al. (1971), and Klemme (1972).
Crude oil is liquid in its natural state and is composed primarily of hydrocarbons often combined with nitrogen, sulfur, and oxygen. Examples of
some hydrocarbons found in petroleum are shown in Fig. 10.1. Natural gas is
a gas in its natural state composed primarily of hydrocarbons often mixed
with carbon dioxide, hydrogen sulfide, and nitrogen. Examples of hydrocarbons found in natural gas are shown in Fig. 10.2.
Organic matter in rocks usually is divided into the part that is soluble in
common organic solvents and the part that resists these solvents. The nonsoluble organic matter is called kerogen, and the amount of kerogen and
soluble matter can be estimated from their respective carbon contents. The
hydrocarbons in the soluble matter are of primary value in evaluating a
source rock. The evaluation of total organic carbon in rocks can serve as an
ALKANES
c-c-c-c-c-c-c
c-c-c-c-c
Porottin
Bronchrd Porottin
Monocyclic
Bicyclic
Tricyclic
AROMATICS
Pyrrne
310
NORMAL PARAFFINS
H
H-C-H
H
Methane
I I
H-C-C-H
H H
Ethone
I 1 I
H-C-C-C-H
I I I
H
Propane
indication of a source rock for further estimation of the hydrocarbon potential of a target area.
Organic matter in all sedimentary rocks is about 2% of the rock mass, and
The Clarke for organic
the amount of trapped oil is about 1.25 x
carbon is 1.14% in shales and 0.24% in carbonates (Gehman, 1962). Forsman
and Hunt (1958) found that the ratio of organic material t o organic carbon
in rocks ranges from 1.07 to 1.22. Philippi (1969) found that the ratio
between soluble carbon and total carbon CJCt must be greater than 3 for
shale before it can be construed to be a source rock.
Good source rocks contain more than 130 ppm of petroleumlike hydrocarbons; fair source rocks, 40-130 ppm; and poor source rocks, less than 40
ppm (Hunt and Meinert, 1954). Philippi (1957) extracted several shale
samples and made a similar conclusion. His ranges were more than 500 ppm
good, 50-500 ppm fair, and less than 50 ppm noncommercial.
Analysis of the gases in cores and cuttings can be used to identify source
rocks (FeugGre and Gkrard, 1970). Hydrocarbons with carbon numbers
below CI4 usually occur in source rocks (Dunton and Hunt, 1962), but the
recent sediments do not contain light hydrocarbons (Erdman, 1967), indicating that long periods of time are necessary in the hydrocarbon generation
process.
Commercial accumulations of oil usually are associated with marine shales
or with organic-rich, fine-grained limestones. A shale commonly contains
0.5% or more organic matter and a limestone 0.2% before oil begins to
occur. The kind and amount of organic matter in a rock indicate its source
potential (Hunt and Meinert, 1954). Less than 5% of the organic matter in
sediments eventually becomes petroleum; therefore, about 95% of it remains
in the source rocks (Hunt and Jamieson, 1956; Philippi, 1957).
Trask and Patnode (1942) studied about 35,000 rock samples and found
that the average amount of organic matter in rocks in close proximity t o
oilfields was about 1.5%. According t o Hunt (1967), more hydrocarbons
appear t o be generated by fine-grained carbonate rocks than by other types
of rocks containing the same amounts of organic matter.
Philippi (1969) concluded that petroleum is generated by chemical
reactions at relatively low temperatures, from source rocks. He further concluded that bacteria alone do not transform organic material into petroleum,
INTRODUCTION
311
312
The precise manner whereby oil leaves a source rock is not known,but it
apparently is related t o the flow of water from compacting sediments. A
better understanding of the migration process will aid in locating reserves of
oil and especially those in stratigraphic traps or in a combination of stratigraphic and structural traps. Fig. 10.3 illustrates these types of traps.
313
Organic compounds
Saturated hydrocarbons
Davis and Yarbrough (1969)invented a geochemical prospecting method
which involves the analysis of formation waters for the saturated hydrocarbons: normal decane, isodecane, butyl cyclohexane, and pentyl cyclohexane.
The presence of these hydrocarbons in the formation water is indicative of
petroleum accumulations.
Buckley et al. (1958)studied the dissolved hydrocarbon gases in waters of
petroleum-bearing strata and determined the escaping pressure or the
pressure at which the gas started t o come out of solution. Most of the gas in
solution was methane with lesser quantities of ethane and heavier gases. The
results indicated that the gases generally diffuse into the edgewater rather
short distances from the margins of oil fields.
Kortsenshtein (1965)outlined a general solution for the problem of determining the oil and gas potential of subsurface strata from data of the gas
saturation of subsurface waters under dephased equilibrium conditions. His
study indicated that water that is saturated or supersaturated with hydrocarbon gases can positively be used t o predict whether oil and gas are present in
traps, while waters that are not saturated with hydrocarbon gases cannot be
used to make a positive prediction.
It was observed: (1)that .the direction of increasing saturation indicates
the direction of the accumulation; (2) that a relatively accurate target
location can be obtained by determining where the increasing saturation
pressure intersects by using data from two or more wells; (3) that an increase
in pressure of saturation stratigraphically upward in a well may indicate an
approach t o a gas-water contact; (4)that a constant saturation pressure
laterally presents an unsolvable problem, unless one has data on changes with
depth; and (5)that interpretation of the size of the postulated accumulation
is difficult (Kortsenshtein, 1964).
Continuous investigations made in the oilfields of the Dnepr-Donets
Basin revealed a number of regularities in the composition and degree of gas
saturation of groundwaters. In the presence of oil accumulations, the gas
saturation of waters and the composition of the dissolved gases were determined with respect to the oil pool in a vertical and horizontal direction. The
regularities of the gas saturation of these waters serve as a basis for oil
exploration (Gutsalo and Krivosheya, 1965).
London et al. (1961)found three classes of gas-water relationships. The
first is represented by formation waters undersaturated with gas in which the
hydrocarbons dominate the chemistry of the water. Commercial gas pools
are not probable under such conditions. Examples of these exist in the
Jurassic and Cretaceous sediments of the West Siberia Lowland. A system in
which predominantly hydrocarbon gases and formation water are in equi-
314
librium (that is, the gases are at saturation pressure) represents the second
class. The third class is represented by a system in which the pressure of the
dissolved gas is greater than the saturation value, free gas escapes, and the
hydrocarbons are oxidized. Gas pools are likely to be found near the highly
saturated water.
Bond (1962)patented a geochemical exploration method which complements conventional gravimetric, magnetic, seismic, and electrical geologic
survey methods. The technique utilizes the analysis of gas samples, collected
from earth or water samples obtained from locations in the proximity of
hydrocarbon-containing reservoirs. The gas is analyzed t o determine the
/13C1H4.
If the samples .of oil-gas have not diffused a
isotopic ratio '*C1H4
considerable distance through the earth, the normal ratio ordinary methane/
heavy methane is in the range of 89.5-93.5. If the gas has diffused up from
a considerable depth, the ratio will be 0.5-2.5 units above normal, which in
turn indicates the presence of petroleum.
Aromatic hydrocarbons
Zarrella et al. (1967)found that the amount of benzene in formation
waters directly reflects the occurrence of a petroleum accumulation in a
formation. They believe that vertical migration of hydrocarbons between
aquifers is restricted and that lateral migration is limited. For example, Fig.
10.4 illustrates how the concentration of a hydrocarbon in a brine may vary
with the distance of the brine from an oil pool.
Zinger and Kravchik (1969)believe that toluene and benzene in water are
hydrochemical indexes which indicate the presence of oil and gas. Accumulations of oil and gas are the principal source of benzene and toluene in oilfield
waters. The ratio benzene/toluene in these waters is greater than 1. Benzene
in waters is considered one of the most important and direct indicators of oil
and gas content (Kortsenshtein, 1968;Kartsev et al., 1969).
If the concentration of a measured aromatic hydrocarbon in a sample of
formation water is equal to a target value, the point from which the sample
was obtained is close to a reservoir of crude oil. Greater differences between
these two values represent greater distance to the crude oil accumulation.
The target value is determined by contacting the type of crude oil expected
in the sampled reservoir with water solutions of salt and measuring the
concentration of the aromatic hydrocarbon in the solutions. This determines
the variation in concentration of this aromatic hydrocarbon as a function of
the salinity of the dissolving water. The salinity of the sample of the water
makes it possible to determine the target value; that is, the value of concentration of this aromatic hydrocarbon existing at the point of contact
between crude oil and formation water (Schmidt, 1970).
daturnted, unsaturated, and aromatic hydrocar'bons
McAuliffe (1969) determined hydrocarbons dissolved in water by gas
chromatographic methods using a number of techniques to separate the
315
Fatty acids
Cooper and Kvenvolden (1967)analyzed samples of water from the subterranean formations t o determine the ratios of selected fatty acids. These
ratios indicate the presence of a petroleum reservoir if the ratio of fatty acids
containing an even number of carbon atoms to those containing an odd
number of carbon atoms is not more than 1.6.
316
Organic acids
Shvets and Shilov (1968) used a quantitative method t o determine watersoluble organic substances in waters. Waters near oil accumulation deposits
contained up to 3,500mg/l of organic acids. Data on organic carbon, organic
acids, and oil hydrocarbons in waters could be used as indicators of oil
accumulations.
Organic acids dissolved in subsurface waters in the form of salts, or in the
free state, indicate the removal of organic substances from rocks. This
indicates the existence of geochemical processes in which deeply buried
organic substances are being broken by decarboxylation, accompanied by
the formation of hydrocarbons. Thus, organic acids and their salts may be
considered a source for the formation of hydrocarbon accumulations
(Shabarova et al., 1961).
Inorganic and organic compounds
Kolodii (1969) found two types of hydrochemical anomalies in the Pliocene deposits of the South Caspian Basin. The first is associated with structures in which the red bed part of the producing formation is at a shallow
depth. It manifests itself in sudden increase in dissolved solids in the water
up to 300 g/l. The second anomaly is related t o the lower section and
decreased dissolved solids 5-40 g/l. These waters are often of bicarbonatesodium type and were formed by mixing oilfield water with condensate
water which reacted with the host rocks. This hydrochemical inversion is
related to processes accompanying migration of hydrocarbons into the zones
of reduced pressure and temperature. The genetic relationship between
hydrochemical anomalies and the presence of oil (gas) deposits can be used
in oil exploration.
Compared to a general background, methane, heavy hydrocarbons, hydrogen sulfide, and carbonic acid concentrations in water increase with the
approach t o a gas and oil accumulation, while the content of sulfates
decreases. The amount of helium in the zone depends upon the difference
between its saturation in the waters and in the accumulation (Savchenko et
al., 1965).
Sudo (1967) studied the major oil- and gasfields of Japan as related to
subsurface water for the exploration of oil and gas deposits. The analytical
data suggested that: (1) the SO,-2 concentration is extremely low, perhaps
resulting from microbiological activity in the initial sedimentary environment; and (2) dissolved hydrocarbons and naphthenic acid salts in the brine
are direct indicators, and I- and HC03 are indirect indicators of oil and
gas accumulations.
Oilfield waters (as well as waters of gasfields and bituminous formations)
are characterized by enrichments of the biophile elements K+, B+3,Br-, and
I-. Alkaline waters with higher concentrations of carbonates and sulfates,
and with naphthenic acids, are associated with naphthenic oils. Alkaline-
317
earth chloride waters with low-numbered fatty acids are associated with
paraffinic oils ( Krejci-Graf, 1962).
Radioactive compounds
Filonov (1969) investigated radioactive elements in underground waters of
the Devonian deposits in the Pripvatsky Depression. He found a uniformity
in distribution of uranium and radium and a correlation between the increase
318
in dissolved solids of the waters and the increase in their radium content. He
concluded that the radium concentration may be used as an indirect indicator of oil.
Gutsalo (1967) studied the geochemical relationship between radium
anomalies and oil and gas deposits. In waters of t h e Dnepr-Donets Basin
associated with hydrocarbons, the amount of Ra concentration depends on
the concentration of dissolved solids and the age of the water-bearing rocks.
Positive hydrogeochemical anomalies exist within the areas of hydrocarbon
influence. The Ra anomalies are related t o the gas component of waters; Ra
concentration is dependent on the partial pressure of hydrocarbons dissolved
in water, which usually amounts t o more than 90%of the total gas pressure.
The Ra concentration in these waters has a direct linear relationship to the
hydrocarbon pressure. The Ra anomalies in the ground waters of the
Dnepr-Donets Basin, near the gas-water or oil-water contacts, appear to
owe their origin t o the hydrocarbon gases, which are genetically related t o
the hydrocarbon deposits.
The formation of radioactive anomalies on the earth's surface, above oil
and gas deposits, is related t o the migration of hydrocarbons, salts, and ions
in water solutions. It is assumed that the radioactive substance is carried
toward the surface by ascending waters and hydrocarbons. The migration of
the water and hydrocarbons is controlled by the permeability of the rock
strata. The infiltration of gaseous hydrocarbons into the surface zone may
increase evaporation, which leads to the increased migration of the water
from surrounding areas. This water may be capable of dissolving radioelements, redepositing them in these places of greatest evaporation, which
leads to the increased migration of water from surrounding areas. Liquid
hydrocarbons, because of fractionation, may deposit bituminous material
which is able to extract radioactive material from ground waters. There are
two schools of thought on the matter of formation of surface radioactive
anomalies. They are: (1) the radioelements have a surface origin; and (2) the
radioelements have a deep-seated origin (Sikka, 1963).
The deep-seated origin is substantiated by MacElvain (1963). In fact, he
concluded that the determination of *l0Pband 206 Pb in near-surface samples
should be more rewarding in oil exploration than the beta radiation techniques.
Furthermore, the 210Pb/206Pbratio might indicate the age of the underlying
hydrocarbon accumulation.
The amount of gases in surface soils is a function of the weather and is
influenced by temperature, rain, and wind. Therefore, geochemical exploration techniques using soil samples must be designed so that samples are taken
from a depth that is not influenced by the weather (MacElvain, 1963).
Filonov (1964) studied the radium and uranium contents in different
oilfield waters occurring in the platformal and geosynclinal deposits, in
particular, the variations of the Ra/U ratio. The results revealed: (1) that
oilfield waters contained an increased Ra content and that chloride-calcium
types had a higher Ra concentration than the bicarbonate-sodium waters; (2)
319
320
600
SO0
I
I
I
I
I
400
> 300
I
I
Q-
---- 1------II
200
100
(3
I
10
I1
PH
Fluid mechanics
Roach (1965) describes how to apply fluid mechanics t o petroleum
exploration. The definition of fluid mechanics as he used it encompasses
complete study of subsurface fluids including physical and chemical characteristics, whether hydrodynamic or hydrostatic, and a complete study of the
characteristics of the reservoir rock.
Maps
Chloride-ion concentrations in water produced from rocks of various ages
and depths were mapped in Lea County, New Mexico, using machine mapplotting techniques and trend analyses. Anomalously low chloride concentrations (1,000-3,000 mg/l) were found along the western margin of the
Central Basin Platform in the San Andres and Capitan Limestone formations
of Permian age. These low chloride-ion concentrations may be caused by
preferential circulation of ground water through the more porous and
permeable rocks (Hiss et al., 1969).
Hanshaw and Hill (1969) studied aquifer systems from: (1) Mississippian
age rocks; (2) Pinkerton Trail Limestone; (3) Paradox member of the Her-
321
mosa formLtion; (4)Honaker Trail formation; and (5) Permian age rocks.
Recharge in the Paradox Basin occurs on the west flank of the San Juan
Mountains and along the west side of the Uncompahgre Uplift. A series of
potentiometric surface maps were prepared for the five systems studied.
With a few exceptions, most wells in formations above the Pennsylvanian age
strata contain fresh to moderately saline water. Much of the strata below the
Permian age rocks contained waters with dissolved solids concentrations
greater than 35,000 mg/l and some areas favorable for hydrocarbon accumulations. Some of the brines in the Paradox formation contained up to
400,000 mg/l of dissolved solids. Cambrian age strata in much of Colorado is
favorable for the accumulation of hydrocarbons.
Chemical analyses of water from five Cretaceous aquifers were used to
compute ion ratios, which were used in conjunction with structural and
stratigraphic information t o interpret hydrologic conditions in the East
Texas Basin. Ion ratio comparisons made by maps and diagrams show that
the aquifers contain water of distinctive character, and that there are interconnections between aquifers, especially near the Mexia-Talco Fault zone
and the Sabine Uplift. A hypothesis is offered that water moves along an
unconformity from the Sabine Uplift eastward toward the East Texas
oilfield where it enters the Woodbine Sandstone. Ion-ratio maps show the
effect of time and of rock composition upon the relative kind and amount of
dissolved solids in the water because- of reactions with minerals and organic
material in the rocks. The hydrodynamic component of the water in the
Woodbine formation from east to west helped form and contain the giant
East Texas oilfield (Parker, 1969).
Karim et al. (1966) studied three exploratory wells drilled on the east
plunge of the Cordillera Isabella, Nicaragua, and all three had gas shows. A
stratigraphic cross section and a localized map showing the relationship of
magnetic highs obtained from an aeromagnetic survey and results of
fluoroanalysis and water-gas surveys are included. The prospect of finding
petroleum in coastal northeastern Nicaragua appears fair.
Water analysis integrated with the existing knowledge of the geologic
framework of an area provides supplementary information t o assist the
exploration geologist in solving geologic problems on both a local and a
regional scale. Isoconcentration maps showing regional variations in the total
solids content of the waters within a given stratigraphic unit are important.
Inorganic water analyses data are useful in the correlation of porous zones,
and benzene analysis is a promising hydrocarbon exploration tool (Noad,
1966).
Maps were prepared delineating: (1) surface outcrop areas of Upper
Cretaceous rocks; (2) axial lines of Upper Cretaceous anticlinal structures;
(3) zones of water types; (4)zones of water groups; and (5) zones of mixed
waters. A diagram of chemical composition of the waters was also prepared.
Using these maps, Galin and Plyushchenko (1963) selected areas in Dagestan
that are favorable for the accumulation of oil and gas.
322
Reviews
Gerard and Feug&re (1969) concluded that geochemical exploration
techniques are useful in offshore areas. Kroepelin (1967)reviewed geochemical prospecting as applied to petroleum and found that several companies had success ratios up to 59% with it in exploration. Johnson (1970)
states that success ratios of about 35% can be attributed to the use of an
inorganic technique of prospecting for oil and gas. The method is useful in
locating stratigraphic trap accumulations and is based on the postulate that
heavy-metal salts concentrate in the soil profile as a result of vertical migration of waters above an accumulation of oil.
According to Boyle and Garrett (1970),geochemical prospecting will
play an ever increasing role in the discovery of hidden ore deposits and
accumulations of hydrocarbons. The methods need no longer be sold since it
has now been generally recognized that they are the only direct approach to
the problems of mineral, oil, and natural gas exploration. The methods are
direct and have generally proved most successful when applied in conjunction with geological and geophysical exploration techniques.
Geochemical methods applied t o petroleum prospecting have not reached
their potential, expecially in the United States.
Karaskiewicz (1966)discussed the geomicrobiological and hydrochemical
research done by the Polish Petroleum Institute in 1962-63 in the LubelNadbuzan region. Specific methods such as the determination of gas dissolved in water were applied in this area, and 215 water samples were studied
from the 9,500-km2 area. Anomalies produced by the bacterial activities
which oxidize methane, propane, and butane were determined. Where
methane was present, the bacterial microflora activity was lowest; where the
biological activity was high, methane was absent.
Important aspects of geochemical prospecting are : (1)analytical methods;
(2)transport mechanisms of the hydrocarbons; (3)anomalies associated with
hydrocarbon accumulations; (4) statistical treatment of the data; and (5) the
final result. Significant findings are mapped and interpreted to locate a target
area for drilling (Kroepelin, 1967).
Case study of the Delaware sand (Bell Canyon formation), Texas, by Visher
(1961)
Preliminary work was carried out on the relation of sapropelic material
found in both dark shales and laminated silts, and the oil occurring in reservoir rocks. The study indicated that the frequency distribution of the
radicals, - benzene, straight chain, CH3, and CH2 -, was identical in both
the black shales and the residual crude present in oil saturated reservoir
rocks. The entire sequence of Permian rocks from the Bone Springs Limestone through the Lamar Limestone member of the Bell Canyon formation is
composed of dark organic sediments, deposited in a reducing environment.
3 23
The total quantity of the sapropelic material available for the formation of
oil was not determined, but 1%would be a conservative estimate, indicating
that source material in the Delaware Basin is of sufficient quantity t o
produce volumes of oil greater than presently discovered. The oilfields which
have been discovered in the basin primarily are confined t o the upper porous
and permeable sands of the Bell Canyon formation. The present distribution
of oil appears t o be controlled by hydrodynamic conditions. Therefore, the
tracing of the times and paths of migration is dependent upon reconstructing
the paleohydrodynamics.
324
-z-
325
246 k g A q cm
Fig.10.7. Relationships of hydrodynamic gradients to permeability; I = decreased hydrodynamic gradient because of increased permeability; 2 = increased hydrodynamic gradient
because of decreased permeability; 3= average hydrodynamic gradient; 4 = decreased
hydrodynamic gradient.
invade the water-filled rock pores. Finally, the entry pressure of the barrier
rock is greater than the invading force of the oil and migration ceases.
The downdip hydrodynamic flow increases the efficiency of the trap by
reducing the buoyancy effect of the oil. The hydrodynamic enforcement of
stratigraphic traps can increase the oil column many times over what it
would be under hydrostatic conditions and probably accounts for the development of commercial stratigraphic oil accumulations in the Delaware Basin.
Formation waters
The initial approach in the study of stratigraphic problems within the Bell
Canyon formation was by the use of formation waters. Over 300 samples of
formation water were collected, analyzed, and processed by computer techniques. Data collected in this manner were posted on maps (Fig.10.8-10)
and contoured. Several aspects of the waters (relative concentration percentages of SO4,Mg, Ca, and total solids) show systematic variations over the
basin. Variation in these parameters is related t o proximity to outcrop and
the degree of transmissibility of the formation. The highest sulfate content is
near the outcrop belt t o the west; the calcium and total dissolved solids
concentrations increase toward more impermeable rocks and areas of low
circulation. In the center of the basin, the waters are characterized by very
high total dissolved solids, high calcium, and low sulfate content, but in the
porous and permeable fingers near the outcrop, salinites are low and sulfate
is high. All gradations between these two extremes exist in the Bell Canyon
formation. In areas where the sand fingers pinch out very rapidly into lowpermeability sediments, the transition between these two extremes of water
composition may take place in a matter of a few well locations. An excellent
3 26
327
328
d
W
329
33 0
331
Kilometers
55.60
I:l,wom
LEGEND
Fig.lO.11. Potentiometric surface map of the Arbuckle formation group in South Kansas,
North Oklahoma, and southeast Missouri.
332
Fig.10.12. Map of the chloride concentrations (mg/l) in the Arbuckle formation waters in
Kansas and Oklahoma
of the upper Wilcox formation, while Fig. 10.16 illustrates the salinity variations at the top of the upper Wilcox formation. Fig. 10.17 is a salinity map
of the lower Tuscaloosa and Woodbine formations, again most of the trapped petroleum is found in areas where the more saline waters occur and in
transition areas.
Salinity maps are useful as a primary tool in petroleum exploration because they provide information concerning sand fingering, diagenetic changes
that affect reservoir and source rocks, and stratigraphic traps. Occurrences of
petroleum accumulations often correlate with salinity transition zones, i.e.,
where the salinity ranges from 50,000 mg/l to 100,000 mg/l.
EEL
S d V N IZIBLVM NOILVNIZIOd
334
Fig.10.15. Salinity concentrations in waters taken from the base of the Upper Wilcox
formation in portions of Texas, Louisiana, Arkansas, and Mississippi.
Fig.lO.16. Salinity concentrations in waters taken from the top of the Upper Wilcox
formation in portions of Texas, Louisiana, Arkansas, Mississippi, and Florida.
CONCLUDING REMARKS
335
LEGEND
II
Greater than
im,ooo
Fig.lO.17. Salinity concentrations in waters taken from the Woodbine (Dexter) and
Lower Tuscaloosa formations in .portions of Texas, Oklahoma, Arkansas, Louisiana,
Mississippi, Georgia, South Carolina, North Carolina, and Florida.
Concluding remarks
Organic acid salts, petroleum hydrocarbons, and other organic compounds
are soluble in water. The ionic composition, the pH, and the Eh of the water
influence the solubilities of the organic compounds. The aqueous solubility
of petroleum hydrocarbons increases with increasing temperature and pressure, and decreases with increasing water salinity. The aqueous solubility of
organic acid salts increases with increasing pH.
A mechanism for the migration of petroleum or petroleum precursors,
therefore, is water. It is known that petroleum hydrocarbons are generated
from organic-rich rocks. The organic material in the petroleum source rocks
is transformed by physicochemical reactions into petroleum precursors
and/or hydrocarbons which are solubilized by water. The water phase moves
the solubilized organics from the source to the reservoir where, because of
temperature, pressure, salinity, pH, filtration, or organic salting-out
phenomena, the organic phase separates from the water.
In the reservoir the petroleum precursors and/or hydkocarbons mature to
crude oil and gas, primarily because of temperature and time. Thermal alter-
336
ation proceeds both in the fine-grained source rock and in the reservoir at
temperatures above 115OC by abiogenic reactions. With increasing temperature the quality of the crude oil improves; however, at higher temperatures
the crude oil is destroyed, leaving methane and pyrobitumen.
The primary mechanism in the migration of petroleum involves water,
therefore, it follows that knowledge of certain characteristics of the water is
useful in exploration for oil and gas. The chapters Classification of oilfield
waters, and Some effects of water upon the generation migration, accumulation, and alteration of Petroleum discuss some of these characteristics.
Fig. 10.18 illustrates some characteristics related to waters that are likely to
indicate an oil or gas accumulation, and some characteristics related t o
waters that are likely to indicate a dry reservoir.
/2
a type water
(a)
Fig.lO.18. Genetic indicators in a water associated with an oil and gas accumulation (a)
compared to indicators in a water associated with a dry reservoir (b).
REFERENCES
337
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344
GEOPRESSURED RESERVOIRS
Dakota.) Normal pressure is that which is normal for the particular area
involved and is related t o the salinity of the reservoir water, rock types, and
geologic setting, but in general, it is that pressure exerted by a column of
water from the surface t o the observed subsurface formation, which is equal
to and will balance the subsurface formation pressure. Abnormally high
pressures are those which exceed this normal hydrostatic head.
Geostatic ratio
Abnormal pressures can be expressed in terms of a geostatic ratio,
which is the ratio of the observed fluid pressure in a subsurface formation t o
the overburden pressure of the overlying sediments. This load at a given
m down t o depths of more than
depth is approximately 0.231 kg
6,100 m, because the density of rocks changes slowly with depth (Pennebaker, 1968). Any abnormal pressure will therefore have a geostatic ratio
in the Gulf Coast area and between
between 0.0327 and 0.0703 kg
in the Rocky Mountain area.
0.0304 and 0.0703 kg
Compaction model
The compaction concept was demonstrated using a model consisting of
perforated metal plate separated by metal springs in water and enclosed in a
cylindrical tube (Terzaghi and Peck, 1948). The springs were used to
simulate communication between deposited particles and with the initial
pressure upon the upper plate, the springs d o not move because all of the
pressure is supported by the water, assuming that water does not escape
from the system. Relating the fluid pressure (FP) t o the total pressure (TP)
one can derive an equation X=FP/TP to record various formation pressures
(X)t o determine the geostatic ratio using the model.
345
minerals and shales. The shales are primarily clay minerals with flat or
tabular grain shapes; with additional overburden, the pressure packs the
grains closer together, with a resultant expulsion of water from the intervening spaces. In the early stages of compaction, the shale possesses high
porosity and permeability, and the expelled water always flows to areas of
least resistance and pressure (often porous sand). As the overburden increases, the porosity and permeability of the shale decrease until equilibrium
is approached and the pressure in all directions is equal. A t this point,
expulsion of additional water is limited. Tectonics, of course, could alter the
subsurface environment.
