Introduction to Geochemical Prospecting

The search for underlying oil and gas by means of surface samplh;ig has its supporters and its detractors. Hunt (1979) observed that nearly all major
companies had t1ried geochemical prospectingi but none had shown significant success; few continued to carry on major efforts in such field programs.

Most mathematical evaluations indicate that any technique based on the diffusion of light hydrocarbons from undedying petroleum accumulations has
little chance of success. In all likelihood, this statement is valid except for reservoirs very close to the surface, or those with poor seals. One mitigating
factor is the recent improvement in detection capabilities. Modern field analytical instmments provide up to an order of mag11itude or more
improvement in detection and resolution over earlier models.

If geochemical exploration programs are to prove successful, their most promising approach is to look for leaky reservoirs and microseeps that
demonstrate a surface expression along natural migration pathways (.Eigiure 1 and figure 2, Surface prospecting by gias detection, San Joaquin basin,
California).

Those that promote the use of microseeps as an exploration tool suggest that the use of surface geochemical detection of microseeping hydrocarbons
is a logical extensio11of the use of macroseeps in the search of oil a11d gas. Surface geochemical prospecti11g methods are most effective as part of an
integrated program that includes geological and geophysical methods. Surface geochemical prospecting is a good complement to seismic. The
acceptance of geochemical prospecting as an exploration tool lies in the fact that surface geochemical anomaly, as a product of leakage from the
petroleum accumulation, does exist.

SW NE

1000

2000

3000

4000

5000
15

6000
18

7000
2.iOO
8000 Lost Hlls
2400
OIi fteld
9000
(b"om Jones and Drozd, 1983; courtl:tsy AA.PG)

,1
•
200
I'
J

Propane

I
•
I Methane
Hydrogen
II
22
I
'
r
::i:: •I
a. I
1200
J
C:
(1)
I
II
i
'
e
Cl
ID
,:,, a..
>, a..
:::c (1)
C:
111
C.
e
a.

(from Jooos and Dro a. 1983; counesy AAPG)

FIGURE 2

An increase in detectable gases is apparent across the Lost Hills field. The sample profile was obtained by soil-gas sampling in which gas was drawn
from augered and packed holes). (Jones and Droid, 1983).

Prospecting for leakage and microseeps is done by looking directly for hydrocarbon enrichment and associated increases (e.g., metl1ane-rnnsuming
bacteria, see Brooks et al., 1986). Traverse or grid sampling is commonly carried out in the prospecting area so that background levels can be
established and anomalies determined.
Concepts of Geochemical Prospecting
A reservoired petroleum pool is an active mass of hydrocarbon molecules. No seal rock is completely impermeable. A network of microfractures
exists in the sedimentary layers above the petroleum pool. Small size hydrocarlbon molecules like C1 through (5 move vertically through the
microfracture system and reach to the earth's surface. A colloidal mechanism is responsible for the migration of microseeps. A microseep is defined
as the migration of C1-Cs hydrocarbon from a subsurface accumulation by a process of vertical ascent of colloidal size particles through a
microfracture system overlying a petroleum deposit. Microseeps generate positive hydrocarbon anomalies on the surface that tend to overlie all or a
large part of the petroleum deposit from which they originate. Microseeping hydrocarbons are present in soils which are sampled. Identification of the
areas with high concentration of hydrocarlbons in the surface soil are mapped and related to the subsurface accumulation,

Adsorbed Gas Survey in Integrated Exploration

Adsorbed gas surveys are used as both as reconnaissance surveys and as a detailed survey tools.

Reconnaissance Survey
The objeotives of a reconnaissance survey are:

■ To identify interesting areas,

■ To select most valuable concessions.
■ To differentiate between oil-prone and gas-prone areas.
■ To differentiate between thermally immature and mature areas.

Detail Survey
The objeotives of a detail survey are:

■ To identify drilling prospects.

■ To rank and prioritize drilling prospects,
■ To assist in deciding which prospects need not to be drilled.
■ To define the areal extent of an oil and gas accumulation to assist orderly field development.

Sampling Technique
The soil samples are generally collected from a depth of 3 to 10m. The sample in this case is a soil/ sediment core. The soil core samples are
collected from holes drilled by hand augers or power augers with the help of a sample catcher at the base of the pipe.

Sample Analysiis
The adsorbed gases are desorbed from the soil sample (2-3g) with the action of orthopohsphoric acid under vacuum in a preparation system called
desorber and then analyzed by a gas chromatograph to get the chemical composition of the microseeps. A typical gas chromatogram of microseep
analysis shows the preser11c.e of methane to per11tanes hydrocarbons.
Interpretation of Geochemical Prospecting
Petroliferous Nature of Microseeps

The composition of gases desor1bed from soil samples is indicative of the petroliferous nature. If the gas contailils only methane or methane and some
negligible ethane, the microseep is not of petroliferous nature. If the microseep sample contains the entire spectrum of hydrocanbolils from methane to
pentanes, this indicates the petrnliferous nature of the microseep. The hydrocarbon composition trend C1 > C2 > C3 > C4 > C5.
Catagenetic Origin of Microseeps

A ratio of methane and ethane ( ) less than 16 and a ratio c,;c, less than 10 indicate the catagenetic origin of microseeps.

Type of Petroleum

A ratio of t less than 1.3 and a ratio of : less than 0.8 indicate association of microseeps with liquid hydrocarbons.

Genetic Correlation of Hydrocarbon Constituents

The concentration values of methane and ethane, ethane and propane, propane and n-butane and n-butane and n-pentane are cross plotted. A linear
relation between the two hydrocarbons indicates that these hydrocarbons are genetically correlated, emanating from same petroleum deposit, and not
altered by any type of secor11dary processes like separation migration or biodegradation. This ensures high reliability of microseep anomalies.

Dellineation and Ranlking of Surface Hydrocarbon Anomalies

In order to identify the areas of anomalously high concentration of surface adsorbed (microseep) hydrocarbons, the concentrations of methane,
ethane, propane, butanes and pentanes are contoured separately. In order to define meaningful alilomalies, background mean (m) and standard
deviation (o-) are computed by using available methods. Contour maps are the iso-concentration maps of methane to pentanes. In the iso
concentration maps, the starting coliltour is generally equal to the background mean plus one standard deviation (m +
o-) of that particular
hydrocarbon and the contour interval is the standard deviation (a-). Most investigators define values as anomalous if they have concer11trations greater
than m plus some multiples (usually 2 or 3) of u-. This is the anomaly threshold value. Although m + +
2a- or m 3a- are considered good indicators
of petroleum, still better criteria (> m +3u} may be employed to resolve the surface hydrocarbon anomalies with increasing levels of confidence in
predicting subsurface accumulation. The greater the value of m, the stronger the anomaly. The evaluation criteria may vary with basin, block, field,
objective of survey and will be guided by the experience of the skilled interpreter. Ethane, propane and butane anomaly maps are generally used for
evaluation purpose.

Advantages of Geochemical Prospecting

An adsorbed gas survey offers several advantages towards enhancing the effectiveness of exploration and development:

• It provides physical evidence of the occurrence of hydrocarbons in an area, in the form of hydrocarbon microseepage.
• It is a direct and therefore reliable method for detection of hydrocanbon accumulations through their surface manifestation.
• It canquickly and cost effectively identify interesting areas in a large basin, concession or play and rank them in order of priority for
subsequent seismic surveys, and can be used to define a field after a wild cat discovery.

• It provides ililfonmation on whether a discovered trap contains petroleum, thereby eliminating dry prospects.
• It canindicate an extension of a producing field.

The main advantage of surface geochemical prospecting is that it is not limited by the type of trap (structural cir stratigraphic).
Organic Carbon Content

A total organic carbon (TOC) value represents all the organic carbon in a sample, including that contained in entrapped kerogen, bitumen, and
petroleum, TOC can be converted to total organic matter (TOM) by multiplying TOC by about 1.2 to include other elements (H, l!J, 0, S, etc.)
contributing to the weight of organic matter. TOC, however, is the reporting format most commonly used in geochemical reports Tablle 1.

Table 1: Selected analytical values for Eocene kerogen samples from the
vicinity of the Mist gas field, Oregon.
Formation Lithology TOC S1 S2 S3 Ro
Keasey Mudstone 0,76 0,10 0.10 1.59 0,16
Mudstone 0,89 0,10 0.10 1.53 0,18
Cowlitz Mudstone 10.07 0,10 0.10 10.44 0,26

Mudstone 0,64 0,10 0.10 0.67 0,20

Skookumohuk Siltstone 4,63 0,14 2.16 2.64 0,35
Coal 48.19 5.16 135.23 11.42 0,38
Coaly Silltstone 7.22 0.40 13,96 2.56 0,37
Slty Mudstone l.55 0,10 0.44 0.80 0,31

When applied to exploration interpretations, an organic carbon value is generally assumed to reflect primarily the amount of kerogen in the sample.
The reason is that in most fine-grained sedimentary rocks those litiwlogies generally assumed to be sources of petroleum kerogen typically makes up
a very high proportion, 80% to 98%, of the organic carbon present (Tissot and Welte, 1984: bitumen ratio). As a result, TDC value is interpreted to
serve as a relative measure of inherent organic richness. This measure can be used comparatively, as between two or more samples, or empirically,
as
in relation to an accepted source potential rating (e.g., < 0.5% TOC = poor source potential rating in shale). One should keep in mind, however, that
the coarser-grained or more permeable a sample is, the greater the opportunity for a TOC value to represent the inf11uence of bitumen and
petroleum migrants. A sample must undergo solvent extraction prior to orgianic carbon analysis if a truly representative measure of kerogen
concentration is desired. One usually takes this step only to answer very specific source potential ciuestions, such as determining if an anomalously
high organic carbon content is reflecting migrated and/or contaminant contributions.

An organic carbon analysis, one of the simplest and least expensive techniques performed by geochemical laboratories, makes TOC data very
applicable for first-round or screening puriposes in source rock studies. General analytical steps taken to measure the amount of orgianic carbon in a
sample are described in the section titled "Organic Carbon Determination" under the heading "Analytical Procedures in Geochemistry." Analytical data
typically are reported in percent TOC and plotted relative to accepted source-potential ratings.

Quality control is maintained by running blanks and standards of known organic content. Analyses of replicate samples show total organic carbon
analysis to be very repetitive when standard analytical procedures are followed, Where wide variations occur among sample.s of the same formation or
even samples from the same cuttings sack, the primary cause of variation is in the rock and/or the sample selection process.
Maceral Separation
Many kerogen evaluations are performed on macerals separated from rock samples. Under a microscope, palynologists or petrographers observe
physical properties of the macerals both in transmitted and reflected light. In the former, used most commonly for thermal alteration index (TAI) or
spore color index (SCI) evaluations, macerals are mounted on glass slides so that light can pass through them. In the latter, used primarily for
vitrinite reflectance (%RO) and fluorescence determinations, kerogen separations are mounted in bioplastic plugs so that macerals can be polished
and evaluated with incident light (Teichmuller, 1985).

For geochemical use, typically during source rock evaluations, kerogen separations are examined primarily to determine two characteristics:

• relative composition (e.g., percent alginite, exinite, vitrinite, inertinite) equated to inherent hydrocarbon source characteristics (e.g., oil
prone, oil-and-gas-prone, gas-prone, nongenerative)

• thermal alteration level (immature, mature, postmature) used to interpret progressive stages of bitumen generation (diagenesis,
catagenesis, metagenesis)

Separation techniques are directed toward concentrating representative kerogen populations; therefore, the amount of material found on a slide or
plug needs have no direct relation to the TOC concentration measured by combustion. Typically large volumes of sample are acid treated for kerogen
separations, particularly in kerogen-lean samples (Egure 1).
Separation, preparation, and evaluation of kerogen samples constitute one of the more time-consuming, thus expensive, laboratory techniques. Once
separated, kerogen concentrates are prepared for visuaI typing and vitrinite refilectance examination (.Elgure 2. and Egure 3).

FIGURE 2

Typing observations, which include quality, relative quantity, and maturity of macerals, plus reflectance data, which qualify macerals and maturity, are
generally presented in both tabular and graphic fonnats.

•
••
(Courlesy Roberlson Research)

FIGURE 3
Quality control for TAI-SCI alilalyses lies primarily with the palynologist performing the evaluation. Standards for equating kerogen coloraticrn of spores
and pollen to thermal alteration level are typically maintained by imlividual analytical services groups (Table la) for their analysts' use. Among
laboratories, slightly different standards are used, and there are no universally accepted color-comparison standards among transmitted-light
techniques for designating comparable levels of maturity. The best systematic approximation appears to have been made by Smith (1983). He
proposed correlations among TAI (1-5), SCI(1-10) and the Batten (1-7) scales (Table 1b) based on transmitted light spectra from ranked kerogen
concentrates.

Palynomorph colour scales

Correia (1967, 1Sl71, Correia (1967,
Batten (1976) Batten ( 1976)
1975) 1971,1975)
Associated
Palynomorph Maturation Pollen & spores
hydrocarbons
1. Colourless Immature 1. Transparent yellow Immature
pale yellow

2. Yellow
Immature 2. Orange to Immature to marginallly
reddish mature

3. l.ight brownish Marginally mature 3. Brown Oil generation

yellow, yellowish gas condensate
orange

4. l.ight-medium Mature oil 4. Opague (black) Dry gas

brown generation

5. Dark brown Mature, gas 5. Brown spherules Trace of dry gas

condensate

6. Very dark Over-mature 6. Indeterminable

7. Black ( opague) Trace of dry gas

Robertson {l 976) Robertson {1976) Staplin {l 969) Staplin ( 1969)

Palynomoirph Maturation stage Organic Matter Associated

colour lhydrocanbons
1. Colourless pale Immature 1. Fresh yellow Wet or dry
yellow

2. Pale yellow Immature 2. Brownish yellow Wet or dry

lemon yellow

3. Lemon yellow Transition to 3. Brown Wet or dry

maturiity

4. Golden yellow Transition to 4. Black Dry gas

maturiity

5. Yellow/range Fully mature 5. Black, with Dry gas to barren

additional!
evidence of rock
metamorphism

6. Orange Optimum oill

generation

7. Orange brown Optimum oill

generation

8. Dark brown Mature, gas

condensate

9. Dark brown Post mature, dry

black gas

10.. Black Post mature,trace of

dry gas

Table :1.a: Color scales used for rating kerogen alteration. Standard palynomorph color scales. The two most common scales used are Staplin (TAI; 1-
5) and Robertson (SCI; 1-10). All scales start in shades of yellow (immature) and proceed to black or opague (postmature),
 Batten Scale SCI TA
I
1.5
1.2

l 2
2

1.5
2 2.5 1.7
3 2.6 (sapropel)
2 3.5 3.0 (sapropel)
3
3 4.0 1.8 (3.1 sapropel)
3 4.5 2.3
4

4 5.0 3.3
4/5 5.5 3.4
6.0
5 6.5 +3.5, 3.5
5 7.0 3.6
(i

6 7.5
8
(i

7
8.5-9 !:!(2 slides)
9.5 !: (sapropel)
4.4 (sapropel)
7 10.0 4.8 (sapropel)

Tablle 1.b: Correlations among three scales based on spectral comparisons.

Variables other than visual perception can introduce inconsistencies in interpretations, such as sample preparation techniques, maceral thicknesses,
and maceral quality. Therefore, it is not uncommon to find a slight maturation bias with different analysts or laboratories (Batten, 1981).

When spore and pollen macerals are not present or cannot be accurately evaluated, analysts often give maturation approximations based on
alternative or less diagnostic features. Conodont alteration index (Epstein et al., 1977) is a most common alternative (Wardlaw and Harris, 1984. Use
of alternative zooclasts, such as graptolites, during reflectance determination can introduce other differences in interpretations of maturation
level(Bertrand and Heroux, 1987). With this in mind, data users should always review data sheets for basis and confidence level of maturation
determinations.

Quality control for %RO measurements is maintained primarily through two processes. The first is objective, in which blanks and standard plugs are
used to calibrate reflectance levels as measured by photomultipliers. This permits reflectance to be et:iiuilibrated among different optical systems and
laboratories. Because reported reflectance values typically represent a number of measurements and an average, some variation is to be expected,
even on repeat analysis of the same standard. The second quality control process is subjective, and requires that the operator select truly
representative macerals. In this aspect, two general sources of data variation are common: (1) selection of a specific macera! type and (2) selection of
a representative population (Toxopeus,1983).

When a specific maceral type is being studied, typically vitrinite, these macerals alone should be positioned for reflectance measurements. If an
improper selection is made so that measurements include pseudovitrinite, semifusinite, and solid bitumen, reflectance values and resulting maturation
interpretations can be biased or imprecise..

When considering maceral type, you should keep in mind that lignin and land plants N the sources of vitrinite N did not evolve until the Middle
Paleozoic. Silurian and older samples depend on alternate macerals for determining maturation level through reflectance properties. Currently,
reflectance values have not beeITTb!roadly established as indicators of maturation levels for noITT1vitrinite macerals (e.g., graptolite periderms; Clausen
and Teichmuller, 1982). Additionally, many carbonate rocks do not contain land-derived detritus and plant materials. These rocks, lacking in vitrinite
macerals, require alternative materials (e.g., exsudatinites, liptinites) for reflectance measurements (Jacob, 1985).

Selection of a representative population requires that an analyst differentiate between first-cycle, indigenous kerogen macerals, which reflect the level
of thermal alteration induced by the present burial cycle, and the many other types of macerals that can be present in a separation. In this latter
category are recyded (reworked) kerogen, generally more mature than first-cycle kerogen, and carbonaceous contaminants from cavings and drilling
muds, typically less mature than the first-cycle population. For example, lignosulfonate, a common mud additive, can be a source of organic matter in
kerogen separations, particularly when cuttings and porous core samples are not adequately cleaned prior to kerogen separation.

Often, recognition of mixing, contamination, and true first-cycle kerogen population becomes most practical only after reflectance values are
determined and plotted. In many ambiguous situations, final selection of first-cycle vitrinite is best made in coITT1junction with operational and geologic
input.

This observation concerning data interpretation needs amplification before we proceed.

Final int,erpretation of geochemical data is best done in the explo,-ation office where influences of the focal geologic setting and drilling ope,-ations can
be considered.
Incoriporaticrn of geology and operational conditions underpins the effective use of geochemistry in exploration, Although we have been consideringi
variations in kerogen data, variations in geochemical data occur with all analyses. Evaluation and interpretation must take outside influences into
account. When feasible, explorationists should incorporate wireline logs, drilling procedures, operating records, and probable geologic

conditions into the overall geochemical synthesis, For example, a discontinuity in TAI maturation level that occurs at a depth where casing was set and
a new mud system introduced might need to be ignored in final decision making; introduction of less-mature mud contaminants is a likely explanation
of the discontinuity. The same type of discontinuity recognized near the depth of a thrust fault could prove to be the difference needed to identify a
shift in prospectiveness from thermal gas back to oil window.

Chemical Composition: General Considerations

The chemistiry of kerogen is most commonly determined by two techniques. In the first, elemental analysis, the relative contents of carbon ( C),
hydrogen {H), nitrogen (IV), oxygen (0), andsulfur (5) in kerogen separations are measured. Data are often presented and plotted in such ratios as
hydrogen:carbon {H: C) and oxygen:carbon (0: C) {figure 1).

Lipids
wwc.,Fata
.,/' LIPTINITE
/ f"TYPE I")
/

I NITE
11;

halides

ITRIN E
'Typa II")

0.5
.It.RTINtiTE . (TyPe IIIB"
org1n, al1er,ed woodor T pe
IV")
matenel

0.05 0.10 0.15 0.20 0.25

O/C AIOO'li Ratjo
I1ncraasi09 tempe,atum
.-- matcsator, pathway

(From Brooks, 1981b)

F

□ ZONt.S OF
GENERATION
C().Ji 2
1

■□
0 FIGURE
OIL 1 GAS

In the second, whole rock and kerogen pyrolysis (Py), pyrolysate volumes are measured (Table 1) and approximations of the hydrogen-carbon
(hydrogen index, HI) and oxygen-carbon (oxygen index, 01) composition of organic materials are determined (8.gure 2,

CROMER IKNOU GROUP

TYPEI

800

xw
/TYPEII
600
c,
z
w
Cl
400
c,
>-
:i::

200

1100
(From Thomas et al., 1985) OXYGEN INDEX

FIGURE 2
.Eigure 3,

KIMMERIDGE CLAY EQUIVALENT

TYPE I

800

T:0.C.,.z.1 to 12.5%

>w< TYPE II
C l
z
z
w
Cl

!2
J:

Z-..., TYPEIII
TYPE IV

50 100 150
(From ThomilS r;I al., 1985) OXYGEN INDEX

FIGURE 3

.Eigure 4,

11::lEAibiEREOBMAIION
TYPE I

800

i.O.C...0.6 lo 10.9%

• • • •
50 100 150
(From illomilS at al., 1985) OXYGEN INDEX

FIGURE 4
 IDUNUN1mmup
TYPEI

800

r.o.c. o-"to 6.9%

r;'j 600 TYPE II
2
z
UJ
0
400
0
:>
r-: • •••
200 I

50 100 1150
(From Thomi,s el al., 1985) OXYGEN INDEX

FIGURE 5

figure 6, and figure 7, Rock-Eva/ pyrolysis ratio plots of Jurassic and Lower Cretaceous units, Norwegian North Sea.

BRE:NT GROUP
TYPEI

800

T.O.C.=0.8 to 37.6%
X
UJ
□ 600 PE II
!!:
z
UJ
Cl
0
a:
!; 400
:r:
•
•
TYPEIII
T Y PE
IV

i.50
(From Thomas et al., 1985) OXYGEN INDEX

FIGURE 6
Distinctive pattems are present in the plots, indicating diffeent dominant kerogen types). From pyrolysis we can supplement our visual estimation of
kerogen chemistry by evaluating the nature of pyrolysate given up ( ratio).

ORGANIC FACIES
TYPE I

SAPROPELIC

X TYPEII
w
600
0 FACIES
zwz • t
(!)
400
0
>-
J:
MIXED FACIES

200
VITRINITIC FACIES

¾,TYPE Ill
INERTINl111C FACIES TYPE IV

50 100 150
(From Thomas et Bl., 1985) OXYGEN INDEX

FIGURE 7

From pyrolysate composition we can also interpret the current state of kerogen's thenmal alteration ( Tmax; productivity index, PI; HI), For example,
as kerogen matures and yields bitumen, it loses hydrogen and undergoes a compositional change; therefore, kerogen constituents become more
condensed and aromatized, as shown by a decrease in hydrogen index. Pyrolysate can also be analyzed by gas chromatography (GC), and further by
mass spectrometry (MS) to determine the molecular composition of products liberated or generated during kerogen heating (Figure 8,

SET-UP TRACE

F A

TRA

(from Horsfield,. 1984)

FIGURE 8
.Eig1ure 9, and .Eig1ure 10).

TRAP

F D
COLUMN

(from Horsfield, 1984)

FIGURE 9

-1- F -=-'-t (fr om 1-

-1 .
Jo,sfie Jd, 18 84)
FIGURE 10
 Table 1: Selected analytical values for !Eocene kerogen samples from the
vecinity of the Mist gas field, Oregon.

Formation Lithology TOC S1 S2 S3 Ro

Keasey Mudstone 0.76 0.10 0.10 1.59 0.16
Mudstone 0.89 0.10 0.10 1.53 0.18
Cowlitz Mudstone 1.07 0.10 0.10 1.44 0.26
Mudstone 0.64 0.10 0.10 0.67 0.20
Skookumclrnk Siiltstone 4.63 0.14 2.16 2.64 0.35
Coal 48.19 5.16 135.23 11.42 0.38
Coaly Silltstone 7.22 0.40 13..96 2.56 0.37
Slty Mudstone 1.55 0.10 0.44 0.80 0.31

The primary uses of data from either elemental analysis or standard pyrolysis (Rock-EvaI) techniques are to determine the general chemicaI type of
kerogen in a sample (Types I, II, III, or IV) a111d its immat1.1re-to-postmature level of thermal alteration. As we have seen, chemical type and
maturation level are typically determined using a van Krevelen style diagram when elemental ratios or pyrolysis indices are available. Chemical typing
usingi gas chromatograms of pyrolysate is generally carTied out by identifying pattern similarities with chromatograms of reference kerogens.
Currently, the combined GC/MS analysis of pyrolysis products is very popular in studying kerogen type, organic source, or generative nature. Almost
every recent issue of geochemical publications or proceedings from geochemical meetings (e.g., Baker, 1986. Organic Geochemistry 3: A selection of
papers from the 3rd Australian organic geochemistry conference) carries the results of new PY/ GC/MS studies (Saiz-Jimenez and de Leeuw, 1986.
Lignin pyrolysis products: Their structures and their significance as biomarkers)

Chemical Composition: Elemental Analysis

Elemental determination is carried out by the general steps outlined in the "Analytical Procedure" section, which is found under tihe heading
"References and Additional Information." The content of C, H, N, S, and o generally is tabulated in relative concentration. Selected ratios are also
included in many tabulations; the ratios H: C, N: C,0: C (or O+S: C) are calculated on a molar basis.

Most variables that adversely affect those kerogen separations used for preparing slides and plugs also affect elemental a111alysis. Inclusion of cavings
and contaminants in the original sample, plus the presence of multicycle (reworked) kerogen in the rock, can modify elemental composition so that
data do not fully represent first-cycle generative kerogen.

Chemical Composition: Pyrolysis

Pyrolysis of whole rock and kerogen samples is carTied out through programmed heating in the oxygen-free atmosphere of an electric furnace. Output
of an analytical run commonly is in the form of a pyrogram and an integrator printout (.Ei.gure 1, Pyrograms.

FIGURE 1

Graphic plots {peaks) of pyrolysate volumes and summary of integrator data are standard products of modem pyrolysis instruments). As observed
previously, data typically are reported in tabular and graphic formats.

When downstream analysis of pyrolysate is performed to evaluate kerogen composition, a number of analytical options are avail-able. Gas
chromatography (GC), mass spectrometry (MS), or a combination of both (GC/MS) are the most common techniques applied to gain added detail
(Analytical Procedure 1.7: Pyrolysate Characterization). Output typic.:illy is in the form of a GC chromatogram or an MS spectrogram or
fragmentogram (figure 2,
 TYPEI TYPE I TYPE II Kerogen R
PyrolySis ,.r-¾
Asphaltene R
Kerogen R
Pyrolysis ,r,- 550°C cb'-'
Pyrolysis ,.uY
550°C o,1.1 550" C riF

c:?l
io' C21

.
; I
.
Q

•
"ii.

- jl .,.t..
;;"ii
1[ t
E
Q

§
.
Q
E
. I.,

FIGURE 2
JJ
Elgiure 6, and figure 7, Fragmentograms of Py/GC/MS analysis of kemgen and asphaftenes from the same host rocks.
FIGURE 3

1 HGURE 4

When narrow molecular ranges of biomarker compounds (m/z 217 sterane) are examined, an apparent genetic relationship can be seen between
pyrolysis of kerogen and asphaltenes).

TYPEII TYPE Ill

Asphaltene R TYPEIII 29
Pyroly,as ..;r-', Asphaltene R
550" C cb'-' Kerogen R Pyrolysis _.r.Jy
Pyrolysis ,.;r-'r 550° C cb'-'
550° C cb'-'

I $'
; I
.
;;
I "ia. "ii
;;

LL
;;
i
._J,
Q.
E; Q.

l l
Q.

J E
l
HGURE 6 HGURE 7
HGURE 5

Since its standardization under the Rock-Eval format (Espitalie et al., 1977), pyrolysis analysis has become a twofold evaluation tool in exploration
geochemistry. Many exploration groups that carry out major efforts in geochemistry use pyrolysis as a first-round screening technique early in a study.
Other groups making only limited efforts in geochemistry use Rock-Eval pyrolysis as their comprehensive evaluation technique. This rapid assimilation
of Rock-Eva I pyrolysis into all levels of exploration geochemistry is due to a number of factors besides the broad nature of data provided. For one,
analyses are rapid and inexpensive; consequently, pyrolysis can be performed on samples taken every few feet or meters down a well. For another,
only a small sample of rock is required; therefore, a fairly broad data base can be acquired even when sample recovery is poor. Other factors include
miniaturization of electronics, automation of operation, and standardization among laboratories, all of which have improved versatility, reliability, and
repeatability among analytical instruments.

Pyrolysis is not, however, without its limitations. Pyrolysis data used for kerogen classification can be influenced by many of the same conditions that
affect organic carbon and elemental analysis data. For example, the peak measuring thermally generated bitumen that is the oil- and/or gas
proneness of kerogen reflects the remaining generative capacity of all the kerogen and other organic material in the sample. The pyrolysate
distinguishes neither between relative amounts of different kerogen types in the sample nor keroge11of different cycles, should they be present. And,
when maturation level is high, all productive kerogen types yield very similar HI and or values (flgure 8, .Eigure 9,

I
l:ICnHE JI

HEATHER FQRMATIQN lUJ llJOWIR 61VI.• li'l\l;J) Q)(.J..t'.?Elit IMDEX

rf ,, ,-
0
: :C 6 o 10o.9%
,n e .,. . ...
,oo

: \'::::::u
 i:· i - ;.. . ..
• ¥ .• •

.: :;
TYPEIV
TYPE 111

50 100 150 50 100 150

From niom,s tJ-, 1985) OXYGEN INDEX 'ti TM mil$ etN., 1985} OXYGHI INDEX

llffilrlll1!IlO

.
FIGURE 8
 In addition, the volume of bitumen generated and released during the 5z_ heating phase can be influenced by rock composition (Espitalie, Makadi, and
Trichet, 1984).

800
/: :r1 c fA C

IE§

PROPELIC

1600 TYPEII

l/,Ac1
400

s,
'i'
J::
MIXED FACIES

200
VITAINITIC FACIES

:
50 100 150
(From Thom&setal., 1985)
(Fmm Thomas ct al., OXYGEN INDEX
1985)

FIGURE 12
FIGURE 13

The presence of carbonate, for example, appears to enhance generation (Katz.,. 1983). Heavy contaminants Hke pipe dope alsoshow up in the higher
temperature heatingi phase. And, of course, when gias ch,-omat:ography or- other downstream analysis is performed on pyro ysate., its results lieflect
these same factors. The added detail provided by chromatography or other high-resolution techniques, however, can make the presence of
contaminants more obvious.

The Si. peak measuring free bitumen in a sample can be even more subject to influences of contaminates or migrated petroleum than tile generated
bitumen Si peak. Rock samples can be contaminated with hydrocarbons during drilling, collecting, storing, and shipping). In addition, migrated
bitumen in permeable rock can give the Si peak an anomalously high reading. Suell anomalous presence, however, is taken into consideration by
most evaluation techniques.

Another limitation related to pyrolysis analysis is introduced by small sample size. The small amount of pulverized material used during analysis
should not be used to characterize a large rock unit, particularly one of heterogeneous lithology. For example, projection of findings from a few
milligrams of variegated stiale to hundireds of feet of thickness oir many square miles of lateral extent must be strongly tempeired with other field
observations.
Along these lines, if the kerogen content of a sample is low, pyrolysate volumes are also apt to be low. Very small 5,_, , and S:i volumes often yield
impirecise values a11d ratios; a ..-elative y flat curve can yield a questionable Tmax temperature value. It is thus advisable to have the ana ytical
laboratory include copies of pyrograms with Rock-Eval data tables (Peters, 1986).

One additional factor can affect pyrolysEs data. To speed up tum-around time.,. exploration departments and service companies have beensetting up
pyrolysis En.strurnents in active exploration are.as rather than leave themso ely in established analytical laboratories. The lack of a caristant electric
power supply, a "sterile" preparation area, and experienced analysts has caused some wellsite and mobile-unit pyrolysis data to be erratic and
unreliable. Explorationists with access to such field capabilities and data should keep this nagging problem in mind. Nevertheless, a tradeoff of some
degree of reliability for decreased turn-around time can prove effective in maintaining an exploration edge in frontier and rank wildcat drilling.

Special Analyses
A numbeir of analytical technEques are available at diffe,-ent laboratories for determining specific properties of kerogen. The most common are nuclear
magnetic resonance (NMR.)., electron spin resonance(ESR), infrared spectroscopy (IR)., rluorescence spectroscopy.,. therrnogravfrnetric
analys;s/differential thermal analys;s (TGA/DTA) and hydrous pyrolys;s (Hpy). Kerogen separations typically are 11eeded ta perform these analyses,
although some of them., when calibrated for rock matirix effectsr use whole rock. Many of tihe techniques are nondest1ructive, so ke1rogen separations
can be recovered for further analysis. In addition, many of the speciaEized t:echniques can be applmed to bitumen and petroleum analyses as well.

Because analytical laboratories geneirally develop t:heir own system for- applying specialized techniques.- onEy birief summaries ar-e given here.
Explor-ationists should be fammar with the specific analytical capabilities and data applications of their laboratories. For detaEled discussion of any
specia I analysis the reader is refer-red again to listed texts (Skoog, 1985,;.Bauer- et: al., l.978).

Nuclear magnetic resonance (NMR) is based on the prlenomenon tl-.at protons tend to aEign themselves within an induced magnetic field,. then precess
to t:lieir original state when the field is rernove.d. Proton interactmon with neighboring atoms causes precession differences shown by distinctive.radio
signals. Arom.atic molecules, for example, give off lower fr-equency spectral responses than aEiphatic (fig ).
FIGURE 1
Comparisons between the aromatic and aliphatic portions of NMR spectra provide the means of grossly quantifying kerogen nature. The general rule
is, the greater the aromatic response compared to the aliphatic, the more like Type HI (or the more mature) the kerogen (Chou and Dickerson, 1985).

NMR analysis uses numerous instrumental and electronic techniques to reduce the number of specific molecules being monitored and to refine the
response. A currently favored system with nuclear magnetic resonance is cross polarization (CP) with magic-angle spinning (MAS) and interrupted
decouplingi ofC molecules. Such an analysis might appear as CP/MAS 13C NMR in an analytical services brochure (Wilson and Vassallo, 1985.
13

Developments in high-resolution solid-state 13C NMR spectroscopy of coals). A direct application of this NMR technique by
13
Miknis and Smith (1984) can serve as an example of gross characterization of kerogen source potential. CP/MSA C NMR measurements of the
aliphatic fraction of kerogen in oil shales showed a direct correlation to the amount of organic matter converted to oil during Fischer assay (figure 2
andEgiure 3, Comparison ofNMR spectra and Fischer asay data.

Ordovician Oil Shales Devonian Oil Shales

Fraction of
Aliphatic Carbon
Carbon Converted Fraction of
Aliphatic Carbon
0.67 Carbon Converted

0.46 0.29
0.65 0.46

0.50 0.34

Nevada 0.58 0.39 0.51

Vinini

Nevada
Vinini 0.54 0.30 Nevada 0.54 0.35
Woodruff
300 200 100 Oppm
Aromatic Aliphatic
200 100 0 ppm
CarlJon Carbon Aromatic Aliphatic
(from Miknis and Smith, 1984) Carbon Carbon
{from Miknis and Smith, 1984)

FIGURE 2
Fff;IIRF .1

The increase in maturity as indicated by the decrease in aliphatic spectra is correlative to the product of Fischer assay).
1

Electron spin resonance (ESR), also called electron paramagnetic resonance (EPR), is a technique that measures the concentration of free radicals
{unpaired electrons) in a substance. As kerogen matures and molecules fragment, splitting between atoms occurs and free radicals are created. If
these free radicaIs are relatively stable, as in kerogen, a dynamic system evolves in which free radicaI ccrncentration builds up. The amount of buildup
is related to both the type of kerogen present and its state of maturation (figure 4).

65

M
,
= :a.I \
• ••• Bit 6a

.....,...
/}\
Mo&uy .aromatic
c-c
55

"'
.
-·- H eml \

! I \.
CcO iphalic
I Ct12;+Cti3-
pt,a1i,c
45 A matic
C-H
ofplane)
0
©

15

\··.
10

o ..,_,..,...,..,.....,.,_.,...,....,.. .,._
Temp("CJ

F[GURE 4 FrGURE 5

For kerogelil identification, the general rule is, the more that free radicals are stabilized by kerogen composition, the more aromatic, or Type III-like,
the kerogen. Concerning kerogen maturation, the rule is, concentration of free radicals is greatest at peak oil-window bitumen generation where
reaction rate is greatest, ESR plots are recognizably different for different keroger11 types, but generally show the same oil-window bulge of bitumen
generation plots (Marchand and Conard, 1980).

Infrared spectroscopy{IR) of kerogen is based on the absorption of different bands of infrared energy by different carbon-carbon and carbon-oxygen
single and double bonds, As a result, saturated alk.ane hydrocarbons and related organic compollnds give infrared responses that differ from
compounds containing unsaturated aromatic (benz.ene) rililgs. The combination of responses provides an infrared signature for the kerogen.

Broadly stated, IR signatures can be used to characterize the nature or maturation level of kerogen (Egure 5).
The general relationship is, the more aromatic the analytical response, the more mature or Type Ill-like the kerogen. IR experimental techniques show
that it is feasible to analyze whole rock samples in some cases and use the infrared analysis as a supplemental inexpensive screening technique in
source rock analysis (Schenk et al., 1986).

Fluorescence spectroscopy is based on the principle that portions of molecules, called chromophores, containing chemical double bonds emit
fluorescent energy (photons) when an electron falls back to a lower level following excitation. Different double bonds have different excitation spectra
and intensity levels. Consequently, kerogen types and their extracts, from the more aliphatic Type I to the more aromatic Type IH, will have different
fluorescent spectral patterns (.Eigure 6).

KEROGEN TYPE II
438

Ro 0.36%
a
KEROGEN TYPE Ill
439

a 1
[
100

75
1
100

75
/\\
1::
1 ii
...;;wz so
336

w
439
b
441
b
!
a:
Ro0.42% Ro 25 !
M E AN=s=Pe CTR=A O F s=Po R ,N ,r=e
25
AN SPECTRA OF ALGINI

0.52% g:i! }vltti11iteRetlectance !.. }Depthof Bu

o,._ ,
0
400 450 500 550 600 650 700 400 450 500 550 600 650 700
(from Von der Dick and Kalkreuth, 1986) ---WAVELENGTH (nm)- ----WAVELENGTH {nm)-

FIGURE 6 HGURE 7 FIGURE 8

Aromatic compounds with the prevalence of double bonds have higher f11uorescence potential than do alkanes with single bonds; in dilute
concentration the two types show this association. In concentrated form, however, such as in kerogen, the actua I fluorescence response is the
opposite because of the quenching effect of aromatic and naphthenoaromatic (benzenering-bearing) condensed com pounds. Thus fluorescence
increases with aliphatic content of kerogen. The general mle for kerogen is, then, the greater the degree of fluorescence, the more aliphatic and Type
Hike the kerogen. In addition, as maturation increases, fluorescence decreases because of the quenching effect of increased aromatic content. There
is also a shift in speotra (figure 7 and figure 8) to higher wavelengths with maturation (Bertrand, et al., 1986).

Thermo-gravimetric analysis/differential thermal analysis (TGA/ DTG) is used to determine the kinds of thermal reactions and alterations that occur as
organic matter is heated in an oxygen atmosphere. TGA measures the progression of weight loss of kerogen during analysis, which in tum can be
equated grossly to kerogen type or maturation level (figure 9 and Elgure 10, Effects ofkerogen type and maturation level on weight loss during
thermogravimetric analysis).

figure 9: TGA weight Joss related to kerog,en type. DTG curve is time derivative (rate change) of TGA curve.

.......Type I , ••••••.••.••••.
l
75
=+::::1 / g
. ,/-- >
J:
(!)
,,,---------------3
," , 50
50
''
I ' ,
/!
/ : _....,.---·-·-·-4
I

/J?Z_TGA

,//!\ 25 _,.-
,t

//./.?\ DTG

o ---=aa;;.-.:;;; .;·;.:.·...;.·.·...._ _, 200 300 400

300 4 5
o oo oo---------------------------------------------------------- T E M P E R A T U R E {°C)
----------+ TEMPERATURE(C) (from Durand--Souron. 1980)

FIGURE 9
FIGURE 10

figure 10: TGA weight Joss related to kerogen maturation). Initial weight loss is due primarily to release of H2 0, COi, 502, andH2S. At higher
temperatures the loss of hydrocarbon fragments is predominant. Therefore, as a general rule, Type I kerogen is more responsive to thermal
degradation (weight loss) than Type II kerogen, which is more responsive than Type III. For any one kerogen type the rule is, the greater the level of
maturation, the less the response.

DTA evaluates the exothermic (heat-producing) and endothermic (heat-using) reactions that occur with heating. Data plots of kerogen typically show
coincidence of DTA exothermic reactions and TGA weight loss (Egure 11 and.Ejgure 12).
 200 400 600
TEMPERATURE (°C) -+
(tram Durand-Sowon. 19.!lG)

FIGURE 12 FIGURE 13
FIGURE 11

In addition,
an increase in strongest exothermic reaction temperature occurs with an increase in maturation (figure 13: Durand-Souron, 1980).

Hydrous pyrolysis (HPy), is carried out by heating kerogen or micronized rock samples in an excess of water in a closed autoclave. Heating generally
is carried out over a number of days, and at different elevated temperatures. The presence of water during controlled heating is thought to more
closely approximate geologic conditions at depth and natural maturation conditions. Experimental results indicate that generated bitumen is more like
natural bitumen and oils than the products derived from conventional {Rock-Eval) pyrolysis {Lewan et al., 1979; Winters et al., 1983; rowland et al.,
1988).

Extraction Techniques

Bitumen and petroleum are extracted by a variety of techniques that allow entrapped natural gases and liquids to escape from their host rocks, The
most common laboratory techniques are

degasihcation

• agitating and abrading samples, generally canned cuttings, so that gases are liberated and concentrated by their natural buoyancy

micronization

• pulverizing host rock so that gases and light liquids escape naturally from fractured pore spaces

vaporization

• heating pulverized host rock so that liquids are volatilized and driven off

solvent extraction

• flushing pulverized host rock with organic solvents so that bitumen and petroleum are solubilized and washed from the sample

Remember also that one additional recovery method is used extensively outside the laboratory and is a primary sample source of petroleum for
analysis: production recovery from reservoir host rock in an oil, condensate, or gas well.
Degasification, the simplest laboratory extraction tech111ique, is 1.Jsed primarily to liberate light hydrocarlbons for C1-C4 and gross C1-C1 gias
chromatographic analyses. Canned cuttings (i.e., fragmetns of drilled rock recovered from the mud ret1Jrns) (Bgure 1, Canned cuttings being prepared
for gas resampling.

FIGURE 1

Headspace gas will be extracted with a syringe inserted through the daub of sealant) are the primary sample type amenable to degasification,
although canned sidewall and piston cores ca111 be used if properly collected and preserved so that gases do 111ot escape. Gas extraction volume can be
reported in total gas, or as headspace gas pl1Js cuttings gas if a two-step extraction process is used (Refer to the section titled "Sample Degassing"
under the heading "Analytical Procedures in Geochemistry." Compositional data commonly are obtained through gas chromatographic a111alysis, which
generally follows the extraction of gases.

From the simplicity of this degassing extraction tech111iq1Je one can readily predict that most problems and erratic data result from sample collection
and preparation i11t1he field rather than from sample handling i11t1he laboratory. Gas extracts make poor representatives of the sampled interval if
collection and containment proceed slowly or 1J nsystematically. Likewise, if bactericide were not put i11t1he container to prevent possible ge111eration of
bacterial methane d1Jring shipping and storage, sampled gases may not be representative of natural composition and concentration. And, of courne,
poorly sealed and leaky containers do not yield representative gas samples.

Gas samples generally are relatively free of contaminants except bacterial methane. Any gaseous contaminants introduced at the wellsite are short
lived. Tlhose, such as acetyle111e lag gas, will be mostly lost after one circulation cycle as the mud is degassed at surface.

Micronization is the technique most commonly used to extract gaseous and light liquid hydrocarbons for detailed gas chromatographic 4-C1 and 4-
C10 analyses. The procedure is rapid, and readily provides the small amount of sample needed for gas chromotography analysis. The premise is
straightforward: mechanically break down the rock sample so that all pore spaces are opened, let indigenous fluid hydrocarbons move into and mix
with hot water, then draw off the extracted light hydrocarbons, which have vaporized and collected above the water. As with degassing extraction, the
volume of fluids extracted during micronization is generally reported as part of the data obtained during gas chromatographic analysis, which typically
follows extraction.

As with degasification, a number of variables can be introduced through sample collection and handling procedures that affect micronization extracts.
Of particular concern at the wellsite is preventing samples from drying before they are packaged in sealed containers for shipping and storage. Drying
permits more volatile light hydrocarbons to evaporate, which, in turn, results in low concentrations a111d erratic analytical data. Naturally, any sample
that is oven-dried by the mud logger or wellsite geologist should not be submitted for extraction in light hydrocarbon or other bitumen analytical
programs. Leaving samples i111open air during cleaning and picking at the laboratory also adversely affects a111alytical results.

Liquid contaminants can be present in cuttings and cores if they were introduced by the mud system during the drilling phase. Crude oil, or even
diesel, often added to drilling mud, typically contains light liquids; they can persist through to analysis. Cuttings contaminated i11t1his manner must be
thoroughly cleaned, and best analytical results are obtained by selecti111g very tight (e.g., shale) samples that do not readily absorlb contaminants into
pore spaces.

Vaporization is carried out by heating finely ground or pulverized samples and trapping volatilized bitumen and petroleum. Most therimal extraction
techniques follow the same basic proced1Jre as that for Rock-Eval pyrolysis, for the removal of i111digenous (51) bitumen. The proced1Jre pulverizi111g,
heating, and trappi111g is carried out with variations in heating and trapping determining the molecular range (C-numbers) of extracts obtained for
further analysis. As with Rock-Eval pyrolysis, the quantity and quality of extract can be affected by sample collecting and handling prior to extractio111
(Bjoroy et al., 1985).

Two additional general problems associated with thermal extraction are (1) the technique is not as effective as solvent extraction (discussed next) and
(2) thermal alteration of organic matter can occur even at low extraction temperatures, thereby yielding a modified extract. Vaporizatio111,
nevertheless, finds use in some specially designed screening analyses of rock samples in which rapid extraction of small volumes is used to evaluate
source potential a111d maturation.

Solvent extraction is the technique generally used when heavy hydrocarbons/bitumen in a rock are to be quantified and/or studied in detail. The
heavy (C101-, C151) extract typically obtained by this method provides samples for such downstream techniques (Sections 1..2.2, 1.2.3) as gas and
liquid chromatography, high-resolution mass spectrometry, and carbon isotope analysis.
Solvent extraction has been i11common use since the formative years of modern exploration geochemistry. Most solve11t extractio11s are carried out in
the laboratory using the Soxhlet technique. 111 this heat-driven procedure, pulverized rock (figure 2, Shatter box type of rock pulverizer.

FIGURE 2

Rock sample is sealed in the container. The eccentric action of the case and floating rings fragments and pounds the rock to a powder) is extracted
rn11ti11uously by a gravity flow of organic solvent (figure 3, Soxh/,et extraction glassware.

FIGURE 3

The prepared rock sample is held by the porous sack within the sealed apparatus. Recirculation of solvent extracts th,e samples). As solve111t reaches
the bottom of the extraction system, it is redistilled (vaporized at the bottom, condensed at the top) continuously, thereby conce11trating the extract
below the rock sample while recycling purified solvent back through the sample firom above.
The prepared rock sample Is held by the porous sack within the sealed apparatus. R,ecirculation of solvent extracts th,e samples). As solvent
reaches the bottom of the extraction system, it is redistilled (vaporized at the bottom, condensed at the top) continuously, thereby concentrating the
extract below the rock sample while recycling purified solvent baok through the sample from above.

Because solvent extraction and downstream chromatography steps are time consuming and exacting, the procedure is relatively expensive. The cost
factor has been one of the principal reasons that quicker, less expensive analytical techniques, such as Rock-Eva I pyrolysis, have come to replace
solvent extraction in many source-rock studies. For correlation work with orude oils and among bitumen extracts, however, solvent extraction is still
the commonly used recovery technique.

The total extract recovered from the solvent extraction procedure is generally reported in recovered volume (ppm) and in percent relative to amount
of organic matter in the rock (EOM/TOC). Extraction data typically are included with data from liquid chromatography, following solvent extraction.

The conventional solvent extract is commonly referred to as a C15f extract or a C151 bitumen. It contains both hydrocarbons and nonhydrocarbons in
the heavy rar11ge. Soluble compounds lighter than C15-1-are removed as a consequence of solver11t evaporation following extraction. Although
compounds in the C14-and-lighter range are present in the extract, their concentrations will have been modified by the evaporation and their preser11ce
generally ignored in any subsequer11t downstream analysis. Many laboratories now perform cor11trolled or vacuum evaporation to remove the solvent
producingi a C101 extract.

Preserving the intermediate do-C14 range in bitumen can have particular value when correlations are attempted between bitumen and crude oils.
Intermediate range hydrocarbor11s normally are preserved in crude oils because most production samples need not go through a heating process prior
to collection. By preserving intermediate range hydrocarbons in bitumen extracts, comparable data on C10-C14 organic compounds can be obtained
for both bitumen and crude oils. The lower a compound's C-r11u mber, the easier it is to identify and work with, because fewer isomeric combinatior11s
are possible.

Solvent extraction procedures are very systematic in any laboratory, resulting in consistent recovery. Consistency is enhanced fiurther by the use of
blanks and standards to ensure the purity of solvents and to confirm extraction repeatability over time. The principal variables inherent in solvent
extraction lie in two areas: (1) the selection of representative samples and (2) the use of different solvents.

When a fresh core is used, the sample-selection variable is generally not of great significance; the rock sample is coherent and can be chosen to
match the lithologiy or depositional environment under study. Caution must be taken in the use of old core, however, because bacteria can alter
bitumen composition while a core is in open storage, resultingi in a degraded, nonrepresentative extract.

Cuttings add one further dimension to selecting a representative sample. Often, such a small quantity of cuttings is sent to the laboratory for analysis
that more than one lithology has to be picked to provide adequate sample volume for liquid extraction. In addition, it is not always practical for
laboratory geologists to identify the specific lithology that represents a rock unit at a selected drill depth. This situation is particularly common when
no stratigraphic or descriptive information accompanies cuttings samples.

Use of differer11t extraction solvents can prove to be a problem when comparing extract composition and downstream analytical data from various
analytical facilities. Common solvents in use include chloroform, trichloroethane, the triple mix benzene-methanol-acetone, and the double mix
benzene-methanol. Each yields a slightly different extract; additionally, the use of acetone can create polymers and other compositional changes in
extracts (Hunt, 1979).

Attempts have been made to increase the speed of extraction by using an ultrasonic probe; this method, however, appears to crack some organic
compounds and yield slightly modified extracts. Nevertheless, rapid extraction by ultrasor11ic stimulation is one method used for source-rock screening
(Welte et al., 1983). In this process, a combination of infrared detection and ultrasonic extraction (IR/US) estimates the C151 bitumen content of
possible source rocks.

Separation Techniques: Asphaltene Precipitation

Asphaltenes are routinely separated from other organic compounds in bitllmen and petroleum by precipitating them from solution. T'his process,
de.3sphaltlng, is carried out simply by adding light hydrocarbons to bitllmen or crnde oil and letting an asphaltene precipitate form (figure 1,
Deasphalting.

I
I
.!
!
Asphaltenes are removed from extracts and crude oils by precipitation with a light solvent like pentane). The process can occur naturally in petroleum
reservoirs, leading to different petroleum compositions at different locations within the same reservoir system (Dahl and Speers, 1986).

Weight, percentage of total sample, and ratios with other components are the principal asphaltene analytical notations on data sheets related to
conventional source rock and correlation studies. Unless the asphaltene portion of the sample is to be analyzed further, such as for biomarlker
ider11tification with mass spectrometry, the precipitate is set aside in storage.

Although deasphalting is simple and leads to rather gross figures, the most common sources of variation reslllt from sample composition, not the
separation procedure. Also, the rather limited use of asphaltenes in routine exploration geochemistry work at this time does not mandate a more
controlled separation technique.
Separation Techniques: Chromotography
Chromatography is the principal method cu11rently used to iso-late major groups of organic compounds from bitumen and petroleum samples and
quantify the presence of common compound types within those groups. Chromatography simply separates different orga11ic compounds based on each
compound's natural retention characteristics as any mixture of organic molernles is carried along through a permeable medium.

liCJ!uid chromatography (LC) and gas chromatography (GC) are the two most prevalent chromatographic procedures used in exploration geochemistry.
liCJ!uid chromatography (figure 1, Liquid chromatography.

(Courtesy Brown and Ruth Laboratories, ExLog)

FIGURE 1
FIGURE 2

Separation os saturates, aromatics, and resins in bitumen or crude oil is cani,ed out using packed columns and different solvents on deasphaltened
samples) is used primarily to separate bitumen and petroleum into saturate, aromatic, and resin groups following asphaltene precipitation. Gas
chromatography is used most commonly to identify and CJ!Ua ntify individual compounds withi11the saturate group (figure 2, Reco,-der is plotting peaks
of saturate fraction of a C15 1 extract).