Deposition and sedimentation of sand are somewhat different because the
sand grains are in contact in the first stage and sand compaction is about
complete with deposition. However, reduction of porosity can occur by: (1)
solution of the sand grains at contact points; and (2) rearrangement of the
grains because of very high pressures.
Clay beds separating aquifers are often referred to as semipermeable membranes. Such beds can separate aquifers containing waters of different salinities, causing a hydrostatic head in the direction of the more saline water.
Fig. 11.1. Sand dikes in the Simpson Sand formed by the actiqn of highly pressured
subsurface waters forcing the lighter colored sand intrusively into the primary sandstone.
The primary sand was formed from white beach sands during Ordovician time.
346
GEOPRESSURED RESERVOIRS
347
Fig. 11.2. Slash lines showing the general area in Louisiana where the samples were
obtained.
Previous work in the area suggested that the abnormally fresh waters were
found in the same part of the section as were the abnormally high pressures
(Dickey et al., 1968). The general locations of the wells are shown in Fig.
11.2. They were from the South Lewisburg, Church Point, Branch, South
BOSCO,North Duson, Duson, Ridge, and Andrew fields, all in Acadia, and
Lafayette Parishes, Louisiana. The water samples were analyzed chemically
by using the procedures published by the American Petroleum Institute
(1968). The analytical data are summarized in Table 11.1.
A subsurface cross section, Fig. 11.3, was constructed in a general northsouth direction showing the stratigraphy and structure across seven oilfields
in the area of study (Fajardo, 1968). The initial pressures of the shallower
reservoirs are normal. However, below 2,450 m many reservoirs contain
fluids with abnormally high pressures. The 4.9-m amplified normal curve was
used to recognize the first appearance of abnormal pressures in the shale
section. The fluid pressure gradients were estimated following the method
described by Hottmann and Johnson (1965). Shale resistivity and fluid pressure gradient versus depth were plotted for 50 wells in different fields of the
study area, and of these, 22 are included in the cross section.
All of the 41 waters belong t o the chloride-calcium class of Sulin (1946),
and none has the composition of meteoric water. The principal cation is
sodium, although the concentration of calcium is always high. In some of the
more concentrated brines, the calcium concentration is nearly 40,000 mg/l
and constitutes over half the reacting value of the sodium. Magnesium is
variable in amount, and in two samples it is absent. Chloride is the predominant anion, amounting always t o more than 49.5% of the total reacting
values. Sulfate usually is absent and never is present in concentrations greater
than 0.5% of the total reacting value.
In Fig. 11.3, the top of the section is 2,100 m below sea level. The electric
logs indicate the lithology, which is quite sandy down t o a depth of 2,700 m
TABLE 11.I
Formation-waters sample locations, constituents found in the waters, shale resistivity (SR),and fluid pressure gradients (FPG)
Sample Location o f
number of well
(S-Twp-R)
1*I
21
3*
41
5*1
6
7
8
9
10
73-105-34E
2l-lOS-03E
2*lOSFo3E
20-10S-aE
17-10S43E
O8-lOS43E
25-07S43E
25-07603E
11
12
13
14
15
16
17**
18
19
20
21
22*
23
24*
25
26
27
28
29
30
31
32
33*
3483
35*3
36
37
38
39*3
40
41*3
* Abnormal pressure.
Depth
(m)
Zone
Specific
gravity
Concentration (mg/l)
(60/600F)
CI
4,66+4,664
3,643-3,645
3,625-3,627
3.613-3,615
4,060-4,063
3,047-3.049
3,325-3,327
3.293-3.296
1.035
1.062
1.057
L. Camerina
1.059
U. Camerina
1.085
Bolivina-mex
Discorbis
1.045
1.060
U. Tweedel
1.069
L. Tweedel
U. Nodosaria
1.083
Daigle
1.051
1.065
U. Nodosaria
1.069
Tweedel
1.062
Tweedel
1.128
Struma
Frio
1.061
Nodosaria
1.149
Klumpp D
1.090
Frio
1.058
Frio
1.058
Frio
1.057
1.144
Frio
1.090
U. Texana
U.Texana
1.092
1.220
Frio
1.202
Frio
l.lS3
Frio
1.139
Nodosaria
1.070
Marg howei
1.144
Homeseeker
1.145
Nodosaria A
Horn-eker D-4 1.088
1.055
Klumpp E
1.089
Brookshire
Brookshire
1.089
Brookshire
1.082
Brookshire
1.089
Nodosaria
1.140
Homeseeker 2-D 1.120
1.069
Marg tex
1.082
U. Moicene
1.050
Marginulina
Bolivina-mex
U. Camerina
39,000
55,600
56,600
50,000
72.800
33,300
51,700
58,000
50,900
45,300
45,600
57,900
52,600
116,000
50,900
135,000
79,300
46,600
47,900
45,800
125,000
84.500
80,300
201,000
184,000
111,000
119,000
61,600
100,000
109,000
80,000
44,400
77,500
78,000
72,300
75,400
129,000
120,500
55,500
74,400
49,700
HCO3
387
541
826
630
448
503
180
363
507
545
574
586
579
322
330
92
334
741
788
694
135
419
363
0
0
112
76
550
66
73
270
244
171
206
234
203
80
240
539
249
482
SO,
0
407
234
38
tr.
50
0
tr.
33
0
tr.
tr.
0
0
67
223
0
60
72
ND
0
122
tr.
352
tr.
ti.
0
0
0
SR at
FPG
spl. depth (kg cm-2
49
62
62
37
43
32
18
26
35
28
29
26
34
38
23
52
48
46
48
44
47
40
45
75
67
42
52
67
42
0 39
77 34
130 36
0 18
0 18
0 33
0 18
0 41
0 43
102 52
0 26
8 8 43
Mg
Br
Na
Ca
35
61
52
57
81
37
21
41
70
38
35
56
45
128
43
154
169
40
52
47
64
20
62
213
204
94
117
18
22
21
21
19
16
15
18
23
18
17,800
32,300
34,200
29,500
41,100
19.200
34,800
34,400
27,500
1,070
78
2,210
369
1,380
213
1,380
194
3,850
583
1,390
224
2,730
544
2,020
194
3,050
719
2,310
167
2,950
447
2,660
389
1,570
0
21,600 2.180
1,890
408
15,200 1,270
2,950
447
2,660 1,010
2,180
303
ND
ND
15,700
159
7,390
565
3,300
972
38,800 2,140
33,200 5,770
14,300
428
18,400 1,200
3.610
17
18,300 1,090
14,400
700
2,760
35
1,510
447
836
3,530
3,270
972
3,270
564
3,370
894
4.560
0
5,610 564
3,210
136
2,950
855
1,780
141
14
201
71
110
70
81
82
58
162
174
134
40
79
60
22
25
20
26
18
24
74
23
21
22
23
22
20
18
19
24
28
5
21
21
34
30
21
19
18
19
24
38
26
18
35
26,000
24,900
33,300
31,700
49,600
29,600
66,800
46,400
24,700
26,600
ND
61,900
45,800
45,800
80,600
68,900
53,600
52,700
35,200
40,600
51,800
47,800
25,800
44,200
44,400
41,200
42,600
77,800
68,800
32,500
42,800
29,600
Li
Sr
518
247
200
204
267
85
208
230
162
134
262
in1
192
427
31 5
813
427
172
166
157
830
324
376
782
640
798
771
137
1,150
631
392
166
236
235
294
232
ND
375
176
264
71
10
7
6
6
6
3
4
5
6
4
4
4
5
9
9
9
10
ND
ND
ND
ND
ND
P:D
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
5
4
15
7
9
17
17
12
18
5
17
15
10
5
2
2
3
2
ND
5
5
2
Ba
ND
ND
ND
YD
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
0
50
0
5
0
5
0
8
0
19
ND ND
0
33
ND ND
ND ND
ND ND
ND ND
ND ND
N D l ND
ND ND
0 110
ND ND
140 97
128 109
265
41
171 102
ND ND
ND ND
0
7
195 85
0
4
6)
NH4 organic
acid as
acetic
246
295
238
650
178
200
538
301
362
279
210
254
364
218
230
250
202
377
206
96
243
110
142
294
282
295
279
180
222
368
349
195
219
214
258
306
152
295
179
167
160
84
48
96
72
96
120
24
76
24
96
72
96
120
144
48
24
144
120
96
72
48
96
144
48
120
48
24
168
72
96
24
12
96
624
144
48
ND
96
192
432
312
0.77
0.59
0.62
ND
0.38
1.1
ND
ND
1.02
0.83
0.97
ND
ND
0.90
ND
ND
0.60
0.84
ND
1.o
0.94
0.35
0.70
0.50
0.35
1.4
1.o
0.38
1 .o
ND
ND
0.83
ND
ND
ND
ND
0.95
0.92
0.65
ND
0.57
0.185
0.159
0.157
ND
0.195
0.107
ND
ND
0.107
0.107
0.107
ND
ND
0.107
ND
ND
0.157
0.107
ND
0.107
0.107
0.191
0.131
0.191
0.203
0.107
0.107
0.193
0.107
ND
ND
0.107
ND
ND
ND
ND
0.107
0.107
0.152
ND
0.16X
?6
*33a34
4.5
il
30
40
50
60
I
70
357
KEY
X AbnzDressure
Normal pressure
80
90
100
110
120
I D
CHLORIDE, g / l
Fig. 11.4. Plot of the depth of the wells versus concentrations of chloride in the formation waters.
--I
2.5
33.
/
KEY
X Abnormal pressure/
?Normal presauro
3p
034
0.5
BICARBONATE, p/l
Fig. 11.5. Plot of the depth of the wells versus concentrations of bicarbonate in the
formation waters.
GEOPRESSURED RESERVOIRS
358
in the north to 3,050 m in the south. Below this depth, the sands become
less abundant and less widespread.
The first abnormal pressure as calculated from shale resistivity is indicated
by an arrow. The location of a producing horizon from which a water sample
was taken is shown by the sample number in a circle. When the water sample
was taken from a nearby well, not shown on the section, it was projected
onto the section and shown as the sample number inside a square in Fig.
11.3.
There is a general tendency for the dissolved salt concentration of the
water samples t o increase with depth. This is shown in Fig. 11.4, which
shows chloride plotted against depth. Since chloride is the predominant
KEY
)< Abnormal pressure
0 Normal pressure
25
K
27
24
\
I
10
CALCIUM, g/l
Fig. 11.6. Plot of the depth of the wells versus concentrations of calcium in the formation
waters.
359
Normal pressure
x
Abnormal pressu&e-Solution
100 O\&o
0%
'0
a0 -
\
0
"\
"
O \
\
0
60-
\
"\
.\O
A
0
0
0
SODIUM, g/l
Fig. 11.7. Comparison of some brines of a bittern type from the Michigan Basin with
some brines from some normal and abnormally pressured reservoirs in Louisiana.
GEOPRESSURED RESERVOIRS
36 0
I50
Normal pressure
x Abnormal pressure
I25
I00
2
5-
75
X
In
50
- x
25
X*
Sodium=mg/l
0.05
Na
+ 40 mg/l
010
BROMIDE,
Ca
0.15
0.20
!5
g/l
Fig. 11.8. Plot of Na versus Br from some brines from normal and abnormal pressured
reservoirs in Louisiana.
Four of the waters from high-pressure sands (17, 22, 24, 25) have normal
concentrations of dissolved solids for their depth. The other waters from
high-pressure sands (1-5, 13, 28, 39, 41) have lower concentrations than
normal. They also have less calcium, more bicarbonate, and a higher Cl/K
ratio.
About 80% of the material in the Gulf Coast shale is clay. Assuming that
the waters have reacted with montmorillonite, there should be a direct relationship of calcium t o sodium. Plotting the calcium and sodium data in
Table 11.1 plus some data for some brines from the Michigan Basin (as
shown in Fig. 11.7) indicate that a relationship of calcium t o sodium does
exist in the Gulf Coast waters and that they probably have reacted with
montmorillonite. Fig. 11.7 also indicates that the Gulf Coast waters are not
an altered relict bittern as are the Michigan Basin brines.
In an ion exchange reaction with montmorillonite, 2 moles of sodium are
exchanged for 1 mole of calcium, therefore, if salt is redissolved the bromide
content in solution should be proportional to the original redissolved solu-
36 1
-Re-solution solt
in pure water
Southwestern Louisiano brines
\*
*\
I
I
9vaporoting
seo water
25
\*
*\
f *\
I
I
.3:
+%mg/l calcium
2
BROMIDE, g/l
m>
Fig. 11.9. Replot of Na' versus Br of the Louisiana brines (Fig. 11.8);plus data for relict
Michigan brines, evaporating sea water, and resolution of salt. Resolution of salt is an
important control for the Louisiana brines
362
GEOPRESSURED RESERVOIRS
normally pressured sandstones range from 600 to 180,000 mg/l, while in the
geopressured sandstones the range is from 16,000 to 26,000 mg/l. The dissolvedsolids in the water in the pores of the shales adjacent to normally
pressured sandstones are lower than the dissolved solids in the water in the
sandstones, but the dissolved solids concentrations are similar in the waters
of the adjacent high-pressure sandstones and shales. The concentration order
> HC03- > Cl-, and in normally pressured
in shale pore water is
sandstone water it is C1- > HC03- > S 0 4 - 2 .
The temperature gradient in the geopressured zone is about O.8l0C/25 m,
while in the normally pressured zone it is about 0.44OC/25 m. This change in
temperature gradient is believed t o be related t o the porosity, where a
greater porosity causes a decreased thermal conductivity (Schmidt, 1973).
The clay mineral composition in the geopressured zone is predominantly a
nonexpandable type, while in the normally pressured zone montmorillonite,
an expandable type, frequently occurs. This change is believed to be related
t o the temperature, and the heat allows the release of water from the clays at
temperatures of about 93-104OC. This released water will dilute the pore
water and cause the dissolved solids to decrease.
The total amount of water released by Gulf Coast shales in geopressured
zones is about 13%of the total in the system (Schmidt, 1973). This can be a
cause of the lower salinity of the waters found in the geopressured zones.
Fowler (1970) studied the Chocolate Bayou field in Texas and evaluated
the relationships between geopressure and the migration and accumulation
of hydrocarbons. He concluded that faults tend t o act as barriers separating
fluid systems in the area; however, cross-formational flow occurs with
geopressure causing shale ultrafiltration of the waters. The ultrafiltration
produces salinity variations in the waters. Hydrocarbon accumulation in the
area is controlled by the hydrodynamic flow.
According to Fowler (1970), hydrocarbons are trapped in the upper sands
because of slight pressure differentials across fault traps in the West Chocolate Bayou field. However, in deeper strata, abnormal pressures have caused
hydrodynamic flow and pressures greater than the displacement pressure in
the fault, resulting in no trapped hydrocarbons.
In essence then, sands with pressure gradients greater than 0.20 kgcm-'
m-' in the Chocolate Bayou field do not contain commercial amounts of
hydrocarbons. It also appears that the size of the accumulation may decrease
with increasing pressure gradients up t o about 0.16 kg cm-* m-'. The
accumulation size may increase with pressure gradients in the range of
0.16-0.19 kg cm-2 m-' and then decreases.
Detection of abnormal pressures
Estimation of formation pressures from electrical surveys is related to the
following assumptions, concerning the origin of abnormal pressures (Foster
and Whalen, 1966):
363
364
GEOPRESSURED RESERVOIRS
decreasing travel time with depth, because of the undercompacted formations. To measure the formation pore pressure, plots of equal pore pressure
gradients are compared, by an overlay, to the abnormally pressured interval
travel time depth plots.
Forgotson (1969),by experience with wells in the Gulf of Mexico, noted
that the presence of high background gas and high trip gas, together with
lower than normal shale density, does not necessarily indicate the proximity
of an abnormally pressured reservoir. He believes that a minimum of 200%
increase in the shale penetration rate when drilling is the best available means
to predict abnormal pressures.
A recent series of papers explains how downhole temperatures and pressures can affect drilling (Fertl and Timko, 1972;Timko and Fertl, 1972).
Methods of detecting abnormal pressures, compensating for them, and evaluating the hydrocarbon potential of geopressured strata are discussed.
References
American Petroleum Institute, 1968. API Recommended Practice f o r Analysis of Oilfield
Waters. Subcommittee on Analysis of Oilfield Waters, API, RP 45, 2nd ed., 49 pp.
Burst, J.F., 1969. Diagenesis of Gulf Coast clayey sediments and its possible relation t o
petroleum migration. Bull. A m . Assoc. Pet. GeoL, 53:73-93.
Dickey, P.A., Collins, A.G. and Fajardo, I., 1972. Chemical composition of deep formation waters in southwestern Louisiana. Bull. Am. Assoc. Pet. GeoL, 56:1530-1533.
Dickey, P.A., Shiram, C.R. and Paine, W.R., 1968. Abnormal pressures in deep wells of
southwestern Louisiana. Science, 160:609-615.
Dickinson, G., 1953. Geological aspects of abnormal reservoir pressures in Gulf Coast
Louisiana, Bull. A m . Assoc. Pet. GeoL, 37:410-432.
Fajardo, I., 1968. A Study of the Connate Waters and Clay Mineralogy. M.S. Thesis,
University of Tulsa, Tulsa, Okla., 50 pp.
Fertl, W.H. and Timko, D.J., 1970. Overpressured formations, 2. How abnormal
pressure-detection techniques are applied. Oil Gas J., 68:62-71.
Fertl, W.H. and Timko, D.J., 1972. How downhole temperatures, pressures affect drilling.
World Oil, 174(7):67-70; 175(1):47-49; 175(2):36-39, 66;175(4):45-50; 176(2):
47-50.
Finch, W.D., 1969. Abnormal pressure in the Antelope field, North Dakota. J. Pet.
Technol., 21:821-835.
Forgotson, J.M., 1969. Indication of proximity of high pressure fluid reservoir, Louisiana
and Texas Gulf Coast. Bull Am. Assoc. Pet. GeoL, 53:171-173.
Foster, J.B. and Whalen, H.E., 1966. Estimation of formation pressures from electrical
surveys - offshore Louisiana. J. Pet. TechnoL, 18:165-171.
Fowler, Jr., A.W., 1970. Pressures, hydrocarbon accumulation, and salinities - Chocolate
Bayou field, Brazoria County, Texas. J. Pet. TechnoL, 22:411-423.
Harkins, K.S. and Baugher, 111, J.W., 1969.Geological significance of abnormal formation
pressures. J. Pet. TechnoL, 21:961-966.
Hottmann, C.E. and Johnson, R.K., 1965. Estimation of formation pressures from logderived shale properties J. Pet. TechnoL, 17:717-721.
Jones, P.H., 1969. Hydrodynamics of geopressure in the North Gulf of Mexico Basin. J.
Pet. TechnoL, 21:803-810.
Pennebaker, E.S., 1968. Detection of abnormal pressure formations from seismic field
records. Presented at API Southern Dist. Meet., San Antonio, Texas, March 6-8,
1968, API Paper, No. 926-13C.
REFERENCES
365
Perry, D.R., 1969. A Correlation of Reserves and Drive Mechanisms with Reservoir Pressure Gradients on Geopressured Gas Reservoirs in Southwest Louisiana. M.S. Thesis,
Southwest Louisiana University, Lafayette, La., 54 pp.
Powers, M.C., 1967. Fluid-release mechanisms in compacting marine mudrocks and their
importance in oil exploration. Bull. Am. Assoc. Pet. GeoL, 51:1240-1254.
Schmidt, G.W., 1973. Interstitial water composition and geochemistry of deep Gulf Coast
shales and sandstones. Bull. A m . Assoc. Pet. Geol., 57:321-377.
Sulin, V.A., 1946. Waters of Petroleum Formation in the System o f Natural Waters.
Gostoptekhizdat, Moscow, 96 pp.
Terzaghi, K. and Peck, R.R., 1948. Soil Mechanics in Engineering Practice. John Wiley
and Sons, New York, N.Y., 56 pp.
Timko, D.J. and Fertl, W.H., 1972. How downhole temperatures, pressures affect drilling.
World Oil, 175(5):73-81; 175(6):79-82; 175(7):5*62; 176(1):45-48; 176(4):.
62-65.
Wallace, W.E., 1969. Water production from abnormally pressured gas reservoirs in South
Louisiana. J. Pet. Technol., 21 :969-982.
Young, A. and Low, P.F., 1965. Osmosis in argillaceous rocks. Bull Am. Assoc. Pet.
Geol., 49:1004-1008.
\
+=
+=
-b
+=
+=
+=
+=
+=
-b
+=
2NaC1+ CaSO,
MgClz +CaS04
C 0 2 + H 2 0 + CaCO,
2NaC1+ C 0 2 + H 2 0 + CaCO
2NaC1+ SrSO,
MgC12 + S r S 0 4
2NaC1+ BaSO,
MgC12 +BaS04
H2 + FeS
6H,O + 2Fe2 S3
33J-
33J-1
335.
where ac = the cation activity, a A = the anion activity in the solution, and
SCA = the solubility product of the compound CA. When two salts with a
common cation (CAI and CA2) are in equilibrium in a solution, the following will hold:
36 8
a~~
I ~ A , = &!Al PCA,
If a A l l a A ,
a~~
I ~ A , <SCA,ISCA,.
369
370
371
372
373
5-80 mg/l of BaSO, and 50-800 mg/l of SrS04 were made and used as
reference counting samples for all of the sulfate determinations.
A nonionic detergent (Triton X-100) and toluene emulsion (Patterson and
Greene, 1965) were prepared, whereby l-cm3 sulfate samples in brine could
be counted with greater than 20%efficiency. The emulsion forms a clear gel
and permits a homogenous dispersion of the aqueous phase in the fluor with
no salting out.
Solutions of various salts, such as those usually found in formation waters,
were made up in strengths of 0.005-1.77 molal, and tagged solid barium or
strontium sulfate was added. The chlorides of sodium, calcium, magnesium,
and potassium were prepared, as were solutions of sodium bicarbonate,
sodium borate, and potassium bromide. All of the solutions were stored in
plastic bottles. To determine sulfate solubility, a 20-cm3 portion of one of
the prepared salt solutions was transferred to a small plastic stoppered vial,
and 0.1 g of the solid, tagged sulfate was added. This suspension was shaken
in a wrist-action type shaker for 72 hours and then allowed t o settle a
minimum of 24 hours without opening the vial.
The samples were prepared in duplicate to assure equilibrium, and the
operation was repeated when better precision was needed. The temperature
of the suspension was raised briefly above the stabilized room temperature
(25OC k l 0 C ) with a heat lamp during the shaking period, but no change was
permitted during the last 24 hours nor during the settling period. When the
sample container was opened, it was quickly filtered through a double
Whatman No.42 filter paper, and 1 ml was transferred t o a counting vial
which contained 12 ml of the Triton emulsion and 7 ml of deionized water.
The sample then was counted in a liquid scintillation counter for 50 minutes.
The chelated sulfate standards were counted in the same time period. By this
method, the correction for radioactive decay could be omitted and the
soluble sulfate values determined from a graph of the chelated standards (in
mg/l) versus the counts per minute. Barium was analyzed by emission spectroscopy, but adequate precision at levels of 1 mg/l and less was difficult to
achieve in the presence of ionic-strength salts encountered in some solutions.
Results and discussion of the experimental investigation
The values obtained from solubility measurements are shown in Table 12.1.
The amounts of the alkaline sulfates which dissolve in other electrolyte
solutions are tabulated alongside the total ionic strength of each solution.
Ionic strength is the most useful concept yet developed t o include the combined effects of the activities of several ionic species in a solution. Lewis and
Randall (1923) state, in dilute solutions, the activity coefficient of a given
strong electrolyte is the same in all solutions of the same ionic strength. It
is defined as s = H m 1 2, , where m 1 = the ionic molality, and 2 , = the
charge of the ion in solution, the summation being taken over all ions,
positive and negative. By definition, the activity of the dissolved species
approaches the concentration value (molality) a t infinite dilution.
374
10.0
0.0-
KEY
-
6.0-
4.0
0
x
2.0 -
CoC12
MgC12
No2 84 07
KBr
NaCl
KCI
__
0
v)
m
lI.
1.0
0+
0.8
SO4 Mo Io I i t ies
0.6
_I
a
0.4
J
0
0.2
0.I
0.5
I .o
I .5
2.0
2.5
4 l O N l C STRENGTH
375
5r504
Bas04
major solute system
Bas04
(mg/l)
SrS04
(mg/l)
total ionic
strength
ca Cl2
0.010
0.015
0.020
0.025
0.045
0.050
0.090
0.100
0.136
0.200
0.226
0.300
0.400
0.456
0.500
0.934
1.000
2.000
(5.0)*
6.2
0.03016
7.6
0.06013
11.5
0.15020
15.5
0.30027
17.7
0.60030
16.2
16.3
0.90028
1.20028
16.6
1.50028
(16.3)*
(10.8)*
11.3
2.5
3.00019
6.00004
(2.9)*
5.4
0.02979
6.9
0.05982
(17.3)*
214
247
0.0347
0.0504
295
260
0.0815
0.1403
508
0.2819
590
0.4197
757
0.6959
1,152
1.3947
1,942
1.8438
172
203
233
0.0188
0.0344
0.0499
295
394
0.0805
0.1571
422
0.2324
530
0.2866
731
0.7782
1,063
1.5993
M m 2
0.005
0.010
0.015
0.020
0.025
0.049
0.050
0.074
0.099
0.125
0.196
0.254
0.474
0.525
0.902
1.637
(44.5)*
9.8
0.14927
13.3
0.29693
18.0
0.58831
25.9
1.42244
32.0
33.2
2.70655
4.93257
376
TABLE 12.1 (continued)
Major solute
(molality)
Bas04
(mg/l)
Na Cl
0.010
0.015
0.020
0.025
0.050
0.086
0.100
0.172
0.200
0.257
0.431
0.500
0.869
1 .ooo
1.771
2.000
KCl
0.010
0.015
0.020
0.025
0.050
0.067
0.100
0.200
0.202
0.338
0.500
0.684
1.000
1.396
2.000
5r504
Bas04
major solute system
SrS04
(mg/l)
total ionic
strength
134
149
0.0129
0.0182
172
199
265
0.0288
0.0543
0.0914
332
0.1756
420
525
0.2667
0.4423
699
0.8840
760
1.7875
144
169
0.0131
0.0185
167
0.0286
375
0.0754
396
502
0.2109
0.3492
742
0.7001
802
1.4139
(5.3)*
3.6
0.01006
(5.6)*
4.2
0.02007
5.4
0.05009
(7.3)*
7.1
0.10012
(11.3)*
10.0
0.20017
14.8
0.50025
(22.3)*
20.2
1.00035
(35.7)*
27.2
2.00047
4.2
0.01007
4.9
0.02008
6.3
0.05011
8.6
11.2
0.10015
0.20019
(3.7)*
(25.8)*
16.8
0.50029
21.6
1.00037
27.2
2.00047
377
(3.6)*
(23.9)*
SrS04
(mg/l)
total ionic
strength
4.1
0.01007
152
163
0.0133
0.0186
4.7
0.02008
215
0.0467
6.3
0.05011
262
0.0900
8.2
0.10014
320
0.1335
11.0
0.20019
420
509
0.2207
0.4378
669
0.8812
320
0.0462
600
0.1307
690
0.2100
114
0.0025
Bas04
(mg/l)
XBr
0.010
0.015
0.020
0.042
0.050
0.084
0.100
0.126
0.200
0.211
0.426
0.500
0.866
1.000
2.000
5r504
Bas04
major solute system
16.2
0.50028
21.8
26.7
1.00037
2.00046
6.0
0.03010
7.8
0.06014
12.9
0.15022
21.0
34.8
0.30036
0.60060
2.5
0.00004
Na2 B4 0 1
0.010
0.013
0.020
0.039
0.050
0.065
0.100
0.200
Pure Water
(23.7)*
(33.9)*
Parentheses indicate barium ion and sulfate. ion determinations made separately.
The effect of high concentration of CaClz on BaS04 solubility is indicated by the solid curve of Fig. 12.1. At concentrations of 2 molal, the
BaS04 solubility has dropped t o values close to that of the compound in
pure Hz0. The maximum value is reached between 0.2 and 0.4 molal where
the decline begins. The accompanying broken line of Hg. 12.1, which is a
plot of Ba+2 + SO4-' ions determined separately, shows the reduced solu-
378
-1 IONIC
STRENGTH
Fig. 12.2. Concentrations of saturated SrS04 in strong electrolyte solutions of NaCl, KCl,
and KBr.
- K a = 2.4 x
I
4 IONIC
STRENGTH
379
< 1.95
TABLE12.11
Sulfate solubilities in synthetic brines
~
~~~
Concentration (molal)
brine 1
brine 2
brine 3
Br1-
1.2179
0.0250
0.0206
0.0051
1.3019
0.0125
0.0001
1.7399
0.0374
0.0823
0.0051
1.9650
0.0188
0.0000
2.4359
0.0499
0.0411
0.0193
2.6113
0.0250
0.0001
60
2.57 x D4
1.3600
63
2.70 x D4
2.1038
66
2.83 x
3.0278
813
44.26 x lo4
1.3777
922
50.19 x lo4
2.1239
Na+
Ca+
Mg+
K+
c1-
o4
958
52.18 x lo4
3.0487
380
Brine stabilization
Efforts to stabilize the brines used in petroleum production have been
extensive and successful in many cases, but the complexity of the problem in
other cases is reported. Water treating units are considered necessary in
waterflooding operations, but none fully satisfy the operators apprehension
that there may be plugging within the reservoir. Addition of solubilizing,
chelating, and clarifying agents to the brine has helped, but economics limit
the quantities used. Tests for compatibility of the fluids as they exist in the
formation and in the wellbore give erroneous results because the subsurface
environment cannot be fully duplicated a t the surface.
To aid brine stabilization programs, several studies of the solubilities of
various relatively insoluble compounds have been made as previously discussed. Usually the results of these studies are reported as solubility products of
various pure compounds (CaS04, BaS04, CaCO, , etc.) in the presence of
other ions, dissolved gases, ion pairs, and various sized crystals of the compound under study. Some efforts have been made using mixed cations and
anions in solution with the compound under study, including limited study
of sulfates in sea water or synthetic sea water (Shaffer, 1967). Various easily
measured parameters such as percent chlorides, total solids, and ionic
strength have been plotted against solubility product of the potential scale
former. Very little correlation suitable for direct field application has been
found. For example, the author has measured BaS04 solubility in CaC12,
MgC12, NaC1, and other salt solutions using ionic strength as the common
property. However, a synthetic sea water containing these compounds and
having comparable ionic strength will dissolve double the weight of BaS04 in
milligrams per liter with respect to any solution containing a single salt.
Fulford (1968) and Vetter and Phillips (1970) proposed useful formulas
and graphs t o use in predicting scaling from calcium sulfate. Fig. 12.443 are
included for possible use in predicting potential scale problems from calcium
sulfate, strontium sulfate, and barium sulfate. The figures are plots of molal
solubility versus ionic strength. The advantage of this plot is that the ionic
strength of any given water can be calculated from its chemical composition,
BRINE STABILIZATION
381
IONIC S T R E N G T H
Fig. 12.4. Solubility o f CaSO4 versus ionic strength of aqueous solutions (Ostroff and
Metler, 1966).
12-
KEY
1
IONIC S T R E N G T H
Fig. 12.5. Solubility of SrS04 versus ionic strength of aqueous solutions containing
CaClz, MgClz, NaCl, KCl, and KBr (Davis and Collins, 1971).
382
01
I
a
I
I ,111
0.01 0.02 0.040.0601
I
a2
I IIII
04 060.0 1.0
I , 1 , 1 ,
6 8 3
IONIC STRENGTH
Similar curves can be made using appropriate solubility data for calcium
carbonate and for iron compounds. However, it should be noted that application of this technique only gives an estimation of the maximum solubility
of a compound in waters of similar ionic compositions. Better data on pressure and temperature and how they affect the solubilities are needed before
adequate prediction equations can be developed.
Mixing of subsurface waters
Mixing of surface and subsurface waters results in solutions which are
either saturated or undersaturated with relatively insoluble compounds such
as calcium carbonate, calcium sulfate, strontium sulfate, and barium sulfate.
These compounds are considered because they often are found in scales
formed because of mixing of formation waters.
Hydrodynamic potentials caused by differences in elevation, weight of the
overlying fluids and rocks, secondary cementation of rock pores (Levorsen,
1967), temperature differences, osmotic pressures, and chemical and
physical reactions cause subsurface waters t o move (Hubbert, 1953).Popov
and Goldshteyn (1957) described a large hydrodynamic system of descending fresh water and ascending saline water which could mix to form a
fresh-saline water mixture. Henningsen (1962)found that recharge waters
into Trinity aquifers were two types of water from strata of different
lithology and with basinward movement of the waters they mixed to form a
third type of water. Mixing of fresh waters with encroaching sea water
occurs according t o Kohout (1960),Columbus (1965),and Upson (1966).
383
"--"I
z
0 1.200I4
I
I 1)
I
I
2.0
3.0
TOTAL IONIC STRENGTH
Fig. 12.7. Solubility of strontium sulfate versus ionic strength of the solution (J. Biles,
written communication, Cities Service Oil Company, Tulsa, Okla., 1972).
384
TABLE 12.111
Composition of a brine that does not contain a stoichiometric combining weight ratio
of strontium and sulfate*
Ion
Na+
mg/l
s04-'
49,000
220
11,500
2,400
25
1,000
101
106,140
170
Total
170,556
K+
ca+'
Mg+'
Ba+'
sr+'
Fe"
c1-
me/l
Molalit y
2,130
6
574
197
< 1
23
4
2,990
4
2.24
0.00589
0.303
0.104
0.00018
0.012
0.00189
3.15
0.00189
Total ionic strength = 3.54;density at 22OC = 1,120 g/l; grams H20/1= 950.
Plotting the data in Tables 12.1 and I1 for the solubility of SrS04 in
sodium chloride and synthetic brine solutions as the product of the molalities of strontium and sulfate versus total ionic strength, as shown in Fig.
12.8,indicates that the brine in Table 12.111 is undersaturated in SrS04 by
d(280 x lo-') - (227 x lo-') molal. This method is in error to the extent
that the SrS04 solubility is affected differently by the ions in the brine in
Table 12.111 than by the ions in the brines shown in Table 12.11. Nevertheless, this approach is valuable in that a reasonable estimate can be made of
the degree of undersaturation of SrS04.
Now consider the advisability of mixing the brine shown in Table 12.111
with another brine which contains less dissolved solids and a comparable
percentage of cations as sodium and about 1,850 mg/l of sulfate. To determine the solubility of SrS04 in various mixtures of waters, the product of
the weighted average molalities of strontium and sulfate was determined for
240
385
200 -
KEY
In NaCl solutions
A In synthetic brines
0
3
TOTAL IONIC STRENGTH
Fig. 12.8. Solubility of strontium sulfate as a product of the molalities of strontium and
sulfate versus the ionic strength of the solution (J. Biles, written communication, Cities
Service Oil Company, Tulsa, Okla., 1972). Filled square shows the product of the
molalities of (Sr )(SO4 ) in Table 12.111 brine.
6
t
J
9
E
a
aw.
600
0
Ia 500
a
-514
g / kiloliter
I-
3
a
2
* 200
??
m
100
100
TABLE 12.X BRINE,
percent
Fig. 12.9. Plot of the supersaturation of a mixture of the brine shown in Table 12.111 with
a brine containing 1,850 mg/l sulfate versus the Table 12.111 brine in percent (J. Biles,
written communication, Cities Service Oil Company, Tulsa, Okla., 1972).
386
each mixture and compared with the comparable values in Tables 12.1 and I1
and Fig. 12.8. It was determined that a maximum supersaturation of 514
g/kl occurred when the mixture contained 60% of the brine shown in Table
12.111 as illustrated in Fig. 12.9. Mixtures containing less than 9%and more
than 97% of the brine shown in Table 12.111 were undersaturated in &SO4
when mixed with a brine containing 1,850 mg/l of sulfate. The same error
mentioned in the above paragraph will be present, but the correction would
not greatly affect the value obtained using solubility data from Table 12.11.
References
Akin, G.W. and Lagerwerff, J.V., 1965. Calcium carbonate equilibria in aqueous solutions
open t o the air, I. The solubility of calcite in relation to ionic strength; 11. Enhanced
solubility of CaC03 in the presence of Mg and SO4-. Geochim. Cosmochim. Acta,
29: 343-360.
Blount, C.W., 1965. The Solubility o f Anhydrite in the Systems C a S 0 4 - H z 0 and
CaS04-NaCl-H2 0 and Its Geologic Significance. Ph.D. Dissertation, University of
California, Riverside, Calif., 179 pp.
Blount, C.W. and Dickson, F.W., 1969. The Solubility of anhydrite (CaS04) in NaCl-HO
from 100 t o 45OoC and 1 to 1000 bars, Geochim. Cosmochim. Acta, 33:227-245.
Columbus, N., 1965. Viscous model study of sea water intrusion in water table aquifers.
Water Resour. Res., 1:318-323.
Davis, J.W. and Collins, A.G., 1971. Solubility of barium and strontium sulfates in strong
electrolyte solutions. Environ. Sci TechnoL , 5:1039-1043.
Ellis, A.J., 1963. The solubility of calcite in sodium chloride solutions at high temperatures. A m . J. S c i , 261:259-267.
Frear, G.L. and Johnstonb J., 1929. Solubility of calcium carbonate (calcite) in certain
aqueous solutions a t 25 J. A m . Chem. SOC.,51:2082-2093.
Fulford, R.S., 1968. Effects of brine concentration and pressure drop o n gypsum scaling
in oil wells. J. Pet. Technol., 20:559-564.
Gates, G.L. and Caraway, W.H., 1965. Oil well scale formation in waterflood operations
using ocean brines, Wilmington, Calif. US.Bur. Min. Rep. Invest., No.6658, 28 pp.
Glater, J., Ssutu, L. and McCutchan, J.W., 1967. Laboratory method for predicting
calcium sulfate scaling thresholds, Environ. Sci Technol, 1:41-52.
Glew, D.N. and Hames, D.A., 1970. Gypsum, disodium pentacalcium sulfate, and
anhydrite solubilities in concentrated sodium chloride solutions, Can. J. Chem.,
48:3734-3738.
Henningsen, E.R., 1962. Water diagenesis in Lower Cretaceous Trinity aquifers of Central
Texas. Baylor Univ. Geol. Studies, Bull., 3~38.
Hubbert, M.K., 1953. Entrapment of petroleum under hydrodynamic conditions, Bull.
A m . Assoc. Pet. Geol., 37:1954-2026.
Kohout, F.A., 1960. Cyclic flow of salt water in the Biscayne aquifer of southeastern
Florida, J. Geophys. Res., 65:2133-2141.
Levorsen, A.I., 1967. Geology o f Petroleum (revised by F.A.F. Berry). W.H. Freeman,
San Francisco, Calif., 724 pp.
Lewis, G.N. and Randall, H.M., 1923. Thermodynamics. McGraw-Hill, New York, N.Y.,
723 pp.
Lucchesi, P.J. and Whitney, E.D., 1962. Solubility of strontium sulfate in water and
aqueous solution of hydrogen chloride, sodium chloride, sulfuric acid and sodium
sulfate by the radiotracer method. J. AppL Chem. (London), 12:277-279.
Neuman, E.W., 1933. Solubility relations of barium sulfate in aqueous solutions of strong
electrolytes. J. Am. Chem. SOC.,55:879-884.
REFERENCES
387
In the early days of the oil industry, oilfield brines were allowed t o flow
by natural drainage into streams until it was noted that some of the once
good fishing streams contained less fish. Fur-bearing animals had disappeared
in these areas and dead trees and barren soils now bordered these same
streams that once had luxurious vegetation. A few years prior t o 1935,
litigation pertaining t o pollution of fresh water was taking a heavy toll from
oil operators. In certair, older oil producing areas, extensive plots of ground
still are barren, with no living vegetation. The litigations against oil operators
combined with legislation for fresh-water protection to force better disposal
techniques.
At first, evaporation ponds were employed; however, usually more brine
drained into fresh-water aquifers than evaporated. Until recently a widely
employed practice for disposal was the dumping of oil brines into salt-water
bodies when they existed nearby. This disposal method was practiced along
the Gulf of Mexico and in California. Authorities in these areas insisted that
oil separation be highly efficient to prevent damage to fish and oyster populations. Recently the State pollution boards have ruled that oilfield brines
can no longer be dumped into surface salt-water bodies. In California excess
oilfield waters are being injected into porous subsurface formations as
rapidly as the injection systems can be constructed.
The Plains States are not only situated in a hard water beit, but seldom
have they had an overabundance of usable or surface ground waters. For this
reason, State legislatures passed laws for the protection of fresh-water supplies, allowing the return of oilfield brines t o subsurface formations and
allowing the repressuring or waterflood of oil properties with salt water.
Subsurface brine disposal has since become the common practice. Since the
laws were passed to allow subsurface disposal, more legislation has both
forced such disposal and set up tight controls for it. A survey of cost data on
subsurface injection in 1968 showed that subsurface disposal costs ranged
from 6.6 to 19.8 cents per m3. These figures were based on operating costs
plus 5-year amortization.
Costs vary with the amount of treatment necessary before injection, the
number of production wells per injection well, and the costs of drilling
injection wells or the depth of the injection formation. The depths of
disposal wells normally encountered required no injection pressure. The
brines flow readily into the receiving formations under the gravity head
alone.
390
Most of the 1.23 billion m3 of saline water that is produced yearly with
petroleum is an expense t o oil producers even though some of these waters
contain salts yielding valuable elements which might be economically recovered (Angino, 1967). Elements found in some brines in economic concentrations are magnesium, calcium, potassium, lithium, boron, bromine, and
iodine. Many of them are recovered by chemical companies from sea water,
salt lakes, and subsurface saline waters (Collins, 1966; Brennan, 1966).
The recovery of minerals from saline waters dates back to the first time
that someone precipitated a compound from a salt solution. Precipitation is
the most used separation process employed in separating minerals from sea
water or subsurface brines. Research continued on the separation methods
which show economic promise in mineral separation from saline waters.
The Office of Saline Water, U S . Department of the Interior, supports
research aimed at mineral recovery processes to be integrated with freshwater plants. The object of this research is to reduce the cost of the
produced fresh water by selling the extracted minerals at a profit. Now
consider mineral recovery as a means of reducing the cost of oilfield brine
disposal. There are additional advantages t o mineral removal other than
profits from the sale of the mineral. For instance, magnesium in sea water
causes great expense because of scale formation in fresh-water plants.
Recovery of iodine and bromine from oilfield brines
Iodine
Iodine consumption in the United States exceeds domestic production.
The Dow Chemical Company is the sole domestic producer of iodine. 75% of
our domestic consumption is imported from Japan and Chile (Miller, 1965).
Chilean nitrate deposits furnish most of the worlds supply of iodine. The
United States and Japan obtain iodine from subsurface brines. In Michigan,
Dow Chemical liberates iodine from brines by chlorination and blows t h e
iodine out with air. Japan recovers iodine from brine by the cuprous iodine,
electrolytic, or active carbon methods.
In the United States, iodine was discovered in an oilfield brine by C.W.
Jones in Louisiana in 1926. The Dow Chemical Company and Jones combined t o produce iodine from a brine well in Louisiana in 1928. At that
time, iodine sold at a price between $9 and $11per kg. In 1929 General Salt
Company began extracting iodine from oilfield brines in California. General
Salt halted operations when Chile cut the iodine price to $3.30 per kg. In
1931 Deepwater Chemical Company began to produce iodine from oilfield
brines in California. Deepwater Chemical halted recovery of iodine from
brines in the late 1950s.
The Dow Chemical Company moved its iodine recovery operation from
Louisiana to the California oilfield brines in 1932. The move was made for
two reasons. The first reason was that California brines contained 60 ppm
391
Bromine
Bromine is another element that is recovered from oilfield brines. One
plant that is located in Arkansas recovers bromine from the Smackover
formation in the Catesville field. The bromine recovery project was originally
included as part of the plans to unitize the field in 1956.
TABLE 13.1
Bromide recovery economics at Catesville
Minimum economical production
Designed production
Designed brine feed
Plant cost
Plant payout period
900,000 kg/year
1,800,000kglyear
1,400 m3/day
$ 1,000,000
6 years
392
TABLE 13.11
Profitability of Catesville bromide project
Return o n investment
Profit as sales percent
Profit per m3 processed
Investment
Profit per year
16.7%
14.3%
$ 0.346
$ 1,100,000
$ 180,000
Location of a bromine plant at Catesville offered several important advantages such as high bromide content (up to 6,000 mg/l) of the brine, field
operation under a single company (unitization), excellent rail and road
facilities, low-cost fuel, and regional market outlets. Production of
Smackover brine in 1956 was approximately 190 m3 daily from four oil
wells. This quantity of brine was not quite economical for a bromine recovery plant. Additional pumping equipment was installed in some of the wells
in order t o provide 795 m3 of brine daily for the bromine recovery project.
Depleted oil wells later were employed for brine production to raise the
plant feed to 1,430 m3 daily. Table 13.1 shows the initial economics associated with the bromine project as reported by Kincaid (1956).
The economic data presented in Table 13.1 are based on the bromine
prices of 1956. In 1956 the price of bromine was 66 cents per kg. The price
fluctuates with supply and demand. The data shown in Table 13.11 were
calculated by assuming that all of the bromine is sold at 70 cents per kg, that
the total investment is not more than $1.1million, and that the payout time
is 6 years (Cox, 1967).
Minerals recovered from saline waters
Sodium chloride
Minerals are recovered from practically every type of saline water. By far
the largest recovery is that of sodium chloride in solar evaporation processes.
From the point of view of oilfield brine disposal, where solar evaporation is
possible, the cost of disposal is small. The salts recovered, if any, would
probably pay for the construction of evaporation pits.
Lithium
Lithium is produced from brines by Foote Mineral Company at Silver
Peak, Nevada, and by American Potash and Chemical Corporation at Trona,
California. American Potash and Chemical Corporation recovers a coproduct
lithium sodium phosphate from Searles Lake, California, brines. However,
the largest lithium production is from lithium ore mined in North Carolina
393
Potassium
Tallmadge et al. (1964) report that the commercial recovery of potassium
from brines only has been attempted on a pilot plant scale. Precipitation
appears the most promising either by the addition of a selective agent
specific t o potassium, or by fractional crystallization of saturated brines.
Potassium compounds occur in many rocks and minerals, but the commercial sources are limited t o soluble salts in bedded salt deposits and brines.
The major deposits of potassium salts in the United States are part of the
Permian Salt Basin that underlies parts of Colorado, Kansas, Oklahoma,
Texas, and New Mexico, and the Paradox Basin of southwestern Colorado
and southeastern Utah. However, commercial beds of potassium minerals
have been found only in New Mexico. Commercial operations have been
limited t o about 1 4 0 km2 east of Carlsbad, New Mexico. These deposits
were discovered by oil well drillers. Commercial recoveries on a limited scale
are made from the brines of Searles Lake, California, and Bonneville Flats,
Utah.
Rubidium
The rubidium-producing industry is very small. During 1958 rubidium
production in the United States was only about 100 kg annually, and during
that year some new technical-grade rubidium compounds were prepared
from alkali carbonate residues of lithium operations. As with many other
minerals found in oilfield brines, the production of rubidium is not
published because it is withheld as confidential company data. However,
with current accumulated stocks and a very small consumption, it is doubtful that the recovery of rubidium from brines would be economical even at
$935 per kilogram.
Cesium
Cesium, both as a metal and as an industry, is similar to rubidium. The
demand for both is small, and the known uses are few. Both cesium and
rubidium are obtained commercially from lepidolite, a lithium mineral.
394
Cesium and rubidium are byproducts of the lithium industry, and both are
recovered from the residues of the lithium production process are
precipitation from solution. The high concentrations of cesium and rubidium
in the residues and the fact that the amount therein greatly exceeds demand
virtually preclude their removal from oilfield brines on a competitive basis.
Magnesium
Magnesium comprised one-third of the value which Collins (1966) attributed to the minerals wasted by oilfield brine disposal, and the price used
was that of magnesium metal. In the primary.meta1 form, magnesium commands its highest price. When magnesium is sold as contained in other compounds, its value is less than 2 cents per kg as compared to 77 cents per kg
for primary magnesium. Magnesium and magnesium compounds are
produced from the following four raw material sources: (1) sea water; (2)
dolomite; (3) ores other than dolomite; and (4) evaporite deposits and lake
and well brines. In 1963, well brines, bitterns, and sea water combined with
calcined dolomite or lime accounted for more than half of the domestic
production of magnesium compounds used as chemicals, filters or bases in
many industrial products including basic refractories.
Magnesium and magnesium compounds are produced and recovered by
several companies in the United States. The Dow Chemical Company produces magnesium chloride crystals, magnesium chloride fluxes, and magnesium hydroxide from well brines and calcined dolomite at Ludington,
Michigan. The Michigan Chemical Company produces precipitated magnesium carbonate, magnesium hydroxide, and magnesium oxide from well
brines and calcined dolomite at St. Louis, Missouri. The Dow Chemical
Company produces magnesium chloride, caustic-calcined magnesia, and
magnesium hydroxide from sea water and oyster shells at Freeport, Texas.
Magnesium compounds are recovered from solution by precipitation of
magnesium hydroxide. This method is so economical that a large part of the
production of magnesium and magnesium compounds in the United States is
derived from sea water. The Dow Chemical Company is the major source of
primary magnesium and in 1963 it had a capacity at Freeport, Texas, of
50,000 metric tons per year; at Velasco, Texas, the capacity was 34,000
metric tons. In 1963 the U S . production of primary magnesium was 69,000
metric tons.
The Dow process for magnesium recovery from sea water first precipitates
magnesium hydroxide. The hydroxide source is calcium hydroxide made
from oyster shells. After settling and thickening, a slurry of 17%magnesium
hydroxide is attained and neutralized with hydrochloric acid to form a 15%
solution of magnesium chloride. After evaporation and dehydration, the
resultant 48% magnesium chloride solution is mixed with dried magnesium
chloride t o form a paste. The paste is dried t o granules which consist of 74%
magnesium chloride, and the granular material is the feed to electrolytic cells
395
which produce magnesium metal and chlorine. The chlorine is then converted t o hydrochloric acid which is used in the neutralization step. Shreve
(1956) lists three economic factors of importance in the precipitation of
magnesium hydroxide. They are: (1) the source of the hydroxide; (2)the
dewaterirg procedures used for removal of the magnesium hydroxide from
the dilute solution; and (3) the purification of precipitates.
The source of the hydroxide is the major economic deterrent factor
against the increased use of well brines. Sea water provides the magnesium,
and the sea also furnishes the oyster shells for calcium hydroxide production. For well brine feed, dolomite often is employed, and a large source of
dolomite must be economically available. Tallmadge et al. (1964) report that
waste sodium hydroxide has been tested in Japan, but in most areas, calcium
salts are the least expensive sources of the hydroxide. Thus the choice of a
raw material must be belanced in cost against plant size and market. While
Michigan brines contain four t o five times the magnesium concentration of
sea water, the reduced size in necessary equipment for processing the brine
does not completely overcome the cost of producing and disposing of the
brine. This would appear t o make oilfield brines more attractive than other
subsurface brines if a hydroxide source is available at an equivalent expense.
Tallmadge et al. (1964) report methods for extracting magnesium from
brines by methods other than hydroxide precipitation. However, none
appear economically attractive when compared to precipitation unless combined with other processes or products. Among those studied are solar
evaporation to produce chloride, use of ion-exchange resins with lime and
carbon dioxide or waste liquor from the ammonia-soda process, and electrolysis.
Calcium
Calcium production from brines does not appear economical when compared to the source of the worlds calcium consumption. The largest amount
of calcium is produced by the mining of mineral deposits (notably gypsum)
found extensively throughout the world. Proposals for methods t o recover
calcium from brines have been made and are under study, but to compete
commercially beyond extremely small, local demands, considerable research
is needed.
Mixed salts
Mixed salts are precipitated by evaporation of sea water and brines, producing crude separations. The costs of these separations are low compared t o
those of highly purified compounds or metals. There are several drawbacks
which prevent greater use of this type of recovery. The product does not
command a high price, the plant must be at the brine sburce, there must be
solar evaporation conditions, and a local market must exist for the majority
396
of the mixed salts. Uses which have been suggested include heat-treating salt
baths in the steel industry, raw materials for refractory or catalyst manufacture, and fertilizer components.
Precipitation other than by solar evaporation is accomplished by cooling
or adding chemical agents. Simple cooling may be all that is necessary for
more concentrated brines, but fractional crystallization is necessary for
dilute brines such as sea water. Again local markets dictate whether cooling
or freezing processes will yield the correct products for a particular area.
Adding chemicals t o precipitate a specific product is the most fruitful of the
nonsolar evaporation processes. Most of the processes have been aimed at the
production of fertilizer. Potassium and magnesium are the minerals in sea
water that are most valuable for use in fertilizers. Salutsky and Dunseth
(1962) report that metal ammonium phosphates (MAP) containing magnesium, calcium, iron, manganese, copper, and many other trace metals comprise a high-analysis fertilizer.
The production of metal ammonium phosphates (MAP) in the United
States was started by W.R. Grace and Company in 1960 on a semicommercial scale. The method which Grace used to produce MAP was not
disclosed until 1962 after it was patented. The fertilizers are nonburning,
long-lasting sources of nitrogen, phosphorus, and various trace metals. Because of their low solubility, MAPs will not cause salt injury t o seeds or
plants.
In magnesium ammonium phosphate, practically all of the P z 0 5 is available, and the size of the MAP granules applied to plants determines how long
the nutrients will be available. Thus, availability of nutrients can be controlled by granulation and, since growing time varies from crop t o crop, MAPS
can be tailored to a specific crop (Anonymous, 1961). Therefore, fewer
applications are necessary with MAPS than with fertilizers of higher solubility and high nitrification rates.
W.R.Grace and Company developed the MAP process for two purposes.
First, it is useful t o remove scale-forming materials from sea water before
desalination. Secondly, it would yield the valuable, high-analysis fertilizer,
magnesium ammonium phosphate. In 1962, W.R. Grace and Company
(Anonymous, 1962) reported that the process was ready for the pilot plant.
The process is based on phosphate precipitation. To descale sea water and
produce high-analysis fertilizer at the same time, wet-process phosphoric acid
and anhydrous ammonia are added continuously t o raw sea water. This
precipitates the scale-forming elements - calcium, magnesium, iron, and
other metals - as metal ammonium phosphates and other phosphates. The
precipitated solids are removed by settling, and the descaled sea water is
pumped to the saline water conversion plant. The descaled water holds only
1%of the original magnesium and 5% of the original calcium. The slurry of
MAPs is dewatered t o about 35--40% solids by continuous centrifuges and
thin it is heated t o 90C. This converts MAP hexahydrate t o monohydrate.
The slurry is filtered, washed, mixed with recycle fines, and granulated. Fig.
397
S e t t l i n g ond
thickeninq
Descoled sea w o t e k
1
Dehydration
1
Wash
Filtrotion ond
wos hing
Gronulotion
Drying
Crushing
1
Undersize
Screeninq
Oversize
Finished product
to storoge
Fig. 13.1. Diagramatic flowsheet for producing descaled sea water and fertilizer.
13.1 shows a process flowsheet for producing descaled sea water and fertilizer.
Several questions surround the economics of the process. For a plant
descaling 3,800 m3 of sea water per day (output: about 10,000 metric tons
per year of fertilizer), the fertilizer would have to command a price higher
than that of conventional farm fertilizers. The estimate assumes 1962 market
prices for raw materials (phosphoric acid and ammonia) and does not take
credit for the increased value of the descaled sea water. The cost is just about
the same for Graces present method of producing MAPS. Because of its
premium quality, MAP can go t o the market as a specialty product.
In the phosphoric acid-ammonia process, 2 moles of ammonia per mole of
MAP are lost. to ammonium chloride in neutralizing the phosphoric acid.