Gas chromatography, however, is effective in separating compounds within any group. A third type of chromatography, thin-layer chromatography
(TLC), is becoming more common in laboratories, though its use is specialized as for rapid separation of very small quantities needed for downstream
analysis (e.gi., porphyrin analysis). TLC is based on solvent movement by capillary action up a treated glass plate (Barwise and Roberts, 1984).

liCJ!uid chromatography is perfonmed usingi a glass column typically packed with silica gel or alumina. The deasphaltened bitumen extract or petlroleum
sample is carried through the column using a sequence of different solve11ts. As the sample moves down the colum11, the interplay between the
different solvents, packed column, and orgianic compounds separates groups of organic compounds so that each is eluted at column bottom at a
different time. The order of elution is first saturates, then aromatics, then resins. This sequence corresponds to the increase of molecular polarity
among the three groups, which controls their natural retention rate during conventional liquid chromatography. llhe quantity in each separation is
generally reported by weight and group percentages of original bitumen or petroleum. Ratios among separations also are calculated and reported by
most analytical services.

For some downstream analyses it may be necessary to separate recovered saturate hydrocarbons into straight-chain (normal) alkanes and branched
chain plus cyclic alkanes. This further separation is carried out by dissolving the recovered C101 or Cl!5 1 saturates in a light solvent (e.g., hexane) and
passing the solution through one of two systems. In one system, molecular sieving, the saturate solution is placed in a column packed with a zeolite.
Normal alkanes are trapped preferentially by zeolite crystal stmcture, allowingi branched alkanes plus cycloalkanes to pass through and be drawn off
first. In the other system, urea adduction, normal alkanes are adducted {pulled) into crystalline complexes while the remaining saturates stay in
solution, pass through, and are drawn off first. Neither molecular sieving nor urea adduction is quantitative.

Variations in liCJ!uid chromatography data may result from sources not directly related to the natural composition of bitumen or petroleum. Bitumen
variations, as we have observed, can be induced anywhere along the sample handling, storage, and extraction chain. Likewise, crude oil variations can
result from sample collecting, handling, and storage, and from preparatory analytical procedures. The topping step, for one, does not always lead to a
uniform C101 or C151 concentrate. Also, if water is present in a orude oil sample, it may be necessary to distill the sample before chromatography;
this procedure ca11 affect the composition of recovered compou11ds slightly by carrying off hydrocarbons with the steam.

Although analytical laboratories mai11tain good internal quality control by running bla11ks and standards, it is not uncommon to find that liquid
chromatography data differ slightly from laboratory to laboratory. This is due, in part, to the use of different elution solvents and calculation
techniques. For example, resins may be expressed either as two weight or percentage figures (eluted and noneluted) or one total figure. T1he
noneluted amount represents the weight difference between the sample introduced and the total weight of the separations recovered from the
column. The single resin figure can represent a weighed recovery by elution or a calculated recovery as a remainder after saturate and aromatic
elutio11. llhus, explorationists should be prepared to adjust data from different laboratories in order to clarify true compositional similarities and
differences among samples.

Explorationists .should also remember that chromatographic .separations obtained by liquid chromatography generally do not represent the end of the
analytical chain; routine analyses follow, such as gias chromatography or carbon isotope determination, which help identify the sources of real or
induced variations in data.

Gas chromatography uses a single inert gas as a carrier or solvent for the mobile phase and a glass or metallic column for the stationary or retention
phase. The column can be thick enough to be packed with a porous medium or thin e11ough for the inner surface to be coated with a nonvolatile
liquid to act as a capillary (figure 3, Capillary column gas chromatograph).
 (Courtesy Brown and Ruth Laboraton·es, ExLog)

FIGURE 3 FIGURE 4

In gas chromatography, the column is heated so that the sample is maintained in vapor phase as it moves along in the carrier gas. Separation ocrnrs
as compounds move back and forth between vapor (movement) ar;id liquid (stationary) phases. Order of separatior;i, therefore, is dependent on (1)
molecular size small molectJles move more rapidly than large becatJse they remain more readily in a vapor state; ar;id (2) compound polarity N
compollnds of similar size but different polarity move at dissimilar rates.

Gas ohromatographic analysis generally deals with specific types and limited ranges of hydrocarbons. As we saw in GL701, common types and ranges
are gaseous saturates (C.-C4 to C.-C7), light li(i!uid saturates and aromatics (C4-C7 to C4-C:m), and heavier li(i!uid saturate, aromatic, and resir;i
separations ( C101 or C15 1 ). The need to analyze specific hydrocarbon types and narrow molecular ranges is the result of two overriding
considerations: (1) To keep analytical runs relatively quick, the number of compounds must be limited to a workable number or range. (2) For
effective chromatographic separation of very similar compounds, analytical columns and programs must be tailored to a limited molecular range.

Typically, compound separation is presented graphically on a gas chromatogram. The concentration of ir;idividual or selected (e.g., r;iormal alkanes)
compollnds is tabulated. Generally, selected ratios (e.g., paraffin:naphthene; pristane:phytane) and calculations (carbon preference index; CP]) are
also ir;icluded.

Two additional causes of irregularities in analytical data are common to samples analyzed by gas chromatography: (1) the incorrect identification of
compollnds (peaks) and (2) the use of different analytical columns and heating programs among laboratories.

Misidentification can occur when a chromatogram is being planimetered by hand or when an integrator is not in full synchronization with emergent
times. The error may show up in a C1H analytical data table, for example, by a marked shift in CPI as from odd-even predominance to even-odd
predominar;ice.

Where diverse gas chromatographic columns and procedures are used, data for the same compound type and range can vary simply because of
slightly different responses by organic compounds. When comparing data from two or more analytical facilities, watch for variations that "correlate" to
laboratories; similarly, always request that copies of gas chromatograms, particularly in the C10+ or C15+ ranges, accompany the data sheets.

A word of catJtion about chromatograms is in order for the explorationist: visual differer;ices can be very misleading. Vertical (peak height) scales on
chromatograms are often changed between and during analytical runs to keep all peaks within recorder limits. This means that when working with
chromatograms, relative similarities or differences in peak heights and patterns are the critical factors to evaluate. Some laboratories now provide
"normalized" ohromatograms that show peak patterns adjusted to a standardized presentation (e.g., tallest peak height set at 90% of plotter limit;
8gure 4).

Separation Techniques: Mass Spectrometry

Mass spectrometry is the technique through which individual compounds are identified by measuring individllal molecular masses or their
characteristic mass fragments. Molecules in a sample are ionized (given an electrical charge), accelerated through a magnetic field, and impacted on a
1
detector. T1he whole molernle may be ionized (M ) by losing an electron, or ionization can ocCllr through molecule fragmentation (figure 1 and .Eigure
Z).

100.. ,. ,
100

CaH1B n-Octane
CaH16 2,2,4-Trimethylpentane

20

o,-......., ------ ------ --- -

10 20 30 40 50 60 70 80 90 100
M+

110 120
10 20 30 40 50 60 70 80 90
M
O!-'....,....,....,_ ,....,"""T-"T- ,._,-,. -.-..,.....,.....--, - .. ..---1
100 110 120
+

_,
m/e
{Adaprea trom Morrison am1 Boyd. 1973)

m/e
(Adapr9d from Morrison and Boyd, 1973>

FIGURE l FIGURE 2

The magnetic field has the effect of bending ion trajectories into a spectrnm according to ion masses; the heavier an ionized molecule or molecular
fragment as determined by its mass/charge ratio (denoted 7 or
the less it is affected by the magnetic field and the straighter its trajectory. Detection and identification by number occurs beyond the magnetic
field as emerging ions strike a sensor. For example, the C21 sterane ion (M+) has an of 372; its major fragment ion has an of 217 ..

To identify more than one ionized molecule or fragment by its mass/charge, a mass spectrometer needs more than one detector spaced across the
trajectory spectrnm, or it must vary the magnetic field so that particles of different masses strike a single detector at different times. The latter is the
common metlrnd used in general mass spectrometers; it provides greater versatility. For very repetitive use, as in determining carbon isotope masses
14 13 12
{ C, C, CJ, mass spectrometers can be set up with relatively fixed magnetic fields and multiple detectors.
Two products are obtained from modern mass spectrometers: mass spectra and mass chromatograms. A mass spectrum is the output of a mass
1
spectrometer (MS) in which a sample containing a specific compound has been ionized and a spectrum of its molecular (M ) and fragmental ( }
composition has been produced {figure 1 and figure 2). Mass spectra, used principally for identifying compounds, are seldom encountered by
explorationists.

A mass chromatogram, also called a mass fragmentogram, is a summation chart of the relative occurrence of a specific mass charge (')fragment
derived from the different molecules in a sample (figure 3,

408.43 PENTACYCLIC #2A 1108.50 PENTACYCUC #4

TERPANES RASTIRITES TERPANES BODA REEF LS.
mlz=191 SHALE
mlz=191 OIL STAINED
318.81 949,91

236.79 709.22

154.97

38.12 41.25 44.37 47.56 50.62 53.75 56.87 63.00 35.00 38.12 41.25 44.37 47.56 50.62 53.75 56,87 63.00

(from Vl,arboom, er al, 1986) (from VJ/erboom. et al, 1986)

FIGURE 3 FIGURE 4

938.33 PENTACYCLIC C30 #5 348.57 PENTACYCLIC

#10
TERPANES TRETASPIS TEAPANES
BLK. TRETASPIS
m/z=191 C29 SHALE m/z=191
741.21
SHALE
279.28

552.00 209.83

382.96 142.48

173.83

-15.20
35.00 38,12 41.25 44.37 47.56 38.12 41.25 44.37 47.56 50.62 53.75 56.87 63.00
50.62 53.75 56.87 63.00
(from VJierboom, st al, 1986)
(from Vlierboom, et al. 1985)

FIGURE 5
FIGURE 6

225.13 PENTACYCUC C30 224.94 PENTACYCUC Co

SOLBERGA
QUARRY TERPANES
TERPANES C29 OIL OIL
m/z=191 mlz=191 Cw
182.42 183.83

130.71 142.94

C27
C20

38.12 41.25 44.37 47.56 50.62 53.75 56.87 63.00

(ftom 1/1,erboom, et al, 1986) (from Vl1erboom, et al, 1986)

FIGURE 7 FIGURE 8

The mass fragmentogram is used principally to determine relative contribution of a particular orgianic stmcture (biomarlcer) to different compounds in
the sample.

The explorationist, for example, can identify the relative abundance of C21, C28, and C29 steranes in a sample by obtaining an f 218 fragmentogram
for that range of alkane molecules (Steen, 1986).
Special Analyses
The same special analyses used in kerogen evaluation geITT1erally can be applied to bitumelil/petroleum samples. However, techniques such as NMR,
ESR, IR, and fluorescence analyses are seldom used in detailed extract or oil correlation studies because results are not discriminating enough.
Nevertheless, such broad techniques cafil be used effectively in combination with other analyses to confirm trends and processes. Curiale (1986), for
13
exampie, used CP/MAS C NMR to demonstrate the inverse relationship of aromaticity of solid bitumen to elemental ratio (Bgure 1, Pfot of
aromatically measu,ed by NMR vs ratio for solid bitumen).

0.70

0.60 u Gilsonite
? Ozocerite
Asphalt
0.50 U 0 Ingramite
Albertites
I uugo .
0.40
pO G
Uraniferous Bitumens O G A G
I Grapnamites A
I lmpsonite G M
G
G
0.20
N
G,
0.10 z
0.00 ._1 . .. ... . ..

0.60
0.90 1.20 1.50 1.80
(from Curiale, 1986)
IH/C

FIGURE 1

These parameters, in combination with others, were used to identify solid bitumefil samples from Africa, Mexico, United States, and Canada as either
pre-oil (immature) or post-oil (postmature). Using another technique, polar nuclear magnetic resonance {lHNMR), Salli et al. (1985) showed that for
mafily aromatic extracts, the percentage of aromatic protons (PAP) is proportional to the level of maturity of its host sediments (Table 1).

Table 1: Comparison of percentage os aromatic protons

(PAP) to other maturation parameters.
Depth (m) Ro (8/o) T.,..,. ('C) PAP
{%)
801 0.35 418 11.2
1075 0.37 424 13.2
1401 0.37 426 14.1
1801 0.38 432 15.0
2483 0.60 436 20.6

Artificial maturntion
I 801m-- •c
300 40 h 19.7

801 m 'C 24.4

350 18 h

Location T ..,. mean PAP, mealil

(number of samples) (S.D.) (S.D.)
I(5) 429(1.7) 12.8 (1.5)
n (6) 436 {3.3) 13.2 (0.7)
m (9) 439 {2.7) 19.8 (2.6)
IV ( 12) 450 {3 .0) 17.6 (5.4)
V (4) > 463 (--) 21.3 (4.4)

In case.s where a sample represents a very narrow molecular separation or where an instrumental technique has been adapted to improve resolution,
special techniques do find effective use in exploration geochemistry. Von der Dick and Kalkreuth (1986) showed, for example, that synchronous
excitation and total-scafilning fluorescence of extracts and oils can be used to distifilguish maturation levels aITT1d monitor migration changes. Such a
refinement of the fluorescence technique, then, can be used for screening oils in correlation studies (Hagemann and Hollerbach, 1986).
Two special techniqLJes with very common use in bitLJmen and petroleum analysis are isotope spectmmetry and ultraviolet spectroscopy.

i ( Z)
z,
Isotope spectrometry wonks with the ratios of stable isotopes in organic compounds, primarily followed by in hydrocarbon compollnds

and : , and occasionally in nonhydrocarbons. BitLJmen and petroleum samples, readily separable into groLJps and series, are analyzed more

often than kerogen with its complex mixture of compound types. For crude oil-source rock correlations, however, kerogen isotope ratios may be
effectively compared with those of total bitumen or asphaltenes becatJse of their close genetic association (Schoell, 1984).

Thegeneral isotope ratio analytical procedLJre used in geochemical laboratories is based on principles of mass spectrometry. A sample is converted to
a gaseous form (i.e., COi, H2S, SOi, /112) at the beginning of an isotope analysis. Using analysis as our example, the ger11eral procedure is to
combust the sample and convert all organic carbon to carlbon dioxide ( COz). This gas is ther11trapped, purified, introdtJced into the spectrometer,
13 12
ionized, and analyzed for C or C carlbon dioxide by m/z properties. As with all isotopic determinations, corrections are made to compensate for
mass effects of other isotopes (i.e., different oxygen isotopes in COi). The amounts of each carbon isotope are ratioed; that ratio is then compared to
a standard and reported in parts per mil (0/00) difference from the standard. For carbon isotopes the standard is the Peedee belemnite (PDB)
(see GL701, Appendix B, for calculation procedure).

Ultraviolet spectroscopy (UV) is one common method used to measure the vanadiLJm/nickel content of organic compounds, primarily porphyrins. UV
spectroscopy can also be used to evaluate maturation and alteration of bitumen and crude oils (Hagemann and Hollerbach, 1986).

Thegeneral procedure used to determine vanadium/nickel content is to place the sample into a dilute solution and submit it to spectroscopy. The
vanadium- and nickel-bearing porphyrins absorb different wavelengths (i.e., vanadium absorbs a higher frequency range than r11ickel). A photometer
scans the UV returning spectra and produces a UV signature for the sample. The vanadium/nickel ratio is determined by comparing absoription levels.
Currently, high-performance liquid chromatography combined with mass spectrometry ( 1-/ C) is replacing UV spectroscopy for making precise
determinations of poriphyrin ccrntent and composition (Barwise, 1983).

In the laboratory, UV spectroscopy for determining maturatior11and alteration of bitumen and crude oils generally is carried out by adsorbing a fixed
concentration of sample onto a slide. Spectiral flllorescence measurements are made by exciting the extract or oil films and recording stJch parameters
as maximllm peak wavelength, red-green qtJotient (ratio of fluorescence intensity at 650 and 500 nm), and spectral alteration with duration of
exposure time.

Organic Carbon Determination

To meastJre organic carbon content:

1. Pulverize and split the rock sample.

2. Weigh out a precise amount typically< 3 g.
3. Acid treat the sample to remove all mineral carbonate (C03).
4. Combust acidized sample in an electric fllmace in an excess of oxygen.

5. Trap COi of combustion and measure volume.

6. Convert COi volLJme to weight percent total organic carbon ( TOC) content.
7. Present data in numeric and diagrammatic format (example, Table 1)

Table 1: Selected analytical values for Eocene kerogen

samples from the vicinity of the Mist gas field, Oregon.
Formation Lithology TOC S1 S2 S3 Ru
Keasey IMudstone ,,76 .10 ,10 1.59 .16
IMudstone ,,89 .10 .10 1.53 .18
Cowlitz IMudstone 1.07 .10 ,10 1.44 .26
Mudstone ,,64 .10 .10 .67 .20
SkookLJmchuk Siltstone 4.63 .14 2.16 2.64 ,35
Coal 48.19 5.16 135.23 11.42 .38
Coaly 7.22 .40 13.96 2.56 ,37
Siltstone
Slty 1.55 .10 .44 .80 .31
IMudstone
Kerogen Separation
To make a kerogen separation(Durand and Nicaise, 1980):

1. Treat cuttings or coarsely ground sample with excess hydrochloric acid (HCI) to remove carbonate minerals (Egure 1).

FIGURE 1

2. Treat residue with concentrated hydrofluoric acid (HF) to digest silicate minerals.
3. Wash liberated kerogen and heavy mineral fluorides free of acid.
4. Separate kerogen from heavy minerals by liquid flotation, typically a solution of 2.0 sp gr zinc bromide.

Note: This step is omitted for some rock types (e.g., clean carlbonates).
5. Isolate kerogen separation for typing and/or reflectance determination.

Kerogen Typing
To determine kerogen type and thermal maturity level {TAI-SCI) using transmitted light:

1. Wash isolated kerngen thoroughly.

2. Wet-·mount kerogeri 011 coverslip a11d bond coverslip permarienUy ta slEde
{Egure 1).

FIGURE 1
3. Examine kerogen macerals with mioroscope, using transmitted light.

4. Quantify percentages of maceral types present.

5. Rate quality and mat1Jration level (coloration) of spore and pollen macerals.

6. Rate maturation level of algal macerals using incident fluorescent light (Bertrand et al.,1986).

7. Prepare data to Sllmmarize results. Headings should be as follows: Sample identity, depth,R0%, Color Index {SCI), and Kerogen
Characteristics (Arn%, Ex%, Vit%, Inert"/o, Flour).

Kerogen Reflectance
To measure kerogen (vitrinite) reflectance (%RO) using incident light:

1. Wash isolated thoroughly.

2. Dry (vacuum, freeze) separation.

3. Mount separation in 1-in. bioplastic plug (flgure 1).

(Courtesy Robertson Research)

FIGURE 1

Note: Whole-rock samples can also be prepared for reflectance and compositional study by mounting rock fragments in a bioplastic plug
and proceeding from Step 4.

4. Polish plug and embedded sample to very smooth surface.

5. Place polished plug under microscope and immerse surface with oil.

6. Expose plug to incident white light and/or ultraviolet (UV) light to excite fluorescence in order to identify vitl'"inite (or other usable)
macerals.

7. Measure reflectance on approximately forty particles (or more) of each maceral type with standardized photomllltiplier.

8. Plot individual reflectance val1Jes (histogram) and determine reflectivity average of representative first-cycle population.
Elemental Determination
To measure elemental contents in kerogen (Durand and Monin, 1980).

l. Prepare a primary kerogen separation in the same manner as that used in TAI-SCI and %RO separations.

2. Make an ultrasonic extraction to remove soluble organic material.

3. Concentrate kerogen further with heavy liquid separation.
4. Combust concentrate in oxygen-charged analyzer and trap carbon dioxide (CCJi), water (H2OJ, and nitrogen oxides (NOX).
5. Combu.st pyrite-free concentrate in oxygen-charged analyzer a!lld trap sulfur dioxide (SOi).
6. Combust concentrate in inert-atmosphere analyzer and trap C·Oi formed from oxygen-bearing kerogen.

Note: When individual determinations of sulfur and oxygen concentrations are not required, Steps 5 and 6 are omitted, and O+ 5 is
calculated as the difference between total saniple weight and C, H, N, plus ash content.
7. Measure individual g1as volumes; convert to molecular C, H, N, S, and 0, plus ash.

8. Tabulate data in relative concentrations and selected ratios plot and f ratios on van Krevelentype diagram (Eg_u_i:e l).

Li
Ww,ce,:s,FaW
/' _,, LIPTINITE
/ ("TYPE
/ 11
I

hnrides
---;-;.Nl]E
["Type II")

--
-------------as,
"t,l;.lfl"ILC A(;l.
LiQ - lutC>Ses
0.5-
, I NERTINIT1E (Type IIIB"
o,g1n: ;;d t"ood or T)' e IV")

OJC AklmiC:Ratio
lncreaslrlg tem,pe<atllf9

□ ■□
.--- ma.tLI•i:litioo
1pa.thway
/ ZONES OF GENERATION

(From Brooks, 1981b)

co.,i,,o OIL G

Pyrolysis Analysis
AS
To carry out a pyrolysis analysis of rock (or kerogen) (Horsfield 1984):

1. Pulverize representative rock sample (or take split of kerogen separation.

2. Place 50 to 100 mg in analytical capsule.
3. Weigh sample and place in rack for analysis.
4. Begin Rock-Eval programmed heating (figure 1).
5. Measure (flame ionization detector, FID, for a discussion of gas detector types and their applications, see Bond, 1986) hydrocarbons/
bitumen (5-i) already pre.sent in rnck that are liberated by heating sample to 250° C in inert atmosphere,

Note: Some pyrolysis programs distinguish between gaseous hydrocarbons given off ear11y in the first heating step (designated 5:i) from
liquid bitumen (51) given off later in the first heating.

6. Measure (FID) bitumen(Si) generated by thermal decomposition of kerngen during progressive heating to 5500 C in inert atmosphere.

7. Measure (them,al conductivity detector, TCD"') carbon dioxide ( ) generated from thermal decomposition off kerogen in inert
atmosphere and trapped during programmed heating (e.g., trapped during 3000 to 3900 heatingi).

Note: Some more sophisticated pyrolysis instruments follow Step 7 by introducing oxygen to the heated analytical system and combustingi
the remaining organic matter in the sample. This CO-i
product (designated 54) is used to calculate a TOC for the sample. Standard Rock
Eval pyrolysis, however, does not include this step, but rather uses TOC obtained from conventional organic carbon analysis.

8. Determine temperature { Tm?x) of maximum rate of bitumen generation,

9. Evaluate pyrogram and make data presentation.

Pyrolysate Characterization
To characterize pyrolysate by gas chromatography (GC), by gas chromatography and mass spectroscopy (GC/MS), or by mass spectroscopy (MS):

1. Split and trap pyrolysate (Sz) generated from kerogen thermal decomposition(see step 6 of Analytical Procedure for Pyrolysis Analysis)
Note: Any portion of S1 or Si pyrolysate can be analyzed by trapping splits during a pre.selected programmed heatingi interval.
2. Introduce Si sample split into gias chromatograph of mass spectrometer.
3. Vaporize (GC) or ionize (MS) sample and carry out GC or MS analytical procedure; introduce selected GC separation into MS if GC/MS
analysis is performed.
4. Evaluate gas chromatogram, mass spectra, mass fragmentogram and/or integrator printout of pyrolysate. Compare gas chromatogram
with standard examples to interpret kerogen type.
5. Ta bulate findings and/or data,

Sample Degassing
To degas a fresh sample of rock:

1. Confinm, if practical, that a bactericide (usually zephrin chloride) was put in the sample container at the time of sample collection,
2. Inspect sample container {metal can, polypropylene jar, glass core vial, etc,) for evidence of leaks and faulty seals.
3. Place sealant (e.g., a dab of latex) on top of container over point through which gas sample will be extracted; allow sealant to set (Elgure
_l).

FIGURE 1
 4. Punch hole in container through sealant.
5. ]nject with a syringe a measured volume (about 5 cc) of distilled water into sample container to create slight positive pressure.

6. Withdraw with the same syringe the same (displaced) volume of gas from headspace at top of container,
7. Transfer gas sample immediately to gas chromatograph {GC) and inject to start analytical rnn.

Note: Some analytical laboratories make a distinction between headspace gas that accumulates naturally during transit/storage from gas
that can be liberated quickly from canned samples by violent agitation and natural abrasion (e.g., sealed sample container agitated by
paint shaker). When two such gas samplings occur, Steps 4 through 7 are repeated following agitation; the quantities of headspace and
cuttings gias measured typically are reported separately and summed to yield a total-gias figure.

Micronization Extraction
To extract light liquid bitumen/hydrocarbons from a rock sample:

1. Select fresh (typically canned cuttings or core) sample of lithology to be extracted (keep sample wet or under water until sealed in
microblender).
2. Place measured volume of sample (about 1 to 2 g) in micro-ble111der with a measured volume of hot water.
3. Seal container and pulverize sample with blender action for spedfic length of time.
4. Sample the gases and light liquids (now in gaseous form) that collect in the headspace.
5. Inject sample into gas chromatograph to start analysis.
6. Determine gas content and composition from gas chromatography run.

Solvent Extraction
To extract liquid (generally C101 or C15 1) bitumen/petroleum from a rock sample:

1. Pick a111d pulverize approximately 100 g of rock sample (.Eigure 1),

FIGURE 1
 Note: Care is generally taken at the analytical laboratory to see that excess heat is not generated in the rock during grinding, so that
organic compounds are not oxidized.
2. Place sample in porous container, weigh, and insert in Soxhlet extraction glassware (figure 2).

(Courtesy Brown and Ruth Laboratories)

FIGURE 2

3. Place sealed Soxhlet apparatus on heating element and extract sample for fixed period of time(e.g., 18 hours).
4. Transfer extract-bearing solve111t to tared container and evaporate solvent at moderate temperattJre(abotJt 40° C) in an inert atmosphere.
5. Weigh extract and store until scheduled for further analysis.
6. Prepare initial data table of weight and extract percentages, to include the followingi column headings: sample identification, organic
5
cal'1bon ( TOC, weight%), EOM (ppm), saturated hydrocarbons (HC, ppm), aromatic hydrocarbons (ppm), saturated arom,at1c(-A ) ratio, HOCC
T
ratio, !l, CPI, where Pr= Pristane, p,r = Phystane. Saturated hydrocal'1bons cJi3C, and Aromatic hydrocarbons ,d13C.
P•

Asphaltene Precipitation
To deasphaltene a liquid:

1. Weigh rock extract or topped orude oil sample in tared flask.

Note: A crude oil sample is topped by placing it in a low-temperature oven with an inert atmosphere so that lighter compollnds are
evaporated off, much in the same manliler that lighter compounds are evaporated off during liquid extraction of bitumen. T1his topping step
removes some variables introduced by crude oil sampli111g and storage and it makes C151 crude oil data more directly comparable to C15+
extract data. The percentage of weight loss from topping is ustJally calculated, and can be one additional geochemical parameter.
2. Treat extract or crnde oil sample with an excess of light orga111ic solvent (e.g., n-hepta111e, n-hexane, n-peliltane).
3. Filter precipitate {asphaltene) from remaining organic compounds (saturates, aromatics, resins) still in solution.
4. Weigh recovered precipitate.
5. Record asphaltene weight and calctJlate percentage of initial sample.