Using disodium phosphate in place of the acid loses no ammonia, and using
monosodium phosphate only loses 1mole of ammonia. If a cheap method
were developed for producing the sodium phosphates, ammonia waste would
be reduced. The simplest method for producing sodium phosphates involves
398
Chlorine
Chlorine is the most abundant element in oilfield brines, and the removal
of all chlorides from oilfield brines would virtually desalt the brine. However, present commercial methods for the extraction of chlorine from brines
requires evaporation to acquire a saturated brine. Solar evaporation first
produces the saturated brine, then electrolytic processes are employed to
generate chlorine gas. The largest production of chlorides from brines is from
solar evaporation of sea water and salt lake brines. Many oilfield brines are
very close t o saturation with sodium chloride at surface temperatures. Subsurface brines are employed as raw materials for chlorine production, but the
amount produced is not significant when compared t o surface brine production.
Shreve (1956)describes the methods still in use for chlorine production.
Caustic soda and chlorine are coproducts in the electrolytic process. Purification of the brine is necessary to produce a purer caustic soda and lessen
clogging of the cell diaphragm with consequent increased voltage demand.
Calcium, iron, magnesium, and sulfate must be removed. The higher concentrations of magnesium and calcium in oilfield brines cause greater expense in
brine purification unless the removed compounds can be sold. Hydrogen,
caustic soda, and chlorine are the products of this type of recovery. The
hydrogen presents a disposal problem and is frequently made into other
compounds such as hydrochloric acid or ammonia or is employed for
hydrogenation of organic compounds.
399
400
Fig. 13.2. How gas, oil, and brine are separated after production from subsurface strata.
Fig. 13.2 illustrates a wellhead through which gas, oil, and water are
produced from a subsurface formation. Often they are produced as a mixture and it is necessary t o separate them in a tank such as that illustrated and
sometimes referred to as a gunbarrel. In this tank the water or brine will
settle to the bottom with the oil interface forming over the brine, and the
gas will rise to the top. The gas is drawn off the top, the oil is pumped off
the top of the water and stored in an oil tank, and the water is siphoned
from the bottom into a skimming tank for further oil-water separation. The
water is siphoned from the bottom of the skimming tank into a settling pond
where additional oil-water separation occurs. The brine or water could be
pumped from the settling pond t o a chemical plant for recovery of valuable
elements or to an injection well.
Fig. 13.3 illustrates a possible scheme for recovery of some elements plus
fresh water from the brine. For example, the raw brine could be concentrated by a desalination process which would also yield fresh water. Sulfate
then could be taken from the concentrated brine and used t o produce sulfur
or sulfur compounds. Next, iodine could be recovered, then bromine, followed by calcium, sodium chloride, and magnesium as suggested in the
figure. The remaining sludge could be dried and disposed of as a solid or it
could be recycled for additional recovery of elements.
FRESH-WATER PRODUCTION
401
RAW B R I N E
1
DESALINATION
PROCESS
I-*
PRODUCT
F R E S H WATER
CONCENTRATED
BRINE
I
I
I
SULFATE
PRECIPITATION
I-*
IODINE
RECOVERY
t
.
BROHINE
RECOVERY
PRODUCT
SULFUR AND
SULFUR COMPOUNDS
PRODUCT
I O D I N E AND
I O D I N E COMPOUNDS
PRODUCT
BROMINE AND
BROMINE COMPOUNDS
PRODUCT
CALCIUM
SODIUM CHLORIDE
RECOVERY
coMp0uM)s
PRODUCT
SODIUM CHLORIDE
OR
SODA ASH
AND
CHLORINE
PRODUCT
MAGNESIUM AND
MAGNESIUM COMPOUNDS
---l---
Fig. 13.3. Diagramatic flowsheet for producing fresh water and valuable elements from
brines.
Fresh-water production
Dwindling fresh water supplies and polluted supplies have increased research on how t o best obtain fresh water from saline water. Several plants
throughout the world produce fresh water from sea water. The price of
water for municipal purposes is a highly specific thing. The availability of
fresh water and costs of obtaining it vary from place to place. Conventional
402
water supplies range in cost from a few dollars per 1,000 m3 to over $260
per 1,000 m3.
The average cost of conventional water supplies in the United States was
$100 per 1,000 m3 in 1952. This was chosen as the goal for saline water
conversion costs. Several authors have estimated ultimate costs of saline
water conversion based on thermodynamic considerations. Dodge and
Eshaya (1960) have examined the minimum expected costs for saline water
conversion. Prior t o their calculations, other authors reported sea water conversion costs to be ultimately less than $79 per 1,000 m3. Dodge and Eshaya
expanded earlier work t o look at departure from isothermal operation, finite
product recovery, differential as opposed to single stage operation, and salt
concentration in the feed. They found that $90 dollars per 1,000 m3 is the
smallest cost for desalination of sea water.
Consider the case for converting brackish water with 5,000 ppm sodium
chloride. For converting 50% of the feed t o fresh water, 187 kWhr per 1,000
m3 was the power requirement. For 35,000 pprn sea-water conversion, the
power requirement was 1,530 kWhr per 1,000 m3. Both calculations were
for 50% recovery of fresh water from feed, where the average power costs
used in determining conversion costs are 1.5 cents per kWhr. At this rate, the
difference in power costs for sea water over brackish water is $20 dollars per
1,000 m3.
Oilfield brines contain up to seven times the concentrations of dissolved
salts compared with sea water. Would the power be seven times again as
expensive per 1,000 m3? At over $132 for power and $92 for other costs,
the cost of obtaining fresh water from oilfield brines probably would be
prohibitive when consideration is given to the other sources for feed t o a
conversion plant in the same area. An additional factor is that most oilfield
brines with their high concentrations are nearly saturated. Removing 50% of
the water would in essence leave a precipitated salt. Therefore, since no
conversion processes under study deal with saturated brine effluents, it is not
technologically feasible to completely desalt oilfield brines at this time.
Preliminary economic evaluation
The brine refinery concept (Collins, 1966) yields a processing plant the
size of a large petroleum refinery. The market prices used were for the
recovery and sale of the pure elements. The $3 billion in sales from 0.95
billion m3 of brine is the highest sales income possible that would result
from recovering and selling the minerals in the form that gives the highest
unit price.
Consider what is probably the best case of a brine refinery, a system
that would gather 22 million m3 per year. The cost of gathering and
disposing of this brine would be approximately 9.4 cents per m3. The
question is whether or not minerals could be sold at a profit such that the
disposal expense would be negated or a profit made. First, the minerals t o be
403
sold must be determined. At 7 ppm lithium, 163 metric tons per year could
be produced. This is a large fraction of present consumption and probably
would depress the sale price. The same holds true for most other elements of
such a refinery.
The assumptions lead to a brine refinery that would process 22 million m3
per year and sell $35 million of minerals. Assuming a 15% return on investment and a profit of 15% of sales, the plant would require $35 millioninvestment and yield 23.6 cents per m3 of brine processed. The original
disposal operation without mineral recovery was such that only $6 million
was invested. The brine refinery would turn brine disposal into a profit.
But the new investment is six times that for disposal only. It is doubtful that
any large oil producer would be interested in a 15%return on investment,
and small ones would never gather the cash.
Would a chemical company be interested in such an operation since they
operate at about a 15% return? Companies that currently remove minerals
from brines use brines that are more concentrated in the minerals desired. It
is doubtful that a process could combine several less economical operations
into a more economical one, and this would probably be true even if the
brine was supplied t o a chemical company free of charge. Only in the special
case where an oilfield brine contained a concentration very near t o a brine
that would be the most economical for separation would the oilfield brine be
a best alternate. Therefore, a tax incentive for pollution abatement or some
other economic incentive such as price increase of recovered chemicals is
necessary.
TABLE 13.111
Dollar value of dissolved chemicals a brine should contain per million kg of brine produced
from a given depth
Value of dissolved chemicals
Depth of well
(m)
$ 462
$ 968
$ 1,430
760
2,130
3,050
404
TABLE 13.W
Amount of element necessary in 1 million kg of brine to produce a chemical worth $ 550
at the market
Element in the brine
Concentration of element
(ppm/106 kg of brine)
Market product
Sodium
Potassium
Lithium
Magnesium
Calcium
Strontium
Boron
Bromide
Iodide
Sulfur
50,000
14,000
170
8,000
11,000
4,000
1,400
1,700
250
5,300
sodium chloride
potassium chloride
lithium chloride
magnesium chloride
strontium chloride
strontium chloride
sodium borate
bromine
iodine
sodium sulfate
price information used to make the approximations was taken from the
U.S. Bureau of Mines (1968).
Factors that must be considered in evaluating a saline water as an economic ore are the cost of bringing it t o the factory, the cost of the recovery
process, and the cost of transporting the recovered products to market.
Assuming that a brine is produced only for the purpose of recovering its
dissolved chemicals, a prime factor is the cost of pumping the brine. It will
cost less to produce the brine from a shallow well than from a deep well.
Therefore, neglecting other factors, a brine must contain a certain amount of
recoverable chemicals before it can be considered economically valuable, and
the farther it must be pumped, the more chemicals it must contain.
Today the possibility of recovering elements from brines that are pumped
t o the surface is increasingly important because the brines present a pollution hazard if their disposal is improper. Consider the fact that 1 m3 of brine
containing 100,000 ppm of chloride is capable of polluting 400 m3 of fresh
water so that they are unfit for human consumption.
Table 13.IV illustrates the value that chemicals recovered from brines have
at the market; however, because the market fluctuates, these values are
approximate. The column on the left indicates the elements that are found
in petroleum-associated brines, and the second column indicates the concentration that a given brine must contain before it can be used to produce a
given amount of chemical. For example, a brine containing 50,000 ppm of
sodium will contain sufficient sodium in 1 million kg of brine to produce
sodium chloride worth about $550.
The data in Table 13.IV indicate that some petroleum-associated waters
contain sufficient sodium to establish them as economic for the production
of sodium chloride. This is not necessarily true, because factors such as
405
market demand, ease of recovery, and proximity to market may be discouraging in certain geographic areas. Such factors must be fully considered
before startup of a chemical from brine recovery operation. One important
goal that should not be discounted nor overlooked is developing a means of
ultimately disposing of these brines so that they are not a pollution hazard.
Coupling of this goal with the fact that many of these brines contain
economic concentrations of several elements should make such recovery
operations more attractive. Additionally, several important chemicals can be
produced from these elements instead of those shown in the market product
column in Table 13.IV. An example is soda ash, which is a basic chemical in
many manufacturing processes. Furthermore, the figures shown in Table
13.111 are applicable only if the brine is produced solely for the recovery of
its dissolved chemicals. If the brines are pooled from several petroleum
production operations, the cost of pumping the brine becomes less, and the
necessary amounts of chemicals dissolved in 454,000 kg of brine become less.
At the present time, many petroleum-associated brines are injected into
subsurface strata, and it is assumed that they are thus disposed of permanently (Crouch, 1964). However, this method of disposal appears subject to
question, because in some instances, fresh waters apparently have been
polluted by disposal of brines. Subsurface disposal operations are suspected
in certain areas as possibly contributing to increased earthquakes and ground
tremors (Evans, 1966; Bardwell, 1966).
The storage of brines in earthen pits is known to cause pollution of nearby
soils and streams. Such ponds which have been abandoned for 10 years still
contribute to soil pollution (Bryson et al., 1966). Sound conservation should
favor the recovery of valuable elements from brines, and with proper planning, the recovery processes should aid in the ultimate disposal of unwanted
brines. Conservation of this type not only will develop new resources, but
will benefit the oil producer and the national economy and will aid in
abating pollution of soils, potable waters, and streams.
406
l l
TABLE 13.V
Geographic location, geologic age of saline water-bearing strata, and concentration of some of the elements found in the brine's
Location* Age of subsurface
strata
1
2
3
4
5
6
7
8
9
10
11
12
13
Concentration (ppm)
lithium sodium potassium magnesium
Mississippian
10
Permian
30
Permian
40
Devonian
100
Cambro-Ordovician ND
Pennsylvanian
5
Jurassic
100
Miocene
15
Devonian
25
Devonian
60
*
Mississippian
Devonian
10
Devonian
90
40
28,000
100 1,000
55,000 2,500
66,000 10,000
8,000 ND
51,000
100
68,000 4,000
73,000
600
74,000
700
14,000 8,000
16,000 9,000
58,000 3,000
72,000
2,000
10,000
25,000
9,000
5,000
11,000
600
5,000
6,000
5,000
15,000
11,000
5,000
4,000
calcium
strontium boron
sulfur
chloride
bromide
iodide
60,000
100
30,000
40,000
20,000
10,000
30,000
30,000
30,000
70,000
14,000
20,000
35,000
3,000
5
ND
2.000
ND
1,000
ND
ND
900
1,500
800
1,000
ND
400
20,000
400
100
350
30
60
60
600
400
20
60
4
179,000
3,200
ND
1,200
700
ND
600
5,000
200
2,000
2,500
1,500
1,300
1,800
40
ND
25
20
ND
1,000
10
20
40
40
40
30
20
40
ND
90
ND
ND
10
ND
60
ND
300
ND
ND
ND
9,000
166,000
198,000
79,000
98,000
175,000
ia4,ooo
182,000
200,000
90,000
143,000
186,000
409
410
'
LEGEND
0
5,000-10,000mg/l
10,000-30,000
> 30,000
DISPOSAL BRINES
411
Fig. 13.8 is a map illustrating some of the areas in the United States where
high concentrations of bromide in brines are located. On this figure the solid
circle represents brines containing 1,500-2,000 mg/l of bromide, the open
circle 2,000-3,000 mg/l, and the triangle more than 3,000 mg/l.
Disposal brines
In an attempt to acquire as much information as possible about salt water
disposal facilities in the various States, the literature was surveyed and State
and Federal agencies and oil companies were contacted. The acquisition of a
true compilation of the exact number of disposal facilities, disposal wells,
and total number of barrels of brine injected was an impossible task without
a large surveillance force; however, the data in Table 13.VI are reasonably
representative.
To determine the value of the minerals in the brines flowing into these
disposal systems, samples were obtained from 40 systems. The samples were
analyzed for concentrations of lithium, sodium, potassium, magnesium, calcium, boron, ammonium, sulfate, bicarbonate, chloride, bromide, and
iodide.
Table 13.VII lists the state, county, subsurface formation, and dissolved
solids (DS) from which the brine samples were obtained. The specific gravity
of each sample plus the ionic values determined in the laboratory also are
given in Table 13.VII. Sample 1is sea water, sample 2 is a brine that contains
a high concentration of iodide, and sample 3 is a brine from which bromine
currently is extracted.
- oper-
The brine value is less than the brine worth by the amount of profit
expected. Although the information necessary to obtahi an accurate calcula-
TABLE 13.VI
States where oilfield brines are disposed, total number of subsurface salt water disposal wells (SWDW) and largest disposal facilities
State
Ah.
Alaska
Ariz.
Ark.
Calif.
Colo.
Fla.
Ill.
Ind.
Kans.
KY.
La.
Mich.
Miss.
Mont.
Nebr.
Nev.
N. M.
N. Y.
N. D.
Ohio
Okla.
Pa.
S. D.
Texas
Utah
W.Va.
wyo.
Total number of
SWDW
14*
no data
4
421
216
25*
5
no data
325
3,150
60**
1,304
52 2
370
20 0
3
300
62
28*
4,900
Largest SWDW
SWDW
SWDW
( m3 /day)
2 4700 m3/day
2 1590 m3 /day
191
9,221
25,120
2,544
954
0
14
159
3,180
111
0
2**
0
2,385
318
1,113
239
135
2,703
318
318
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
4
0
0
0
7,173**
3**
95**
19*
Remarks
143
159
0
0
2
most of this is by ponding
ponding used
number of SWDW permitted from
1950-1971
0
0
* Salt water disposal Systems that may have more than one salt water disposal well per system.
* * Approximate.
2P
_.
2--
TABLE 13.VII
Analyses of some disposal brines, seawater, and a proven economic brine*
Brine State
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
Seawater
Okla.
Ark.
Kans
Kans.
Kans.
Kans.
Kans
Kans.
Ark.
Ark.
Ark.
Ark.
Ark.
Ark.
Ark.
Ark.
N.M.
N.M.
N.M.
N.M.
N.M.
Texas
Texas
Texas
Texas
Texas
Texas
Texas
Texas
Ala.
Ala.
Ala.
La.
La.
La.
Calif.
Calif.
Ariz.
Okla.
Okla.
Miss.
County
Formation
Sp. gr.
1.025
Kingfisher Oswego
1.124
Columbia Smackover
1.230
Pawnee
Arbuckle
1.036
1.025
Barton
Arbuckle
1.012
Butler
Hunton
1.034
Ellis
Arbuckle
1.020
Pratt
LKC-Arb
Barton
LKC-Arb
1.050
1.046
Palm
Graves
1.048
Ouachita L. Graves
1.046
Ouachita L. Graves
1.192
Union
Smackover
1.192
Union
Smackover
Union
Smackover
1.199
1.191
Union
Smackover
1.162
Columbia Smackover
1.020
Lea
San Andres
1.036
Lea
Devonian
1.028
Lea
Devonian
1.043
Lea
Penn
1.039
Lea
Devonian
Gaines
Devonian
1.025
Cherokee Woodbine
1.056
Rusk
Petit
1.153
Cherokee Woodbine
1.070
Wood
Woodbine
1.065
Wood
SubClarkville 1.037
Wood
Paluxey
1.076
Hopkins
Paluxey
1.010
Mobile
Rodessa
1.031
Mobile
Rodessa
1.039
Mobile
Rodessa
1.052
LaSalle
Wilcox
1.064
Calcasieu 1.084
Cameron Miocene
1.076
Fresno
1.026
Kern
Kern
1.000
Apache
L.Hermosa
1.012
Woods
Hunton
1.123
Oklahoma Wilcox
1.151
Wayne
Wilcox
1.003
Constituents (mg/l)
Na
Ca
Mg
Li
NH4
CI
Br
SO4
HCOi
DS
10,500
56,250
74,000
14,430
9,850
5,990
16,800
9,400
23,300
19.900
21,100
20,500
64,200
63,900
63,300
64,500
54,500
9,150
18.200
i3:goo
21,600
19,350
12,380
30,000
58,700
36.200
34;OOO
21,200
34,600
5,640
12,180
14,500
18,400
35,600
44,800
42.600
13,600
210
7,760
57,600
68,750
2,880
400
8,300
44,440
2,480
1,450
760
2,630
1,200
4,300
3,500
3,800
3,800
34,500
38,500
36,300
37,300
27,600
1,500
1.850
1,350
260
4,340
700
490
260
690
320
1,300
900
1,030
930
3,950
3,850
4,040
3,895
1,315
500
500
340
770
410
365
345
1,130
690
110
205
970
40
480
550
680
600
230
135
780
5
50
1,640
2,460
10
380
180
4,410
260
75
70
190
105
160
200
160
140
1,845
1,945
1,370
2,000
3,500
245
370
20
150
560
400
105
790
860
550
360
250
50
400
320
460
310
300
200
200
15
20
1.000
980
10
0.17
14
370
20
3
3
10
5
5
5
5
5
160
180
170
165
230
5
10
2
10
10
5
2
35
2
5
2
10
2
5
10
10
5
5
5
1
4.6
18
200
10
10
0
5
3
12
10
16
12
140
150
140
140
160
10
0
0
40
5
5
40
10
0
5
10
20
10
0
12
30
25
10
12
5
0
0
40
0
0
19.000
98,300
202,050
32,850
19,460
10,380
30,500
17,YOO
45,100
42,200
43,100
42,400
178,100
180,800
197,600
182,600
150,000
17,800
32,650
24,300
42,600
37,240
22,400
49,100
135,500
61,300
57,100
31,800
68,700
8,350
29,400
37,000
47,540
62,500
74,600
68,900
28,870
330
11,600
115,500
138,600
3,861
65
1,500
5,725
60
50
20
50
50
150
500
400
600
2,450
2,340
4,800
3,390
3,500
50
30
25
210
40
40
270
210
400
370
180
100
70
40
50
30
70
25
30
15
2
20
326
540
3
0.06
1,300
15
10
5
2
2
3
10
10
10
10
5
5
5
10
5
3
0
0
5
2
0
30
30
35
30
35
25
5
10
10
12
20
20
20
20
0
12
150
10
0
3,468
180
220
2,000
2,350
1,400
2,880
1,100
2,270
140
50
95
450
350
60
315
250
260
170
160
60
100
190
200
600
200
1,000
500
600
380
490
590
400
0
300
400
450
300
500
190
160
140
380
140
300
240
130
170
120
85
255
35,308
166,652
335,865
53,290
34,123
18,855
54,072
30,332
76,895
67,439
69,819
68,495
286,420
292,560
345,235
295,955
241,250
32,329
56,428
42,687
69,055
62,137
38,865
89,232
207,045
103.1 57
103,200
55,107
112.185
15,417
49,135
59,742
76,652
101,410
124,115
114,549
45,616
803
21,165
187,096
225,365
7,479
i$oo
2,840
2,400
1,970
8,650
10,320
3.300
10;530
840
6,750
630
5,630
6.750
8,860
1,650
3,960
2,335
1,855
70
1,520
10,120
13,270
50
1
10
10
0
300
20
30
0
0
0
30
45
40
40
320
260
260
100
50
70
60
0
90
0
100
50
50
40
10
25
40
0
90
80
90
250
25
12
0
0
12
260
140
0
0
0
0
650
440
350
255
190
2,000
2,260
2,000
360
1,630
610
240
270
30
90
0
420
120
710
300
400
0
0
0
0
40
0
350
520
410
414
TABLE 13.VIII
Formulas for calculating maximum worth, brine worth, and brine value
____
Compound
Cation ($/ton*)
Compound ($/ton)
Na
Mg
Li
Sr
K
Ba
Ca
NH4
NaCl (rock)
MgClz (99%)
MgS04
LiCl (technical)
SrC13
KCl
BaClz (technical)
CaClz
NH4 C1
18.09
259.38
346.99
11,515.10
518.89
58.88
284.29
120.64
412.26
7.11
66.14
69.22
1,87 3.91
286.60
30.86
187.39
43.54
138.89
Anion
Compound
Anion ($/ton)
Compound ($/ton)
NazB40, * lOHzO
NaCl (rock)
NazS04 (salt cake)
MgS04
NaBr
NaI (U.S.P.)
NaHC03
CaC03
c1
so4
Br
I
HC03
(303
Metric tons.
519.72
11.72
45.64
86.75
1,135.69
9,114.61
81.24
26.20
55.39
7.11
30.86
69.22
881.84
7,716.10
59.03
15.71
41 5
TABLE 13.X
Value of brine constituents*
Assumed brine composition (kg/rn3 of brine):
Calcium
Magnesium
Potassium
Lithium
Boron
Sodium
Bromide
Iodide
Sulfate
Bicarbonate
23.36
2.25
5.27
0.34
0.31
57.65
1.95
0.04
0.11
145.60
146.01
64.73
8.75
10.06
2.05
2.97
2.52
0.04
0.13
0.10
7.ll/ton**
at $
43.54lton
at $
at$
66.14/ton
at $
30.86/ton
a t $ 1,873.91/ton
at $
55.39lton
at $ 881.841ton
at $ 7,716.10/ton
at $
69.221ton
at $
59.031ton
= 1.04
= 2.82
= 0.58
= 0.31
= 3.84
= 0.16
= 2.22
= 0.31
= 0.01
= 0.01
416
TABLE 13.XI
Brine worth, brine value, and ratio commercial brine value/disposal brine value
Brine
Brine worth
($/m3)
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
0.19
3.69
3.86
0.28
0.17
0.10
0.28
0.14
0.39
0.41
0.41
0.82
2.38
2.50
2.99
2.61
2.48
0.18
0.22
0.16
0.33
0.25
0.19
0.52
1.11
0.48
0.64
0.26
0.51
0.10
0.32
0.37
0.53
0.34
0.38
0.33
0.23
0.01
0.17
1.06
0.96
0.02
Brine value
($/m3)
0.08
1.45
1.55
0.P1
0.07
0.04
0.12
0.06
0.16
0.17
0.17
0.33
0.95
1.00
1.19
1.04
0.99
0.07
0.09
0.07
0.13
0.10
0.08
0.21
0.33
0.19
0.25
0.11
0.05
0.04
0.13
0.15
0.21
0.14
0.15
0.13
0.09
0.01
0.07
0.42
0.39
0.01
State
Ratio
~
19.38
1.07
1.00
14.09
22.14
38.75
12.92
25.83
9.69
9.12
9.12
4.70
1.63
1.55
1.30
1.49
1.57
22.14
17.22
22.14
11.92
15.50
19.37
7.38
4.70
8.16
6.20
14.09
31.00
38.75
11.92
10.33
7.38
11.07
10.33
11.92
17.22
155.00
22.14
3.69
3.97
155.00
Sea water
Okla.
Ark.
Kans.
Kans.
Kans.
Kans.
Kans.
Kans.
Ark.
Ark.
Ark.
Ark.
Ark.
Ark.
Ark.
Ark.
N.M.
N.M.
N.M.
N.M.
N.M.
Texas
Texas
Texas
Texas
Texas
Texas
Texas
Texas
Ala.
Ala.
Ala.
La.
La.
La.
Calif.
Calif.
Ark
Okla.
Okla.
Miss.
indicating that the majority of the brines probably do not contain enough
valuable minerals t o be considered commercial by themselves. However,
these six brines may warrant further investigation, it sufficient brine is available.
CONCLUSIONS
417
Brine 1 is sea water, and some chemicals are recovered from sea water.
Therefore any brine that is disposed of in large volumes and has a ratio of
less than 20 may warrant investigation as a source of minerals because these
brines may be considered as polished ores. Brine 40 along with brine 2 may
contain commercial amounts of iodine. Although the current market for
iodine is attractive, this market may change, depending upon the international political atmosphere. Nevertheless the market for iodine once established should be fairly stable.
Brines 38 and 42 cannot be considered brines; in fact, brine 38 is almost
potable and with little treatment would be potable. Brine 42 could be used
for irrigation and as drinking water for certain types of livestock.
Conclusions
Some brines contain valuable minerals that if recovered would help pay
for part or all of their disposal costs. Recovery of certain minerals and
potable water should lower the potential of the disposed brine as a pollutant.
Brine value and brine worth formulas should be applied to disposal waters to
determine the relative value of their recoverable minerals.
References
Angino, E.E., 1967. Dissolved salts in oilfield brines - a wasted resource? In: E.E.
Angino and R. Hardy (Editors), Proceedings 3rd Forum o n Geology of Industrial
Minerals -State GeoL Sum. Kansas, Spec. Distrib. PubL, No.34, pp.120-125.
Anonymous, 1961. Grace moves ahead with new fertilizer. Chem. Eng. News, 39:83-84.
Anonymous, 1962. Descaling: route to MAP. Chem. Eng. News, 40:52--53.
Anonymous, 1971. Current prices of chemicals and related materials. Oi4 Paint, Drug
Rep., 200:24-37.
Aries, R.S., 1954. Marketing Research in the Chemical Industry. Chemonomics, New
York, N.Y., 220 pp.
Bardwell, G.E., 1966. Some statistical features of the relationship between Rocky Mountain arsenal waste disposal and frequency of earthquakes. Mountain Geol., 3: 37-42.
Brennan, P.J., 1966. Nevada brine supports a big new lithium plant. Chem. Eng.,
7 6 :86-8 8.
Bryson, W.R., Schmidt, G.W. and OConnor, R.E., 1966. Residual salt of brine affected
soil and shale, Potwin area - Butler County, Kansas. Kansas State Dep. Health, Bull.,
3( 1):28 pp.
Christensen, J.J., McIlhenney, W.F., Muehlberg, P.E., Hunter, J.A., Heintz, J.A., Jebens,
R.H. and Bacher, A.A., 1967. A feasibility study on the utilization of waste brines
from desalination plants, I. U.S. Off. Saline Water Res. Dew. Progr. Rep., No.245, 359
PP.