Liquid Chromatography
To separate a deasphaltened extract or oil sample into its major groups (saturates, aromatics, resins):

1. Introduce a deasphaltened bitumen or oil sample to the top of the packed column (.Eigllre 1).
 (Courtesy Brown end Ruth Laboratories, ExLog)

FIGURE 1

2. Pour a light, no11polar solvent (e.g. ,11-hexane) into the colllmn and let gravity preferentially move dissolved sat1Jrates down column.

Note: A modern variation of gravity flow is to apply pres.sure at the top of the colllmn to speed llp solvent movement and the
chromatographic process. This is l!Sllally referred to as high-performance liqllid chromatography (HPLC), and is most commonly used for
separating closely related compounds(Killops and Readman, 1985).
3. Collect saturate group as it is eluted at bottom of colllmn.
4. Pour a light, slightly polar solvent (e.g., benzene) into the column, and let gravity move dissolved aromatics preferentially down column.
5. Collect aromatic group as it is eluted at bottom of column..

Note:A few sulfllr-bearing resins can be eluted with the aromatic group; when present, these resins increase aromatic value slightly at the
expense of resins.
6. Pour a light, polar solvent (e.g., chloroform) into the column and let gravity move remaining dissolved resins down the colllmn.

7. Collect resin grollp as it is eluted at bottom of column.

8. Wash separations into drying containers and evaporate off solvent in inert atmosphere.
9. Weight separations and ro1Jte to any downstream analysis.
10. Prepare data tables on weights, separation percentages, and ratios of original bitumen or petroleum sample.

Gas Chromotography
To separate compounds by gas chromatography:

]. Inject separated or narrow-range sample into tieated port and carrEer gas flow as recorder a11d Entegrator are started (zero time).

2. Allow chromatographic separation to occur as carrier gas moves compounds through heated column.
3. Detect (FID) arrival(emergent times) of separated compounds at end of chromatographic column.
4. Convert (electronically) magnitude of detector response to peak area plotted on strip chart (gas chromatogram) (flgure 1).

FIGURE 1

5. Identify compounds(emergent times) represented by peaks, and measure (planimeter) are.as under peaks to determine quantities.

Note:Wtien an integrator is used in place of a planimeter to measure quantitiesi as is ttie case En most modeir11 recorders., Steps 4 a11d 5
occur simultaneously.

6. Prepare data table of compound types and quantities while gas chromatograph is backflushed in preparation of next analysis.
General Guidelines
The cornerstone to any successfully planned and executed exploration geochemistry program lies with sample selection and preparation, The platitude
"rubbish in rubbish out" applies most aptly to the methodology "sampling analysis --t evaluation," which typifies most geochemistry programs,
The success or failure of a geochemical program is predetermined to a large degree by the quality of samples chosen and the relevance of these
samples to geochemical questions needing answers, Explorationists, then, must put as much thought and care into selecting and handling samples
prior to analysis as they put into evaluating analytical data that come back,

The following general guidelines apply to the collection and handling of virtually all sample types prior to analysis.

• Know what you are sampling before you sample, When conducting an outcrop study program, for example, have the rock units selected,
their preferred sampling sites located, and appropriate field maps in hand before any sample collection begins, Be just as systematic in
selecting warehouse cuttings and core samples.
• Collect fresh, unaltered, uncontaminated samples. If this is not fully feasible, as when drilling with a high-speed downhole turbine or an
oil-base mud, be sure that precise notations accompany the samples to the laboratory.
• Collect and submit more sample material than is normally needed for the planned analyses. There are a variety of reasons for this
requisite. Not all rock and fluid samples submitted will prove usable. Additionally, if analytical results appear erratic or questionable to
laboratory managers, most will choose to have samples rerun. Similarly, when analytical data are returned to the exploration office, you
may decide to have specific samples rerun or additional analyses performed on selected samples to verify an anomaly or break in trend.
• Collect all samples in relativ,ely permanent, preferably inorganic containers. Remember, the composition of an oil can be changed if the
sample reacts with a rubber seal, or partially evaporates through a plastic bottle.
• Identify all samples with permanent markers, and retain copies of identifying information that accompanies samples to the laboratory.It
does not matter how well samples have been collected, prepared, and shipped if you cannot match analytical data confidently with sample
identities.Note:Analytical laboratories generally assign their own identification numbers to samples as they are received a11d logged in,
Laboratory numbers will have to be reidentified with original sample numbers unless dual labeli11gi is i11cluded in analytical data
presentations,
• Perform as much of the routine preparatory work as is practical in the exploration office.Generally, operatio11s personnel are in a far better
position to determine which core or cuttings lithologiy best represents an interval than a re laboratory personnel. Results from the analytical
laboratory can be improved further by providing operational information such as tops, lithologies, and wireline log prints with the samples.
These guides are of value to laboratory geologists and technicians even if you choose to keep formation names, ages, and locations
confidential by using designations such as Unit A, Unit B, ...; Well No, 1, Well No. 2, . , ..
• Make clear the final disposition of samples after analysis,Generally, analytical laboratories will discard samples after a short storage period
if no instructions are received from the exploration office. State which samples should be discarded and which should be returned to the
exploration office for storage. These instructions should be in writing and accompany samples to the analytical laboratory, Certainly, one
of-a-kind samples, such as drillstem test fluids, should always be returned to permanent storage,
• Maintain your own quality control program. Analytical laboratories, like exploration offices, are only as good as their staff, and we all know
that any staff can have a bad day. To assess confidence in data, we recommend that about one out of every ten-to-twenty samples be a
replicate submitted under a second identity. When truly replicate samples are submitted and analytical procedures are consistent, data
from comparative runs should fall within analytical variation for the analysis performed.

Outcrop Samples
Outcrops provide many samples in basin or regional source rock and correlation studies. Outcrop sampling is the norm for frontier areas where drill
cuttings and cores are lacking. Although physical and chemical weathering can modify the properties of outcrop samples and complicate the sample
selection process, outcrop sampling has one advantage seldom found with other sample-producing teohniques: specificity. In geochemical surface
sampling programs, rock specimens are taken specifically for planned or active geochemical st1Jdie.s. Except for canned cuttings, this is seldom the
case for samples obtained through drilling and downhole coring operations. Restated, outcrop samples avoid a number of limitations inherent in
conducting geochemical studies using conventional and sidewall cores, dried rnttings, or drillstem test samples taken and stored with no thought of
future geochemical use (.Eigure 1 and figure 2, Possible introduction of handling errors.

FIGURE 1

Mishandling of samples can occur anywher;e from w,el/site collection to warehouse retrieval.

FIGURE 2

For example, large quantities of cuttings are often sent to the field office to be cleaned, described, sacked, and stored. Technicians must emphasize
consistent sample preparation and transter to avoid early errors and loss of sample validity).
Hand Specimens
Outcrop sampling follows the basic rules geologists learn for selecting fresh, representative samples for har11d specimen study.

Hand specimen samples typically find application in both source rock and crude oil-source rock correlation work Shales in particular are used routinely
in organic carbon (TOC), and elemental analysis (C, H, 0, N, 5), Rock-Eval pyrolysis (Py), kerogen microscopy (OMT, TAT/SCI, %R0), and
heavy hydrocarbon (C101, C151-) extract analyses. Oil-stair11ed rocks can be used cautiously for correlation studies if seep and production samples are
not available.

Carefully collected, fresh hand specimens do not have as many limitations for source rock geochemical analysis as might first be expected when we
recognize that most surficial alteration processes have a diminishing effect on organic content. Therefore, a TOC or C151 extractable organic matter
(EOM) value seldom overstates source potential and can be used as a minimal value with a good degree of confidence. Similarly, a tight shale retains
bitumen and gives a minimal I value during pyrolysis analysis. Kerogen macerals, in turn, generally retain their maturation characteristic and remain
unoxidized in well-lithified, tight rock. When alteration occurs, the effect tends to increase apparent maturation level; consequently, kerogen
maturation is seldom understated from outcrop samples (Mork and Bjoroy, 1983). In addition, if modem organic matter is contributing to the organic
carbon of the sample, its presence can be recognized during transmitted or incident light microscopy of kerogen by the presence of modern
palynomorphs.

Cored Specimens
When direct sampling of fresh hand specimens is not practical in outcrop, as in heavily overgrown, tropical, or low-relief areas, one may cut surface
cores. Surface. coring is commonly ca11ried out with a smalldiameter, highly portable, gasoline-powered drill. Although advertised as "one-man" drills,
portable back-pack drills typically require two people to move, support, and operate on a continuous work schedule.

Surface coring and sample handling follow the same general procedure used in hand specimen sampling, except that more time and cost are required
to collect each sample. Because of these factors, it behooves the exploratior11ist to take extra care while selecting the sampling site.

Cores from portable drills generally are less than 1 in. (2.5 cm) in diameter. This means that to obtain enough rock sample for a bitumen extraction
(100 grams or more), approximately 4 in. (10 cm) of fresh core should be recovered. Eight to 10 ir11. is an adequate core length for most analytical
options and possible reruns.

Surface cores can be used for any rock sample analytical need, with the probable exceptions of C1 -Ct
and volumetric4-C7 analyses. For gasoline
range compositional analysis the core must be canned in water immediately after coring in the same manner as fresh cuttings. Oil-stained surface
cores should be preserved in the manner of cor11ventional core.

Two important cautions must be taken while cutting surface core. The first is to keep the bit cool enough with water so that kerogen and bitumen are
not altered during drilling.. The second is to keep the coolingi water free of organic materials (e.g., grease and gasoline) so that the recovered core is
uncontaminated.

Cuttings Samples

Cuttings are the mo.st common type of rock sample available for geochemical study. Cuttings are routinely gathered by mud loggers and/or wellsite
geologists during virtually all exploration drilling.

Historically, drill cuttings have been collected for a variety purposes; correlation of stratigraphic and paleontologic intervals and evaluation of rock
properties and downhole conditions are the most common. When archived, most of these samples fall in the category of dried cuttings.. They generally
are stored in sample sacks and have a long shelf life. Common procedures for collecting and preparing dried cuttings at the wellsite are described in
Whittaker (1985). Because procedures vary widely with rock type and operator, dried cuttings samples found in warehouses can have a variety of
handling histories that affect their utility in geochemical studies.

In more recent years, it has become more common to collect drilled cuttings specifically for geochemical purposes. These cuttings are collected in
metal or plastic containers at the mud tank and preserved in water or drilling fluid. Called canned {or fresh) cuttings (Figure 1), their shelf life is
dependent almost entirely upon the corrosive life of the container. The utility of both dried and canned cuttings for geochemical study is covered
below.
Dried Cuttings
The preponderance of cuttings currently available in storage are dried cuttings collected systematically at the wellsite at predetermined downhole
intervals (e.g., 30 ft [10 ml). The following conditions are common to dried cuttings and must be kept in mind when planning a geochemical program
or selecting samples:

• The amount of sample now available at each depth interval probably will be small unless multiple sampling was requested in the drilling
program. At some depths of interest, the cuttings may already be used up. The typical paper sample sack found in most company
warehouses (.E_jgure 2) holds less than 100 grams of cuttings when full, and only one sample sack per sampled depth is generally archived.
• Not all samples will be usable. The quality and size of cuttings recovered at the drill site depend on a number of factors, including rock
type, bit condition, and rig operation.
• Cuttings, by nature, do not totally represent the rock at the sampled interval. Cavings and contaminants are to be expected in cuttings
samples and require removal before samples are submitted for geochemical analysis.
• Routine wellsite handling may have altered the organic composition of cuttings samples. Excessive oven drying, for example, can have the
effect of partial thermal extraction.
,. Most archived cuttings were not collected for geochemical use; therefore, they most Iikely have been handled or examined already for
other purposes. As a result, available cuttings may have been picked through, tested with solvent and acid, or partially discarded.
• Warehouse storage conditions often receive little attention or are poorly controlled; consequently, climatic conditions, inclement weather,
and long-term storage factors can affect the quality of cuttings. Cuttings sacks and boxes can deteriorate from moisture or soak up
contaminants from other stored samples; also, aerobic bacteria will degrade bitumen in porous and permeable cuttings samples over a
period of time,

• Samples may not represent what tihey pu17port to be. The reliability of cuttings identity, like all samples, is no better than the wellsite crew
that collected them, the warehousemen who stored them, and the exploration and production personnel who have already worked with
them. If all else fails in resolving a discrepancy, look for the human error.

Despite inherent problems, dried cuttings, by virtue of their availability and geologic and geographic distribution, are the common sample type used in
most local source rock and many crude oil-source rock correlation studies. In addition, dried cuttings often provide the basis for regional studies in
mature exploration areas.

Access to dried cuttings generally is good, with most major exploration offices maintaining a warehouse for their own samples. Suites of cuttings
samples are also assembled and stored by some regional scout associations. In addition, universities and natural resource agencies of petroleum
producing states and provinces typically operate cuttings (and core) sample libraries for public and industrial use. In some cases, to remove a portion
of the cuttings permanently, it may be necessary to provide the sample library with general analytical information obtained from the samples.

The common alternative to using in-house and public samples is to trade information or samples with other companies in exchange for needed
samples from their wells. Such trading is often carried out between company scouts.

As cuttings are picked (.E_jgure 3), they usually are identified by stratigraphic position or located in a stratigraphic column. Placing cuttings in such a
well-profile fonmat generally makes presentation and interpretation of analytical data easier

FIGURE 3

Most clean, well-prepared cuttings can be used effectively for measuring organic content and elemental composition, for visually typing kerogen, and
for estimating maturation level. These parameters are affected little by most consequences of storage. Heavy bitumen solvent extraction is routinely
performed on dried cuttings; quantitative results generally are good if the amount of picked cuttings (shale) is adequate and samples have not been
oven-dried excessively or stored at high temperatures. Pyrolysis results can be erratic due to loss of 51 bitumen during storage; Si, .sj, and Tm,,,,_
values run on rnttings generally are valid.
Canned Cuttings
Cuttings collected fresh at the bell nipple Cff shale shaker and immediately preserved in a semipermanent container can serve as versatile samples for
many geochemical programs. The sealed container protects the cuttings from oxidation and retains gases (headspace gas) that normally escape from
cuttings and drilling fluid standing at surface. Light liquids, which usually evaporate quickly, also are preserved. These fluids and heavier bitumen in
the sample are protected from anaerobic bacterial degradation, generally with a bactericide,

Canned cuttings are sampled in unlined metal cans approximately one quart (one liter) in volume with press-on (paint-can type) lids. Polypropylene
containers with screw-on caps provide more permanent cuttings storage. These containers generally cost five to ten times more than conventional,
unlined metal cans and are used mostly at offshore and tropical drill sites, where metal containers do not stand up well to the elements.

Canned cuttings provide reliable samples for nearlly all routine source rock and crude oil-source rock studies. Kerogen suffers no adverse effects from
canning; it may, however, reaot with diesel or caustic mud additives during extended storage, Bitumen, including gases, is retained at near-surface,
collection conditions. Post-collection generation of biomethane gas is the principal modification that can affect poorly preserved samples.

One limitation in the use of canned cuttings lies primarily with the nature of headspace gas. When cuttings are canned in mud, the entrapped
headspace gas includes the mixture of liberated, produced, and recycled gases arriving at surface in the drilling fluid. This mixture is nearly an
equivalent to total gas measured during mud logging. High gas readings need not always correlate with tme indigenous gas content of the
cuttings(Haworth et al., 1985). Also, as observed above, bacterial methane generation can increase headspace hydrocarbon content during
transit/storage; this post-collection effect can be recognized by very erratic and excessive dry gas concentrations among samples taken in sequence.

A second limitation with canned cuttings is their selection. Since the picking of cuttings for kerogen and bitumen analyses has to be done entirely at
the analytical laboratory after cans are opened, exploration personnel are effectively excluded from sample selection. Exploration staff input,
therefore, is largely dependent on records and sample descriptions made at the wellsite and shipped to the laboratory with the samples.

A canned-cuttings sampling program typically collects samples at short downhole intervals. Frequencies of 30 ft (10 m) and 50 ft (15 m) appear to be
most common. We recommend, however, that sample firequency be at least doubled whenever mud-logging gas readings signal a "show" is in
progress. When these closely spaced samples are analyzed, it may be practical to confinm compositional ohanges across a reservoir that occasionally
are seen in mud-logging gases. Common criteria include relatively high C1-C2 content above gas-oil contact, relatively high C3-4 content below gas
oil contact, and nearly total C1 content below oil-water contact. It is also routine practice to can mud samples either once a day, after trips to surface,
or after major mud-system modifications. These find use in the laboratory for evaluating mud influences.

Although many canned samples may be shipped and not used during routine analysis, over-collecting is recommended. The cost of canning is minimal
and an excess of samples allows explorationists to reexamine and confirm anomalies and trends with follow-up analyses 011 unopened samples.

Final disposition of canned samples poses a peculiar problem to the exploration office. Since the shelf life of metal cans is not longi, returning
unopened containers for permanent storage can be a costly nuisance. On the other hand, opening containers and converting both their cuttings and
those from analyzed intervals to dried sample cuttings also adds cost and may merely duplicate dried cuttings collected at the wellsite, Simply
discarding unopened containers, however, eliminates any further use of the fresh cuttings.

The most common final disposition is to save a reference set of dried cuttings from all analyzed samples. After six months or so, have the laboratory
routinely dispose of all remaining and unused samples. The objective in saving the canned samples for a short duration is to penmit explorationists
working with the geochemical data to have samples available for supplemental mns. An alternative disposition is to open containers and save cuttings
from any intervals not adequately represented by dried cuttings collected at wellsite.

Core Samples
Core types include conventional bottomhole cores and special-purpose cores such as sidewall, rubbersleeve, sponge, pressure, and piston.
Techniques of coring, sample recovery, and well-site handling are presented in Whittaker (1985), as are routine core analyses used to determine
porosity, permeability, and fluid saturation.

Because cores are seldom, if ever, cut solely for exploration geochemistry purposes, most pass through routine reservoir properties and petrographic
analysis and are relegated to storage before they become candidates for geochemical study. Conventional cores often rest in storage a number of
years before being included in a suite of geochemical samples (Bgure 1).

,,

(Courtesy Core Laoorarorles

FIGURE 1
Conventional Cores
For geochemical purposes, conventional cores can be thought of as two types: stored cores and fresh cores.

Stored Cores.: Core samples available in company and public warehouses ca11 be used for most kerogen and heavy bitumen analyses, if the following
limitations are kept in mind while selecting samples.

• Cores commonly contain a large proportion of reservoir lithologies. Fi11ding shale and fine-grained carbonate samples for source-rock
studies can be difficult or impossible in specific intervals or in many wells.
• Cores from reservoirs commonly contain formation fluids, i11cluding migrated petroleum. If very mobile, migrated oil can contaminate or
mask properties of indigenous bitumen.
• Cores are often plugged and slabbed duringi routine reservoir and depositional environment studies. When core-plugging and slabbing
are not done carefully with clean water, they can introduce contaminants in the sample.
• Ught hydrocarbons generally have evaporated from old cores, and heavy bitumen and crude oil extracts can show the effects of oxidation
and bacterial degradation..

Sampling stored conventio11al cores for geochemical analyses typically is carried out under two broad guidelines:

• Know the objective of sampling before you start. For a broad evaluation of source potential, do not sample just the darkest shales and
expect to get tnily representative results.
• Look at a large number or all available samples before starting to collect. Do not settle for what is convenient to the warehousemen; they
are not the ones who have to evaluate data and make interpretations.

Because the principal analytical limitation on conventional cores is the loss of light hydrocarbons and biodegradation of heavier bitumen and cmde oil
that occurs with storage, it follows, then, that fine-grained larger-diameter cores work better for most kerogen and bitumen analyses. Reservoir
lithologies are the common core samples extracted for migrated petroleum.

Fresh Cores: When the opportunity to collect fresh core samples at the wellsite presents itself, the general procedure for geochemical sampling is to
follow that used in collecting canned cuttings transfer samples as rapidly as possible to containers, cover with water, add bactericide, and seal. Since
time is short duringi core recovery, all storage equipment and materials need to be at hand and a well-oiled sampling and marking procedure in place
when the core arrives at surface.

Fresh core undoubtedly provides the best rock samples for nearly all geochemical analyses because it most closely reflects true subsurface
composition and content of both bitumen and petroleum. Never pass up an opportunity to obtain fresh core when samples are applicable to ongoing
geochemica I programs.

Nearly fresh core samples may be obtained in some cases at the warehouse if routine sample handli11g and preservation has been thorough at the
wellsite. Conventional core samples have a moderate shelf life as nearly fresh core. Often, recently cut core that has been sealed in plastic wrap or
aluminum foil and dipped in paraffin shortly after retrieval can be treated as fresh samples for most geochemical purposes. Gaseous hydrocarbons
most likely will have escaped from surficial pores, but as long as a fine-grained core remains wet, most: bitumen and petroleum will be retained
relatively unaffected in tight core interiors during short-term storage.

Special-Purpose Cores
A variety of downhole coring devices are used to obtain rock and fluid samples for very specific study. Common examples:

• · sidewall core guns and core slicers, generally used to sample reservoir intervals for permeability, porosity, and fluid properties

• · rubbersleeve core barrels used to recover poorly consolidated sediments for fluid properties and depositional environment studies

• pressure and foam-lined (sponge) coring devices used to entrap formation fluids for reservoir-conditions evaluation

Special-purpose coring is relatively expensive for the amount of sample recovered. Except for some sidewall coring, special-purpose cores are used for
geochemical samplingi only when part of a broader study. However, when such core material may apply to exploration geochemistry programs, you
should make an effort to obtain samples or participate in the coring program. The following discussion covers the general utility and limitations of
specia 1-pu rpose cores to exploration geochemistry.

Sidewall Samples: Samples of the borehole wall are generally taken to study reservoir and fluid properties of rock. The most common sidewall
sampling device, the wireline core gun, can recover short, 1-in.. diameter samples from moderately consolidated sediments (_Figure 2 and .Eigure 3).

FIGURE 2
FIGURE 3

The rnre gun can be precisely placed for sampling and numerous cores can be ta ken on a single run.
Upon recovery at surface, most sidewall cores are pressed from their coring cylinders {bullets) and sealed in small jars to preserve formation fluids
and core integrity.

Note:If there is a possibility that unopened sidewall cores will be used subsequently for geochemical analysis, bactericide should be added to the core
jars before sealing,

Most sidewall cores are destrnctively analyzed (thermally extracted) to determine fluid content and properties, Tlhese recovered fluids, if specially
handled during core analysis, can be analyzed for oil geochemistry much in the manner of topped oil samples. Destructively analyzed core material,
however, has very little utility as a geochemical sample, Kerogen and bitumen will contain thermal artifacts of core analysis.

Not all sidewall cores undergo reservoir-prnperty study and set-aside cores may be available for analysis. Shaly or non-reservoir lithologies, if cored,
often are not submitted for routine study, In other situations, reservoir lithologies can be withheld from destrnctive analysis because of duplication
(double shooting) or analytical-number limitation. Such sidewall core samples can be treated like fresh core and canned cuttings samples if they have
been sealed in jars at surface. They can even be used for headspace analysis if bactericide is used in preservation.

A prime consideration in the use of analytical data from poorly consolidated and permeable sidewall samples is the fact that drilling filuid can have
flushed bitumen and petroleum from pore spaces during the drilling phase. In fine-grained intervals, this flushing influence should be no greater than
in cuttings from the same interval.

Their geochemical utility points out an aspect of sidewall cores that is relatively unexploited by many companies. Sidewall sampling is often ignored as
a primary means of geochemical sampling because most coring programs are laid out in a reservoir engineering perspective. Typically no funds are
allotted in the AFIE for geochemical core sampling,

Sidewall sampling, particularly shooting sidewall cores, is sure to receive greater geochemical emphasis in exploration wells in the future. In addition
to providing relatively large samples, compared to individual cuttings, sidewall samples are far less likely to reflect influences of mixing and cavings.
Samples, moreover, can be taken at relatively precise depths as determined critical by cuttings and wireline log evaluation.

Rubber Sleeve Core: Most core material brought to surface in a mbber sleeve device is relatively unconsolidated. The sleeve holds the core together
and preserves its fluids and sedimentary struotures until they can be sampled and studied in the laboratory, A common approach is to freeze the core,
remove the sleeve (often by slabbing the core), and then study and sample the core while it is in this temporarily consolidated state. Liquid nitrogen,
a common coolant used to freeze, slab, and plug the core, has no adverse geochemical effects on the organic properties of the frozen sample.

Rubber sleeve core samples, like all fresh samples, can be used for nearly all types of geochemical analyses, Naturally, their high cost, very limited
availability, and short shelf life all preclude routine use. Nevertheless, bitumen and petroleum extracts obtainable from such cores are very reliable
and, when possible, should be included in crude oil and crude oil-source rock correlation work

Pressure and Foam-lined Cores: The unique feature of cores taken with pressure or foam-lined core barrels is that formation fluid conditions and/or
volumes are adequately preserved for reconstructing fluid properties at reservoir (coring) depth. As with rubber sleeve cores, the coring process is
expensive. Consequently, the availability of both rock and fluid samples is very limited, although both types of samples retain very representative
geochemicaI properties,
Where solid rock has been taken by pressure or foam-lined devices, core material may be archived in a warehouse after reservoir fluid analysis and be
on hand for routine sampling like any conventional core. Over-handling and frequent reservoir analyses often perfonmed on these special cores,
however, can affect their utility for subsequent geochemical work.

Piston Cores: A recovery method commonly used to sample unconsolidated sea- or lake-bottom sediments is the piston coring device. In this
technique, a hollow tube is driven into soft bottom sediments, then retrieved with the cored sediments entrapped inside. The core is removed and
preserved as intact as possible, often following freezing (figure 4).

FIGURE 4
Until recently, the principal use of piston coring was to sample relatively young water-lain sediments for sedimentological and biological study. Over
the past few years, however, this samplingi technique has been adapted to collect samples for geochemical prospecting programs i11o1ffshore areas
{Section 5.; Emmel, Bioroy, and van Grass, 1985). The principal adaptation step has been either to analyze the core 0111 board the sampling vessel
immediately after recovery or to freeze and/or can the recovered core to preserve gases and light liquids for analysis at an onshore geochemical
laboratory.