Collins, A.G., 1966. Heres how producers can turn brine disposal into profit. Oil Gas J.,
64: 112-1 13.
Cox, R.L., 1967. An examination of the feasibility of mineral recovery from oilfield
brines. Dep. Chem. Pet. Eng., Univ. Kansas, 41 pp., unpublished.
Crouch, R.L., 1964. Investigation of alleged groundwater contamination Tri-Rue and
Ride oilfields, Scurry County, Texas Texas Water Comm. Rep., No.LD-O464MR, 16
PP.
418
Dodge, B.F. and Eshaya, A.M., 1960. Thermodynamics of Some Desalting Processes.
Advanced Chemistry Series, No. 27. American Chemical Society, Washington, D.C.,
246 pp.
Evans, D.M., 1966. The Denver area earthquakes and the Rocky Mountain arsenal
disposal well. Mountain Geol., 3:23-26.
George, D.R., Riley, J.M. and Crocker, L., 1967. Preliminary process development studies
for desulfating Great Salt Lake brines and sea water. U S . Bur. Min. Rep. Invest.,
No.6928, 34 pp.
Kincaid, E.E., 1956. Two moves pay off at Catesville. Oil Gas J., 54:96-98.
Klein, G., Cherney, S., Ruddick, E.L. and Vermeulen, T., 1968. Calcium removal from
sea water by fixed-bed ion exchange. Desalination, 4:158-166.
Miller, W.C., 1965. Bromine. US. Bur. Min. Bull., 630:159-164.
Salutsky, M.L. and D u m t h , M.G., 1962. Recovery of Minerals from Sea Water by
Phosphate Precipitation. Advanced Chemistry. Series, No. 38. American Chemical
Society, Washington, D.C., 199 pp.
Shreve, R.N., 1956. The Chemical Process Industries. McGraw-Hill, New York, N.Y., 2nd
ed., 1004 pp.
Tallmadge, J.A., Butt, J.B. and Solomon, H.J., 1964. Minerals from sea salt. Ind Eng.
Chem., 56:44-56.
U.S. Bureau of Mines, 1968. U.S. BuMines Minerals Yearbook, Metals, Minerals, and
Fuels. Washington, D.C., Vol. 1-11, 1208 pp.
U.S. Bureau of Mines, 1969. U S . BuMines Minerals Yearbook, Metals, Minerals, and
Fuels. Washington, D.C., Vol. 1-11, 1194 pp.
Waters, Jr., O.B. and Salutsky, M.L., 1968. Separating potassium and sodium sulfate from
brines and bitterns. U.S. Bur. Min., W.R. Grace Company, U.S. Patent, No.3,402,018.
420
SUBSURFACE DISPOSAL
not overcome in the summer months. In cases where evaporation ponds are
well-lined to prevent drainage, the problem of how to handle the salt
deposits begins to mount up. Where solar evaporation conditions are favorable, very little salt is needed for the roads when it snows because it seldom
snows there.
The expense of oilfield brine disposal is the least where salbwater bodies
are nearby, but even here some care must be taken. The oil content must be
less than 30 pprn for disposal into the oceans in coastal areas, otherwise, the
oil collects on the shore and becomes a hazard to oyster and fish life. Along
the Gulf of Mexico strict controls by wildlife authorities and oyster and fish
industries monitor the brines disposed in the Gulf. A small quantity of oil
gives both fish and oysters a bad taste.
Subsurface injection
Injection may not be the proper word since pressure is not always necessary. The Plains States are in a hard water belt and have the strictest controls
on subsurface disposal. Whether or not subsurface disposal expenses should
always be considered the 'most expensive means of disposal is debatable.
Pressure maintenance by injected brine assists oil production rates. Oilfield
brines are also used for waterflooding; therefore, not injecting the brine may
decrease production and result in a more expensive method of disposal.
Shallow well disposal was one of the first subsurface disposals employed
where a shallow well is defined as one using a horizon less than 305 m in
depth. A shallow well takes considerable input brine for a time, but increasing pressures become necessary as time goes by and this continually
increases disposal costs. Shallow wells are also more likely to allow the
injected brine t o reach fresh-water supplies in some areas.
When a deep-seated bed is known to be available, it is less costly in the
long run to make use of the deeper formation. Deep disposal wells accept
immense volumes of brine by gravity, and eliminating the necessity of injection pressures reduces disposal expenses. It often was discovered that clogging occurred near the bore of the injection well and treatment was necessary to reduce clogging. Today treatment plants compose a large fraction of
the subsurface disposal operations.
Early in the history of subsurface brine disposal, legislation simply
allowed any means of disposal. Since then legislation has for all practical
purposes forced subsurface disposal and set up tight controls and safeguards
for protection of fresh water. In the 1930's, the Railroad Commission of
Texas allowed the increase of oil allowable by 1 m3 for every 50 m3 of brine
returned to subformations. The increase was fixed at a maximum of 0.8 m3
(Laurence and Leusler, 1958) and this incentive program did a great deal to
encourage subsurface disposal of brines in the East Texas field.
PRESENT-DAY TECHNOLOGY
421
Costs ($/m)
(cm)
cleaning machine
acidizing
replacement
10.2
15.2
20.3
25.4
0.249
0.174
1.050
1.234
0.958
1.919
4.259
5.899
4.04
5.77
7.64
9.61
422
SUBSURFACE DISPOSAL
ECON OM ICS
423
only one or two producing wells. Some deep disposal wells show a potential
capacity of 1,600-3,200 m3 of brine intake per day under actual test.
Therefore, it is evident that it is possible for several operators to use the
same disposal well.
The largest oilfield brine disposal association is the East Texas Salt-Water
Disposal Company. This company serves the East Texas oilfield located in
northeast Texas, which is located in parts of five counties, and the company
handles approximately 90%of the brine produced in this field. In 1942, with
disposal costs averaging in excess of 12.6 cents per m3 and the amount of
produced brine increasing, the disposal company was formed by 250 large
and small operators. During the second year of operation, costs of disposal
dropped t o about 10.7 cents per m3. Table 14.11 shows the history of
disposal costs for the East Texas Salt-Water Disposal Company (1953).
Table 14.11 shows that although there was a large difference between the
costs of labor, equipment, materials, etc., from 1944 through 1958, the
companys cost per m3 of disposed brine changed very little. This probably
indicates that in this case, increasing costs have been balanced by technological improvements. The amount of brine disposed per year roughly follows
inverse variations t o disposal cost variations. In the data gathered by Elliston
and Davis (1944) on disposal system costs, investment amortization was
roughly 63%of the total disposal costs. With greater fixed costs than variable
operating costs, the unit costs should increase as the amount of brine injected decreases.
TABLE 14.11
East Texas Salt-Water Disposal Companys costs
Year
Brine injected
(m3)
1942
1943
1944
1945
1946
1947
1948
1949
1950
1951
1952
1953
1954
1955
1956
1957
1958
88,600
6,454,000
12,606,000
14,034,000
17,546,000
21,666,000
22,932,000
22,715,000
21,535,000
19,458,000
19,310,000
18,320,000
18,514,000
20,O27,000
20,979,000
21,488,000
21,969,000
0.450
0.108
0.088
0.090
0.089
0.086
0.087
0.091
0.091
0.096
0.089
0.086
0.092
0.084
0.084
0.086
0.087
424
SUBSURFACE DISPOSAL
425
Water is injected into an oil reservoir that does not possess a natural water
drive; this injection water is obtained from water supply wells, and in many
cases some of it is recycled.
In oilfield waterflooding operations, an injection well is used to introduce
water (often brine) into the strata t o be flooded. In such an operation the
oil-water interface is kept as uniform as possible to clearly sweep in-place
oil out of the formation and to a production well, i.e., to obtain maximum
sweep efficiency. The injection pressure and injection rate usually are low
and slow during the beginning of a waterflood, and the input well usually is
not fractured because channeling is thus less likely.
Disposal wells are used in oil-production operations t o dispose of the
waters that are produced with petroleum from a natural water-driven reservoir, and some petroleum reservoirs produce large quantities of such brine
water. Disposal wells usually are fractured so that the subsurface formation
will accept large quantities of fluids at little or no injection pressure; many
of these wells initially operate on a vacuum. In a disposal operation, a
uniform flood front and absehce of channeling is not required. The primary
consideration normally is to put large amounts of fluid into a reservoir at the
least possible cost.
Acceptable geologic areas
Most of the major synclinal basins contain favorable locations for d e e p
well injection (Warner, 1967). The most acceptable areas are in porous sedimentary rock strata, e.g., sandstone, limestone, or dolomite. Such strata are
found under about 50% of the land area in the United States, mainly in the
Central Plains States and southwest coastal areas.
Some areas such as the west coast are underlain by complex geologic
strata, which has not been satisfactorily studied. Areas where volcanic rocks
are present at the surface usually are not acceptable for disposal wells.
McCann et al. (1968) reported on possible disposal sites in the New York
area of the Appalachian Basin. They found some suitable and some unsuitable areas. Hardaway (1968) reported on the possibilities of waste
disposal in a structural syncline in Pennsylvania and found that disposal into
certain horizons appeared promising but that additional seismic and well-test
data are needed. Similar studies were made by Briggs (1968) for the
Michigan Basin; Edmund and Goebel (1968) for the Salina Basin; Garbarini
and Veal (1968) for the Denver Basin; and Peterson et al. (1968) for the San
Juan Basin.
In summary, the most likely acceptable areas are found in the Puget
Willimette Valley and Great Valley of California, in the Mid-Continent and
Great Plains, on the Gulf coast, in the central and eastern Great Lakes area,
and in much of the Mississippi River drainage basin. Areas that are likely to
be unacceptable are the Western Mountain ranges; the Ozark, Wichita,
Arbuckle Llano Uplift area; the Mexia fault area; the Atlantic Coast area; the
4 26
SUBSURFACE DISPOSAL
Appalachian Mountain area; most of the New England States; and certain
areas near western Lake Superior and Lake Michigan.
Geologic maps
To conduct a feasibility study of a project in depth, it is desirable to have
a suite of maps that show the following (L.R. Reeder, written communication, 1972): (1)surface geology; (2) subcrop at various horizons; (3)structure; (4) tectonics; ( 5 ) convergence; (6)isopachs of various reservoirs; (7)
potentiometric gradient of various reservoirs; (8) depth to base of fresh
water zones; (9) fresh-water wells; (10)all wells other than fresh-water wells,
showing total depths.
Suitable disposal zones
The development of subsurface disposal operations by the oil industry
indicates that almost all types of rocks possess large enough porosities and
permeabilities to accept large amounts of fluid under favorable conditions.
The injected wastes must be confined t o the disposal formation so that fresh
water and other valuable natural resources are protected. Some of the
characteristics that are required of an acceptable disposal zone are as
follows:
(1)The rocks in the disposal strata should have large porosity, permeability, and thickness so that a significantly large volume is available for fluid
injection at relatively high rates and at reasonably low pressures.
(2) The disposal reservoir should be of large area extent suitable for injection of large quantities of fluid.
(3) The reservoir rocks should be uniform and not too heterogeneous to
allow calculations concerning the behavior of injection fluids, injection pressures, and possible fluid rock reactions.
(4) The injection zone should contain brackish or salty water (a
salaquifer). Waters containing more than 1,000 mg/l of dissolved solids are
used for domestic, irrigation, and industrial water in some areas (Warner,
1968).
(5)The proposed injection zone must be separated from fresh-water zones
both laterally and vertically. Such a zone should be vertically below the level
of fresh-water circulation and confined vertically by strata that are impermeable. A rule of thumb is the depth at which a confined salaquifer is present;
however, this is not always applicable because in some areas salaquifers
overlie fresh-water aquifers.
( 6 ) There should be no unplugged or improperly plugged wells penetrating
the proposed zone in the vicinity of the disposal well.
(7) The fluids t o be injected should be compatible with the rocks in the
injection strata and with the fluids in the strata. If they are not, precipitates
will form and plug the well. Wastes incompatible with the native fluids can
427
Methods
Fresh-water zones
Porosity
Permeability
Minerals in strata
Fluid pressure in strata
Subsurface formations and
thickness
Temperature of strata
Injectivity profile
428
SUBSURFACE DISPOSAL
Reservoir transmissibility
The reservoir transmissibility can be calculated using knowledge obtained
from the following first two items, but it is influenced and may change
during disposal operation because of phenomena associated with items
shown in (3)through (8).
(1)Core analysis data.
(2)Reservoir transient tests (Matthews and Russell, 1967).
(3)Behavior of fractured reservoirs;
opening of natural fractures during pumping (Snow, 1968)
(4)Artificially induced fractures (DeLaguna, 1966).
(5)Dissolution of rock by injected fluid.
(6)Accidentally induced fractures.
(7)Plugging from suspended solids;
bacteria;
corrosion products.
(8)Plugging by clay swelling.
(9)Plugging by incompatibility of fluids (Ostroff, 1964).
Compressibility of rock and water
Both the reservoir rock and interstitial fluid are compressible to a very
small degree. It is the compression factor that provides the space needed t o
inject extraneous fluids into an otherwise full reservoir. Waters and rock in
the salaquifer are compressed by the injected waste liquids in an everexpanding cylinder away from the wellbore. Since the rock and water compressibility is of small magnitude, the salaquifer must be of large areal extent
t o distribute the pressure buildup. If the formation is confined by faulting,
sand pinch-out, or restricted permeability in the region of the disposal well, a
very limited area will be available t o compress the formation rock and water,
and pressure will build up rapidly or injection rates will decline to a point
where the operation becomes impractical.
Water compressibility
The compressibility of pure water is known to be dependent upon the
pressure, temperature, and gas in solution in the water. Note that there is a
wide range of compressibilities and that increasing pressures reduce the
value, whereas increasing temperatures enlarge it. The compressibility of
pure water at 408 atm and 93.3"C is approximately 4.2 x lo-" cm2/dyne.
Since with increasing depth higher pressures and temperatures are encountered, it is expected that compressibility will increase, but the magnitude will
depend upon the relative increases in pressure and temperqture.
A t a given pressure and temperature, the effect of gas in solution in pure
water is t o increase the compressibility over that of pure water at the same
429
pressure and temperature. A graphical method of correction for gas solubility indicates that the effect of gas solubility on the compressibility of
water is great, and a reservoir water containing 3.56 m3 of natural gas per
m3 will have a compressibility approximately 18%greater than that of pure
water at the same temperature and pressure (Amyx et al., 1960).
Rock compressibility
The porosity of sedimentary rocks has been shown by Krumbein and Sloss
(1963) t o be a function of a degree of compaction of the rock. The compacting forces are a function of the maximum depth of burial of the rock.
Sediments which have been buried deeply, even if subsequently uplifted,
exhibit lower porosity values than sediments which have not been buried a
great depth.
Apart from the effect of compaction on grain arrangement, rock minerals
are also compressible. Three kinds of compressibility must be distinguished
in rocks: (1) rock matrix compressibility; (2) rock bulk compressibility; and
(3) bore compressibility (Amyx et al., 1960). The compressibility of each
parameter above is the fractional change in volume of that parameter with a
unit change in pressure. Data correlated with net overburden pressure
indicate that the pore compressibility is a function of pressure. In summary,
pore volume compressibilities of consolidated sandstones are in the order of
7 x lo- t o 14 x lo- cm2/dyne.
430
SUBSURFACE DISPOSAL
431
beds. This postulate assumes that the beds act as semipermeable membranes
where the membranes separate waters of different salinity. Transport of
water across a shale can result in lower pressure on one side of the shale
versus higher pressure on the other side. Assuming that the shale acts as a
membrane, the lower pressured side will be the effluent side and will contain
filtered or fresher water while the high pressured side will contain the more
salty water which will become even more salty as the filtration process
proceeds.
Because hydrodynamic conditions exist in many ground-water aquifers, it
should be a mandatory requirement that the hydrodynamic conditions of
the proposed sedimentary disposal aquifer be thoroughly determinzd. Water
flow in aquifers usually is determined by use of contour maps cf water
elevation in wells plus aquifer permeability and aquifer thickness. This
method will not give a true calculation if much water is transported through
semipermeable shale or clay beds. Pressure maps are necessary in establishing
such transport and the low-pressure aquifer should be used for a disposal site
rather than the high-pressure aquifer.
t Injection
432
SUBSURFACE DISPOSAL
FLUID TRAVEL
433
Fluid travel
The pressure radius increases but at a decreasing rate when a liquid is
pumped into a homogeneous uniform aquifer of infinite areal extent because
of the available expanding storage area. Nonequilibrium equations can be
used t o compute the distance that the higher pressures move out radially
from the injection wellbore and the rate at which the pressures increase
434
SUBSURFACE DISPOSAL
(Wright, 1969; Davis and Dewiest, 1967; Ferris e t al., 1962). Hydraulic
gradients and potentiometric levels should be determined for disposal zones
to calculate and monitor the injected fluid movement.
Hazards of underground waste disposal
Earthquakes
The most notable example of a hazard attributed t o deep-well disposal
thus far is the Rocky Mountain arsenal well located about 16 km northeast
of Denver 1,581 m above sea level, completed September 11, 1961.The well
was drilled t o a total depth of 3,671 m, and injection was made into a zone
of fractured gneiss from 3,650t o 3,671 m. From March 1962 until February
1966, a volume of 0.625 million m3 was injected at a maximum rate of 1.95.
m3/minute and 75 atm (average rate 0.76 m3/minute and 34 atm). The
seventh week after injection began, an earthquake of magnitude 1.5 was
recorded (April 24, 1962). From April 24, 1962, through August 1967,
1,514 earthquakes were recorded with magnitudes ranging from 0.5 t o 5.3;
all were relatively shallow in origin and from an area about midway between
central Denver and the arsenal well (Hollister and Weimer, 1968).
Present consensus is that the earthquakes are products of a regional stress
field of tectonic origin, triggered by the local incremental strain from injection into the arsenal well. In several aspects, however, the stress-strain relationship in the vicinity of the arsenal well seems not t o have been resolved
fully. Injection-triggered earthquakes were tentatively identified.
State regulations and tax incentives
Regulations
Regulations concerning construction and operation of disposal wells are
not standard and vary from State to State (L.R. Reeder, written communica-
435
tion, 1972). Missouri, Ohio, Texas, and West Virginia have regulations
dealing specifically with disposal wells. Apparently no States have regulations which specifically prohibit disposal wells; however, Ohio permits disposal only into the Mountain Simon sand. Texas probably has the most
specific and perhaps the most equitable regulations, which are obtained from
the Texas Water Development Board. Some of their regulations shown on
their Form GW-14 are as follows:
A preliminary report is required before application can be processed.
This report should include but not necessarily be limited to the following
information:
(a) An accurate plat showing location of proposed injection well.
(b) A map indicating location of water wells and all artificial penetrations
(oil and gas wells, exploratory tests, etc.) of the proposed injection interval(s) in the general area of the proposed injection well. Reasonable diligence
shall be used to locate such penetrations. Well and abandonment records for
all exploratory oil and gas tests located within the area owned and operated
by application should accompany map. (Details within 5 km radius generally
acceptable.)
(c) Description of local topography and geology pertinent t o injection
program. Depth of deepest strata containing fresh water or water of suitable
quality for potential beneficial development as determined by well development and/or electrical logs. (Generally required minimum of 91 m of shale
between injection zone and base of fresh water.)
(d) A detailed description of the chemical, physical, and biological characteristics of the waste to be injected. Complete chemical analyses of all inorganic constituents should be reported in ppm or mg/l. If organic fractions are
present, all such constituents should be reported in ppm, mg/l, as individual
percentages by weight, or in other appropriate terms.
(e) The anticipated average and maximum rate of injection in gallons per
minute or barrels per day. Estimated yearly volume of injected waste and
anticipated life of project. (Semiannual reports of monthly volumes, injection rates, pressures, cumulative volume, workovers.)
(f) Data on completion and operation of proposed injection well:
(1)Total depth of well.
(2) Casing size, grade, type, weight, and setting depth of all strings; size
and type of tubing; name, model, and depth of tubing packer setting.
(3) Cement-type and volume of cement t o be used on each casing string
and calculated top of cement behind each string. Describe and give percent
of all cement additives. Run a cement bond log.
(4) Proposed injection interval(s) and perforations. This should include
the interval(s) t o be utilized initially and the entire zone requested for future
development.
(5) Diagramatic sketch of proposed well.
(6) Anticipated maximum and average wellhead injection pressures.
(7) Description of possible hydraulic fracturing and/or acidizing programs, if anticipated.
436
SUBSURFACE DISPOSAL
Tax incentives
Some states give preferential tax advantages to enterprises utilizing subsurface disposal for water pollution abatement. The following examples were
taken from Wright (1969).
(1) Connecticut. Exempts pollution control facilities from property tax.
(Conn. General Stats. Anno., Sec. 12(81)(51), (Supp. 1966).)
(2) Florida. Very limited incentive. Provides lower valuation on control
facility for ad valorem tax purposes; no tax on sale of facility, etc. (14A Fla.
Stat. Anno., Sec. 403.241.)
(3) Georgia. Exempts control facilities from ad valorem tax. (Georgia
Code Anno., Sec. 2-5405.)
(4) Idaho. Exempts facilities from ad valorem tax. (Idaho Code Anno.,
Sec. 63-105T.)
( 5 ) Illinois. Provides limited incentive, much like Florida, exempts portion
of value of facility from tax on sale of property. (Ill. Anno., Stats., Ch. 120,
Sec. 502.)
(6) Indiana. Exempts personal property from ad valorem tax when the
same is used for pollution abatement. (Ind. Stats., Anno., Sec. 64-241.)
(7) Massachusetts. Exempts control facilities from ad valorem tax. Also
gives credit against corporate or income tax for portion of cost of facility.
(Mass. General Laws Anno., Ch. 59, Sec. 5 (Supp. 1968).)
437
438
SUBSURFACE DISPOSAL
million, and they disposed 58,800 m3 of brine per day from 28 fields. Brine
disposal costs can represent 2% of net oil sales and up to 25%of total lifting
costs (Smith, 1970).
Conclusions
The storage capacity of potential salaquifers, although considerable in
certain areas, is nevertheless limited if long-term continuous disposal is concerned, so that space should be treated as a natural resource. Deep-well
disposal has been successful in many cases, and the evidence for questionable
operations is inconclusive. However, a high success ratio does not preclude
caution in the use of the method. Neither does it relieve the operators of the
responsibility of close monitoring of the injected fluids and the reservoir,
and the meticulous maintenance of the well facilities.
Additional research is needed to develop better methods of evaluating
potential disposal reservoirs, of confining and monitoring the lateral movement of fluids in disposal zones, and of determining the rate of mixing of
injected fluids with native fluids. Regulations and laws concerning disposal
operation should be standardized.
References
Amstutz, R.W. and Reynolds, L.C., 1968. Is the earths crust going to waste, 11. Types of
fluids injected and treating procedures Presented at Natl. Pet. Refiners Assoc., MidContinent Regional Meet., Wichita, Kansas, June 12-1 3, 1968.
Amyx, J.W., Bass, Jr., D.M. and Whiting, R.L., 1960. Petroleum Reservoir Engineering.
McGraw-Hill, New York, N.Y., 610 pp.
Bleakley, W.B., 1970. Shells SWD meets pollution standards. Oil Gas J., 68:144-146.
Briggs, Jr., L.I., 1968. Geology of subsurface waste disposal in Michigan Basin. In: J.E.
Galley (Editor), Subsurface Disposal in Geologic Basins: A Study o f Reservoir Strata A m . Assoc. Pet. Geol., Mem. 10, pp.128-153.
Case, L.C., 1970. Water Problems in Oil Production. The Petroleum Publishing Company,
Tulsa, Okla., 133 pp.
Davis, S.N. and Dewiest, R.J.M., 1967. Hydrogeology. John Wiley and Sons, New York,
N.Y., 463 pp.
DeLaguna, W., 1966. Disposal of radioactive wastes by hydraulic fracturing. NucL Eng.
Design, 3:338-352, 432-438.
Donaldson, E.C., 1964. Subsurface disposal of industrial wastes in the United States. U.S.
Bur. Min. Inform. Circ., No.8212, 34 pp.
East Texas Salt-Water Disposal Company, 1953. Salt-Water Disposal East Texas Field.
Petroleum Extension Service, Austin, Texas, 116 pp.
Edmund, R.W. and Goebel, E.D., 1968. Subsurface wastedisposal potential in Salina
Basin in Kansas. In: J.E. Galley (Editor), Subsurface Disposal in Geologic Basins: A
Study o f Reservoir Strata - A m . Assoc. Pet. GeoL, Mem. 10, pp.154-164.
Elliston, H.H. and Davis, W.D., 1944. A method of handling salt-water disposal including
treatment of water. Presented at API Meet., Tulsa, Okla.,May, 1944, API Paper,
N0.851- 18F.
Ferris, J.G., Knowles, D.B., Brown, R.H. and Stallman, R.W., 1962. Theory of aquifer
tests, ground-water hydraulics. US. Geol. Sum. Water Supply Paper, No.l536-E, 174
PP.
REFERENCES
439
Garbarini, G.S. and Veal, H.K., 1968. Potential of Denver Basin for disposal of liquid
wastes. In: J.E. Galley (Editor), Subsurface Disposal in Geologic Basins: A Study o f
Reservoir Stmta -Am. Assoc. Pet. G e o l , Mem. 10, pp.165-185.
Hardaway, J.E., 1968. Possibilities for subsurface waste disposal in a structural syncline in
Pennsylvania. In: J.E. Galley (Editor), Subsurface Disposal in Geologic Basins: A
S t u d y of Reservoir Stmta - A m . Assoc. Pet. GeoL, Mem. 10, pp.93-125.
Hollister, J.C. and Weimer, J.C., 1968. Geophysical and geological studies of the relationships between the Denver earthquakes and the Rocky Mountain arsenal well. Colo.
School Min. Q., 63(1):1-251.
Jones, O.S.,1945. Disposition o f oilfield brines. University of Kansas Press, Lawrence,
Kansas, 45 pp.
Krumbein, W.C. and Sloss, L.L., 1963. Stratigraphy and Sedimentation. W.H. Freeman,
San Francisco, Calif., 2nd ed., 660 pp.
Laurence, L.L. and Leuszler, W.E., 1958. ABC's of treating and handling injection water.
Pet. Eng., 30:B52-B54, B59.
Matthews, C.S. and Russell, D.G., 1967. Pressure Build-up and Flow Tests in Wells.
Society of Petroleum Engineers, AIME, 167 pp.
McCann, T.P., Privasky, N.C., Stead, F.L. and Wilson, J.E., 1968. Possibilities for disposal
of industrial wastes in subsurface rocks on north flank of Appalachian Basin in New
York. In: J.E. Galley (Editor), Subsurface Disposal in Geologic Basins: A Study o f
Reservoir Strata - Am. Assoc. Pet. G e o l , Mem. 1 0 , pp.43-92.
McLean, D.D., 1969. Subsurface disposal - precautionary measures. Ind. Waste Eng.,
August 1969: 20-22.
Morris, W.S., 1959. Cleaning asbestos-cement pipelines in salt-water disposal service. Pet.
Eng., 31:B46-B49.
Morris, W.S., 1960. Subsurface disposal of salt Water from oil wells. Water Pollut. Control
Fed. J., 32:l-20.
Ostroff, A.G., 1963. Compatibility of waters for secondary recovery. Prod. Monthly,
27 :2-4-9.
Ostroff, A.G., 1964. Introduction to Oilfield Water Technology. PrenticeHall, Englewood Cliffs, N.J., 412 pp.
Peterson, J.A., Loleit, A.J., Spencer, C.W. and Ullrich, R.A., 1968. Sedimentary history
and economic geology of San Juan Basin, New Mexico and Colorado. In: J.E. Galley
(Editor), Subsurface Disposal in Geologic Basins: A S t u d y of Reservoir Strata - A m .
Assoc. Pet. G e o l , Mem. 1 0 , pp.186-231.
Rice, I.M., 1968. Salt-water disposal in the Permian Basin. Prod. Monthly, 32(3):28-30.
Ross, R.D., 1968. Industrial Waste Disposal (Reinhold Environmental Engineering Series).
Reinhold, New York, N.Y., 340 pp.
Selm, R.P. and Hulse, B.T., 1959. Deep-well disposal of industrial wastes. Proc. 14th Ind.
Waste C o n f , Purdue Univ. Eng., Ext. Ser., No.104, pp.566-586.
Smith, W.W., 1970. Salt-water disposal: sense and dollars. Pet. Eng., 42:64-65.
Snow, D.T., 1968. Fracture deformation and change of permeability and storage upon
change of fluid pressure. Colo. School Min. Q., 63:201-244.
Warner, D.L., 1967. Deep wells for industrial waste injection in the United States summary of data. US. Dep. Inter., Fed. Water Pollut. Control Adm., Water Pollut.
Control Res. Ser. PubL, No.WP 20-10, 45 pp.
Warner, D.L., 1968. Subsurface disposal of liquid industrial wastes. In: J.E. Galley
(Editor), Subsurface Disposal in Geologic Basins: A Study o f Resenroir Stmta -Am.
Assoc. Pet. GeoL, Mem. 1 0 , pp.11-20.
Wright, C.C. and Davies, D.W., 1966. The disposal of oilfield waste water. Prod. Monthly,
30:14-17; 22-24.
Wright, J.L., 1969. Disposal wells - a worthwhile risk. Presented at 98th Annual Meet.,
AIME, Washington, D.C., February 16-20 1969, Reprint, 1 5 pp.
Composition (wt.%)
illite
kaolinite
montmorillonite nontronite
serpentine
SiOz
A12 0 3
Fez03
FeO
MgO
CaO
Naz 0
K2 0
Hz O+
Hz 0Ti02
MnO
56.91
18.50
4.99
0.26
2.07
1.59
0.43
5.10
5.98
2.86
0.81
44.82
37.20
0.41
0.07
0.25
0.58
0.40
0.43
12.92
1.76
1.26
49.91
17.20
2.17
0.26
3.45
2.31
0.14
0.28
7.70
15.77
0.24
0.04
39.92
5.37
29.46
0.28
0.93
2.46
7.00
14.38
0.08
44.16
0.90
0.27
2.10
40.07
0.02
7.15
5.01
0.01
0.02
442
443
Hz 0
0.23
0.46
0.13
0.25
0.42
HzO + CaClz
Hz 0 + CaClz
Hz 0 + MgClz
Hz 0 + MgClz
HzO + NaCl
Hz 0 + NaCl
Hz 0 + NaHC03
H 2 0 + NaHC03
0.88
0.30
0.61
-0
t-
.03I
,040
,046
,044
0
-I
.042
.04 I
loo
1,000
HOURS
10
xx)
Fig. 15.1. Silicon concentration as a function of tim: for illite-Hz O,-H2 O-CaClz,
-Hz 0-NaHC03 ,-Hz 0-NaCI, and -H2O-MgCl2
at 25 C. a = Hz 0; b = CaC12,0.23M;
c = NaHC03, 0.30M; d = NaCl, 0.42M; e = MgClz, 0.13M.
444
-0
E"
.03I
I-
"
,048
.046
,044
0
2
.z
,042
.04 I
I00
1,000
I o.oO0
HOURS
HOURS
Fig. , 15.3. Silicon concentration as a function of time foro kaolinite-H2 O,-Hz 0NaHC03 ,-HzO-NaCI,-Hz
0-CaC12, and -Hz O-MgCl2 a t 25 C. a = Hz 0; b = CaClz,
0.23M; c = NaHC03, 0.30M; d = NaCl, 0.42M; e = MgClz, 0.13M.
.04 I
100
1.000
I I I Ill
IC
00
HOURS
Fig. 15.4. Silicon concentration as a function of time forokaolinite-H2 0,-Hz 0NaHC03 ,-HZO-NaCl,-Hz
0-CaC12, and -Hz 0-MgClz at 25 C. a = Hz0; b = CaClz,
0.46M; c = NaHC03, 0.61M; d = NaCl, 0.88M;
e = MgClz, 0.25M.
445
5 . 0 3 4 1
In
.03I
100
,,
I(
10.000
I.000
HOURS
Fig. 15.5. Silicon concentration as a function of time for montmorillonite-H2 O,-H2OCaC12 ,-H2 0-NaHC03 ,-Hz 0-NaCl, and -Hz 0-MgC12 a t 25'C. a = Hz 0; b = CaClZ,
0.23M; c = NaHC03, 0.30M; d = NaCl, 0.42M; e = MgC12, 0.13M.
.04
.
I
I00
1,000
10,000
HOURS
Fig. 15.6. Silicon concentration as a function of time for montmorillonite-H2 O,-Hz 0CaClz ,-Hz 0-NaHC03 ,-HZ 0-NaCl, and -Hz 0-MgC12 at 25'C. a = H2 0; b = CaCl2,
0.46M;c = NaHC03, 0.61M; d = NaCl, 0.88M;e = MgCl2, 0.25M.
100
1,000
HOURS
10 100
446
i00
1,000
HOURS
.032
.031
,048-
l.000
HOURS
IC
Fig.' 15.9. Silicon concentration as a function of time for serpentine-Hz 0,-HzOCaClz ,-Hz 0-NaHC03 ,-HZ 0-NaCI, and -Hz 0-MgC12 a t 25'C. a = Hz 0; b = CaClz,
0.23M; c = NaHC03, 0.30M; d = NaCl, 0.42M; e = MgC12, 0.13M.
,032
,031
.048
I
100
I I I
Ill
1.000
noum
1 1 1 Ill1
10
Fig. 15.10. Silicon concentration as a function of time for serpentine-Hz 0,-Hz 0CaClz,-H? 0-NaHC03,-HzO-NaCI,
and -HzO-MgCIz
a t 25'C. a = H z O ; b = CaC12,
0.46M; c = NaHC03, 0.61M; d = NaCI, 0.88M;e = MgClz, 0.25M.
EXPERIMENTAL EQUIPMENT
447
Experimental equipment
Because the silicates, which cause scale deposits in desalination equipment, react and equilibrate slowly with aqueous solutions, pressurized thermal equipment was used t o approach equilibrium more rapidly. No appropriate equipment was commercially available; therefore, the U.S. Bureau of
Mines designed and built the equipment shown in Fig. 15.11-14, based on
the type used by Dickson et al. (1963).
The pressure vessel was machined from sonic-tested stainless steel, and the
sample container was machined from pressure-formed Teflon 7. A Teflon
filter disk 1.429 cm in 0.d. by 0.318 cm thick (item 7 in Fig. 15.14) was
used t o filter the aqueous phase when a sample was collected for analysis.
44 8
EXPERIMENTAL METHOD
44 9
e,
v,
v!,
! d
4'
Fig. 15.13. Muffle furnace with pressure vessel, tubes, and thermocouples in place; 1 = thermocouple; 2 = sampling tube,lined with
Teflon spaghetti tubing; 3 = pressure control tube; 4 = insulation; 5 = heating elements; 6 =closure piece; 7 = steel piece for hoist lift;
and 8 = front view.
I'
Fig. 15.14. Pressure vessel with Teflon sample container in place; 1 = pressure vessel; 2 = thermocouple well; 3 = Teflon seal; 4 =
sample tube lined with Teflon spaghetti tubing; 5 = high-pressure tubing; 6 = closure piece; 7 = Teflon filter; 8 = Teflon sample
container; and 9 = sample bottle closure pieces.
45 1
FUNDAMENTAL EQUATIONS
where the change in molality with pressure at saturation and constant temperature is (am/aT)T. The effect of temperature on-the solubility of serpentine at constant pressure and the quantities s, S,, and (aG/am)p,T is
shown by:
where (am/aT)pequals the change in molality with temperatures at saturation and constant pressure. At saturation and constant composition, the
relationship between the effect of pressure variation on the equilibrium tems, and & is given by:
perature and the quantities u,
v,,
v,,
452
1
6
(7)
Most of these parameters, except y+, are reported in the literature (Klotz,
1950); the parameter yk for H4Si04 in solutions more concentrated than
0.01 molal is not reported. These values can be obtained graphically (Klotz,
1950) by plotting the logarithm of the molal concentration of H4Si04 in
solution versus the square root of the ionic strength of the solution, drawing
a smooth curve through the experimental points, and extrapolating to zero
EXPERIMENTAL DATA
453
ionic strength to obtain the logarithm of the square root of the equilibrium
constant K,. The y? can be calculated from:
yk = Ka'h/m
(11)
30
50
76
100
125
150
175
200
176 kg/cm2
352 kg/cm2
703 kg/cma
1,055kg/cm2
0.1045 x
0.1120
0.1150x
0.1075 x
0.9650x
0.7200x
0.4200 x
0.1150 x
0.1735 x
0.1810 x
0.1795 x
0.1705 x
0.1535 x
0.1270 x
0.90oo lo4
0.5500 x lo4
0.2045 x
0.2110
0.2120
0.2050 x
0.1895 x
0.1655 x
0.1350 x
0.10oo
0.2585 x
0.2660 x
0.2670x lo-'
0.2605 x 10"
0.2455 x
0.2210
0.1905 x
0.1590 x lo-'
10-~
lo4
lo4
lo4
lo4
various temperatures and pressures. Table 15.VI contains the coefficients for
first, second, and third degree equations derived from a least squares fit of
the data in Table 15.V. Table 15.VII presents the smoothed data for the
amounts of silicon that went into solution when reacting serpentine with
aqueous 0.05M sodium chloride solutions at various temperatures and pressures. Table 15.VIII contains the coefficient for first, second, and third
degree equations derived from a least squares fit of the data in Table 15.VII.
454
TABLE 15.IV
Coefficients for empirical equations and resulting standard deviations (a) derived from the
data in Table 15.111
Pressure
176 kg/cm2
S=a+bt
a
b
U
352 kg/cm2
703 kg/cm2
0.14567 x
0.22177 x
-0.55728 x 10 -0.71175 x
0.16388 x lo4
0.17652 x
S = a + b t + c t2
a
0.86221 x
b
0.81657 x
c
-0.60087 x
U
0.21557 x
S = a + b t + ct2 + d t 3
a
0.77886
b
0.11362
c
-0.92296
0.93284
d
U
0.18318
0.24774 x
0.30126 x
-0.61810 x 10 -0.59899 x
0.16566 x lo4
0.16282 x
lo4 0.15754 x
lod6 0.77264 x
lo- -0.64922 x lo-
lo- 0.18634 x lo-
lo4
lo-
x lo-
x lo-
x lo-
x
x
0.14803 x
0.11370 x
-0.10164 x
0.10636 x
0.13391 x
1,055 kg/cm2
lo-
lo-
lo-
lo--
0.18723
0.78028
-0.61160
0.99021
0.18125
0.10095
-0.84257
0.66894
0.56229
lo-*
x
x
x
0.24202 x
0.77015 x 10
-5.59881 x lo-
0.17255 x lo-
loW3
lo-
x
x
lo-
lo-
lo4
0.23157
0.11707
-0.10025
0.11693
0.97345
lo-
x lo-
x 10
TABLE 15.V
Smoothed molal silicon solubilities from serpentine in 0.05 molal calcium chloride solutions at various temperatures and pressures
Temperature
Pressure
(C)
30
50
75
100
125
150
175
200
176 kg/cm2
352 kg/cm2
703 kg/cm2
o.1010
0 . 2 0 4 5 ~lov3
0 . 2 1 0 5 ~lov3
0.2025 x
0.1955 x
0.1850 x
0.1720 x
0.1540 x
0.1325 x
0.3165 x
0.3355 x
0.3175 x
0.3170 x
0.2975 x
0.2840 x
0.2735 x
0.2525 x
10-~
0.1030 x
0.9850 x loW4
0.9300 x
0.8650 x lo4
0.7250 x
0.5650 x lo4
0.3650 x
EXPERIMENTAL DATA
455
TABLE 15.VI
Coefficients for empirical equations and resulting standard deviations (a) derived from the
data in Table 15.V
-.
Pressure
176 kg/cm2
352 kg /cm
703 kg/cm2
S = a + bt
a
b
(3
0.12328 x lo-
-0.37430 x
0.76194 x 10-
S = a + bt + ct2
a
b
C
0.95751 x
0.26192 x
-0.27826 x
0.12056 x
lo4
lov6
lo-
lo-
S = a + bt + ct2 + d t 3
a
0.98227 x lo4
b
0.16698 x 10C
-0.18257 x lo-
d
0.27713 x lo-
U
0.11573 x lo-
0.23102 x loV3
-0.43229 x 10
0.80191 x lo-
0.34775 x
-0.42874 x
0.93876 x
0.20276 x
0.21998 x
--0.28487 x
0.20391 x
0.32185 x lo-
0.16988 x 10
-0.26181 x lo-
0.61658 x lo-
lo-
lo-
0.19892 x
0.36685.~10
-0.43253 x lo-
0.42652 x lo-
0.19706 x lo-
0.29920
0.10385
-0.11373
0.25355
0.53361
x
x
x
x
x
lo-
lo-
lo-
lo-
lo-
TABLE 15.VII
Smoothed molal silicon solubilities from serpentine in 0.05 molal sodium chloride solutions at various temperatures and pressures
Temperature
(C)
30
50
75
100
125
150
175
200
Pressure
176 kg/cm2
352 kg/cm2
703 kglcm
0.1700 x lo4
0.1950 x lo4
0.2100 100.2200 lo4
0.2200 lo4
0.2100
0.1950 x 100.1700 x lo4
0.3700
0.3950
0.4100
0.4300
0.4200
0;4100
0.4000
0.3700
0.5300
0.5500
0.5600
0.5700
0.5600
0.5500
0.5250
0.5050
x 10x lo4
x lo4
x
x lo4
x lo4
x lo4
x lo4
lo4
x lo4
x lo4
x lo4
x lo4
x lo4
x lo4
x 10-
1,055 kglcm
0.7400 x 100.7700 x lo4
0.7750 x lo4
0.7900 x lo4
0.7650 x lo4
0.7600 x lo4
0.7400 x lo4
0.7150 x lo4
456
TABLE 15.VIII
Coefficients for empirical equations and resulting standard deviations
data in Table 15.VII
((7)
Pressure
176 kg/cm2
S=a+bt
a
b
U
S = a + bt + ct2
a
b
C
0.19939 x
-0.56601 x
0.18996 x
lo4
lo-
352 kg/cm2
0.40047 x lo4
0.56299 x
-0.13533 x 10- -0.17005 x
0.2Q454 x lo-
0.18211 x
lo4
x
x
x
x
lo4
lov6
lo4
x
x
x
x
x
lo4
0.13066 x lo4
0.32714
0.15828 x
0.16960
-0.69472 x 10*-0.74119
0.28312 x
0.40924
S = a + bt + ct2 + dt3
a
0.12438
b
0.18236
C
-0.93739
d
0.70283
U
0.26986
lo4
0.31912
0.20036
x
-0.10512
x lo- 0.89777
x 10
0.39434
703 kg/cm2
x 10
0.49784 x
0.13354 x
-0.65845 x
low6 0.38334 x
lo-
10-
0.48420
0.18585
-0.11856
0.15266
0.33519
x
x
x
x
x
lo-
lov9
lo4
10
lo-
1,055 kglcm
0.77924 x
-0.19774 x
0.19618 x
lo4
loU7
lo-
0.71234 x
0.13485 x
-0.67625 x
0.71101 x
lo4
low6
low9
0.68299
0.24740
-0.18106
0.32852
0.58769
lo4
x
x
x
x
x
lo-
10-
TABLE 15.IX
Smoothed molal silicon solubilities from serpentine in 0.1 molal sodium chloride solutions
at various temperatures and pressures
Temperature
(C)
Pressure
176 kg/cm2
30
50
75
100
125
150
175
200
0.2350
0.2800
0.3100
0.3300
0.3200
0.2900
0.2700
0.1750
lo4
lo4
x lo4
x lo4
x
x
lo4
x lo4
x lo4
35 2 kg/cm2
0.3200
0.3650
0.4000
0.4150
0.4350
0.4050
0.3600
0.2500
x
x
x
x
x
x
x
x
lo4
lo4
lo4
lo4
lo4
703 kg/cm
1,055 kglcm
0.5700
0.6100
0.6500
0.6600
0.6450
0.6150
0.5700
0.4950
0.1355
0.1435
0.1475
0.1495
0.1480
0.1450
0.1415
0.1325
x
x
x
x
lo4
lo4
lo4
x lo4
x lo4
x lo4
x lo4
x
x
x
x
x
x
x
lo4
lo4
lo4
lo4
low4
lo4
lo4
457
Coefficients for empirical equations and resulting standard deviations (a) derived from the
data in Table 15.IX
Pressure
176 kg/cm2
S=a+bt
a
b
a
S = a + bt + ct2
a
b
c
703 kg/cm2
0.30724 x
-0.27390 x
0.45114 x
lo4
lo4
lo-'
0.39656 x
-0.24585 x
0.54718 x
lo4
0.14511
0.34728
-0.16387
0.84998
10-
0.20125 x
0.42680 x
-0.19742 x
0.12037 x
S = a + b t + ct2 + d t 3
0.16424
b
0.27393
c
-0.89940
d
-0.21411
a
0.80897
352 kg/cm2
x
x
lo-'
x 104
0.27529 x
lo-'
low6 0.14290 x
x lov9 -0.88707 x
x lo-' '-0.82867 x lo-'
x
0.65538 x lod
x
0.64963 x
-0.42217 x
0.46091 x
0.47371
0.37802
-0.20340
0.10033
0.63945
'
lo4
lo-'
1,055 kg/cm2
0.14527 x
-0.21139 x
0.56072 x
lo-'
0.12509
0.44518
-0.20395
0.10164
lo-'
lo-'
x
x
x
x
x
x
x
x
lo4 0.12176 x
lov6 0.57294 x
lo-' -0.33271 x lo-'
lo-'' 0.37291 x lo-'
0.90915 x 10"
'
Table 15.IX contains smoothed data for the amounts of silicon that went
into solution when reacting serpentine with aqueous 0.W sodium chloride
solutions at various temperatures and pressures. Table 15.X contains the
coefficients for first, second, and third degree equations derived from a least
squares fit of the data in Table 15.IX. Plots of the silicon solubilities versus
temperature are shown in Fig. 15.15.
Summary and conclusions
Solubility determinations were made of five clay minerals in aqueous
saline solutions. In general, the dissociation of silicon as silica from the clay
minerals decreased with increasing concentrations of dissolved salts at
ambient temperatures and pressures. Solubility determinations of a serpentine mineral in aqueous saline solutions at elevated temperatures and pressures were determined in specially designed hydrothermal equipment. The
standard deviations of the experimental data were acceptable within the
limits of the equilibria time, and the smoothed data yielded acceptable
empirical equations. The equipment proved to be of excellent design and
construction.
The solubilities of silicon from a serpentine in aqueous salt solutions at
various temperatures and pressures can be calculated with the coefficients
458
- ,031 ,040
:-
- -
,046/
2 .034.-
x - x y
,031
.048 .O 46
KEY
.O 44
0
352 KQ/Cm2
.042x
.04 I
20
1,055 Kg/Cm2
703 Kg/Cm2
176 Kg/Cm2
40
60 00100
200 20
TEMPERATURE, "C
40
60 00100
200
Fig. 15.15. Molal silicon solubilities from serpentine in aqueous chloride solutions at
various temperatures and pressures.
VI, VIII, and X. The first-degree equation can be used to make a rapid
calculation with fairly good accuracy; the third-degree equation can be used
to calculate a more accurate value consistent with the experimental data.
Although equation 11 can be used to obtain approximate activity coefficients, considerably more data are needed for calculating accurate activity
coefficient values.
The solubility values obtained in a study of five clay minerals in aqueous
saline solutions indicated that in general the silicon solubilities decreased
REFERENCES
459
No detailed studies have been made about how drilling fluids, drilling
muds, well cuttings, and well-treatment chemicals may contribute to pollution. Studies of well blowouts and possible development of communication
between a fresh-water aquifer and an oil-bearing sand have been made
(Vedder et al., 1969) as have studies of possible pollution related to poor
production practices (Schmidt and Wilhelm, 1938). The fact that the brines
produced with oil and gas can contribute t o pollution is well known
(Crouch, 1964; Grandone and Schmidt, 1943; Taylor et al., 1940; Wilhelm
and Schmidt, 1935), but no universally satisfactory method of their disposal
is available. Disposal of brine by solar evaporation in evaporating ponds has
been investigated (Gunaji and Keyes, 1968), but final disposal of the residue
salts needs further development. Some brines contain valuable minerals
which are economically recoverable, and treatment or disposal of such brines
should be coordinated with mineral-recovery processes whenever possible
(Collins, 1966).
Several publications are available about oilfield brine disposal by subsurface injection into porous and permeable strata (Morris, 1956; Payne, 1966;
Rice, 1968); the staff of the East Texas Salt-Water Disposal Company (1953)
has prepared a comprehensive report that describes gathering systems,
pumps, treatment methods, and injection wells. Subsurface injection of
oilfield wastes provides a good method for disposal of potential water pollutants, but the results are not always satisfactory (Donaldson, 1964; Watkins
et al., 1960). This disposal method has been blamed as the possible cause of
earthquakes, and if a natural disaster, such as an earthquake, occurs, new
faults or fractures in subsurface strata may provide communications between
the strata containing the waste and fresh-water aquifer (Bardwell, 1966;
Evans, 1966; Warner, 1966).
Drilling
* Reprinted
43~2383-2393 (1972).
462
of the hole t o keep the drill bit and the bottom of the hole clean. The
drilling fluids are pumped from ground surface through a drill pipe and bit to
the bottom of the hole and returned t o the surface through the annulus
between the hole and the drill pipe. The flow of formation gas, oil, and brine
into the drill hole is blocked by a fluid-mud column which produces a
hydrostatic pressure that counterbalances or exceeds the formation pressures.
In certain geological environments, abnormally high-fluid pressures are
encountered, i.e., the hydrostatic pressure is greater than 0.107 kg cm-*
m-' of depth. When oil or gas wells are drilled into such an environment,
there always is the possibility of a blowout unless elaborate precautions are
taken and correct drilling muds are used. A situation can develop in uncemented or poorly cemented environments if degradation or sloughing
around the casing in a high-pressure zone occurs, allowing the pressured
hydrocarbons t o flow along the outside of the casing to a zone of lower
pressure; Fig. 16.1 shows how this can happen. Drilling fluids may include
gases, liquids, foams, and solids suspended in liquids. Liquid drilling fluids
include crude oil, fresh water, and salt water. Most of the solids suspended in
Conductor casing
Surface casing
Possible pollution
Siough o f f area
Fig. 16.1. Manner in which heaving shales or incompetent zones slough off and permit
communication of a lower zone with an upper zone.
DRILLING
463
TABLE 16.1
Some constituents used in drilling fluids and muds
Quebracho extract
Lignosulfonates, calcium and chrome derivatives
Acrylonitrites (such as hydrolyzed polyacrylonitrite)
Sodium salts of meta and pyrphosphoric acid
Natural gums
Tannins
Molecularly dehydrated phosphates
Subbituminous products
Protocatechuic acid
Barite
Lignins (such as humic acids)
Bentonite
Sugar cane fibers
Lime
Granular material, such as ground nutshells
Corn starch
Salt water
Soluble caustic/lignin product
Carboxy methyl cellulose
Crude oil
Sulfonated crude oil
Oil emulsions
Sodium chromate
Anionic and nonionic surfactants
Organophylic clay
Soaps of long-chain fatty acids
Phospholipids (e.g., lecithin)
Asbestos
liquids are called drilling muds and include the following: suspensiuns of
clays and other solids in water (water-base muds); suspension of solids in oil
(oil-base muds); oil-in-water emulsions (oil-emulsion muds); and water-in-oil
clay emulsion (inverted emulsion muds). Table 16.1 lists some of the compounds in drilling muds (Caraway, 1953; Simpson et al., 1961).
Sulfonated drilling muds are prepared by: (1) sulfonating asphaltic crude
oil with sulfuric acid, followed by neutralization with sodium silicate and ion
exchanging with hydrated lime; or (2) absorbing concentrating sulfuric acid
on a porous carrier, e.g., diatomaceous earth, and then sulfonating asphaltic
crude oil with acid carrier, followed by partial neutralization with sodium
hydroxide and ion exchanging with hydrated lime.
The usual asphaltic crude oils that are used yield a 5- t o 7-wt.% carbon
residue and have an API gravity in the range of 26'-31'.
Some blends may
contain an 18' API asphaltic crude oil with a 12-wt.% carbon residue blended with a paraffinic 42' API crude oil with a 0.5-wt.% carbon residue. These
muds are usually mixed with oil a t the drilling site and used in the drilling
464
operation. As the cuttings plus the used drilling mud are recovered from the
well, the drilling mud is usually separated from the cuttings and reused.
Some, of course, will be lost because it adheres to the cutting; therefore,
some will present a possible water or land pollution hazard (Messenger,
1963).
The use of quebracho, starch, and carboxy methyl cellulose in formulating
drilling muds has decreased in the last decade, whereas the use of chrome
lignosulfonates has increased. The use of lime-treated mud systems has also
decreased, whereas the use of low-solid muds, invert emulsions, and chrome
lignosulfonate systems has increased.
Considerable money is invested in drilling muds, especially in the heavier
muds; consequently, they are recovered for reuse. Such muds are primarily
used for emergencies, such as lost circulation and high-pressure kicks from
both gas and salt water. Many of the used muds are treated with high
concentrations of lignosulfonates t o produce a stable mud with specific
properties.
Possible sources of pollution from drilling fluids and muds are the fluids
and muds that may be spilled during drilling, those that may escape into a
subsurface fresh-water aquifer, those that cling to the drill cuttings, and
those that are not reused. The data in Table 16.1 indicate that several constituents in drilling fluid and mud are capable of polluting water and land.
Hydrochloric
Formic
Acetic
3.3
7.6 x
3.8 x
lo5
lo2
lo2
DRILLING
46 5
Corrosion inhibitors
According to Hurst (1970), a universal super inhibitor has evaded the
researcher for 40 years. Such an inhibitor would be useful to prevent steel
casing and tubing from corroding as a result of acid treatment of a well. The
best available high-temperature inhibitor is a combination of sodium arsenite
with an alkyl phenolethylene oxide surfactant, and arsenic-type inhibitors
have been used for both low- and high-temperature applications since the
1930s. Table 16.111 lists some of the inhibitors used in the United States
(Cowan, 1970).
TABLE 16.111
Types and amounts of inhibitors used in oil- and gas-well treatment
~~
Inhibitor
Sodium msenite
Imidazoline
Abiethylamine
Coal tar derivatives
Acetylenic alcohol-alkyl pyridine
4.54
5.68
3.18
1.14
1.36
lo5
lo5
lo5
lo5
lo5
~~
TABLE 16.IV
Types and amounts of other additives used in oil- and gas-well treatment
Additive
Lactic acid (44%)
Citric acid
Alkylaryl sulfonic acid
Zirconium oxychloride (20%)
Quaternary ammonium derivatives
Polymers
Gum gum
Fluid loss agents
Emulsion preventers
2.61 x
9.08 x
2.27 x
1.14
9.08
4.54
2.61 x
8.17
2.04
lo5
lo3
lo5
lo5
lo4
lo4
lo6
lo5
lo5
466
Other additives
To reduce friction, reduce loss, sustain permeability, prevent emulsions
from forming, and prevent precipitation, additives are added to the oil- or
gas-well systems. Table 16.IV lists some of the compounds used for these
purposes and the approximate amounts used in 1year.
Possible break
Conductor casing
Pass i b Ie po I Iu t ton
Surface casin
Fig. 16.2. Probable manner whereby a well blowout can develop communication between
an upper sand and a lower sand.
PRODUCTION
467
46 8
Once the crude oils escape upon land or water, they are subjected to
evaporation, oxidation, solution, dispersion, and utilization by microorganisms. The lighter crude oils will evaporate more readily than will the
heavy ones. The lower hydrocarbons, e.g., methane and benzene, though
relatively insoluble in water, will be more soluble than the higher molecular
weight hydrocarbons; the crude oils containing sulfur compounds probably
will oxidize less rapidly than will those containing metallo compounds.