Generally the objective of a geochemical bottom-sampling program is to locate surface anomalies indicating exploration potential at depth). In such
studies, exploration perso111nel have littile direct co111tact with the samples; cores are immediately preserved or go almost directly to the analytical
laboratory for gias extraction and analysis.

Piston core analyses typically aim to identify the type, quantity, and isotopic composition of light hydrocarbons. Although routine kerogen and
extraction analyses can be performed on pisto111core samples, analytical data reflecting modern organic contributions have very limited application
to most conventional source rock and correlation geochemistry programs.

P'etroleum Samples
Natural gas and crude oil samples provide essential materials for corirelation studies. The composition of petroleum also provides insight into the
organic nature and maturation level of its source rook and, therefore, also has direct application to corollary studies of kerogen (Philp and Gilbert,
1986).

Petroleum samples are of two general types: naturally occuriring surface fluids and mechanically recovered subsurface fluids. Gas and oil seeps
characterize the first type; samples taken by downhole devices, at the wellhead, or from separators and storage tanks characterize the second.

During petroleum sampling in particular, every practical effort should be made to obtain a fresh sample, to collect it near its source, and to protect it
from biodegradation prior to analysis.

Surface Fluids
Oil seeps and gas emanations are the common forms of petroleum found at the surface. Oil seeps are readily visible, generally as small pools or as tar
balls and oily scum on water: Escaping gases are apparent only as bubbles rising through a liquid or often by a sulfurous smell.

Oil seeps are best sampled by gathering the liquid in a small bottle or metal container. Each type of container has its own advantages. Crude oil in a
glass bottle can be inspected visually for water content, volume, and obvious contaminants. A metal container is less apt to break during shipping and
handling. Where practical, the container should be of a size so that it will be nearly filled by the seep sample. As with wine, a full container retards
alteration and degradation.

Sampling should take place at the seep's point of surface appearance. This may require skimming off inspissated (evaporated, thickened) oil to get to
fresh liquid, or digging into soil or loose rock to find the migration pathway. When no fresh material is collectable, tar balls, residue, and solid bitumen
can be sampled. Although these materials might be badly altered, they have use in correlation studies based on chromatographic and mass
spectrometric analyses of very stable biomarkers and on isotope techniques.

The amount of fresh sample collected needs be only one or two fluid ounces (a few cubic centimeters), as virtually all chromatographic and follow-up
laboratory analyses use minute amounts. Naturally a large quantity, up to a quart (liter), ensures more representative sampling and provides material
for measurement of some physical properties (e.g., AP! gravity, distillation fractions).

Sample collecting, marking, transmittal for analysis, and storage follows the general procedure used for outcrop samples, except that the sample
container is gas-tight. Use of a bactericide is recommended, particularly for small samples and those such as tars and scums, which already are being
degraded. It is common practice to place a layer of metal foil across the container opening before setting the licl. Tlhis ensures that any organic (e.g.,
cork) or petrochemical material used to make a seal will not come in contact with the oil sample. Some companies recommend that the sample be
stored upside-down to reduce the chance for gas or volatile liquids to escape.

Gas emanations are generally trapped for sampling by buoyancy. If gas samples are being taken under clry conditions, as in geochemical prospecting
using soil gases, special funnel and bell-shaped baffles are emplaced to direct upward-migrating gases to traps. Each trapping system has its specific
set of collecting procedures, which are provided by the manufacturer or service company.

The principal analyses performed on gas emanations determine gaseous hydrocarbon (C1 - Cd composition and carbon isotope (::: )ratio;
the objective generally is to evaluate whether the gas is of bacterial or maturation origin.

Subsurface Fluids
Most natural gas and crude oil samples used in geochemical studies are obtained at or near the wellsite. Samples closest to the reservoir are taken by
wire-line formation testers {figure 1 and figure 2) and drillstem tests {GL302).

PACKER

I
i
i'f .. ,
,

'
b
Ii
a
FlGURE 1 FIGURE 2

Downhole sampling is normally done during the well-drilling phase.

It provides a first, often one-time look at recoverable formation fluids, The difficulty in obtaining fresh downhole fluid samples in geochemical studies
is timeliness; a study's sampling program must be in gear at the moment that borehole testing takes place. This aspect is least difficult to coordinate
when a single well or a specific crude oil problem is being studied.

It is important to remember, however, that oil samples from completed formation tests are often archived with cuttings and cores in sample
warehouses, and remain available for analysis. U formation tester and drillstem test samples are well sealed at the time of collectio11a1nd storage, they
may not show serious degradation. These test samples should be sought out and used like any other oil sample. Such samples, in fact, generally are
the only fluid samples obtainable for wells that were abandoned or never brought into production.

Oil and gas samples collected at surface from downhole production are generally taken at one of three sites the wellhead, the separator manifold, or
the storage tank depending upon accessibility and study objective. A practical guideline is: the closer to the wellhead a surface sample is taken, the
more representative it is of petroleum at depth. The sample-collecting procedure for liquids is straightforward and uses the same general identifying
and quality control format followed for canned cuttings samples,

For formation tester and drillstem test samples, depressurized cuts are taken at the time that samples are being recovered for formation fluid
analyses (.Elgure 1 a111d .Elgiure 2). Only a small volume will be available from most formation testers; there should be little difficulty in obtaining a full
size sample from a successful drillstem test.

For collection at the wellhead, or downstream at the separator or storage tank, oils are generally drawn off through a samplingi stop valve open to the
atmosphere. It is just as essentiaI to record descriptive detail for fluid samples as for outcrop and other rock samples.

Two limitations in using separator and tank samples need to be remembered. Separators isolate gas, water, sediment, and oil from eaoh other by a
variety of physical processes (e.g., buoyancy, centrifugal force, heating, and filtering and chemical processes) (e.g., emulsion breaker) These
processes can modify an oil's bulk composition and related geochemical properties mar1kedly. Storage tanks, in turn, often hold crude oil from a
number of wells concurrently or over a period of time; therefore, a sample can be a composite of produced crude oils. Since crude oil segregation
occurs in a tank over a period of time, the time and depth at which a sample is taken are factors in obtaining a representative sample,

When gias is sampled at the wellsite, collection is commonly made in a pressure bomb (Figure 3).

FIGURE 3

The bomb is generally constructed with two stop valves so that a gas flow can be established through the sampler. A pressure gauge is an integral
component of the bomb during sample collection; it monitors internal pressure buildup during sampling and indicates that sampled gas is still present
upon arrival at the analytical laboratory,

As with surface emanations, common analyses performed on pressurized gases identify gaseous hydrocarbons and carbon isotope ratios, Because the
pressuriz.ed sample is unaffected by evaporation, it can retain ligiht liquid hydrocarbons (condensate) plus otl1er contained gases (Ni, CCJ.i, H2S, etc.)
and be analyzed for many more constituents.
Outcrop Specimens
To gather rock exposed at the surface for geochemical analysis:

1. Locate the general area where the stratigraphic unit to be sampled crops out.
2. Examine fresh outcrops, as in cuts or quarries, and clear or bardown the surface until fresh rock is exposed.
3. Select fist-size or larger samples that show minimal signs of discoloration or weathering (avoid rocks associated with rootlets and soil
zones where possible); collect a minimum of two pounds (one kilogram) of fresh sample.
4. Mark the sample (or sample fragments) with a sequential identifying number (also referred to as a station number) using a permanent
marker or marker system.

Note: A common annotation system is to use the sampler's initials, the collection date, and the sample's sequence in the day's collection.
An identifyingi number DD-8-29-88-4 would indicate the fourth sample collected on August 29th, 1988, by Dave Donohue. Such a system
makes it easy to return to the right field notebook and the right descriptive material (see Step 7).
5. Wrap the sample (preferably with plastic wrap followed by aluminum foil) and place it in a storage container (sample sack, box, etc.) with
the same identifyingi number.
6. Plot sample site and identifying number on the base(location) map.

7. Make permanent field notes concerning sample and sample site.

Note:We strongly recommend that each field sampler or party chief keep a daily, very complete, permanently bound field notebook while
samplingi; this notebook will come into use throughout the geochemical program. For example, when field personnel return to the
exploration office for final description and selection of samples for analysis they will find some confusion in sample identities or
uncertainties in stratigraphic correlations regia rd less of the care taken in the field. Good field notes can resolve many questions and
alleviate the need to return to the outcrop or discard samples. Additionally, when analytical data have retunned from the laboratory, field
notes will be needed to help clarify the validity of anomalous values and make final geochemical interpretations.
8. Pack samples systematically for transit to exploration office; include a duplicate copy of field notes with each sample lot.

Note: As a completeness check, each eveningi the field party should compare the day's field records with the day's sample collection. For
backup purposes, each field notebook should be photocopied at least weekly whenever possible,
9. Unpack samples systematically at the exploration office, verify sample inventory, determine sample suite to be analyzed, and describe
individual samples selected.
10. Prepare sample for analytical work by chipping away altered surfaces and making a composite of representative fragments.
11. Pack selected samples (witl1 tiheir descriptions, analytical program, and disposal instructions) for shipment and dispatch to the analytical
laboratory.

12. Pack remaining outcrop samples for pernianent storage and dispatch to warehouse; place duplicate copy of field notes in project reference
file.

Dried Cuttings
To prepare cuttings samples for routine geochemical analyses:

1. Pour dried cuttings into holder to determine quality of cuttings; evaluate under binocular microscope (8gure 1).

FIGURE 1
2. Remove large cavi11gs, if present, with a11 8-mesh screen, or hand pick with tweezers; remove obvious contamina11ts.
3. Ri11se mudcake, particularly if excessive, from cuttings with clear water.

Note: Acetone can be substituted for water when picking water-sensitive shales. If oil or diesel was used in the drilling mud and the
cuttings have not been previously clea11ed, a rinse i11 warm, soapy water is probably the best compromise for removing most oily
contarni11ants without greatly affecting indigenous bitumen.
4. Describe gross lithology of sample, noting relative percentages of rock types; incorporate observatio11s into a generalized downhole
lithologic column.

Note: Most exploration offices and analytical laboratories use abbreviations and desoriptive shorthand whe11desoribing samples (Swanson,
1981).
5. Make stratigraphic identification, if possible, and determine probable representative lithology.

Note: This step generally requires a wireline log or local stratigraphic column. Remember, if samples are being picked in the analytical
laboratory, identifyingi stratigraphic units is nearly impossible without effective exploration input.
6. Determine representative lithology or lithologies to be picked for analyses; pick adequate amounts for scheduled analyses and place
in clearly ide11tified containers for transport to site of analytical preparation,

Note: If the amount of cuttings present in one sample interval is not adequate for performing the scheduled analytical work, a composite
sample is usually made from cuttings collected at adjoining sample depths.
7. Prepare analytical list; cross-check sample numbers with containers and analytical program.
8. Return unused, unpicked cuttings to original sample sack for return to storage.

Canned Cuttings
To collect and preserve fresh cuttings samples in one-quart (one-liter) metal cans:

1. Collect approximately two cups (500 cc) of fresh cuttings as they pass across the shale shaker.
Note: If drilling rate is slow or cuttings recovery is poor, cuttings can be caught in a fine sieve or screen as they exit the bell nipple.
2. Place unwashed cuttings in sealable container.

Note: Some companies rinse the samples slightly, particularly if diesel or crude oil is in the mud. Consistency is the important factor in this
step; always follow the same picked in the analytical laboratory, identifying stratigraphic units is nearly impossible without effective
exploration input.
3. F111 the container to the three-quarters level with clean (distilled or potable) water.
4. Put bactericide in container.

Note: Zephrin chloride is the generally recommended bactericide. Two methods of application are common. One is to add two or three
drops of concentrated bactericide into the water; the other is to spray a dilute solution onto the water surface with a squeeze applicator.
5. Seal the container tightly; when a press-on lid is used, tap it firmly into place with a rubber mallet and attach three retainer clips at equal
distances around the top.

Note: a slight gas pressure buildup can occur in containers, particula11ly with extended storage; clips are needed to hold the lid firmly in
place and prevent gas leakage.

6. Mark sample identity (well name, location, sample depth) on botih the container and its lid,
7. Pack canned samples sequentially for shippingi.

Note: We recommend that no more than twelve canned samples be put in any one shipping container to keep handling weights
reasonable. Experience shows that the heavier tihe parcel, the more abuse the samples will receive during transit, Containers can be
punctured or lid seals broken by rough handling.

8. Include copy of sample inve11tory with each parcel of samples,

9. Ship parcels of canned samples periodically; include copy of analytical program, wellsite sample descriptions, and listing of samples
previously shipped.

Note: Routine shipping, as once a week or with periodic supply boat runs, is recommended so that analyses can begin while the well is
being drilled. Final analytical results can then be forthcoming shortly after the completion of drilling.
Stored Core
To select core samples for geochemical analysis:

1. Lay out open core boxes from a seleoted well in downhole sequence and locate the most representative, best quality rock.

2. Select as much core sample (up to two pounds [one kilogram]) as will be needed for analytical program.

Note: This sample can be a single specimen from the core, or a composite of fragments, depending on the objectives of the analytical
program.
3. Clean the sample, if necessary, to remove remnants of drilling fluid or other effects of handling.

Note: If a heavy bitumen or petroleum extraction is scheduled for the sample, the surface of the sample may be chip-cleaned a second
time (or the sample broken to obtain interior fragments) at the analytical laboratory. This provides the freshest possible material from the
core for analysis.
4. Describe sample and annotate stratigraphic position; build stratigraphic column, if appropriate to the study.
5. Wrap core material (preferably i11plastic wrap followed by aluminum foil) and mark with number identifying geochemical project, core, and
sample.
6. Place wrapped sample in sample sack or container and mark with identifying number.
7. Add sample number to study inventory.
8. Assemble core samples with copy of inventory list and disposal instructions, and pack for transfer to analytical laboratory.
9. Ship parcels, together with copy of analytical program, to laboratory.
10. Return unused core to warehouse where it can be recovered if supplemental analyses are needed.

Gas Emanations
To collect gas rising through water:

1. Submerge an open sample container until it is filled with water.

2. Invert the submerged container over the rising gas.

Note: Where very controlled gas sampling procedures are being followed, the sampling container can come sealed and filled with distilled
water. In this case, Steps 1 and 2 are reversed. The sealed sample container is inverted and submerged in the water, then opened for
sampling.
3. Continue catching bubbles in the container until the gas has displaced most or all of the liquid.
4. Seal the inverted container while still submerged in the water.
5. Mark sample container, record field data, and proceed in the general manner of the Sample Handling Procedure for Outcrop Samples,
beginning with Step 4.

Crude Oil
To collect crude oil through a sampling valve at the wellhead, on a distribution manifold, or at a tank:

1. Open the sampling valve slightly for a short cleanout period.

Note: Initially, the sampling valve should be oracked open only slightly to determine pressure on the system. The valve then can be
throttled to establish a desired flow rate. In addition, any fluid released during the cleanout period should be caught and disposed of
according to local procedures.
2. Fill a clean container, once a representative sample is ensured.
3. Close the sampling valve.
4. Place bactericide in the sample (ifthat preservation procedure is beingi followed) and seal the container.
5. Give the sample an identifying number, enter the number and descriptive material (see below) into the sample inventory, and proceed as
outlined in the sampling procedure for Canned Cuttings, from Step 5 onward.

Note: When well samples are being collected for a geochemical study, a notebook on sample sites and identities should be kept similar to
the field notebook for outcrop samples. Identification information should include well name and location, sampler and sampli11gi date,
sample recovery site and method, production depth or perforations, reservoir interval, and related data. If production summaries or other
information, such as gas-oil ratio (GOR), 0API giravity, and sulfur content, are available, these data should be added or attached to the
notebook.
Pressurized Gas
To sample pressurized gas:

Note: Care must be taken with the gas sample because it is under pressure. Most companies have their own set of procedures for sampling the gas,
and for moving and shipping gas bombs that meet company and government safety regulations. The steps listed below are only a general guideline,

1. Attach the sample bomb (figure 1) to a purged sampling valve at the wellhead or on the distribution manifold.

FIGURE 1

Note:This connection must use high-pressure fittings.

2. Open both valves on the bomb.
3. Open the sampling valve slightly and establish a moderate gas flow tihrough the system to scavenge the bomb.

Note: Remember, the scavenging gas is flammable and could be poisonous; take all necessary safety precautions.
4. Close the downstream valve and let gas pressure build up as gas sample accumulates,

5. Close sampling valve and upstream valve, in that order, when pressure gauge on bomb indicates that buildup has ceased or sample is
approaching predetermined pressure limit,

Note: The objective in closing the sampling valve first is to avoid putting full head pressure on sampling connections.
6. Depressurize the sampling connections and disconnect the bomb.
7. Give the sample an identification number and description, as with subsurface oil samples, and add to inventory, as with other geochemical
samples.

eochemical Programs in Petroleum Exploration

Introduction
Exploration geochemistry programs can be short-lived or ongoing for a number of years. A short-term program might be a kerogen examination (i.e.,
TAI, SCI, or %Ro) of a few cuttings samples to confirm that an exploration well has fully penetrated the oil window and bottomed in the thermal gas
regime, The objective of such a study is focused and narrow and can be met quickly with a few analyses. A long-term program might be a regional
source-potential evaluation that evolves as exploratory wells are drilled. Objectives here are manifold and require many types and cycles of analyses.

Whether a job is to be short-term or long-term, an explorationist should take the planning steps necessary to ensure that the program (1) is feasible,
{2) will have exploration significance, and (3) will be cost effective. Subdivision speculators never start to construct a house without plans and
blueprints, without an idea of probable labor and material costs, and without confidence that the house, when completed, will recover expenditures
plus a profit. Explorationists should follow a similar rationale when initiating geochemical programs.
Program Feasibility
Although thorotJgh planning cannot guarantee the llltimate success of a geochemical study, failllre is likely to dog a program that lacks clear
objectives, timely analytical support, and adequate samples, These factors mllst be addressed when evaluating the feasibility of a proposed
geochemica I study,

Exploratiion Objectives
The use of geochemistry in exploration has one overriding dictum: it must reduce the economic risk of exploring at a fair tradeoff of costs.
Explorationists who propose any geochemical study must address this fact, A cfllJde oil correlation sttJdy designed to demolilstrate that two oil families
are present in a basin may be academically interesting but prove to have little exploration significance and, thus, a negative cost effectiveness. Yet, a
cfllJde oil correlation study desigliled to detenmine whether two oil families are present in a basin and whether these two families represent intersecting
geologic trends can have great exploration significance alild cost effectiveness. Although, from a program-design point of view, the only difference in
these two oil-family sttJdies might be in the choice of sampling sites, the latter shows a clear possibility of reducing exploration risk. In other words,
the study of intersecting trends has a clear exploration objective that can be balanced against probable costs.

Anallyticall Approach
Most exploration geoohemistry programs follow analytical methodologies developed through experience. Proposed programs should make use of
standard techniques whenever practical and have study objectives compatible with them. Over the past 25 years the following general pattern of
geochemical programs has evolved.

Initially, analytical and evaluation programs asked one of two questions:

• source mck evaluation: Was enough organic matter deposited in the rock to produce petroleum?

• crude oil correlation: Are oils in the area related?

Although now much more sophisticated, these two are still basic programs in exploration geochemistry (Dembicld and Pirkle, 1985).

As analytical programs and techniques improved, qtJestions were asked that tied the first two geochemical approaches together,

Thus:

• crude oil-source rock correlation: Which source rock intervals generated which oil families?

As relationships between sotJrce rocks and petroleum became more clearly defined particularly the varied roles played by kerogen type, maturation,
and migration each of the above approaches was refined to be more diagnostic (Bein and Soffer, 1987). In addition, exploration geochemistry moved
progressively into three-dimensional and temporal regimes, The resulting approaches can generally be referred to as

• basin or regional studies: What is the exploration potential of a large region, typically containing undeveloped and frontier areas?
• basin modeling: What is the theoretical geochemical evolution of a region, and its ultimate

productivity? (Evamy et al., 1984).

And, of course, as the industry's level of geochemical knowledge grew, very specific exploration problems could be attacked. Often problem solving
required the tailoring of very specific analytical programs to obtain critical bits of data.

Explorationists shollld note one trend in the development of geochemical approaches and analytical programs. As a worldwide body of geochemical
knowledge accumulated, exploration geochemistry expanded its horizons from being primarily a diagnostic tool to being a predictive tool as well.
Initially we would have asked, "Are source rocks present?". Today we can ask, "When did bitumen generation occur in the source rock and where
would expulsed oil and gias have migrated as a result of later structural movements?". This predictive nature of modern exploration geochemistry
should be a main thrnst of proposed studies; it can reduce exploration risk even further and thereby enhance program utility and feasibility.

Sample Type and Availlability

Determining to what extent good quality samples can be obtained for a proposed geochemical study is essential in establishing program feasibility.
Reviewing the literature, digging out proprietary and public domain records, and collecting and preparing samples for broad-area studies can i111Volve
as much time and cost as laboratory analysis; it is an effort that should not be undertaken lightly.

In active exploration areas, sample availability for basic source rock evaluation and crude oil correlation studies as for evaluating a scheduled wildcat
or new discovery well, or comparing cmde oils within a field is generally known or can be readily established at proposal time. On a pendingi well, a
geochemical samplingi program can be recommended for the well-site collection routine and, if approved, included in the AFE. For stored samples,
availability can be assessed rapidly using office files or scouting reports and contacts. In near11y all local situations, then, sample limitations on study
feasibility are apparent almost immediately.

Locating and gathering a suite of samples for a broad-area study as for evaluating regional source potential or crude oil families presents a more
complex problem. The sample sources that must be tapped often involve other companies and agencies, In broad-area studies requiring substJrface
samples, you need to know about past and preselilt exploration in order to locate and evaluate the best samples. You can gain a quick review from
your company's library, from state publications and inventories, and from compilation and activity maps of service companies. Whatever the effort
required, identifyililg and locating all abandoned wells and producing or shut-in fields is critical. Essential cores, cuttings, and fluids from abandoned
wells most likely reside somewhere in company and public warehouses. Seek out fresh rock and flluid samples in areas of active drilling or production.
In this situation, pin down curirent activity. If you find that samples from drillingi or production wells are not directly available to you, per1haps they can
be obtained by trading samples, exchanging analytical data, or even developing a joint-participant study. Remember that the extra effort taken at this
time to improve sample quality and coverage almost certainly will improve study feasibility, and if the study is undertaken, enhance study application.
General Program Sequence

Most exploration geochemistry programs are carried out in phases; within each phase are decision points for selecting the portions of a study that
should proceed further and the samples and/or analyses that should be used. Once samples have been assembled, the general sequence of laboratory
and follow-up work is as follows:

• screening analytical phase

• detailed analytical phase
■ fina I interprntation phase

]f the exploration geochemistry program is large, such as a crude oil-source rock correlation or a basin study, separate portions of the study often
progress independently and can be in different phases coi1currently. Often samples from outcrops and active wells are not available at the same time;
in such a case, basin margin and basin interior analytical programs probably function best if handled separately. Similarly, canned samples from a
deep exploration well can take many months to collect as drilling proceeds slowly ahead. The screeningi analytical phase for shallow samples can be
completed before samples near projected total depth (TD) have even been cut.

Regardless of the rate at which different portions of a study progress, exploration personnel should be involved in decision-making during laboratory
screening and detailed analytical phases. To keep analyses moving ahead rapidly, however, it is common for analytical staff members to make
decisions based 011 program guidelines agreed upon at program inception by exploration personnel. For example, a laboratory guideline might be as
follows: conduct liquid extractions (detailed analytical phase) on shale samples containing over 1.0% TOC and 0.2 P] (screening phase) but spaced no
closer together than 500 ft (150 m) downhole.

The final interpretation phase should involve full participation by explorationists with ultimate conclusions and recommendations formulated in the
exploration office. These should consider, however, any interpretations made by the laboratory personnel during the analytical program.

Screening Analytical Phase

The first round of laboratory analyses typically focuses on sample soreening. Screening analyses are rapid, and, being relatively inexpensive, can be
run on many samples. In typical source rock evaluation programs for exploration wells, a variety of screening options are available (flgure 1).
 Name of IL
SCREENING _ROCI( SJI.ME'LES_
SlUDY CANNED ROCK SAMPLES

G MAT;) SAS)
G OIL1)
Screening Study Analysis EVALUATION
G/R 1 • Gas development/ LHC - Light hydrocarbons
organic ric mess TOC - Total organic carbon
SA 1 - Source rock ident. 1 PYR - Rock-Eval f)yrclysis
SR 2 - Source rock ident. 2 IRUS- Infrared ultrasonic elctraction
MAT - Maturation indicatioin TAI - Thermal alteration index
SR 3 - Source rock ident. 3 MAC - Maoeral type
OIL 1 • Crude oil character WO - Whole oil
(from Welte, et 81. 1983)

FrGURE 1

One common screening methodology performs lignt hydrocarbon (C1-C4; C1-C7) and organic carbon (TOC) analyses on canned rnttings or fresh
core. Data from these analyses are combined with lithologic descriptions in order to identify rich (possibly source) intervals and estimate their level of
bitumen generation (thermal maturation). By substituting Rock-Eval pyrolysis for light hydrocarbon analysis, a comparable data base is established for
first-round decision-making. Pyrolysis substitution is common where outcrop and dried well sample-.Sare used. A third alternative uses rapid
infrared/ultrasonic extraction in place of light hydrocarbon analysis or Rock-Eval pyrolysis to measure bitumen generation.

With any of these source-rock options, sample spacing (analytical interval) during the screening phase is generally less than 100 ft (30 m) across the
zone of interest, so that a vertical well profile is created (figure 2).

VertiC-11fl,,,-.-1====!
Scaia.....,....,_.._.._..._..._...._.... ..._..._.._.._.._,_ _ _..,

FIGURE 2

This profile is then used to determine which intervals are of no further source-rock intere-.St and which samples will be submitted to the second-round
detailed analytical phase. Where multiple-well and/or outcrop samples are included in the screening program, a good lateral representation of air
stratigiraphic units generally is i11cluded in the suite of samples so that both vertical (profile) a11d horizontal (map) patterns emerge for decision
making (.Ei.gure 3 and figure 4).
 ---
I

': '1 •

-
-- -@ --r- - I •

-
20 I it e,

--- I :

-- r "

ti'I

I
(from Dl;Jmblck! and PirKICi, 1985: COUrtfJSy AAPG)

FIGURE 3

Where possible, well sampling should be tied to logs for lateral calibration and mapping.

(from Demblc i end Pirkle, 1985; counesy

AAPG)

FIGURE 4

When we consider the screening phase of crude oil analysis programs, again a number of rapid analytical options are available. To provide first
approximations about similar compositions and alteration levels, gasoline-range Ct-C4 analysis can be rnn Qn all oils sealed following sampling.
Whole-oil gas chromatogiraphy in the light liquid (approximately C6+) and heavy hydrocarbon ranges also provides adequate data to make some
screening decisions. Various fluorescence data can group oiIs that may be source-related or of similar histories.

Following screening analysis, rock and fl'uidl samples are either eliminated from further work or selected for more detailed examination, In source rock
studies, for example, all shale samples with less that 0.5% TOC are often routinely excluded from second-round analysis, thereby screening out rock
intervals that probably have weak source potential.. Representative richer samples, in turn, can be selected for detailed analysis; ideally samples are
selected that provide good geologlic coverage and a rangie of organic contents and maturation levels.
In crude oil correlation studies, comparable screening selections are made to meet study objectives. For example, when screeningi data show many
oils in the same field to be similar, it is common to eliminate a number of them from the detailed study phase to avoid duplication and unnecessary
costs. This permits concentration on (1) similar-appearingi oils in different fields to see if they represent lateral distribution of single oil families, and
(2) different Qils in the same field to determine the characteristics Qf oil families present.
Detailed Analytical Phase

Source Rock Detailed Analytical Phase

rocK.sample
111.1.Ull":illl: HCNSO
lignl HG
kerc;en
sol\'erd iluor
e:r1r IIQu1ld
c.hrc, i.1$-M$
13,/t2c
MS-ARO
ll)'r I •& MS-SAT
chm

IHRDC

In the second-round, detailed analytical phase, a sequence of analyses typically are chosen to resolve specific questions,

In source rock evaluations, the kerogen maturation level estimated duringi the screening phase is generally confirmed by systematically determining
wither vitrinite reflectance (%Ro) or thermal alteration level (TAJ/SCI) of kerogen separations, Further confirmation, if needed, can be made with
the alternative method (above) on about 25% of the kerogen separations,

Kerogen type is determined concurrently from visual examination of separations, When pyrolysis a11alysis was performed during the screening phase,
visual a11d pyrolysate data are compared to confirm kerogen type. Kerogen type and maturation level are often confirmed further during this phase by
elemental analysis of selected samples,

Solvent extraction and analysis of bitumen components are major aspects of most detailed analytical phase programs, both for source rock and crude
oil-source rock correlation studies. Selections of samples for bitumen extraction are based on screening results; choices in downstream
chromatography and mass spectrometry analyses depend on the specific objectives of the study,

Using extracts, realized source potential is evaluated by comparing total extract (EOM) to total orga11ic content (TOC). Maturation level is evaluated
further from extracts usi11g molecular composition and character of liquid and gias chromatography separations (e.g., carbon preference index [CPI]
and pristane-phytane ratio of saturate separates). During the detailed analytical phase, carbon isotope analysis is often scheduled for bitumen
separates if depositional environment or relationships with oil families are being evaluated. When extract data are used for correlation purposes,
detailed molecular/biomarker analyses are scheduled to match those of oil samples (Brooks, 1986),

Crude oil analyses parallel those of extracts starting at the liquid chromatography stage, The same maturation and depositicrnal environment
evaluations are made and, when both oil and extract data are available, rough correlations can be attempted, Crude oil correlation and crude oil
source rock correlatio11studies, however, generally require additional analyses in this phase, Typically, analysis of biomarkers on selected samples
is i11cluded in the study and these very detailed analyses can be within saturate, aromatic, or resin separations (Palacas et al., 1986). Some
companies also analyze light hydrocarbons ( 4-C1, Ct-C10) by gas chromatography for comparison with the same hydrocarbons in rock extracts.

Final Interpretation Phase

The third-round interpretation phase begins with a compilation of analytical results in appropriate formats. These initial compilations are done
routinely at many analytical laboratories through computer programs. In a source rock study of a well, for example, analytical data a re generally
tabulated and sent to the exploration office in well-profile format with related parameters (e.g., maturation indicators) grouped together (Price et al.,
1981). In anareal source rock evaluation of different formations, routine data assemblage is by fonmation and geographic distribution (Leenheer,
1984).

Once data are in a systematic format, the interpretation phase is ready for input from explorationists.
In source rock st1.Jdies, explorationists evaluate apparent similarities between analytical data and accepted values (e.g., 1.0-2.0%
TOC= very good source rock; 0.6-1.4% Ro= oil window; .Eig1.Jre 1, Evaluation maps, Bakken shale members, Canada-United States border area.
 ---0.40•

.o.oo(_f4
.
C@[IS.!l •• . • • • ..
!-

, 1 ....
- - I- - -

I,
-

50Mllei.

FIGURE 1

Current maturation level of vitrinite reflectance. Shaded area indicates Ro is greater than 0. 6%). Anomalies or breaks in trends are marked and
annotated for later review. General interpretations are then compared with local and regional geologic patterns to evaluate their level of agreement.
One common step is to reconstruct maturation history to determine timing of bitumen generation and logical secondary-migration directions (figure 2,
Souroe potential rating index map.

(frOm Demt:JiC l llncf Pirkle, 1985; courtesy AAPG/

FIGURE 2

Contouring is based on combination of organic richness ( TDC) times catagenic maturity level [%Ro]). Again anomalies (ff mismatches are marked
and an notated for further study.

Next, explorationists refine their source rock evaluations and resolve causes of annotated anomali1es, breaks in trends, and discrepancies. As a result,
they often find themselves returning to field notebooks, reviewing wellsite operational conditions and wireline logs, or confirming sample identity. At
this point, tlney may find they need to schedule repeat or supplemental analyses.

Explorationists base their final source rock interpretations on the best agreement of the geochemical data wrth the geologic setting and operational
conditions. They write their findings in a project report, which includes tabulations of all samples and analytical data, copies of all final interpretation
maps, a summary, and conclusions and recommendations. Conclusions and recommendations should address the objectives of the study, particularly
in regard to reduction of exploration risk.
Studies involving crude oils follow a similar progression through the third-round inte17pretation phase: assemble data --+ make general interpretations
--+ resolve a111ornalous conditions--+ make final interpretations--+ present findings. In crude-oil a111d crude oil-source rock correlation studies, oil and
extract data assembled at the laboratory are apt to be tabulated or plotted i11t1wo formats. One much-used format groups or orders oil samples by
similar geologic associations, well depths, or geographic locations, comparable to most rock data. The other groups both oil and rock samples by
similar a111alytical parameters (e.g., isotope ratios, biomarker compounds; figure 3, Cross plot of rock extract and crude oil isotopic data, northern
North Sea.

■ oils

D Source Rocks
s
[.,20 0 35/8-1
0
c,Q ® 30/3-1

© 30/7-7

I AHC I
-140 -,11 .. , _,
-30 -28 -26 -24

(tram Scliov, et al, 1985)

FIGURE 3

Isotope comparisons of aromatic hydrocarbons (AHC} show rock extracts from three wells (1,2,3) to have different charactenstiC5; likewise, two oil
families (I,Il) appear to be present. Type II oil is tentatively corr;elated to Lower Jurassic sediments in wells 2 and 3). The latter is often the result of
statistical or multivariant computer techniques, now integral parts of many detailed analytical procedures (0ygard et al., 1984).

Interpretation of detailed crude-oil and bitumen data in the exploration office focuses on deterrni111ing whether geochemical groupings of crude oils, or
crude oils and extraots, are compatible with the geologic setti111g (or operational influences). Agai111, anomalies and breaks are noted and resolved,
follow-up analyses are scheduled if necessary, and findings with conclusio111s and recommendations are prepared.

Scheduling and Costs

For general scheduling and economic purposes, a geochemical study can be broken into about three equal parts:

■ planning and sample collection

• geochemical analyses
• interpretation and implementation

The planning and sample-collecting portion of a major study typically takes anywhere from three months to one year to carry out. Virtually all
activities are handled directly through the exploration office so cost ca111 be calculated directly from staff daily rates, company overhead, and routine
wellsite and travel figures. On large studies this initial segment can equal 20 to 35% of total study cost.

The geochemical analysis segment can nm from a few days to many months, but cost is based almost entirely 0111 analytical charges. Screening
analyses of routine source rock and crude oil studies often can be completed within a month after receipt of final samples. Screening charges for TOC,
Rock-Eval pyrolysis, and headspace analyses are generally less expensive than analyses carried out during the detailed analytical phase

The final interpretation and implementation portion of a geochemical study generally should take no more than three months after completion of
analyses in a small geoohemical study (e.g., core sample source rook) and up to nine months on a large study (e.g., basin evaluation). As with the
initial planning and sample collection portion, cost of the final portion can be estimated using standard exploration office rates, except where the
analytical laboratory also provides a111 interpretation. Such interpretations typically add approximately 25% to total analytical charges.

Total analytical costs for a geochemical study can range from a few hundred dollars for small source rock studies to more than 550,000 (US) for a
very deep-exploration-well source-rock or a complex crude oil-source rock con-elation study.
Geochemistry and Basin Evaluation
Introduction
In exploration geochemistry, the term basin evaluation has come to cover a wide variety of analytical and mathematical programs. Program objectives
range from determining the identity of source inteivals across a productive region (Baird, 1986). to evaluating ultimate petroleum recovery from
productive sources (Moshier and Waples, 1985). For discussion purposes, we may categorize basin evaluations into three oversimplified groups:

• Analytical basin studies rely primarily on laboratory analysis of rock and petroleum samples to provide geochemical data for evaluating
exploration potential.
• Thermal-history basin studies combine geochemical data with graphic methods and computer programs to reconstruct the post-burial,
generative history of a basin

• Mathematica/ basin studies work primarily with deterministic basin models for predicting exploration potential and use geochemical and
production/reserve data to test model validity.

The three categories of basin studies represent somewhat of an evolution in the use of exploration geochemistry for broad-area studies, and the
categories overlap. (Welte and Yukler, 1980).

Analytical Basin Studies

Analytical basin studies can be thought of as representing extensions of source-rock potential, orude oil correlation, and crude oil-source rock
correlation approaches to regional evaluatio111s. Tlhe principal methodology places geochemical data into a geological and geophysical framework so
that a three-dimensional picture of basin petroleum potential emerges. In other words, available data from geochemistry, geology, and geophysics are
merged into one synthesis that presents a best-fit interpretation of probable petroleum generation and distribution, and therefore exploration
potential. However, the balance in geochemistry, geology, and geophysics is often disproportionate. For example, in frontier areas where no wells have
been drilled or where little subsurface information is available, geochemistry of seeps and outcrop samples can play the leading role (Anders and
Magoon, 1986).

Our example of an analytical basin study is the evaluation of the Bass basin, offshore Australia (figure 1) by Williamson et al.

♦ Ory l!barll;lor.ed

J
0 Stiow of 9il'» i!bandor.ed
♦6ils disl;overy
♦ Sh ,Qf oil J gas, a_ban(ji;,,etj

I
:i:
♦Oil J 9u<:lisi;;O"ery
0 6il'>, ava,,done<11

'o -11- 6M 1982$ei,mic n.,

.2!L Herntite Pty llt;l ""'i$mrc
line

<E

.&"
1
.' :;!.
,-:

.".i .
Ji;

f- 100km

l FIGURE 1

(1987). This study contains good representative maps, cross sections, and plots. As the review of selected presentations progresses, you will see. that
principal geochemical conclusions of the Bass basin study include the following:

a, Suitable organic-rich source rocks are present in Upper Mesozoic and Lower Tertiary coal measures deposited in an extensional rift basin.
• The base of Cretaceous coal measures entered the oil window about 40 million yearn ago and maturation has continued since that time
and progressed up-section.
• Oil and gas shows confirm that generation has occurred in the basin.
,., Basin depositional models indicate that probable reservoir sands are now within the oil window, giving deep unexplored portions of the
Bass basin considerable petroleum potential; other prospects lie above fault zone conduits.

From the geochemical perspective, most analytical basin studies lay out a sampling and laboratory program comparable to more fundamental studies.
This routine provides a kerogen, bitumen, and/or petroleum analytical data base to be merged with the regional framework.
In the Bass basir11study, many geochemical data came from previous source potential evaluations and included organic carbon determinations,
solvent extractions, Rock-Eval pyrolysis, and vitrinite reflectance measurements. Data represented cores from eleven wells plus other sources
(Nicholas et al., 1981). In addition, Williamson et al. incorporated other obtainable, but unpublished data on kerogen classification and themilal
alteration index into the study. The data in hand show that lowermost basin fill contains dominantly gas-prone kerogen (vitrinite); up-section kerogen is
gas- and oil-prone (vitrinite and exinite). TAI and %Ro values indicate mature source rocks at drill depths between 6650 ft (2000 m) and 9850 ft
(3000 m), depending upon location in the basin (Egure 2, Gene,-aiized cross sections of Bass basin. (a) Seismic s,ection. (b) Interpreted stratigr-aphic
section. Matu,-ation
levels of0.7 and 1.3 % Ro are projected across the section).

(tro,n Wil amSD11 N al,., S87; coortcsy Ai.istrali8Jl Bureoo ot Mineral •cesJ

FIGURE 2

The regional framework has as its prime consideratior11s the reconstruction of (1) depositional and compaction history, (2) possible source and
reservoir bed associations, and (3) syndepositional and postdepositional structural movements

Large flood basinRiversySlem .

(from WI/Uamson er al, 1987; courtesy Australian Bureau of Mineral Resources)

(from WJlllamson e! al, 1987; courtesy At1strauan Bureau of M/llfl(aJ Resources)

FIGURE 3
FIGURE 4

(from Wilflamson et al, 1987; cour1esy Ausfratlan Bureau of Minaral Resoorcas}

(from Wlfrlam.son ef al, 198 7,·courtesy Australian Bureau of Minera/ Resources)
 FIGURE 6
FIGURE 5
formation of extensional basin with fluviaf filling (Early Late Cretaceous) through (4) decreased subsidence with flood plain dominance (Early
Paleocene) through (5) g,eneraf stability with marine transgression (Late Eocene) to (6) shallow-marine submergence with carbonate-shelf deposition
(Oligocene)).

The framework on which to hang geochemical data is assembled in cross section

(Bgure 2) and map (8gure 7, Structure of Bass basin.

/from Williamson Al /11., 1987; oor!My AuYa/Jall Bulll"'1 Of Mjnl0(/11 R"""'11'""")

FIGURE 7

Structural contours and faults are based on depth to pre-rift unconformity forming floor of Bass basin) views. The diagrammatic northeast-southwest
seismic cross section of the Bass basin shows both stratigraphic and structural interpretations. Projected maturation lines based on vitrinite
reflectance from the geochemical data base have been included in the cross section to depict present-day maturation levels within the basin. The
lesser reflectance value (0.7 %Ro) is in the weakly mature portion of the oil window (catagenic) interval; the greater {1.3 %Ro) is near the base of
the postmature, thermal gas (metagenic) interval. The structural base map included here is drawn on the prebasin (prerift) unconformity and serves
to reflect thickness of rift-basin fill. In basin studies, when appropriate sections and maps are on hand, geochemical data such as the identity of
probable source intervals and maturation levels are plotted for individual units (8gure 8, Maturation level at present) to estimate disposition of source
rocks interpreted to have given up bitumen.

145° 146° 147°

Ao X 10
■ 7-10 ;39•
010-13
0 501km
OMa

41°

FIGURE 8
Williamson et al. also carried out a geohistory analysis of sixteen wells in which vitrinite reflectance is cross-plotted against a depth curve for each well

CORMORANT 1 (Basin axis)

Tlme(Ma)
150 100 50 0

r,
L...LJTori:auay GrQ\JR and r..teai.: red i:;i . I
□ TaquayGroup and .
Derrons Bltiff FormatJoo
D EMt:1!1"·1'\1lill!!lw Co.al Measurea
6

D
Demons.Bluff FormatiQll

Otway Cirtiup
•

D
1,,1 • "Q va \JeJ.:

Ea:a:Mrn V'aew Coal MM&J

D Otway Group • Measued R0 value

FIGURE 11
FIGURE 10

BASS 3 (Basin margin) j AROO 1 (Basin high)

150 100
Time(Ma)
50 j 150 -----l OO TI_me_(_M_aJ_ so

J
:;
b

! -0.6
Log R.,
I
• 25
"-
0 "

TD
4 3892m
0.5 0.7 •• • 4

I
16
0.5 0.7

fL"7..;, TO<Q"'V G,oupForrnetion

Demons Bluff ·"" D Eastern View Coal Measures r-=-7 Torqua:,o
Demons Group ancl
Bli.rffFormation

!D d Otway G•o • Ml:!'asured R0 values

DotwiryGrQ

FIGURE 12 FIGURE 13
(Falvey and Deighton, 1982). The geohistory analysis interprets the maturation history of a well or an arna and estimates maturation conditions at
selected times in the past (Elgure 9), T1his analysis is based primarily on vitrinite-reflectance parameters (Lernhe et al., 1984). The inclusion of a
geohistory analysis in a typical analytical basin study demonstrates how our discussion categories are oversimplifications.

145° 146° 147°

R0x 10
•7-10 39•
010-1:,
50 km
40 Ma

(from Williamson et el.• 198 7: courtesy Ausra/ian Bureau ot Mineral Resources)

FIGURE 9
In analytical basin studies where geoohemical correlations can be made between source beds and petroleum in reservoirs (not the case in the
relatively unexplored Bass basin), associations generally are plotted. These are evaluated to determine whether source-reservoir relationships (e.g.,
source-rock generation history and likely migration routes) are compatible with the geologic setting (Northam, 1985). Conclusions are then refined to
explain variations and anomalies in the overall picture and recommendations are presented to apply to the findings in exploration programs. In the
case of our Bass basin example, favorable settings for further prospect generation are outlined (figure 14

20km
(lrom Williamson e1al., 1987; courtesy Aoolralian B1Jreau ot Mineral ResoorcegJ

FIGURE 14

and .E[giure 15).

a.... r -•-··-··- - ----- • ·- ···--22.!..

, . ..
........,·---,..,_ ...,,o
-
-- ---
<ii'
"O
C
0
0

.!
Q)
E
+l
C
.Q;
]
ai
a:

(frQm William etI., 1987; cwrt y A lr.-lianreao.iof Mine<al fl

r,;;esJ

FIGURE 15
Thermal History Basin Studies
Thermal-history basin studies evolved as the worlldwide geochemical data base grew and principles of petroleum generation became better understood
(Tissot et al., 1987). The thermal-history approach combines and relies heavily 'upon two fundamental geochemical concepts:

,. Maturation changes are pr;edictable. Maturation of buried orgianic matter (e,g,, coalification, thermal alteration) is systematic and proceeds
irreversibly, as first demonstrated in the coal industry (van Krevelen, 1981),
,. Maturation rates are pr;edictable. Buried organic matter matures in response to both time and temperature; their combined effects on
kerogen, bitumen, and petroleum are approximated by the Arrhenius equation (Equations 1, 2 in this section, see Connan, 1974).

Thermal-history basin studies, therefore, include some method of reconstrncting the rate and cumulative effects of maturation on basin sediment
related to burial time and temperatures (GR: Waples, 1984). T1he three more common reconstruction methods used by various groups in industry are

• Tissot-Espitalie kinetic method

• Lopatin time-temperature index (1TI) method
• Shell level of maturation (LOM) method

These three thermal-history methods have often been adapted or modified by modeling specialists. Modifications handle specific postdepositional
conditions, such as fluid overpressure or compaction effects, or evaluate influences of different kerogen types. Reports on such adaptations and
modifications can be found in many recent publications and issues of petroleum industry literature (e.g., Tlhomas et al., 1985. Nakayama, 1987).

Equation 1: Arrhenius Equation

The dependence of the rate constant on activation energy and temperature is expressed:

where:

k= reaction rate (rate constant): the rate at which chemical change (maturation) occurs

A= frequency factor (pre-exponential factor, Arrhenius constant): the frequency with which particular molecules collide in proper
orientation so that a particular reaction occurs. This constant varies among individual components making up any kerogen types.

Ea= activation energy (critical energy): the amount of absorbed energy needed to break a particular molecular bond and form a new
product
1
R= gas constant (e.g., 82.0575 ccstm°K mo{e 1
)

T =temperature° Kelvin; "K = 273 +" C

When applied, the equation shows that the reaction (maturation) rate (R) is primarily a function of the concentration of reactants and absolute
temperature ( T) , with temperature having an exponential relationship.

Note: If a catalytic reaction is involved, the concentration and activity of catalysts also must be considered in the activation energy.

Equation 2: Modifi,ed Arrhenius Equation

If it is assumed (Connan 1974) that up to the time of measurable bitumen generation (catagenesis), kerogen udergoes little thermal degradation, the
time-temperature relation of the Arrhenius equation for the initiation of bitumen generation can be expressed:

Int=(:; )-A
where:

t= time

Ea= activation energy

R= gas constant

T= temperature °Kelvin

A= frequency constant

In this form it can be seen that a linear relationship exists between the logarithm of burial time (geologic age) and the reciprocal of temperature. In
other words, as temperature increases the time needed for catagenesis (thermal maturation) to begin decreases.
Tissot-Espitallie IKiinetiic Method
The Tissot-Espita lie modeling approach is a highly mathematica I and computerized method for estimating bitumen generation and petroleum
alteration (Tissot, 1969; Tissot and Espitalie, 1975). llhe modeling is based on a series of activation energies that prompt different chemical reactions
to take place within organic materials as burial temperature increases (Egure 1,

SURFACE TEMPERATURE: 20° C SURFACE TEMPERATURE: 20° C

in TEMPERATURE GRADIENT: 0.0:l5,° C/m SURFACE TEMPERATURE: 20° C TEMPERATURE GRADIENT: 0.035° C/m
IE 1.0
f-
SUBSIDHICE: 100 m/MY
-- !PETROLEUM (OIL & GAS)
ffw 1.0 TEMPERATURE GRADIENT: 0.035° C/m
- PETROLEUM (OIL & GAS)
in
IE 1.0 SUBSIDENCE: 100 m/MY
1- f- -- PETROLEUM (OIL & GAS)
:w. --OIL
:w.
-OIL
:w . --OIL
ls 2.0 ls 2.0 ls 2.0
/J)
□
z
u3:, 3.0
0
J:
4.0
"c:':
Ig
,;
w
i!l
:l:
5.0

i :,:
6:: 6.0
w
□
7.0 7.0 ---------- - 7.0 - -- -------
$' 0.0 20.0 40.0 60.0 80.0 0.0 20.0 40.0 60.0 80.0
! 0.0 20.0 40.0 60.0
PERCENT CONVERSION
TYPE I KEROGEN
80.0 PERCENT CONVERSION
TYPE I KEROGEN
PERCENT CONVERSION
TYPE III KEROGEN

FIGURE 1 FIGURE 2 FIGURE 3

and .Eigure 3, Percent conversion of kemgen types based on the Tissot-Espitalie model (1) Type I k,erogen, (II) Type II kerog,en.

{3) Type III kerogen) (Mullan, 1984). This modeling approach can yield qua111titative estimates of oil and gas generation. When using the Tissot
Espitalie method to reconstruct the thermal-history effect in any one area, a key determination is the calculatio11o1f conversion value or transformation
ratio for bitumen. The transformation ratio ( TR) is the fraction of generative potential (X) remaining in a sample compared to its initial generative
potential (XO); the relationship is expressed:

TR= XO-X
XO
As depicted by percent conversion in Bgt],!@_L figure 2, and figure 3 the transformation ratio ranges from approximately O: 1 (0%, immature), when
all generation potential remains, to about 1: 1 (100%, postmature), when all generatio11p1otential has been realized.

During a Tissot-Espitalie reconstruction, the cumulative transformation of kerogen to oil and gas is calculated for each depth where TOC, kerogen
type(s), and thermal history are known, using a two-step process (note: that more recent kinetic methods use more complex reactions):

Kerogen

oil+ COi + H20+ carbonaceous residue

gas + CO:z + H20 + carbonaceous
residue

In each thennal-history predictive calculation, twenty-one parameters are applied to each type of kerogen present to relate the amount of oil and gas
to time and temperature. The twe111ty-one parameters include six covering inherent generative potentials for kerogen related to breakage of different
molecular bonds, one to express initial oil content, seven for activation energies (Ea), and seven for frequency (Arrhenius) factors (Ae). The results
are combi111ed proportionally to the relative amounts of reactants present. This technique determines rates of formation of oil firom kerogen and gas
from oil and kerogen. The results provide an estimate of original and generated bitumen (petroleum) for the proposed thermal history, The model
assumes, however; that generated oil remains in or near the source rock and experiences the same thermal conditions as the source kerogen,

The geochemical data used to develop the Tissot-Espitalie method are those common to source-rock evaluations. Developmental parameters included
organic carbon content (TOC), extractable orgar11ic matter (bitumen; EOM), types and relative concentrations of different kerogen (Types I, n, and HI),
total generative potential of kerogen types (I and 2 from Rock-Eval pyrolysis), and the thermal history of sediments involved.

Lopatin Time-Temperature Index (TTI) Method

The Lopatin method uses geologic assumptions to generalize subsidence/ compaction and uplift/erosion rates. It also uses chemical reaction
assumptions to simplify activation energies (Ea) of the Arrhenius equation {Equation 1). Tlhe resulting model causes maturation rate (k) to be
constant with time and double with each 100 c increase in burial temperature (Lopatin, 1971; Waples, 1980). Modelir11g is carried out using the
general relationships:

interval maturation ( TTI} = interval time factor x initerval temperature factor

Time factor is measured in units of millior11s of years, during which a sediment is projected to be buried within a 10° C temperature range.
Temperature factor is a numerical scale that doubles with each 10° C increase in burial temperature (Tablle ta).
(a) Temperature Range (OC} Temperature-Factor (-y)

1
30-40
128
_!_
40-50
64
_!_
50-60
32
1
60-70
16
70-80 .!
8
1
80-90 4
1
90-100 2
100-110 1
110-120 2
120-130 4
130-140 8
140-150 16
150-160 32
160-170 64
Tablle la: Lopatin relationships. (a) Temperature factor to burial temperature.

The level of maturation attained by a sediment at any point in its burial history is the sum of all interval TTt values from initial burial to that point in
time:

progressive maturation= TTtl +TT12 + TT/3

It follows that when modeling the present level of maturation, all interval TT/ values from time of sediment burial to the present are summed.
Summations include all burial time, whether sediments were subsiding, in static burial, or being uplifted. Consequently, maturation levels move up
section with burial time, even if subsidence has ceased or uplift is underway. However, the rate of up-section movement of such features as the oil
window are most dependent on burial temperature (Ejedawe and Coker, 1984).

A general scale has been established that equates summed interval TTI values to maturation level (Tablle :t.b). Catagenesis generally is considered
to have begun by the point at which cumulative TT/ value is 15. Peak bitumen generation occurs near a cumulative TTI of 50; the oil window is
closed by the point that TT/ reaches 180.