Crude oils, when spread on salt water, such as the sea, will quite rapidly form
highly stable water-in-oil emulsions, as was exhibited in the Torrey Canyon
disaster.
This type of emulsfon forms thick blobs of oil which are fairly resistant t o
dispersal, oxidation, and bacterial reactions. The reason that this type of
emulsion forms with salt water has not been clearly established. A means of
readily reverting such emulsions t o an oil-in-water type would be desirable
for quick dispersal (Dean, 1968).
Emulsions of petroleum and brine or mixtures of crude oils and sand that
are difficult to break can be found on surface disposal ponds. Should these
ponds overflow, the surrounding land or surface streams will be polluted.
Crude oil also may escape from leaky connections, improperly plugged wells,
improperly cased and cemented wells, holes in lines or storage tanks, or as a
result of an accident. Burning of the petroleum or emulsions, or both, that
enter brine ponds can contribute to air pollution, and all of the petroleum
will not be completely consumed by the fire.
Oil production may produce pollution in onshore or offshore areas from
blowouts of the wells, dumping of oil-based drilling muds and oil-soaked
cuttings, or losses of oil or brine in production, storage, and transportation.
Over 320,000 km of pipelines operating at pressures to 70 kg/cm2 are used
throughout the country and in offshore areas. Any rupture or accidental
puncture of any of these lines results in pollution.
PRODUCTION
469
(K+), barium (Ba+ ), strontium (Sr+), ferrous iron (Fe+ ), ferric iron
(Fe+3), chloride (Cl-), sulfate (SO4- ), sulfide (S- ), bromide (Br- ),
bicarbonate (HC03-), and dissolved gases, such as carbon dioxide (CO),
hydrogen sulfide (H,S), and methane (CH,). The stability of petroleumassociated brine is related to the constituents dissolved in it, the chemical
composition of the surrounding rocks and minerals, the temperature, the
pressure, and the composition of any gases in contact with the brine
(Fulford, 1968).
Scale inhibitors are added to waters and brines t o prevent the precipitation
reactions. Some of the chemicals used in these inhibitors are listed in Table
16.V.
TABLE 16.V
Chemicals used in scale inhibitors
Ethylenediamine tetraacetic acid salts
Nitrilotriacetic acid salts
Sodium hexametaphosphate
Sodium tripolyphosphate
Sodium carboxymethyl cellulose
Aminotrimethylene phosphate
470
DISPOSAL
471
soil and shale in the pond area. This amount of soluble or leachable salt
remaining in the area indicates that the return of the subsurface water and
soil t o their prepollution level is a very slow process and may take several
decades. Network pollution zones appear to form where formation fracture
conjugates occur. Leaching appears to be entirely dependent upon the
flushing mechanism provided by meteoric water.
The cation concentrations in the clay minerals were evaluated by X-ray
diffraction techniques to trace cation transportation rates. Chloride analysis
was selected as the most useful single means of detecting the presence of
oilfield brine pollution, but the associated cation concentration should also
be determined t o formulate a more complete picture. Cation adsorption
studies are apparently useful in differentiating brine-polluted soil and shale,
clay mineral studies provide the information on the environmental characteristics of the pollution media, and cation exchange information aids in
explaining the apparent differential transportation rates of ions in brine
seepage solutions (Bryson et al., 1966; Siever, 1968).
Disposal
Subsurface disposal
A problem associated with subsurface brine disposal is casing leaks in the
disposal well, which could allow the brine to enter fresh-water aquifers. Fig.
16.3 shows how an improperly designed disposal well and a leaky oil well
can pollute a fresh-water aquifer. Erroneous geologic knowledge of the subsurface formation into which the brine is being pumped presents another
problem. Brine usually is pumped into a subsurface formation that contains
similar brine; however, exact knowledge of the faulting and fracturing of
such a subsurface formation is difficult t o discern. Because the brine is
pumped into the formation, bottomhole pressure must not exceed 0.23 kg
cm- m-l of overburden, or the hydraulic pressure may cause fracturing
and in time, the wastes may migrate t o a fresh-water zone.
Petroleum-associated brines from two different formations may form
precipitates if they are mixed. For example, with a well used for disposal of
brines produced from several producing oil wells, it is imperative that precautions be taken in mixing and treating the brines before injection. If the
brines are incompatible and inappropriate precautions are taken, there is a
possibility that deposits will form and filter out on the face of the injection
formation, thus reducing the permeability. The quantity of deposits formed
from incompatible brines depends on ions present. The more common
deposits resulting from reactions of incompatible brines are gypsum
(CaS04 * 2 HO), anhydrite (CaS04), aragonite (CaCO,), calcite (CaC03),
celestite (SrS04), barite (BaS04), troilite (FeS), and siderite (FeCO, ).
Subsurface brine disposal can be categorized as confinement or containment; confinement is the placement of brines in a horizon where any move-
472
Fig. 16.3. Routes by which salt water can enter fresh water wells from faulty oil or
disposal wells.
DISPOSAL
473
474
REFERENCES
475
Evans, D.M., 1966. The Denver area earthquakes and the Rocky Mountain arsenal
disposal well. Mountain GeoL, 3:23-26.
Fulford, R.S., 1968. Effects of brine concentration and pressure drop on gypsum scaling
in oil wells. J. Pet. TechnoL, 20:559-564.
Grandone, P. and Schmidt, L., 1943. Survey of subsurface brine-disposal systems in
western Kansas oilfields. U S . Bur. Min. Rep. Invest., No.3719, 20 pp.
Gunaji, N.N. and Keyes, Jr., C.G., 1968. Disposal of brines by solar evaporation. U.S. O f f .
Saline Water Res. Dev. Progr. Rep., No.351, 213 pp.
Harris, O.E., Henrickson, A.R. and Coulter, A.W., 1966. High-concentration hydrochloric
acid aids stimulation results in carbonate formations. J. Pet. TechnoL 18:1291-1296.
Hem, J.D., 1961. Stability field diagrams as aids in iron chemistry studies. J, Am. Water
Works Assoc., 53:211-232.
Hurst, R.E., 1970. Market for completion and stimulation chemicals. Div. Pet. Chem.,
A m . Chem. Soc., Meet., Houston, Texas, February 22-27, 1970, p.l5(12)F9
(abstract).
Messenger, J.U., 1963. Composition, properties and field performance of a sulfcnated
oil-base mud. J. Pet. TechnoL, 15:259-263.
Morris, W.S., 1956. Salt waters disposal from the engineering viewpoint. Presented to the
Res. Comm., Interstate Oil Compact Comm., Dallas, Texas, May 31, 1956.
Payne, R.D., 1966. Salt water pollution problems in Texas. J. Pet. Technol., 18:
1401-1407.
Research Committee, Interstate Oil Compact Commission, 1960. Production and Disposal
of Oilfield Brine in the United States and Canada. The Interstate Oil Compact Commission, Oklahoma City, Okla., 95 pp.
Research Committee, Interstate Oil Compact Commission, 1968. Subsurface Disposal of
Industrial Wastes. The Interstate Oil Compact Commission, Oklahoma City, Okla., 109
PP.
Rice, I.M., 1968. Salt water disposal in the Permian Basin. Prod. Monthly, 32:28-30.
Schmidt, L. and Wilhelm, C.J., 1938. Disposal of petroleum wastes on oil producing
properties. U.S. Bur. Min. Rep. Invest., No.3394, 36 pp.
Siever, R., 1968. Establishment of equilibrium between clays and sea water. Earth Planet.
Sci. Lett., 5:106-110.
Simpson, J., Cowan, J.C. and Beasley, Jr., A.E., 1961. Some recent advances in oil-mud
technology. Presented at 36th Annual Meet., AIME, Dallas, Texas, October 8-1 1 ,
1961, SOC.Pet. Eng. Paper, No. 150, 16 pp.
Taylor, S.S., Holliman, W.C. and Wilhelm, C.J., 1940. Study of brine disposal systems in
Illinois oilfields. U.S. Bur. Min. Rep. Invest., No.3534, 20 pp.
Vedder, J.G., Wagner, H.C. and Schollhomer, J.E., 1969. Geologic framework of the
Santa Barbara channel retion. U.S. GeoL Sum. Prof. Paper, No.679, pp.1-11.
Warner, D.L., 1966. Subsurface injection of liquid wastes. In: N.E. Grosvenor, J.D. Haun
and D.T. Snow (Editors), Natural Gas, Coal, Groundwater: Exploring New Methods
and Techniques in Resources Research. University of Colorado Press, Boulder, Colo.,
pp. 1 07-1 2 5.
Watkins, J.W., Armstrong, F.E. and Heemstra, R.J., 1960. Feasibility of radioactive waste
disposal in shallow sedimentary formations. NucL Sci Eng., 7:133-143.
Wilhelm, C.J. and Schmidt, L., 1935. Preliminary report on the disposal of oilfield brines
in the Ritz-Canton field, McPherson Co., Kansas. U.S. Bur. Min. Rep. Invest.,
No.3297, 20 pp.
REFERENCE INDEX*
*Only page references to text pages are made in this index. References to pages
containing bibliographic details have been omitted. These details are given at the end
of each chapter.
478
Bryson, W.R., 405, 471
Buckley,S.E., 12, 169, 181, 313
Buckman, H.D., 138
Burges, A., 186
Burmistov, D.F., 162
Burnam, C.W., 185
Burriel-Marti, F., 54
Burst, J.F., 140, 209, 240, 294, 343
Bush, P.R., 224
Butler, G.P., 205
Butt, J.B., 393, 395, 399
Califet, Y., 182
Caraway, W.H., 207, 297, 372, 463
Carpelan, L.H., 203
Carpenter, A.B., 226
Cartmill, J.C., 210, 298, 311
Case, L.C., 195, 433
Castagno, J.L., '43
Chapman, G., 182
Chave, K.E., 207, 240
Chebotarev, I.I., 226, 262, 265, 267, 289
Chenoweth, P.A., 330, 331
Cherney, S., 399
Chilingar, G.V., 207, 245, 321
Christ, C.L., 50, 167, 198
Christensen, J.J., 399, 411
Christman, R.F., 186
Clark, S.P., 194
Clarke, F.W., 197
Claussen, W.F., 179
Clayton, R.H., 243
Cloke, P.L., 168, 208
Coggeshall, N.D., 12, 181, 314
Collins, A.G., 15, 27, 29, 37, 43, 54, 60,
61, 63, 83, 94, 96, 107, 108, 109, 110,
111, 135, 137, 140, 143, 145, 156,
1 5 7 , 1 6 9 , 1 7 1 , 204, 219, 226, 227,
229, 232, 233, 238, 297, 346, 369,
372, 3 9 0 , 3 9 4 , 4 0 2 , 4 4 1 , 4 6 1 , 4 7 4
Collom, R.E., 272
Columbus, N., 382
Conolly, J.F., 180
Cooper, J.E., 184, 297, 311, 315
Corbett, C.S., 293
Coulter, A.W., 465
Cowan, J.C., 369, 370, 372, 463, 465
Cox, D.L., 392
Craig, H., 91
Crocker, L., 399
Crouch, R.L., 4 0 5 , 4 6 1
Czamanske, G.K., 224
REFERENCE INDEX
Dall'Aglio, M., 1 5 2
Dapples, E.C., 208
Davidson, M.J., 308
Davies, D.W., 437
Davis, J.B., 185, 301, 302, 313
Davis, J.W., 145, 147, 369, 372
Davis, S.N., 430, 434
Davis, W.D., 422, 423
Dean, J.A., 54, 80
Dean, R.A., 468
Deffeyes, K.S., 203, 204
Degens, E.T., 181, 182, 207, 210
DeLaguna, W., 428
Deroo, G., 309
DeSitter, L.Y., 242
Dewiest, R.J.M., 430, 435
Dickey, P.A., 1 , 205, 210, 226, 274, 288,
298, 311, 343, 346
Dickinson, G., 343, 344
Dickson, F.W., 369, 371, 447
Diehl, H., 96
Dingman, R.J., 132, 226
Disteche, A., 371
Disteche, S., 371
Diterikhs, O.D., 308, 314
Dodge, B.F., 402
Donaldson, E.C., 419, 461
Drescher, W.J., 472
Dressman, R.C., 25
Drong, H.J., 209
Dudova, M.Ya., 308, 314
Duffy, J.R., 180
Dunham, K.C., 224
Dunlap, H.F., 32, 3 5
Dunseth, M.G., 396
Dunton, M.L., 310
Dutoit, M.M.S., 1 8 6
Duursma, E.K., 178
East Texas Salt-Water Disposal Company,
421,423,461
Ebrey, T.G.,
94, 9 6
Eckhardt, F.J., 238
Edmund, R.W., 1 7 7 , 4 2 5
Egleson, G.D., 226, 234
Eichelberger, J.W., 25
Eley, D.D., 177
Elliott, Jr., W.C., 256
Ellis, A.J., 227, 370
Elliston, H.H., 422, 423
Emery, E.M., 184
Emery, K.O., 201, 207, 293
Engelbrecht, R.S., 1 8 3
Enright, R.J., 473
REFERENCE INDEX
Epstein, S., 91
Erdman, J.G., 309,310
Eshaya, A.M., 402
Ettre, L.S., 185
Evans, D.M., 405,461
Evans, E.D., 296
Evans, G., 205
Evans, M.E., 177
Ewing, G.C., 203
Fabricand, B.P., 65,207
Fajardo, I., 346, 347
Fash, R.H., 308
Ferguson, W.S., 311
Ferris, J.G., 434
Fertl, W.H., 346, 363,364
Fettke, C.R., 2
Feugere, G., 310, 322
Filonov, V.A., 317,318
Finch, W.D., 343
Fisher, F.L., 107
Fleischer, M., 133, 136, 141, 143, 145,
147,149,150,151,152,153,156,
158,159,161,162,164
Forgotson, J.M., 364
Forsman, J.P., 310
Foster, J.B., 362
Fowler, Jr., W.A., 245,343, 362
Frank, H.S., 177
Frear, G.L., 370
Friedman, G.M., 202,207,234
Friedman, I., 91,243, 244
Fuchtbauer, H., 209
Fulford, R.S., 369, 371, 380, 469
Fulton, Jr., R.B., 154, 216,217
Furman, N.H., 44
Gaida, K.H., 294
Galin, V.L., 321
Garbarini, G.S., 425,427
Garrels, R.M., 50,167,198
Garrett, R.G., 322
Garrison, A.D., 2
Gates, G.L., 207,297,372
Gautier, A., 108
Gehman, Jr., H.M., 310
Geodekyan, A.A., 308
George,D.R., 399
George, W.O., 107
Gerard, R.E., 310, 322
Gevirtz, J.L., 202
Gibbs, J.W., 449
Ginsburg, R.N., 202
Glater, J., 371
479
Glew, D.N., 371
Goebel, E.D., 425
Goldberg, E.D., 149
Goldschmidt, V.M., 133,136,138, 140,
141,145,147,150,151,155,158
Goldshteyn, R.I., 382
Goncharov, Yu.,152
Gordon, W.C., 3
Gorgy, S., 108
Grabau, A.W., 205
Grabowski, R.J., 157,216, 217
Graf, D.L., 243
Grandone, 461
Grauer, A., 211
Graves, Jr., R.W., 201
Greene, R.C., 373
Grim, R.E., 230, 232
Griswold, W.T., 1
Gullikson, D.M., 297
Gunaji, W.N., 461
Gutsalo, L.K., 313, 318,319
Haddenhorst, H.G., 209
Halliburton Company, 74,118
Ham, W.E., 201
Hames, D.A., 371
Hanshaw, B.B., 224, 320
Hanson, W.E., 181
:Hardaway, J.E., 425
Harkins, K.S., 343, 344
Harris, O.E., 465
Hastings, W.W., 107
Hawthorne, R.R., 32, 35
Hays, J., 245
Hedberg, H.D., 178, 309
Heemstra, R.J., 461
Heintz, J.A., 399,411
Helgeson, H.C., 224
Hem, J.D., 133,135,147,155,159,161,
168,170,469
Hemley, J.J., 152
Henningsen, E.R., 382
Henrickson, A.R., 465
Herrmann, R., 59, 227,228
Hill, G.A., 224, 320
Hiltabrand, R.R., 239
Hiss, W.L., 320
Hitchon, B., 244, 245, 296, 297, 299
Ho, A., 186
Hocutt, C.R., 12,169,181,357
Hodges, Jr., R.M., 241
Hodgman, C.D., 34
Hodgson, G.W., 180,210,296,299,311
Hoerr, C.W., 183
480
Holliman, W.C., 461
Hollister, J.C., 434
Holser, W.T., 163, 205
Hood, D.W., 183,184
Horvitz, L., 308
Hottmann, C.E., 343, 344, 347, 363
Howell, J.V., 1
Hoylman, H.W., 321
Hubbert, M.K., 382
Hulse, B.T., 432,433
Hunt, J.M., 178,205, 210, 296, 298, 310
Hunter, J.A., 399,413
Hurst, R.E., 464, 465
Ibert, E.R., 107
Illing, L.V., 202
Imbimbo, E.S., 65,207
Jamieson, G.W., 205, 310
Jankowsky, W.J., 209
Jebens, R.H., 399,413
Jeffery, L.M., 183, 184
Jeltes, R., 181
Jobelius, H., 211
John, L.M., 183
Johnson, A.C., 322
Johnson, R.K., 343, 344
Johnston, J., 370
Jones, B.F., 223, 225
Jones, O.S.,419
Jones, P.H., 245,298,343,346,347,363
Jones, P.J., 32
Kabot, F.J., 185
Kaley, M.E., 201
Kaplan, I.R., 82, 170, 208
Karasik, M.A., 152
Karaskiewicz, J., 322
Karim, M., 321
Kartsev, A.A., 297,308,314
Kawai, K., 165,179
Kazmina, T.I., 153
Keefter, R.M., 179
Kelley, W.P., 230
Kellog, M.W., and Company, 172,173
Keyes, Jr., C.G., 461
Khitarov, N.I.,140, 232, 240
KidwelI, A.L., 178,298
Kimura, S.,241
Kincaid, E.E., 392
King, R.M., 150
Kinsman, D.D.J., 205
Klein, G., 399
Klemme, H.D., 309
REFERENCE INDEX
Klotz, I.M., 352
Knopf, A., 155
Knowles, D.B., 434
Knudsen, M., 172
Kwrner, W.E., 184
Kohout, F.A., 382
Kolodii, V.V., 316
Koons, C.B., 311
Kopp, J.F., 25
Korobov, D.S., 317
Kortsenshtein, V.N., 313,314
Kovieheva, I.S., 210
Koyama, T., 165
Kozin, A.N., 233
Kozlov, M.F., 43
Kramer, J.R., 225, 226, 240
Krause, H.R., 183
Krauskopf, K.B., 107
Kravchik, T.E., 314
Krejci-Graf, K., 232, 317
Krivosheya, V.A., 313
Kroepelin, H., 322
Kroner, R.C., 25
Krouse, H.R., 303
Krumbein, W.C., 204,205,429
Kudelskii, A.V., 43
Kuznetsov, S.I., 301, 302
Kumetsova, Z.I., 211
Kvenvolden, K.A., 205, 315
Lagerwerff, J.V., 371
Lamontagne, R.A., 182
Landes, K.K., 309
Lane, A.C., 3
Lane, E.C., 272
Larson, T.E., 150
Larson, T.J., 241
Latimer, W.M., 29, 167
Laurent, P., 183
Laurence, L.L., 420,422
Leobourg, M., 11
Leuszler, W.E., 420,422
Levorsen, A.I., 197, 295,382
Lewis, G.N., 373,452
Lichtenberg, J.J., 25
Linnenbom, V.J., 181
Litchfield, C.D., 183
Lochte, H.L., 185
Loeb, S., 241
Loleit, A.J., 425
London, E.E., 313, 317
Long, F.A., 180
Longbottom, J.E., 25
Lotze, F., 204
REFERENCE INDEX
Louis, M., 182
Low, P.F., 242, 346
Lowenstam, H.A., 202
Lucchesi, P.J., 379
Lucia, F.J., 203,204
Lutz, F.B., 108
Lyon, T.L., 138
Mandl, I., 211
Manheim, F.T., 223
Manjikian, S., 241
Manuel, O.K., 227
Marcy, V.M., 43, 101,122
Margoshes, M., 83
Marsden, S.S., 165,179
Marsh, G.H., 47
Martell, A.E., 145
Mason, B., 138, 143, 144, 149,150, 151,
153,158,159,161,163,165
Matthews, C.S., 428
Mayeda, T.K., 91, 243
Maxey, G.B., 243
McAlister, J.A., 11
McAuliffe, C.D., 180, 181,210, 311,314,
315
McBain, J.W., 183
McBermott, E., 308
McCann, T.P., 425
McCutchan, J.W., 371
McDevit, W.F., 180
McElvain, R.G., 318
McIlhenney, W.F., 399,413
McIver, R.D., 295
McKelvey, J.G., 242
McLean, D.D., 429
McLeod, H.O., 307
McNellis, J.M., 132
Meents, W.F., 243
Meinert, R.N., 310
Meinschein, W.G., 298
Mellon, M.G., 35
Merritt, Jr., L.L., 92
Messenger, J.U., 464
Metcalfe, L.D., 184
Metler, A.V., 371
Meyer, H.W.H., 185
Meyerhoff, A.A., 212
Michaels, A.S., 241
Middleton, F.M., 183
Midgett, M.R., 25
Miholic, S., 150
Miller, E.E., 209
Miller, J.C., 226
Miller, W.C., 390, 399
481
Mills, R. van A., 2, 272
Milne, I.H., 242
Mitgarts, B.B., 153
Moeller, T.,133, 135,136, 141
Mogilevskii, G.A., 297
Moore, C.A., 202
Moore, D., 170, 208
Morgan, C.O., 130
Morgan, J.J., 199
Morris, R.C., 205
Morris, W.S., 421,424,461
Mousseau, R.J., 12,324
Muehlberg, P.E., 399, 411
Muir, R.O., 228
Mun, A.I., 162
Munn, M.J., 1, 2
Murata, K.J., 107
Myagkov, V.F., 162
Nagy, B., 180
Nalco Chemical Company, 186
Namoit, A.Y., 177
Natural Gasoline Association of America,
186
Naumor, G.B., 168
Nektarova, M.B., 185, 316
Nemethy, G., 177
Neuberg, C., 211
Neruchev, S.G., 210
Neuman, E.W., 372
Neumann, H.J., 211
Noad, D.F., 11, 321
Nordby, H.E., 186
Norris, M.S., 12, 314
Nutter, B.P., 11
OConner, J.T., 183,474
OConner, R.E., 405
Oden, S., 185
Odum, H.T., 145
Ostroff, A.G., 169,256,274,371, 428,
437
Oudin, J.L., 309
Ovchinnikou, N.V., 165
Packman, R.F., 186
Page, H.J., 186
Paine, W.R., 343, 347
Palmer, C., 254,256, 257
Parker, J.W., 224, 321
Pate, B.D., 108
Patnode, H.W., 310
Patterson, M.S., 373
Pavolva, G.A., 165
482
Payne, R.D., 461
Peake, E., 180,296,311
Pearson,C.A., 108,109,110,111
Peck, R.B., 206, 294, 344
Pennebaker, E.S., 344, 363
Peterson, J.A., 320,425
Peterson, J.B., 425
Pettijohn, F.J., 197
Philipp, W., 209
Philippi, G.T., 295, 296, 300, 309,310
Phillips, R.C., 368,369, 372, 380
Phleger, F.B., 203
Piper, A.M., 132
Piper, T.J., 183
Pirson, S.J., 169, 208, 308
Pirsson, L.V., 155,168
Platte, J.A., 101
Plumley, W.J., 201
Pollard, T.A., 207
Popov, A.I., 382
Posner, A.M., 183
Potter, E.C., 27
Pourbaix, M.J.N., 30, 167
Powers, M.C., 294,343
Prescott, J.M., 183
Presley, B.J., 82
Price, L.C., 178, 296
Privasky, N.C., 425
Pugin, V.A., 140, 232, 240
Pusey, 111, W.D., 311
Pytkowicz, R.M., 371
Pyushchenko, V.G., 321
Quaide, W., 205
Querio, C.W., 226,234
Rae, A.C., 182
Rainwater, F.H., 31
Rakestraw, N.W., 108
Ralston, A.W., 183
Ramirez-Munoz, J., 54, 67
Ramsey, T.R., 320
Randall, M.H., 373,452
Rankama, K., 197
Ransone, W.R., 308
Reed, W.E., 210
Reeder, L.R., 426,430,434,436
Reichertz, P.O., 207
Reistle, Jr., C.E., 131,272
Research Committee, Interstate Oil
Compact Commission, 473
Rettig, S.L., 223
Reuter, J.H., 181,182,210
Reynolds, L.C., 432,433
REFERENCE INDEX
Rice, I.M., 437,461,473
Rich, J.L., 2
Rieke, 111, H.H., 245
Riley, G.A., 206
Riley, J.M., 399
Ringwood, A.E., 194
Risley, G.A., 201
Rittenberg, S.C., 207
Rittenhouse, G., 157,216, 217, 229
Roach, J.W., 320
Robinson, J.W., 65
Robinson, L.R., 183
Rogers, G.S., 256
Rogers, W.B., 1
Rosaire, E.E., 308
Rosenqvist, I.T., 207
Rosin, J., 23
Ross, C.S., 197
Ross, R.D., 426,427,433
Rubio, F.E., 303
Ruddick, E.L., 399
Russell, D.G., 428
Russell, W.L., 242
Sahama, T.G., 197
Salutsky, M.L., 396, 399
Sandell, E.B., 98,99
Sanders, J.E., 207,234
Saraf, D.N., 180
Savchenko, V.P., 316
Scheraga, A.A., 177
Schilthuis, R.J., 1, 3
Schmidt, G.W., 294, 314,343,361, 362,
405
Schmidt, L., 461,471
Schoeller, H., 232, 254, 267,271
Schollhomer, J.E., 461
Schrayer, G.T., 12, 314
Schrink, D.R., 107
Schwab, R., 317
Schwanenbek, F.X., 272
Scribner, B.F., 83
Selby, S.M., 34
Selm, R.P., 432,433
Serebriako, O.I., 317
Sestini, F., 186
Shaborova, N.T., 185, 316
Shaffer, L.H., 369,371,380
Shankland, R.S., 34
Shaw, D.R., 166,244
Shaw, T.I., 166
Shearman, D.J., 205
Shilov, I.K., 316
Shimp, N.F., 243
REFERENCE INDEX
Shiram, C.R., 343, 347
Shiskina, O.V., 165
Shreve, R.N., 395
Shvets, V.M., 211, 316
Siegel, A., 182
Siever, R., 207,471
Sikka, D.B., 318
Sillen, L.G., 145, 166
Silverman, S.R., 311
Simons, H.F., 308
Simpson, J., 463
Skinner, B.J., 193
Sloss, L.L., 429
Slowey, J.F., 184
Smales, A.A., 108
Smith, G.F., 96
Smith, H.M., 303
Smith, N.O., 180
Smith, P.V., 211
Smith, W.W., 419,438
Snow, D.T., 438
Sokolov, V.A., 308
Solomon, H.J., 393, 395, 399
Souriragan, S.,241
Spencer, C.W., 425
Spencer, D.W., 311
Spiegler, K.S., 242
Ssutu, L.,371
Stallman, R.W., 434
Stead, F.L., 425
Steelink, C., 186
Stiff, H.A., 131,132,371
Stormont, D.H., 308
Stratton, G., 108
Stumm, W., 199
Subotta, M.I., 297
Sudo, Y.,316
Sugawara, K., 165, 166
Sulin, V.A., 254, 257, 258, 347
Swigart, T.E., 272
Swinnerton, J.W., 181
Tabasaranskii, Z.A., 297
Taggart, M.S.,12, 169,181,313
Taguchi, K., 296
Takahashi, T., 202
Tallmadge, J.A., 393, 395, 399
Taylor, D.W., 206
Taylor, S.S., 461
Templeton, C.C., 369, 372
Terada, K., 165, 166
Terzaghi, K., 206, 294, 344
Tickell, F.G., 128
Thatcher, L.L., 31
483
Timko, D.J., 346, 363, 364
Tissot, B., 309
Tollin, G., 186
Tooms, J.S., 227
Torrey, P.D., 1, 2
Trask, P.D., 310
Trelease, S.F., 160
Tronko, I.V., 317
Truesdell, A.H., 223, 225
Trump, R.P., 242
Tunnell, G., 447
Tunyak, A.P., 185, 316
Ulrich, R.A., 425
Upson, J.E., 382
U.S. Bureau of Mines, 254, 272, 393, 404,
41 5
Usiglio, J., 203
Valyashko, M.G., 162,227
Vandenburgh, A.S., 223
Van Everdingen, R.O., 223
Van Nostrand Press, 211
Vasilev, V.G., 313
Vasileuskaya, A.Ye., 152
Vdovyking, P., 319
Veal, H.K., 425,427
Vedder, J.G., 461
Veldink, R., 181
Vermeulen, T., 399
Vetter, O.J.G., 368, 369, 372, 380, 461
Vilonov, V.A., 319
Vinogradov, A.P., 316
Vinogradov, V.L., 228,316
Viher, G.S., 200, 322
Von Engelhardt, W., 240, 294
Wagner, H.C., 461
Wallace, W.E., 8,343, 344
Walton, G., 183
Wangersky, P.J., 184
Waring, G.A., 135
Warner, D.L., 425,426,461
Washington, H.S.,197
Water, C.J., 111
Waters, Jr., O.B.,399
Watkins, J.W., 47, 108, 109, 110,461
Watson, J.A., 65
Weast, R.C., 34
Weaver, C.E., 294
Weimer, J.C., 434
Weintritt, D.J., 369, 370,372
Welcher, F.J., 40
Weller, J.M., 206
484