(b) % Vitrirnte TTJ Generation

Reflectance

0.40
< 1 Condensat,e fron1 1iesii1nt,e
0.50
3 from S-rich kerogen O. 60 10
0.65
15 early
0.70
20 peak
0.85
40
0.90
75
1.15 110 late
1.35
180
1.50
300 Wet gas
1.75
500
2.00
900
2.50
2,700 Dry gas
3.00
6,000
4.00
23,000
5.00
85,000

Tablle J.b: Lopatin relationships. Cumulative TTJ values to other geochemical parameters.
Calculated TTJ values for present-day levels of maturation can often be cross-checked with other, directly measurable present-day maturation
parameters such as vitrinite reflectance. This permits the validity of a basin thermal-history model to be evaluated and, if necessary, for basin-history
parameters to be revised (e.g., change geothermal gradient or erosional history) so that the model comes into agreement with other discriminating
geochemical data.

It is important to keep in mind that the objective of revising model parameters is not simply to make the model fit known conditions, but rather, by
having the model agree with available data, to make it more effective in predicting conditions elsewhere in the basin where no data are available. This
latter is a common exploration objective of a thermal-history basin study. Restated, it: is these revising attempts which fine tune a model to a
particular basin or to a specific set of local geologic conditions that reduce exploration risk. Of course, when few data are available, basin modeling
has to use bestgues.s approximations or look to even more empirical approaches (Pigott, 1985).

Compared to the other two thermal-history modeling approaches discussed, the Lopatin method appears to meet the modeling needs of
explorationists most easily. It requires relatively simple information and, as we shall show, can be constructed easily in a field office. The method
gives a good representation of the timing of bitumen generation using predetermined TTI threshold values and can be adjusted rather easily to
compensate for alternative geothermal gradients and basin histories (Nwachukwu, 1985). As with the Tissot-Espitalie model, computer programs are
available for developing Lopatin plots; in addition, many service companies can provide computer-generated Lopatin plots as part of their routine
interpretation of analytical and geologic data. A principal limitation of the Lopatin model is that it can present a ciuestiona ble maturation interpretation
if it is not calibrated to the area under study.
The Lopatin method predicts maturation based on the intervals of burial time that a sediment spends within each 10° C temperature range. The
graphic base needed to determine TTI is a geologic time scale spread arithmetically across the horizontal and geothermal isograds stacked vertically
to depth (.Eig.!!.Le....1:, Time temperature grid.

. MYE!P
Pa leogene I Neogene II
.
Cretaceous

. .
Suri:: 20i:i
100 50 . .
1/128
1/64
1000
5()"
1/32
1/16
2000
V 1/8
u ,
1/4 . ;
0)
1/2 :::;:
100"
1 3000

2
4
BHT-1-
4000
8

FIGURE 4

Geothermal gradient d,epict,ed is uniform and adjusted to d,epth). Because the maturation effe.ct of temperature Es assumed to double with e.ach 100 C
Encrease of burial temperatuire., the vertical geothermal gradient grid is given a proportEona multiplier or temperature factor. As annotated on Elgure 4.,
the multiplier for geothermal interval 100-110° c is 1; 90-100° c is o.s; 110-120° c is 2.0, and so forth.

Interval TT} values a ire calculated by taking the temperature multiplEer ·t:Emes the number of mEllions of years that any sedimentary unit remains
within that burial temperature range (e.g., 1 for the 100-1100 C range x 5 for 5,000,000 years= interval TTI of 5). The millions of years that a
sediment resides within temperature intervals is determined graphically on the time-temperat1..1re grid by the explorationist. This is done by
reconstructing tile subsidence,,. static1 .and uplift llistory of the stratigraphic co umn at the point of study. Briefly., the approach is to plot the prese11t
geologic section at the Recent end of the time scale (Table 2,. £igur-e 5, Stratigraphic s,ection.

MYBP
Cretaoeous Paleogene
I Neogene II I Stan II
. 100 . .5 0
. A
Surf - 20"

B
moo
50"

2000 D
!!!
$
a,
:;;;
1000 E
3000

BHT-130"
4000

FIGURE 5

Time-depth control paints are based on geologic ages and cumulative thicknesses of stratigraphic units) and back calculate the depositional and uplift
history of the oldest formation Present (.Ei.gure 4 ). The approach combines age and thickness for each geologic unit and progressively removes
(backstrips) the units in reverse order of deposition.

desi gnation age thickliless depth

Formation
(mybp) (m) (m)
Surface 0 0 0
A 7 300 300
B 25 700 1,000
C 38 700 1,700
D 65 650 2,350
E 82 1,050 3,400
F 110 300 .3,700
Corrected bottom-hole temperature - 130° C

Average surface temperature - 20° C

T,able 2: Time-stratigraphic data, The age and thickness of each stratigraphic unit is used to reconstruct a Lopatin diagram, In this data table
sedimentation is considered to be continuous with no unconformities or uplifts present. Geologic age is for the base of each formation.

Note: The restJlting diagram (figure 4) depicting formation burial depth against time has the appearance of a geologic cross section along the flank of
a basin. Remember, the Lo pa tin diagram is not a cross section but represents one geographic location; time is the horizontal scale, not distance.

In the completed plot, figure 6 {Lopatin diagram.

MYBP
Cretaceous

Surf - 20° A

B
50"------- --- ,,, ....,....,_...,...-1000_--

2000 D

$
"'
E
3000

4000

FIGURE 6

Burial history curves. The stratigraphic column is plotted to depth with a depth profile reconstructed back to time of deposition), all sedimentary units
within a depositional se uence (no unco111formities) show parallel subsidence and uplift histories through time, and progressively cooler geothermal
histories up-section, To obtain TTI on this plot, the interval of geologic time (horizontal measurement) that any fonmation resided within each
geothermal temperature range (vertical stack) is taken times that geothermal multiplier (figure 7, Temperature intervals.

MYBP
Cretaceous

Surf - 20°

....._-++------2000
D

!
E
.........3000

FIGURE 7
The nurnber oF millions or years that strac,graphic unit F spenC 'Within a 1 o° C ternperaCure r-ange is noCed belolN' ,the set:. of curves). The TT I
.sunimation values annotated along foJTnation contacts are ttle cuniulative measure of niaturatEon from burial to that younger- point in geologic time
(TabEe 3; Ei_gure 8.,. Anno,ta,ted Lopatin diagrarn.

I
MYBP
Cretaceous Neog,ene

Surf - 20"' A

--- ----i 2000

e!

::.s
:_..:....,_::..:..; ...,...,.,'l"i-,--+3000 E

FIGURIE 8

TT I values are shown for base of fonnation F where isothermal lines are intersected and individual TT I values are calculated) ..
Ternperature Tirne TT I
Range oc Factor MYBP Factor Interval Curnulative

20-30 11256 82 28 0.11 0.11

30-40 11128 77 5 0.04 0.15

40-50 1164 72 5 0.08 0 23

50-60 1132 67 5 0.16 0 39

60-0 111648 18 1.13152

70-80 118 33 15 1.88 3.40

80-90 114 29 5 1.25 4.65

90-100 112 24 5 2.50 7.15

100-110 1 16 8 8.00 15 20

110-120 2 8 8 16.00 31 20

120-130 4 0 8 32.00 63 20

130-140 8

140-150 16

Tablle 3: TTIcalculations. These data are numerical values calculated foir Unit Fon the LopatEn diagram of figure B.

When upEift and erosEon (unconformity) are part of the basin cyde the effects must be incorporated into the diagram. SEmilarly, changes of geot:henmal
gradient with time must be plotted.

The thermal effects of loading must also be considered in cases where overt:hrustEng occurs i11 the n..opatin reconstn.Jction. Because the timing of
petroleum generation is of prime concern in a basin study, it is essential to determirie whether catagenesis occurred before, during, or after thrusting
in the dffferent source strata. In general., units above and below the thrust are consEdered separatemy (figure 9,

TIME\Ma)

_., tz..".-- /:...:--:.---·----. ?

TIME{Ma)
M40
240 200 160 120 80 40 o2 4 0 +200
,o :--:-:-:-::-:-::-:-i ========--- O+-,
.- 160 120
. . . . . . . . . ...... ....
. 4000 CJ' 4000

8000 61rt-----
o· 8000 8 OO°C------------
120Cl0
r
!l: i10000
-20,000'
i 12000
fu '"'"
Cl 16000 24000
Awrollim11 l0fl9Qt
-Mquidhydr..:WW!l
20000 gencrauon
20000
32000
{trom Furlong 1111d ElilTIIJn. 1964: courtaey MPO)
(from FulfooQ and Edman, 1964; cOln-fesy MPG

FIGURE 9 FIGURE 11 FIGURE 12

Figiure 11, and Figure 12, Lopatin diagrams for thrusted sections.) (9) Effects of thrusting on isotherms.
(10) Overburden effects of thrusting and erosion on a pre-Cenozoic section. {11) Lopatin TTI plot for thrust plane, point F. (12) Lopatin TT] plot for
overthrusted section, point E. Note shi in isotherms with thrusting) in order to distinguish preloadir11gi from postloading maturation effects. These can
be difficult to differentiate because of the dynamics of thrusting, inequities in resultant loading, and modification to geothermal gradient ( Wanner and
Royse, 1987; Edman and Furlor11g, 1987).
ShelI Level of Maturity (LOM) Method
The LOM thermal history model categorizes maturation level on an arbitrary scale of zero to twenty. Each level represents the combined effeot of (1)
the millions of years that a sedimentary rock spent at (2) an effective heating temperature ( Teff) (.Eigure 13, Relation of LOM, T ma,,, Tetf, and
activation energy (Ea).

0.1 1.0 rn 100 1000

Elfactive Healing lime, MIiiions of

Vaars (leff Time within 15 C of T
ma

FIGURE 13

Two different thermal histories have been plotted which obtain an LOM of 10.). Effective heating temperature is defined to include the 15° C
temperature range below maximum burial temperature (Tma:,). (Hood et al., 1975).

Note: Burial-temperature Tmax of LOM method and tihermal-peak Tmax of Rock-EvaI pyrolysis are entirely different measuremeITT1ts and should not be
confused.
LOM modeling assumes maturation level is primarily related to activation energies of highest 15° C burial temperatures. As is apparent in figure 13,
an LOM of 10 can be attained by a Tma>e of 135° C and a Teff of 10 millior;i years; the same level of LOM can be attained by a Tmax of 105° C anda
Teff of 100 million years. LOM values for a strata are determined as a thermal-history model using _Figure 13 when Tm;,x and Teff values are available.
LOM values can be estimated as well, based on other maturation indicators (e.g., TAI, %Ro) iITTI the strata (Elgure 13). OITT1ce determined, LOM values
are equated to levels of diagenesis, catagenesis, and metagenesis, and to possible intervals of petroleum generation. In regard to the latter, James
(1983) determined LOM values for the Marilin field, Gippsland basin, offshore Australia (flgure 14, L0/'11plots of Marlin field, offshore Australia.

Marlin on
Calculated LOM
Structure
0 I I I I I I I 11 I I I
5 6 7 8 9 10 11 12 13 14 15

6()0

1lillY15

*, .i
12{)0 I

..E 1800

C
'
.;
24-00
'E¥ . 65
O> 3000-
Cl

3600

42{)0
• Measured!maturity from,R0 max
• Cal'culated maturity
4000

(from james., 1983; courlesy AAPG)

FIGURE 14
LOM profile), The LcOM value of 13 was equated to gas and condensate production, which suggested an Upper Cretaceous source for Marlin field
production that extended well down the flank of the structure (.E!gure 15, LOMlevels on structural section. Gas and condensate of upper catagenic
zone is interpreted to originate near LOM 13),

s
'
Marlin Field N

12my
A
I
15my
LOM
8
52my
10
12
Source
12 14 Interval

14

16

1200m

(from James., 1983; courtesy AAPG)

FIGURE 15

The Shell LOM model is the simplest of the three methods to use because it confines itself to predicting maturation from burial time spent only at
highest 150 C burial temperature. "Tlhis can be a limitation; timing of any earlier (or later) generation is not apparent and, therefore, is lost in
reconstmcting a complete petroleum generation history.

Mathematical Basin Studies

Mathematics effectively entered the thermal-history basin study picture as temporal and three-dimensional computer capabilities were adapted to
petroleum exploration. Typically, selected thermal histories, subsidence and compaction rates, fluid dynamics and rock porosities, and structural
histories are modeled for specific basin types in an attempt to reconstruct paleogeology and resulting petroleum potential {Yuk.ler and Kokesh, 1984).

There are two main approaches in mathematically oriented basin studies: (1) statistically derived models calculating probabilities related to
exploration potential, or {2) predictive deterministic models based on geological and geochemical principles. In both approaches, theoretical levels of
organic richness, kerogen maturation, total bitumen generation, effective migration, and oil and gas accumulation are types of outputs. These results
typically are compared with available observation and analytical data to serve as bases for exploration planning.

Statistically derived models have most application in evaluating unexplored regions and in predicting probabilities of possible discoveries. Often the
statistical approach applies more to decision making by upper-level management than to prospect development by exploration personnel (Sluijk and
Nederlof, 1984. Thedeterministic method for modelingi has the most direct application in exploration offices active in prospect generation and basin
evaluation. Types reviewed below show that geochemical principles contrnllingi the subsurface alteration of organic matter to petroleum are critical in
all deterministic models (Mackenzie and Quigley, 1988),

The classification system (Bgure 1, Flow diagram for determining modeling) presented by Ungerer et al. (1984) broadly categorizes deterministic
models and their application during exploration. We use their system in this discussion.

INPUT DATA
(Peor accuracy data may be rete-ased 1f OUTIPl.ff
nacEtss.ery torth1:1co111&1&-tencyo1 the ra!!Ult!I) RESULfS
S1,11;i;;05J.:1iv0
i ic;: i::ro!Ss Cf"O:"j,.l'.I .t10clion5
ti B.:u::lt,:"j,1nppin!] T.,c•onic:
Slr;:iti91 ph)' mOOel J.:l lh .;m..-;.(;1'
P;Jl IJ,;:1•hym0try Hi..!';tlJl)I

S0i mii;;ra:;:1t:;ifl d.:il.i

Prn nt h fh:yu
m1<1.i ,m0m0111

s
Thermal conductiintie&
-of rocks
SJJrfa.ce teimp,3ra.1uriit
H p,othe&it.s

Pet1clt:1urn puat:tr1bal
or:sourc-e--roc1<9;
L1lh6lcig
Sb"atlg li:(

Ov@.all com posAion r1ount9;01 ail i::arri.ed m

of HC mi;ii:ture 1:1.:rS1:1uus g.c,lutlon 0"1:1
tl1t:11r11gratlon pat 119.
The general sequence of modeling during early basin evaluation is:

,. backstripping model reconstruction of basin geologic history through development: of successive cross sections
,. geodynamic model reconstruction of heat-flow (geothermal) history
,. thermal/maturation model reconstruction of paleotemperatures and resultant organic matter maturation
As exploration proceeds, basin development modeling includes:

,. migration model reconstruction of bitumen generation and expulsion and amounts of petroleum accumulated in traps
,. thermodynamic model reconstruction of amount and composition of hydrocarbons that could migrate and their phase behavior

The three early basin evaluation mathematical models bear strong similarity to the thermal-history basin study approach. They inco17porate, for
example, many of the concepts and principles generalized in the Lopatin diagram. Backstripping techniques are used to reconstruct basin subsidence
and uplift through geologic time, geodynamics are used to determine paleogeothermal gradient effects, and some thermal/maturation assessments
are comparable to sophisticated TTI calculations,

Computer capabilities aid deterministic modeling to digest far more data than noncomputer approaches and thus test many more variables and
conditions for early exploration use. As one example, modelEnig car, simulate transient phenomena such as overpressure. In such dynamic-compaction
models, the fact that the thermal conductivity of water is substantially lower than that of mineral grains can be taken into account and the progression
of maturation adjusted accordingly. Output, however, still seeks to answer basic questions about source rock and petroleum potential inherent in all
levels of basin studies (Guidish et al,, 1985),

Migration and thermodynamic models, coming more into play as basin development operations proceed, add more engineering oriented concepts to
the evaluation package. These models build on bitumen generation and data from previous modeling, and incorporate compaction effects, fluid flow,
phase behavior, and pressure-temperature interdependencies. Modeling objectives include determination of timing, driving force, and consequences of
migration in conjunction with physical and chemical properties of petroleum at different locations within the migration-reservoir system. Output from
these models may have increasing utility in production consideration.

Geochemical Problem Salving

Biomarker Applications and Molecular Configurations

The additions of GC/MS, Py/GC/MS., and other very discriminating analytical procedl!lres to routine geochemkal techniques now permit the
explorationist to look in detail at molecular composEtion of kerogen.r biturnen.r and petroleum. Tile carbon-skeleton structure of biomarkers.r tliose
organic molecules tliat retain recognizable identity from biotic origin to petrole.urm.r is one prime consideration. As biornarkers persist but aHter dudng
diagene.sis, catagenesEs, and metagenesis, their compositions find use in the int:erpretion of origin.al souirce materials.r deposEtional environments,
maturation, mEgr.ation, a11d alteration effects, and c1rude oEI and crude oil-source rock relationships and age-dating. These broad usages are possible
because different but very closely related bEomarkers react (or do not ireact) to post-burial conditions En predmctable,. irecognizable manners(Mackenzie,
1984).

Molecular-Configuration
Organic molecules, indeed all molecules, are three-dimensional. As discussed in detail by Mackenz.ie (1984), this three-dimensional, or stereo,
clia1r.acter allows many molecules of the same. composition (C-number) and basic structure (e.g., isoprenoids.r steranes) to have slightly different
conflgur.ations. A methyl branch,,. for example.r can project in one of two different dkections in the third dimension (Egure 1, Isometric structures.

(a) A A

C B B C

Acyclic

(b)

HO
Cyclic

FIGURE 1
(a) Acylic. (b) Cy/ic). As showr,, wher, stoms A, B, ar,d Care different, D can be in two different positions; that is, the tetrahedron can have mi,iror
image fonms. To indicate how bonds project in the third dimension, one cor,ventior, is to have solid triangles denote a bond above the plane of the
paper and a dashed line denote a bond below. The relationship, as with a carbon-hydrogen bond, can also be written fJ (H) above and a below. In
addition, the orderir,g of atoms in the branch can be clockwise (R) or counterclockwise (S). When two stereo isomeric molecules have mi,iror-image
configuration, they can be considered stereo pairs; they are al.so ireferred to as enantiomers. Stereo isomers not of mirror- Emage are called
diastereoisomers. "Tlheir presence or absence,,.orratio to one another, can reveal the history of the Esomers.

The fact that diastereoisomer pairs are slightly different and, therefore, have slightly different physical and chemical properties pe,imits them to be
separated by discriminating analytical techniques such as Gas Chromatography/Mass Spectrometry. Stereochemistry is the identification and
description of such molecular distinctions. Using stereochem!st:ry to recognize both Enherent variations in m o ecu les and post-buria I rearrangements
through isomerization is fundamental to applying biomarkers in the identification of source materia Is and postdepositional changes (Egure 2).

OH

6(S) 1O(S)

111
6(R) 1 O(S)

II 6(R) 1 O{R)

(from Mackonzio, 't984) IV

FIGURE 2

As shown, the precursor phytol (]) from chlorophyll produces the biomarker pristane (II). With increasing temperature isomerization produces
(III and IV) in whioh carbon-carbon bonds at 6 and 10 take on different orientations in third dimension. Pristane II
additional forms of pristane
(mesopristane) is configured 6(R), 10(5); pristane III 6(5), 10(5); pristane III 6(5), 10(5); pristane IV 6(R), l0(R).

Not all modifications to biomarkers are made through isomerization. The loss of a methyl group can result in making an unsaturated biomarker out of
a saturated one. In many specific situations, loss of methyl groups proceeds systematically and predictably to form naphthenoaromatic compounds
(.Elgiure 3, Maturation of biomarkers.

FIGURE 3
Aromatization of stem/). This prncess, called aromatizatio11, also is tracked by molecular evollltion. ]n conversion, a11other form of modification,
molecules are altered by the rnpturing of bo11ds, so that the skeletal structure takes 011 a different form (Elgure 4, Conversion of porphyrin.

IR2 IR3 R2 R3

R1 R4 R4
R11

'...
-
Ml
RUPTURE

R7 R5
' R5
Rs

R7 IR6

DPEP type ETIO type

(f(om M&ckettzie. 1 4)

FIGURE 4

Progressive loss of hydrogen during maturation is shown by development of aromatic rings from saturate rings. By convention, solid and open circles
of saturate rings (I, V, VI} indicate bonds projecting above and below plane of the drawing. Rupture of ring structur;e converts DPEP porphyrin structur
to ETTO type).

Principal biomarkers currently used in exploration geochemistry programs (figure 5) are acyclic (e.g., pristane) and cyclic (e.g., carotane) isoprenoids,
polycyclic triterpe11oids (e.g., pentacyclic hopanoids), steroids, and porphyrins. Examples of hydrocarbolil biomarker general mass spectral GC/MS !J!
ranges are givelil in and Tablel. The systematic approach by which organic compounds, such as steralile and hopane biomarkers (Elgure 6, Typical
numberi11g a11d lettering system for orgnaic compou11ds.

(a)

(bl

24 (from Mackenzie, 1984)

FIGURE 6
(a) Steranes. (b) Hopanes. Carbon site plus bond orientation form the shorthand to differentiate isomers), are described and differentiated can be
reviewed in any modern organic chemistry text. Theimportant factor for the explorationist, however, is to recognize that notations used (e.g., DPEP or
ETIO porphyrin; C29(20R) or C29 (20S) sterane) distinguish different molecular arrangements that have interpretive value.

Chemical notations,rather than depictions of organic structures or molecular arrangements, are the norm in exploration geochemistry (Table 1). This
is somewhat analogous to using different names for chemically similar, but structurally dissimilar minerals in petrology (e.g., quartz, ciuartz). In each
case, the designation is of as much use in interpretation as specific knowledge of the molecular structure.

By using a skeleton-structure shorthand, individual biomarkers can be readily "fingerprinted" and cornered. Skeletal annotations indicate:

/J bond projects toward viewer at carbon atom noted

a bond projects away from viewer at carbon atom noted

S orientation of atoms arou11d carbon is counterclockwise

R orientation of atoms around carbon is clockwise

-20 numbered carbon atom is missing (pentacyclic terpanes)

Diasteranes (rearranged steranes)

(1) 13 /J,
17a, 20s-C27 ( 2) 13/J, 17a, 20R-C21
(3) 13/J, 170, 20s-C28 (4) 13/J, 170, 20R-C28
(5) 13/J, 17, 20s-C29 (6) 13/J, 170, 20R-C29

Steranes

(1) sa, 140, 170,20s-C21 (2) sf], 140, 17a, 20R-C21

(3) Sa, 14/J, 17 /J, 20R-C27 ( 4) 5a, 14/J, 17 {3, 20S- C27
(5) Sa, 140, 170, 20R-C21
(6) through (10) same annotations for C28 molecules
(11) through (15) same annotations for C29 molecules
Monoaromat:ic ste.--anes

(1) s{J, 2os-C27 (2)s, 20R-C27

(3) Sa, 20s-C27 (4) S/J, 20S-C28
(s) sa, 20R-C27 + sa, 20s-C28 + so:, 20R-C29 + sfJ, 20s-C29

(6) 500, 20S-C29 (7) son, 20R-C,.,. + sfJ, 20R-C20

(8) 500<,20R-C29

Triarornatic stera11es

(1) 20s-C26 (2) 20R-C26 + 20s-C27

(3) 20s-C26 (4) 20R-C27
(5) 20R-C29

Tricyclic terpanes

(1) C20 (2) C2:1.

(3) C23 (4) C24
(5) C25 (6) 22s-C25
(7) 22R-C:,,; (8) 22s-C2s
(9) 2 2R- C28 ( 10) 22S- C29
(11) 22R-C29 p2) 22s-C30
(13) 22R-C30

Pent:acyclk terpanes

(1) 180< (H)-22, 29, 30 - trisnorhopane ( C27)

(2) 170 (H)-22, 29, 30 - trisnorhopane (C27)
(3) 17o ( H), 21/1 (H) - 28, 30 - bisnorhopane ( C2a)
(4) 170 (H), 21/1 (H) - 29 - norhopane (C29)
(5) 17fJ (H), 2 la (H) - 29 - normoretane ( C2.0)
(6) 170< (H), 21fJ (H) - hopane (C30)
(7) 17fJ (H), 21a (H) - moretane (C30)
(8) 17a (H), 21{1 (H), 22S - homohopane (C31)
(9) 170 (H), 21/1 (H), 22R - homohopane ( C3i)
(10) 17a (H), 21/J (H), 225 - bihomohopane ( C32)
(11) 170' (H), 21/J (H), 22R - bihomohopane (C32)

Biomarker Interpretation

BEornarkers can reveal information about organic source rn.aterial; postdepositiori.al maturation.I migration. and .alteration; .and rel.ationships among oiEs
and/or source rocks. Here we show two examples of biornarlker application.I one for ideritifying source m.aterial and one for dete11mining maturation
level.
 Identification of Source Environments Moldowan et al. (1985) examined approximately forty oil samples taken worldwide that represent (1)
nonmari11e, (2) marine shale, and (3) marine carbonate source rocks. The study's main objective was to establish parameters to differentiate
between organic source contributors. Combinations of biomarker and other analytical data were used to make the differentiations (Table 1; figure 1).
Biomarkers of C30 sterane were found to be most definitive in identifying marine-source contributions.

a b Source fype C

■ 1 Nonma11ine shale
■ Marine shale

t
1

■ 1 Marine carbonate

i2 0 .PLI\ II _l
:. 0.2 0.2-0.3 >0.3 d). 0-1 1-2 2-3 >3 0-0.4 >0.4
Steranes/,Hopanes C31IC19
c13
0- ·0/00
c12
ID15 d e

1
-a

t! :1J. ',,,.ii ,J! I If. !,-,.,"",! ..!

CPI IPriistane/Phytane Sulfur,%
(from Moldowan, ef al., I985; coortesy .MPG}

FIGURE 1

Distribution of monoaromatized steroid hydrocarbons was found to be an indicator of the amount of higher plant contributions. A low pristanephytane
content, plus high sulfur and low CPI value ( < 1.0), gave satisfactory resolution between marine carbonate and marine shale sources (Moldowan et al.,
1986).

Nonmarine Nonmarine Nonmanine Marine

vs. Marine vs. Marine vs. Marine Shale vs.
Shale Carbonate Carbonate
C30 steranes ++++ ++++ ++++ N
Sullfur(b) ++ ++ +++ ++

MA-steranes ++ ++ ++ +

High molecular-
++ ++ ++ N
weight paraffi11

Carbon NI +++ +
preference i11dex
rii

Pristane/phytane N NI ++ +

Steranes/hopa11es + + + N
Carbon isotope rii NI iii N

Gammacerane
rii NI iii ?
index
++ + De nitive
++ Strong indicator (may be affected by secondary processes).
+ Weak indicator.
1 Not indicator.