Welte, D.H., 297, 298, 309
Weyl, P.K.,203,204
White, D.E., 107,135,162,194,195,
206,232,240
White, W.A., 3, 243
Whitehead, H.C., 108
Whiting, R.L., 429
Whitney, E.D., 379
Wilhelm, C.J., 461
Willard, H.H., 92
Williams, J.A., 302, 303
Williams, P.M.,184
Wilson, A.L., 186
Wilson, D.F., 182
Wilson, J.E., 425
Winter, J.A., 25
Winters, J.C., 302,303
REFERENCE INDEX
Witherspoon, P.A., 180,182
Woodcock, A.H., 91
Wright, C.C., 437
Wright, J.L., 434
Wyllie, M.R.J., 32, 242
Yakoylev, Yu.I., 316
Yarbrough, H.R., 313
Yasenev, B.P., 308
Young, A., 244, 346
Yurovskii, Yu.M., 308
Zarrella, W.M., 12,181, 314
Zinger, A.S., 180, 314
Zobell, C.E., 30, 167,302
Zorkin, L.M., 313
SUBJECT INDEX
486
Bathyal-abyssal deposits, 201
Bell Canyon formation, 322, 327-329
-, calcium concentration, 329
-, chloride concentration, 328
-, dissolved solids content, 327
-, potentiometric surface map, 323, 324
Bell Creek field, Wyoming, 303
Benzene, 315
-, solubility, 179
Benzene method for prospecting, 181,
314
Beryl, 140
Beryllium, atomic absorption method, 65
-, constituent of oilfield waters, 141,142
-, emission spectroscopy method, 89
-, properties, 141
Bicarbonate, concentration and depth, 357
-,- and economic profit, 413
Bioconcentration, 228
Biogenic origin, 205, 293
Biological degradation of hydrocarbons,
301
Biological weathering, 197
Biosphere, 193
Bischofite, 162
Bittern-type brines, 359
Boiling point, 172
Bolivar Coastal field, 303
Borate boron, titrimetric method of boron,
37
Borehole temperature, 364
Boron, 21, 37
-, abundance, 153
-, concentration and economic profit,
404,413
-,- by evaporating, 154
-, - and geologic age, 408
-, constituent of oilfield waters, 153
-, emission spectroscopy method, 83
-, properties, 171
-, recovery, 415
Bradford Sand, 1, 2
Brine value, 414,416
Brine worth, 414,416
Brines (see also Oilfield brines and Oilfield
waters), 13, 27, 117, 159,160, 181,
213, 269,319,348,380,395,427,471
-, analyses, 272
-, classification, 225, 254, 257, 260,267
-, commercial, 415,416
-, composition, 384
-, concentrations of elements, 395
-, containing high bromine, 391
SUBJECT INDEX
Brines (continued)
-, operations, 389,395
-, ponds, 389,470
-, refinery, 390,395, 396,402,403
-, stabilization, 380,381
-, state regulations, 434
-, concentration, 361
-,
-,
-,
-,
Cadmium, 152
abundance, 152
atomic absorption method, 65
colorimetric method, 103
properties, 153
sphalerite as carrier, 153
Calcite, 194,198, 201, 208,370, 371,
461,471
-, solubility, 370
Calcium, 40, 73,140, 143, 283-289, 370,
395
-, abundance, 144
-, atomic absorption method, 65,72,75
-, complexometric method, 40
-, concentration, 289,361
-,- in Bell Canyon formation waters, 329
-,- and depth, 358
-,- and economical profit, 404,413
-,- by evaporating, 143,144
-,- and geologic age, 408
-, constituent of oilfield waters, 141,143
-,
-,
-,
-,
-,
SUBJECT INDEX
487
Calcium (continued)
-, recovery, 415
-, solubility, 370
Calcium carbonate, precipitate, 144, 171
-, solubility, 202
229-239
properties, 171
-, recovery, 415
-, titrimetric method (Mohr), 44
Chlorine, 161,398
-, abundance, 161
Chlorinity, 24
Chocolate Bayou field, 245, 362
Chromatographic techniques, 181-185
Chromium, atomic absorption method, 65
Chrysotile, 442
Cinnabar, 151,152
Classification of oilfield waters, 253, 276
Classification systems, applications, 274289
Clastics, 200
-, depositional environments, 200
Clay minerals, 140,209, 230, 240, 345,
430,433,441,442
-, authigenic, 201
Cleaning pipelines, 421
Coal ashes, 133
Colorado, 323
Colorimetric methods, interferences in, 93
Combination factor, 127
Compaction, 206,294
Compaction model, 344
Compatibility of oilfield waters, 367
Completion of disposal wells, 432
Composition of minerals, 441
Composition of oilfield waters, 213
Compressibility of rock and water, 428
Concentrating by ion exchange, 95
Concentrating brines, 240
Concentration change during evaporation,
134, 204,227,229,231-234, 238
Concentration ratios in brines, 236, 237
Concentration versus proximity to an oil
accumulation, 315
Confining beds, critical pressure of, 429
Connate water, 3, 169, 194, 270, 271
Contamination of shallow aquifers, 434
Continental slope drill hole, 223
Copper, 150
-, abundance, 150
-, atomic absorption method, 65,80
-, colorimetric method, 95,96, 150
-, properties, 148
Cordellera Isabella, Nicaragua, 323
Core samples analysis, 310
Corrosion inhibitors, 465,469
-,
488
Cretaceous age, 135, 154, 163,215, 227,
229
-, lithium concentration, 135
-, magnesium concentration, 143
-, potassium concentration, 139
-, sodium concentration, 137
-, strontium concentration, 146
Cretaceous age rocks, brines from, 237
Cretaceous system, concentration of
elements, 213
Critical pressure, 429
Cymric fields, California, 152
Decarboxilization, 185
Deep well injection, 420
-, acceptable geologic areas, 425
Delaware Basin, 329
Delaware sand, 322, 323
Deltaic deposits, 201
Density, 172
Denver Basin, 343
Deposition, organic matter, 205
-, silica, 206
Depositional basin, 200
Depositional environments, 200, 201,203
Depth, 226
-, versus concentration, 357, 358
Description for water sample, 16
Deuterium, mass spectrophotometric
method, 91
Devonian age, 234
Devonian deposits, 317
Devonian system, 185, 213, 217, 261
Dexter formation, 335
Diagenesis, 133, 207, 208, 232, 245, 267,
346
Diagenetic water, 194
Dilution technique, 41
Disodium 1,2-~yclohexanediaminetetraacetic acid, 40
Disposal, 471
Disposal brines, 411
Disposal costs of brines, 422
Disposal systems, cost of, 437
Disposal well, 412,424,425,432
-, cross section, 431
Disposal zone, 426,427
-, evaluation, 427
Dissolved gases, 12
Dissolved solids, 117,216, 284-286, 323,
325,362,410,419
- in Bell Canyon formation waters, 3,327
Dnepr-Donets Basin, 313,318
SUBJECT INDEX
Dolomite, 142, 194, 203, 234, 239
Dolomitization, 195,203, 204, 208, 234,
238
Dolostone deposits, 234
Dow Chemical Company, 391,399
Dowex A-l,96
Drilling, 463
-, disposal wells, 432
Drilling fluids, 461,463
Drilling muds, 8,170,343, 461, 463,468
Drill-stem test, 8, 12, 181
Earthquakes, 434
East Texas Basin, 224,232,272,283288, 321
East Texas field, 420,424
East Texas Salt-Water Disposal Company,
423
Economic value of brine, 403
Eh, 14,19,29, 166, 170, 199
Eh, unfiltered and filtered petroleum
producing wells, 320
Eh/pH plot, 159,168,170, 199
Electric log, 153, 341
-, cross section of southwest Louisiana,
349-352
Elements, minor, 220
Emission spectroscopy, 83
-, calibration curve, 88
-, emulsion calibration curve, 87
-, gamma curve, 87
Eocene age, 104,114,130, 152, 167,185,
212
Eolian deposits, 160
Epm (equivalents per million), 24, 274
Equivalents per million (epm), 24, 126,
269,275
Erosion, 198
Escape routes, 429
Evaluation, economic, 402
Evaporites, 137, 223, 238, 239
-, basin, 203
-, depositional environments, 203
Exchange reactions, 211
Fatty acids, 183,315
SUBJECT INDEX
Filtered petroleum-producing wells, pH
and eH values, 320
Flame spectrophotometric methods, 53
Florida, 333-335
Flow diagram of solubility equipment,
448
Flow line, 13
Flowsheet for descaled sea water and
fertilizers, 397
Flowsheet for fresh water and valuable
elements, 401
Fluid mechanics, 320
Fluid travel, 433
Fluoride, colorimetric method, 109
Fluorine, abundance and properties, 161
Fluorite, 161
Fluorspar, 124, 161
Ford field, Texas, 323
Formation damage, 368
Formation interval tester, 10
Formation pressure, 12
Fossil water, 3
Freezing point, 172
Fresh-water conversion, 401
Fresh-water production, flowsheet for,
401
Fresh-water well, 471,472
Fulvic acid, 185
Gas analysis, 12
Gas chromatographic methods, 147, 181,
182,184,185
Gases in petroleum, reservoir waters, 271
Gas/oil ratio, 11
Gasoline Association of America, 186
Gaslwater relationships, 256
Generation and migration, 295
Genetic indicators, 336
Genetic types of waters, 260
Geochemical case histories, 308
Geochemical methods, exploration, 307
Geochemistry versus geologic environment,
266
Geologic maps, 426
Geopressure, 343
Geopressured reservoirs, 343
Geopressured zones, 343, 362
Georgia, 335
Geostatic ratio, 344
Gibbsite, 155
Glass electrode, 27
Graphic plots, 128
Graphite, 295
489
Gravimetric methods, 24, 114
Green River formation waters, alkalinity,
156
Groznyv oil district, 247, 302
Gulf Coast area, 128, 129, 181, 343, 346,
360
Gulf Coast Basin, 243
Gulf Coast shales, 179, 240, 360
Gypsum, 194, 203,204,235,317,471
Hackberry field, Louisiana, 304
Halite, 162, 163, 194,203, 227-229
Heaving shales, 462
Holocene age, 165
Honaker Trail formation, 321
Host rock, 133
Hot brines, 227
Humic acids, 182,184,185,186
-, chromatographic technique, 185
Hydrocarbons, 12, 178, 194, 211,298,
310
-, accumulation, 178,298
-, alkanes, 309
-, alteration, 299, 301
-, aromatic, 298, 309
-, bacterial attack, 302
-, biological degradation, 301
-, compaction, 294
-, containing nitrogen, 182
-, diffusion, 180
-, generation-migration, 295, 296, 362
-, hydrochemical indicators, 258
-, maturation, 295
-, migration, 299, 314, 316
-, in natural gas, 180
-, origin, 57
-, in petroleum, 181
-, in recent sediments, 244
-, in sedimentary rocks, 245
-, solubility, 178, 179,296
-, water washing, 300
Hydrochemical anomalies, 308, 316
Hydrochemical indicators, hydrocarbons,
258
Hydrodynamic gradients, 295,325
Hydrodynamic potential, 382
Hydrodynamic zones, 266
Hydrogen chloride, free, 120
Hydrogen sulfide, 51,156,159,309,468
-, method for determination, 51
Hydrogeochemical exploration, 311
Hydrogeochemical research and exploration
313
490
Hydrolysate, 139, 141, 171
-, rocks, 195,197
-, sediments, 141
Hydrolysis reactions, 15
Hydrosphere, 193
Hydrothermal equipment, 447
Igneous rocks, average composition,
196
Illinois Basin, 243
Illite, 138-140, 209,230, 239, 240, 269,
441,443,444
Index base exchange (IBE), 267,270,
271,283
Inhibitors, 465
-, chemical, 465
-, corrosion, 465,469
Injection of subsurface brines, 420
Injection well, 424
Instrumental methods, 20
Interior regions of the earth, 193
Internal standard solution in emission
spectroscopy, 84
Interstitial water, 3, 194, 206, 207, 209
Iodate, 166
Iodide, 45, 110,226
-, colorimetric method, 110
-, concentration and economic profit,
404,413
-,- by evaporating, 166
-,- and geologic age, 408
-, properties, 171
-, recovery, 390,415
-, seaweed and coral, 228
-, titrimetric method, 45
Iodine, 164, 390, 398
-, concentration by algae, 165
-, recovery from brines, 390
Iodoargyrite, 164
Iodoembolite, 164
Ion association, 225
Ion exchange, 230
-, concentrating by, 95
Ionic potential, 133, 142,171
Ionic radii, 171
Ionization interferences, 66
Iron, 149
-, abundance, 149
-, atomic absorption method, 65, 79
-, colorimetric method, 94,95
-, emission spectroscopy method, 83
-, properties, 148
Isotopic fractionation, 243
SUBJECT INDEX
Jurassic age, 135, 154, 163, 227, 229
lithium concentration, 135
magnesium concentration, 143
potassium concentration, 139
sodium concentration, 137
strontium concentration, 146
Jurassic system, 213, 214
Juvenile water, 3, 195
-,
-,
-,
-,
-,
Kainite, 162
Kansas brines, 226
Kaolinite, 155, 184, 209, 230, 269, 441,
443,444
Kazhim stratigraphic well, 185
Kerogen, 205, 309, 311
Lacustrine deposits, 200
Lanthanum, 83,84
Lea County, New Mexico, 320
Lead, 152
-, abundance, 152
-, atomic absorption method, 65,81, 82
-, colorimetric method, 95,99
-, dithizone method, 99
-, ion exchange, 99
-, isotope ratio, 318
-, properties, 119,148, 152
Lepidolite, 140
Limestone, 51, 197,201, 235, 320
-, dolomitization of, 204
Liquid exchange, chromatography, 182
Lithium, 133,392
-, abundance, 133
-, atomic absorption method, 68
-, concentration and economic profit,
404,413
-,- by evaporating, 135,136
-,- and geologic age, 408
-,- in Mississippian and Pennsylvanian
age formation waters, 136
-,- in Tertiary, Cretaceous and Jurassic
age formation waters, 135
-, constituent of oilfield waters, 133
-, flame spectrophotometric method, 54
-, properties, 133,134,171
-, recovery, 415
-, toxicity, 133
Lithology, 225
Lithophile, 147
Lithosphere, 193
Locations of valuable brines, 406
Louisiana, 135, 142, 144, 146, 163,231,
333,335,349-352, 359-361
SUBJECT INDEX
Magnesium, 40,142,283-289, 394
-, abundance, 142
-, atomic absorption method, 65,71, 74
-, complexometric method, 40
-, concentration, 289,238
_ , _ and economic profit, 404,413
72
Magnesium ammonium phosphate, 396
Manganese, 40, 149
-, abundance, 149
-, atomic absorption method, 65,78
-, emission spectroscopy method, 83
--,flame spectrophotometric method, 61
-, properties, 148
Maracaibo Basin, Venezuela, 303
Mass spectrophotometric methods, 91
Maturation, 295
Maximum worth, 414
Membrane-concentrated brines, 240
Membrane effect, 240
Metals, 65
Meteoric water, 194, 227, 253, 267, 270,
271,289
Methane, 178, 181, 295, 300, 316
-, measurement of, 12,180,181
-, solubility, 180
Mercuric iodide in brackish water, 152
Mercury, 151
-, abundance, 151
-, atomic absorption method, 65
-, properties, 151
Mexia-Talco Fault, 321
Mica, 140, 232,433
Michigan, 361
Michigan Basin, 205,226, 243, 359, 360
Microcline, 140
Microphotometer criteria, in emission
spectroscopy, 85
Micropipet, 41
Microsyringe-evaporating flask, 186
Miersite, 164
Migration, 2, 293, 295
Milligram per liter (mg/l), 25, 269, 275
491
Mineral-acid acidity, 37
Minerals, formation, 234
-, recovered from saline waters, 392
Minor elements, 220
Miocene age, 165
Mississippi, 333, 335
Mississippian age, 135, 145,154, 164,166,
213
240, 294,360,441,445
Mud filtrate, 11
Nalco Chemical Company, 186
Naphthenic acids, chromatographic
technique, 185
National Bureau of Standards, 23
Natural gas, 178,307,309, 310
-, deposits, 178
Neogene age, 245
Nernst equation, 167
New Mexico, 224
Nickel, 98
-, atomic absorption method, 65
-, colorimetric method, 95,98
-, ion exchange, 95
Nitrate nitrogen, colorimetric method, 107
Nitrogen containing hydrocarbons, 182
Nitrogen-free organic compounds, 178
Nodules of manganese oxide, 149
Nontronite, 441, 442,445,446
Normal pressure, 359
North Carolina, 335
Ohm meter, 32
Oilfield brines (see also Brines and Oilfield
waters), 25, 193,219, 273, 389, 422
-, analysis, 25, 272
-, disposal, 389, 420
-, economics, 422
-, field sampling methods, 273
-, origin, 193
-, pollution, 468
Oilfield waters (see also Brines and Oilfield
brines), 215, 226, 367,372, 374, 389
492
Oilfield waters (continued)
altered, 242, 243
analysis, 272
classification, 253
compared t o sea water, 227
-, concentration of elements, 217, 238
-, incompatibility, 367
-, physical properties, 133
Oil in water, 186
-, determination, 186
Oklahoma, 136, 139, 143, 145, 146, 157,
164,166,335
Optical density, 94
Ordovician age, 213, 218, 345
Organic acids, 186,216, 311,312,316
-, chromatographic technique, 186
Organic compounds, 156,178,184-186,
188,205,317,433
-, deposits, 293
-, in oilfield brines, 188
-, in petroleum-associated waters, 186
-, in saline waters, 177
-, in subsurface water, 185
Organic matter, deposition, 205
-, in sea water, 178
Origin of brines, 219
Origin of oilfield waters, 193
Osmotic pressure, 173
Oxygen, 47,91,158
-, method for "0
-, solubility, 157
-, titrimetric method, 47
-, Winkler method, 47
-,
-,
-,
-,
SUBJECT INDEX
Permian Basin, 473
Petroleum, 195,210,211, 244, 295, 299,
310,315
-, accumulation, 178,225, 298,309,310,
313
-, alteration, 293, 299, 304
-, compaction, 294
-, degradation, 301
-, exploration, 307,320
-, generation, 210, 212, 219, 295,297,
310
-, migration, 211,295, 297
Petroleum Abstracts, 307
pH, 10,14,15,27,37,168-170,198,
207
-, temperature and, 28, 29
-, unfiltered and filtered petroleumproducing wells, 320
pH meter, performance characteristics, 29
Phenol, chromatographic technique, 181
Phosphate, 105
-, colorimetric method, 105,106
Phosphorus, 158
Photosynthesis, 165,206
-, by algae, 165
Pinkerton Trail Limestone, 320
Plasma arc, 83,84
Plate development in emission spectroscopy,
85
Playa deposits, 223
Pleistocene age, 150
Plugging of formations, 432
Polarization, 171
Pollution, 466-468
-, of uppersand by well blowout, 466
Porosity, 207,303,345
Porosity reduction, 345
Potassium, 138, 393
-, abundance, 138
-, atomic absorption method, 70
-, concentration and economical profit,
404,413
-,- by evaporating, 139
-,- and geologic age, 408
-,-, in Pennsylvanian and Mississippian
age formation waters, 139
-, -, in Tertiary, Cretaceous and Jurassic
age formation waters, 139
-, constituent of oilfield waters, 134, 138
-, depletion, 140,240
-, flame spectrophotometric method, 58
-, properties, 134,171
-, recovery, 415
SUBJECT INDEX
Potentiometric surface map, 331
Powder River Basin, 303, 343
Precipitates, 432
Precision, 20
Precursors, 210, 212, 216, 293, 297, 311
Preliminary evaluation, marketing research,
405
Pressure equalizer, 1 2
Pressure-distance-time relationship, 430
Pressure head, 11
Pressure relationships, 433
Pripvatsky Depression, 317
Produced water, 4
Production, 467
Quality control, 19, 20
Quartz, 194,201, 209,433
Quartzite, 155
Quebracho, 464
Radioactive anomalies, 318
Radioactive compounds, 317
Radium, 318
-, anomalies, 318
-, concentration, 317
Radium/uranium ratio, 317-320
Reacting values, 126
Reaction coefficients, 126
Reagent chemicals, 23
Reagent solutions, 23
Recovery, 4, 390, 392,415,474
Redox potential (Eh, pE), 29, 157, 166
Reef carbonates, 202
Regressive marine deposits, 200
Reistle diagram, 131
Replacing power of ions, 230
Reporting analytical results, 25
Reservoir transmissibility, 428
Residual salt concentration, 470
Resistivity, 32, 33, 35, 317
Reverse exchange, 233
Reverse osmosis, 240, 241
Rio Bravo fields, California, 152
Rocky Mountain area, 156, 343
Rodessa formation, 284, 286-288
Rounding-off numbers, 26
Rubidium, 59, 140, 393
-, abundance, 140
-, constituent of oilfield waters, 139, 140
-, flame spectrophotometric method, 59,
61
-, properties, 134
-, standard-addition technique, 6 1
493
Saber field, 323, 326, 330
Sabkha sediments, 224
Salinity, 24, 226, 254, 257
-, concentration, 333-335
Salt water disposal, 4 12
Salting out effect, 179
Sample container, 16
Sample treatment, 22
Sampling, 8
-, methods, 273
Sand dike, 345
Sandstone, 152,158, 201, 345
San Juan Basin, 224, 343
San Juan Mountains, 321
Saturated hydrocarbons, 314
Scale, 368, 370
Scale inhibitors, 469
Schoellers system,.267, 268
Searles Lake, 135
Sea water, 137, 143, 149, 152, 158, 194,
215,227,245,392, 394,402
-, average composition, 195
-, composition, at dolomitization or
bacterial reduction, 235
-, -, at gypsum precipitation, 234
-, fatty acids in, 184
Sedimentary basins, 212,406
Sedimentary rocks, 11,51,135,140,147,
195,210,245
-, average composition, 196
Sediment compaction, 206
Sediment diagenesis, 207
Seleniferous vegetation in the U.S.,160
Selenium, abundance, 160
-, colorimetric method, 111
Sensitivity for metals in atomic absorption
methods, 65
Separation of gas, oil and brine, 400
Serpentine, 446,449,453,458
-, silicon solubility from, 453-458
Shales, 141,152, 158,179, 206, 240, 245,
360,430
Shallow aquifers, contamination of, 434
Siderite, 471
Significant figures, 25
Silica, 107
-, abundance, 156
-, analytical procedure when dissolved,
442
-, colorimetric method, 107
-, deposition, 206
-, spectrophotometric method, 107
Silicate, 149, 240,443
494
Silicate (continued)
-, solubility, 458
-,-, from serpentine, 453-458
SUBJECT INDEX
Stable-isotopes analysis, 15
Standard-addition technique, 50, 55, 57,
60,61
Standard solutions, 23
State regulations, 434
Stiff diagram, 131
Stinkfluss, 161
Stratigraphic interval, 11
Stratigraphic problem, 325
Stratigraphic traps, 312, 323,325, 326
Strontium, 62,76, 83, 145,385
-, abundance, 145
-, atomic absorption method, 76
-, concentration, 239
-,- and economic profit, 404
-,- and geologic age, 408
-, -, in Pennsylvanian and Mississippian
age formation waters, 146
-, -, in Tertiary, Cretaceous and Jurassic
age formation waters, 146
-, constituent of oilfield waters, 141,145
-, emission spectroscopy method, 83
-, flame spectrophotometric method, 62
-, properties, 141, 171
-, recovery, 415
Strontium sulfate, 385
-, concentration, 145
-, concentration and ionic strength, 378
-, saturation in waterflood makeup brines,
383
-, solubility, 145,370, 372,375-377,
379,381,383,385
Structural trap, 312
Structure of minerals, 441
Subsurface brines, 143, 159, 225, 315
420
-, analyses, 321
-, classification, 216, 234
-, contents, 159,313-315
-, hydrochemical anomalies, 316
-, maps, 320
-, mixing, 382
-, properties, 214
-, sampler, 9,224
Subsurface disposal, 419,421, 426, 471
Subsurface waters, 7,9,135, 253, 289,
382
Sugars, chromatographic technique, 181
Sulfate, 114,385
-, concentration and economic profit,
413
-, determination, 53
-, gravimetric method, 114
SUBJECT INDEX
Sulfate (continued)
-, properties, 171
-, recovery, 415
-, reduction, 208,317
-, solubilities in synthetic brines, 379
Sulfide, 51
-, determination, 52,53
Sulfur, 52, 159
-, abundance, 159
-, concentration and economic profit,
401
495
Uinta Basin, 157, 210, 212
Uncompahgre Uplift, 321
Underground waste disposal, 434
Unfiltered petroleum producing wells,
pH and eH values, 320
Units for water analysis, 24
Unsaturated hydrocarbons, 314
Unstable properties, 15
Upper Cretaceous, 321Uranium, 318
Utah, 157
Valuable brines, 406,407
Valuable elements, 474
-, production, flowsheet for, 401
Value of brine, constituents, 415
Value of dissolved chemicals versus depth,
403
Value estimate, 414
Vapor pressure, 172
Viscosity, 173
Valence, 171
Volcanic waters, 58
Volga region, 180
Vorobyevite, 140
Waste disposal, 471
Waste disposal well, 472
Water, compatibility, 12, 290
-, compressibility, 428
-, properties, primary, 214, 261
-, washing, 300
Water analysis, 24, 130, 321
-, interpretation, 130, 131
Water and hydrocarbons, 311
Water exchange coefficient, 265
Waterflood makeup brines, 383
Waterflooding, 4, 369, 420,473
Waters, composition, 280
-, connate, 3, 194
-, diagenetic, 194
-, formation, 195
-, fossil, 3
-, interstitial, 3, 194
-,juvenile, 3, 195
-, meteoric, 194
-, subsurface (see also Subsurface waters),
297
Weathering, 197,198, 200,262
-, cycles and types of products, 263
Well blowout, pollution by, 466
Wellbore, 368
Wellhead, 14,15
496
Wellhead sampling, 13
Well treatment, 13
-, pH for determining of, 170
Wilcox formation, 331-334
Williston Basin, 129
Woodbine (Dexter) formation, 335
Worth estimate, 414
X-ray diffraction, 201, 471
SUBJECT INDEX
Zinc, 80, 101, 151
-, abundance, 151
-, atomic absorption method, 65, 80
-, colorimetric method, 101