Tablle 1: Crude oil source-type indicators. Statistical evaluation of organic source parameters indicate that specific C30 sterane biomarkers give the
strongest indication of nonmarine versus marine source.

Determination of Maturation Level

Isoprenoids car11 be used to track maturation, by observing that the pristane-phytane ratio decreases as maturation effects increases. Pristane may be
interpreted to be generated more effectively than phytane, so with increasing maturation, the ratio value between tihe two decreases, More
sophisticated use or biomarkers is often applied whe11 dete11mining maturation. Isomerization, aromatization, and conversion proceed systematically
and inreversibly with increasing maturity in some biomarkers (Beaumont et al., 1985). As depicted in figure 2 (Maturation and its effect on molecular
composition. The range of occurrence of different molecules is a strong indicator of maturation.
 MoltK:ularAatios
Aromat {TRI) Prophyrins

-,- -
S ht ra n8 $(%) Nk;kel llaJJadyl

1.25

I
2;0
(ll'MIMeX6M ,19BfJ

The relative degr;ee of maturation is indicated by the vitrinit,e reflectance scale and bitumen generation curve on left), relative concentrations of
selected isoprenoid, hopane, and sterane molecules vary proportionately with increasingi maturation; the same condition occurs in selected aromatic
steranes and porphyrin biomarkers,

Tracing maturation trends, however, need not be complicated, In our example we use Chou and Wood (1986) and their study of New Albany shale
extracts. In this study of three Illinois locales, a very systematic southeasterly decrease in a bun dance of a high-molecular-weigiht aromatic compound
(Cro Hoo) could be measured (figiure 3, Maturation in aromatic extracts, New Albany shale.

(a} (b)

(A)R.,-0.41
0.5

o , :tr:+ ntbs

J
Carl

0.5

FIGURE 3

(a) Mass spectra of aromatic fraction. (b) R,e/ativ,e abundance of high molecular w,eight aromatic compounds. Note the overall shift in aromatic spectra
(a) and the marked decreas,e of aromatic molecules at m/z 546 (b) with maturation. Maturahon increase is based on vitrinite reflectance increase).
The decre.ase paralleled the maturation gradEent established through vit1rinite reffilectarice of kerogen iri the samp es. In order to fuUy classify the
arom.atic compourid, it wa.s .ana yzed by mass spectro,neters operating in tandem (MS/MS). The compound1 with a molecular weight (M1-) of 546, was
identified as a carotenoid derivative and a probable reduction product of plant-derived organic matter. The organic derivation made it a logical
candidate for a maturation biomarker in that setting (Krnge, 1986),

Migration Effects

o ,.o
Migration of petroleum falls into two regimes:

• prirnary migration, which occurs under forces expelling bitumen from its source rock
• secondary migration, which commences when buoyancy becomes a principal factor in bitumen movement

Processes in effect during primary and secondary migration leave their marks on migrating fluids. They are interpreted to be a major cause of
differences between bitumen E11 a source rock and related petr-oleum in a reservoir that complicate crude oil arid crude oil-source rock conrelatEon
studies,
Primary Expulsion
Durililg the formative years of exploration geochemistry, four general theories of primary migration were held. Bitumen was thought to migrate
possibly (1) by diffusion, (2) in solution, (3) in a prebitumen soluble (soapy) form (labile bitumen), or (4) as a separate phase in formation water.
Each theory had its apparent Iimitatio11s. Diffusion appeared not to be effective enough at larger molecular sizes to accou11t for the volume and
composition of accumulated petroleum within single fields and gathering areas. The solubility of hydrocarbons in water was too low to move the large
volumes of bitumen required during compaction dewatering. No abundance of labile bitumen was found by extraction of probable source rocks or in
petroleum reservoirs. Pore sizes were considered too small in shale source rocks to allow bitumen to migrate as discrete droplets in compaction water.

As a consequence of the incompatibilities, proposed migration processes were thought to possibly work together, or to depend upon special subsurface
conditions. Diffusion rates and solubilities might increase adequately under typical burial pressures, compaction levels, and geothermal conditions to
cause effective primary migration; they might also be enhanced by rock matrix effects. Oil phase migration, in tum, could be more effective along alil
organic wick formed by org1anic matter stringers. Proposals and experimentation continued; often with results applicable to very specific migration
conditions but not necessarily satisfactory for explaining natural acrnmulations.

As the kerogen ---t bitumen ---t petroleum evolution became clear, thus aiding evaluation of mass balance and bulk volume during transformation
(figure 1. Generation and expulsion of bitumen.

Immature
zone

Zone of incipient and gradual

2 incre.asing oil generation

Main oil generating zone

3H

4 Zone of decreasing oil

generation

Postmature for oil

(from Konlorovlch, 1984; cour1esy AAPG)

The total amount of b,-turnen generated by a sourc,e rock typically is Tar greater than that retained. The difference represents that lost F-rorn th,e source
rock by rni"gration. SB indicat,es syngenetic bitumen. SRB indicates syngenetJc residual biCurnen), a firactu1re expuEsion hypothesis arose for- primary
migratiori (Momper, 1978). Fracture expulsion molie adequately explairied the effectiveness of primary migration the conclusiori was that oil-pti",ase
bulk movemerit could occur along fracture planes induced by bitumen overpressuring. This hypothesis is fiindingi current favoli amo119 many in
explaining primary migr·ation for large volumes of bitumen.

An alternative to overpressuring and oil-phase bulk-movement has recently been eluddated; it calls upon phase behavior of gases and liquids under
subsurface conditions to be the drivEng force of rnigratE011 (England et al., 1987). By U1Es method, neairly all petroleum flow in the subsurface is
considered to occur as bulk transport, driven by gradients in petlioleum fluid potential. Capillary forces dominate; diffusEon is only effective nea1r trle
source rock and in lighter components. Consequently, overpressure fracturingi of the source rock is riot required to move petroEeum liquids and gases
in the compacting water syste.rn. Be.cause all migration is interpreted to be part of a co11tinuurn responding to buoyancy and water flow En compacting
sedEments, the distinctions typically made between primary migration, secondary migration, and reservoir accumulation are generalEy unnecessary
(Mackenzie et al., 1986).

Older hypotheses still have their followingi under certain geological co11ditions. Foli example, Meissner (1978) concluded that oi -phase migration was
possible, as in the Bakkan format.ion, whe.n a continuous bitumen-wet network was estabmished in the rock. Aoyagi and Asakawa (1980) concluded
that if bitumen maturation .and I.ate-stage compaction dewatering of argillaceous sediment occurTed concurrently, as interpreted for the Akita area,
Japan, large volumes of carrier water would be availabme to effect primary migratEon by solution (..Ei.gure 2 Plot ofcornpact,-on zonesr oil generat,-onr
and geoChermalgradiencs.

Geothermal Temperature (°C}

100 150
200 250

:GeneratlOfl.

T.smperatut
f
Early Compaction Zone
... otOil -:
1000
E' t:-_-, .-- _-,---;-=""<,--ct"'-.:::---:---:-----:--r ,--_ ,-- .- ---- ,-- t-,--. ,---_· 1, 1270
..c
li ompaction zone
tl> 2000
D,
tci>
·=>
Cl:l1
3000

4000,
Primary rnigration with late cornpaction water could occur wh,ere the geothermal gradient brings sediments into catagen,esis in the 1270-2620 m depth
range). Khavari-Khorasani (1984) also interpreted oil-phase primary migrat:mo11 to be possible during early maturation.r as recorded by bitumenite in
Uinta basin, Utah, when veryrich source rocks remeased immature lipid-rich bitumen.

RegardEess of ttie method of primary migratEon, it is clear that compositional modification occurs between the time bitumen begEn.s primary migratior'I
and the time it enters a carrier bed. These cti.anges are most compatEbEe with oil-pti.ase. movement.

General trends during primary rnmgration (figure 3,.. Migration effect onbiturn,en composition. Bt-tumen are modin"ed in diffe,r;ent rnanners by different
rock matrices and organic content.

Migration Effects
Source Reservoir

extract oil

FIGURE 3

Theneteffect, however, is in incrnased hydrocarbons relative to resins and aspha/tenes) are as follows:

• More-polar compounds are held back preferentially to less-polar compounds (asphaltenes > resins > aromatics > saturates).

"' Heavier bitumen molecules are held back preferentially to lighter molecules ( C30 > C20 > C10).
• Isoprenoids are held back preferentially to their straight-chain isomers (iCrn > nC19).
• Source rocks commonly show a depletion gradient in bitumen from interior to exterior in the vicinity of potential carrier beds.

However, migration by diffusion processe.s during early maturation (Leythaeuser et al., 1984) also can account for some of these compositional
differences between bitumen and petroleum in interbedded shale-sandstone sequences. Difference.s also are attributed to diffusion separation in
source rock, which lets the more mobile compounds escape from closed pores (micropores) to open pores and then exit the source rock (Sajgo and
Maxwell, 1983; Lindgreen, 1985). Selective adsorption and molecular sieving of different hydrocarbon molecules in dense argillaceous sediments may
cause compositional changes during primary migration (Lindgreen, 1987), as does absonption by organic matter in the rock (Whelan et al., 1984).

Secondary Movement
Bitumen that enters the secondary migration cycle continues to be modified as it moves by buoyancy and hydrodynamic flow as droplets. Exchange ot
more-polar, thus more water-soluble, compounds occurs across the droplet oil-water interface so that migrating bitumen becomes further depleted in
the more-polar asphaltenes and resins and, to a lesser degree, aromatics. Lighter molecules also move more effectively than heavy through pore
networks, and migrate faster. Once in a reservoir, however, lighter hydrocarbons may become depleted relative to heavier by going preferentially into
solution during water washing (Palmer, 1984a. Light hydrocarbons also can be depleted by penetrating a reservoir seal more effectively.

lnteirpretation Approach
To tie crude oil back to its organic source, it is essential to compensate for primary and secondary migration effects. Common approaches in
comparing bitumen and crude oil data include selecting properties or compounds that are little affected by migration, or using parameters that permit
migration effects to be estimated or bypassed altogether. Three of many possible choices are noted here.

Carbon Isotopes of the Aromatic Fraction Bonilla and Engel (1986) studied the chemical and isotopic redistribution of hydrocarbons during migration.
In laboratory simulation studies it was determined that aromatic hydrocarbons do not show significant 13C fractionation during migration. Therefore,
comparison of :: ratios in aromatic hydrocarbons of bitumen extracts and petroleum offers one general correlation approach.

Comparison of Asphaltene Composition in Oils and Extracts Pelet et al. (1986) traced the general evolution of asphaltenes and resin from kerogen and
the effects of migration on them. The conclusion was drawn that if asphaltene molecules represent moieties (large fragments, halves) of kerogen,
then they should have similar compositions in bitumen and petroleum even though asphaltenes have been held back preferentially during migration.
Restated, asphaltene molecular composition should not be greatly altered by migration although the asphaltene concentration in petroleum is depleted
compared to source bitumen. One method used to make the comparison is to pyrolyze kerogen and asphaltenes and compare similarities in
pyrolysates (Py/GC/MS).

Comparison of Specific Biomarkers Riolo et al. (1986) studied the distribution of aromatic steroids in geological samples and evaluated their use as
geochemicaI parameters. Migration and other alteration effeots can be minimized by selectingi those biomarkers mo.st resistant to outside influences.
Specifically, certain large aromatic biomarkers (e.gi., monoaromatic steroids) can provide adequate discrimination to pair source rock and crude oil.
Other related molecules can be used to approximate or confirm migration conditions and effects (Carl son and Chamberlain, 1986).
Biodegradation and Alteration of Crude Oil

...

Crude oi I in reservoirs is subject to degradation and alteration by a variety of natural processes . [_§ l (Degradation of petroieum .
.Ei_gJJ

<: :
g
o- !Bacteria

Biodegradation

+
Oxidation I
Evaporation
Near
S1.r1face

robitumen

-- APII Gravity c,.

(Adapted from Miner, et al, 1977)

FIGURE 1

Once petroleum has accumulated in a reservoir it is subject to a variety of factors which can alter its original composition. Factors range form bacterial
degradation at near surface to continued maturation with deep burial) shows that the end product of intense thermal alteration of oil is methane gas
and pyrobitumen. We also lilote the effect of deasphalting, which occurs in the presence of a light solvent or gas and leads to a lighter oil and a
heavier precipitate and water washing which modifies composition of alil oil by preferentially removing lighter and more soluble. Here we review
biogenic near-surface effects that alter petroleum composition (Connan, 1984).

Petroleum can be biodegraded or altered whenever it migrates close to the surface or is exposed to oxygenated water recharged from the earth's
surface. Water-bonne bacteria selectively alter petroleum composition by first attacking the alkanes, starting with nonmal alkaliles, then movingi on to
simpler cyclic and branched alkaliles, and finally on to large multi-cyclic alkaliles and aromatics (Eigure 2, Biodegradation of crude oil, Duval County,
Texas.

Biodegredalicn,
Sequence Piedras Pirttru;
10
Pr/Ph 4.1 45.S API

25

io
a>
a,
3

AJUJ
Jk-- , i
26.3A.PI

'"-a; 11 1 -•L
" w.
::E' 4 lGover met'lt Wells

E
t I I -.il

FIGURE 2
Least altered oil is denoted 1; most altered is 4. Early biodegradation of whole oil is indicated by progressive loss of nonmal parafins, isoprenoids, and
other prominent saturate compounds in the C13-C17 range). This systematic progression is often used to classify biodegradation level (Tablle 1). The
general effects of biodegradation on petroleum are summarized in .Eigure 3 (Effects of biodegradation on petroleum properties.

1- GASES IC1 - Ce) Iii,

2- GOR(GAS/OIL RA1110) \ (from Connan. 1984)
- GASOLINE RANGE (CG - C15) \
4· API GRAVITY Iii,
5- IIISCOSITY ;ti
6- CHANGES IN GROSS COMPOSITION OF C1,;+ COMPOUNDS
atkanes "'-
aromallcs 1'
NSO's OOITIP,C:Mmds. JI'
asphalt8nes JJI
7- SULPHUR CONTENT ;ti
S- NITROGEN OONCTENT ;ti
- \/AND N; ;ti
10 OPTICAL ACTIVITY If
allkanes ,t'
11· POUR POINCT\
12 5
13c
whoki oil ,t
alkane,> ;ti
aromalic:s ==-or \_
asphaltenes
"1-2- Cl-lAN(JES IN 01LTYPES
paraHlnlc oil ---------•napt,1110,nic oils
paraffwlit:: QI" paraffinic>-rlWIPh1henic: Qiils.,. aa-omant:-nsphthenic Qil
parat11nlc condoosates-------------naphlh8t11c COl"ldensates
oondensates-------------------------1►light oils
aromalic: - lntennedla•.0 oils. ----aromatlc-asptialdc oUs

FIGURE 3

The direction in which change occurs wfth biodegradal:ion is indiCated by the arrow).

Level Che1nical cornposition Extent of

biodegrc1datio11

1 Abundant n-alkanes Not degraded

2 Light-end n-alkanes removed Mino,-

3 > 9% n-a!kane removed

Alkylcyclohexanes and alkylbenzenes Moderate

4 rem1oved; .acyclic isopll'"enoid alkanes
and naphthallene reduced

Isoprenoid alkane and

5 met::hylnaphtlhalene.s ,-emoved; selective
rem1ovall of C2-naphthallenes

6 1
C1_4-C11b Bicyclic .alkanes removed Extensive

::> 50% (20R) - Sa(H), 14.o(H), 17o(H) Very extensive

7
ster.a ne.s rem1oved

Distributiion of steranes and tri.a romatiic Severe

8 steroids altecedl; demethylated hopanes
aburidant

INo ster-anes; demethylated hopanes

9
pll'"edomi nate
Table 1: Progressive biodegradation of crude oil. The 1-to -9 level of alteration is an arbitrary scale based on general response of mature paraffinic
oils to bacterial alteration.

When using biodegraded oils for correlation purposes, it is essential to work with compounds resistant to bacterial attack. Asphaltenes and resins are
most resistant to biodegradation, with aromatics only slightly less so. Aromatic compou.,ds are generally selected over the nonhydrocarbons because
of their greater amenability to analysis a"d less complex molecular composition. Two approaches using, biomarkers are 01.1r examples.

Use or Aromatic and Very Resistant Polycyclic A!kane Compounds Williams et al. (1986) studied biodegradatio" in south Texas Eocene oils for its
effects on aromatic hydrocarbons and other biomarkers. The study determined that large polycyclic aromatics were preferentially resistant to
biodegradation over simpler aromatics. Similarly, steranes, aromatized steranes, diterpanes, and tri- and tetracyclic terpanes showed no alteration in
highly degraded oils, and could be used to ascertain the kindredship of related oils in vario1.1s stages of biodegradation (figure 4,

"
Hoffma
2

Sam: ]I
W76 _§
1 7
t
Retention time (min) i 411
Retent:n time {m )

figure 5, and figure 6, Comparison of selected resistant biomarkers, Duval County, Texas oils. ( 4) Triaromatized steroids ( 7 231 ).

(5) Monoaromatized steroids( 253). (6) Bicyc/ic and tricyc/ic diterpanes ( 191). GC/MS analyses show the persistence of these compounds
through various stages of biodegradation (e.g., 2 < 5 < 7, after Figure 2). Strong oil correlation is apparent among these biomark,ers).
Use of Surviving Biological Structures and/or Carbon Isotopes Seifert et al. (1984) looked in detail at polycyclic structures in biodegraded seeps from
western Greece in an attempt to correlate them into source-related families and with oilfield samples. The study determined that even tihough
saturated and aromatic compounds are biodegraded, remnants of polycyclic aromatized sterane and triterpane molecules do retain their biological
identities during alteration and can be used for correlation (figure 7 and .Elgiure 8, Comparison of terpane r-7
191) biomarkers, Greece.

:LJJk
Llk
Marathopolis Baou i
Oil - Soa ed Roell; Extract Oil-Soaked Rock Ext aet
Group
424 I Group Ila

:: , -
449

OilSoQp
Group I

Mg a
Killlnl

44B
LJ1L g a
Gr'ooplla
446

Tritou
Oil Seep
Gr4;Klp lib
447

KCaotanld<oonlosnale, - 2500m

,Gnroup Ila

(from Seifert. et al.• 1984) GC Time Direction

GC Time Direction
(from Seifert, et al., 1
9641

FIGURE 7
FIGURE 8

Similar pattems are apparent within groupings.

Correlation between Group Ila seep and condensate samples also is apparent). Terpanes, too, can be used for determining maturation. With a
multiparameter approach, including carbon isotopes, the seeps were divided into families I and 11, with family II related to the K.atakolon condensate.
(No seep was interpreted to be related to the undegraded Prinos oilfield sample, family III.

Less Common Source Rocks

The majority of geochemical principles used in exploration today were built around shale source rocks. The association is natural; these fine-grained
sediments can be organically rich and generally show strong geological and geographical associations with oil and gas fields. On the periphery,
however, are other source-rock types. Carbonate and associated evaporite lithologies have been sources of petroleum at many localities even though
they generally are leaner in organic content than shales. Coals, on the other hand, are very rich organically but commonly only rate marginal
potentials to generate crude oil. We look further at these rock types to see how exploration geochemistry can apply to them.

Carbonate/Evaporite Lithologiies
Middle East oil production attests to the prolific nature of some carbonate/ evaporite intervals as petroleum sources. Still, the low organic content of
most limestones and anhydrites has led to the contradiction in thinking of organic-rich sediments and carbonate/anhydrite sediments being source
intervals. To compensate, partial adjustments are generally made during geochemical evaluations by giving carbonate/evaporite rocks lower threshold
values on source-rock scales (e.g., fair source potential: shale 0.5-1.0% TOC, carbonate 0.3-0.5% TOC). A question naturally arises: Is such an
adjustment realistic or just a matter of making geochemistry fit the picture?

At least four factors support the concept that carbonate/ evaporite intervals have natural characteristics that permit them to be source rocks even
through they do not match the richness standards we apply to shales. These factors (1) type of organic matter deposited, (2) bacterial enrichment
during earlly diagenesis, (3) relatively high sulfur content, (4) and effect of lithology are the focus of this discussion (Murris, 1984).

Organic Matter 'fype

a, Organic matter associated with carbonate and evaporite depositional environments generally is enriched in nonterrestrial (oceanic,
bacterial) carbonaceous material relative to other marine environments. Evaporites, forming when the influx of water and incorporated
terrestrial material is low and circulation restricted, favor Type II derivation (e.g., Tannenbaum and Aizenshtat, 1985). In carbonate
platform environments, open marine conditions favor the progressive increase in deposition of oceanic orgianic matter away from the
shoreline and sources of terrigenous matter (e.g., Rafalska-Bloch and Cunningham, 1986).

Bacterial Enrichment
a, The enrichment effect of bacterial degradation under anoxic conditions observed in a number of carbonate/anhydrite studies (e.g., Cannan
et al., 1986; Brukner-Wein and Veto, 1986) results in a corresponding sourcepotential increase in carbonate/anhydrite deposits during
very early diagenesis.

Sulfur Content
• Anoxic biodegradation leads to the generation of hydrogen sulfide (H25) In carbonate/anhydrite environments there are seldom many
metallic ions available to react with the H2S and remove the sulfur (e.g., pyrite formation). Sulfur enrichment in organic molecules
decreases the activation energies (cf, the Arrhenius eciuation), which permits early evolution of bitumen (Tannenbaum and Aizenshtat,
1984). Increased sulfur content also increases relative yield of bitumen from kerogen (Connan et al., 1986).
Lithology Effe,ct
■ Carbonate lithologies give up bitumen more effectively than argillaceous lithologies (Tannenbaum et al., 1986). Whether the cause is
retention by clay adsorption in shale or increased generation in a carbonate substrate, increased source potential favors carbonate over
argillaceous rocks.

To summarize, carbonate/evaporite rocks merit a discrete source-potential perspective. Natural circumstance.s favor bitumen generation in
carbonate/evaporite lithologies over shales given similar organic richness and maturation histories. The potential, then, for carbonate/anhydrite rocks
to yield petroleum is similarly enhanced, provided, of course, that organic content is great enough to induce primary migration (e.g., expulsion).

Coall
Coal inherited the stigma of being a poor source rock for petroleum particula11ly crude oil, because of only weak association with oil production. This
lack of association, however, should rn1ot have been considered a criterion of source for a number of reasons:

,., Most coals of economic interest are in higher bituminous and anthracite ranks the higher the rank, the more BT!Js produced. These coal
ranks are attained at the upper end of catagenesis and during metagenesis as far as bitumen generation is concerned (%Ro> 1.0).
Higher ranks of coal, then, are relatively incompatible with the preservation of crude oil. Furthermore, coal is generally mined at the
surface, where shallow oil accumulations would have been lost. Further, accumulation of petroleum downdip from coal deposits will have
experienced even more intense maturation.
• Much coal mined is of Upper Paleozoic age, which by nature tends to be more gias-prone in carbonaceous material tihan many more recent,
less mature (poorer quality) coals,

■ Coal, generally deposited in swampy, terrestrial, and often antiseptic (tannin) conditions, lacks the anaerobic bacterial alteration and
enrichment of orgarn1ic debris so critical to oil-prone residue. In addition, this same depositional environment is not generally conducive to
the development of good adjoining reservoir beds,

The stigma of poor oil-source potential probably has been fostered further by the categorization of Type III kerogen (vitrinite) as gas-prone and its
general association with humic coals. There is, too, a common tendency to over-generalize"a coal is a coal is a coal" so that different varieties (i.e.,
sapropelic coal versus humic coal) are not afforded separate evaluations.

A number of investigators have demonstrated that many coal deposits now have or once had oil-generation potential (Thompson et al., 1985).
Inclusion of liptinic kerogen is the principal requirement for an oil-generative coal, Bailey (1981) demonstrated the potential of spores and cuticles in
coals to generate waxy-crudelike pyrolysate (£igiure 1, Gas chromatograms of pyrolysates (py/GC) from selected coaly materials.

{c)

llIilllllL
lfromB•k>y.,98'1

FIGURE 1

(a) Wood/vitrinite. (b) Spore coal. (c) Cuticle coal. A very gas-prone nature is exhibit,ed by woody material; pyro/ysate contains products less than
C12'Coals rich in spor;es and cuticles have a mor;e oil-prone nature; they can produce pyro/ysates extending well beyond C25J. Durand and Paratte
(1983), in documenting1the source potential of coals, showed that organic matter in coal passed through the same bitumen-generating pattem as
other source rocks (Elgure 2, Rock-Eva/ pyrolysis analysis of coals around the world.
(a) Generativ,e potential( )- (b) Realized potential (Si). Coalification band shows the same mattJration pattern as other productive kerogens with
maximum bitumen production near 435° e, Their studies also failed to support the contention that coal beds do not expel bitumen, if formed, because
of their microporosity and plasticity.

On a worlldwide basis, coals can be demonstrated as sources of crude oil. High-wax oils associated with coals occur in the Saar region, Germany, in
central France, and in the Midlands, Great Britain {Tissot and Welte, 1984). Crude oils of the Mahakam delta, Indonesia (Durand and Oudin, 1979),
Officina area, Venez.uela (Banks, 1959), and Gippsland basin, Australia (Thomas, 1981) all are in close association with coal source rocks. Oil potential
of the remote Norton basin, Alaska, is based on resinite-rich coals of the region (Waples, 1985), though to date no oil discoveries have been made
there,

The primary concern, then, in evaluating coals as potential source rocks is to thoroughly evaluate the nature of orgianic matter irn1the rock, particlllarly
the types of kerogen present and their level of maturation {Hue et al., 1986).
Geochemical Prospecting
The search for underlying oil and gas by means of surface sampling has its supporters and its detractors. Hunt (1979) observed that nearly all major
companies had tried geochemical prospecting but none had shown significant success; few continued to carry on major efforts in such field programs.

Most mathematical evaluations indicate that any technique based on the diffusion of light hydrocarbons from under11ying petroleum accumulations has
little chance of success. In all likelihood, this statement is valid except for reservoirs very close to the surface, or those with poor seals. One mitigatingi
factor is the recent improvement in detection capabilities. Modem field analytical instruments provide up to an order of magnitude or more
improvement in detection and resolution over earlier models.

ff geochemical exploration programs are to prove successful, their most promising approach is to look for leaky reservoirs and microseeps that
demonstrate a surface expression along natural migration pathways (.E[gure 1 and figure 2. Surface prospecting by gas detection, San Joaquin basin.
California).

Those that promote the use of microseeps as an exploration tool suggest that the use of surface geochemical detection of microseepingi hydrocarbons
is a logical extension of the use of macroseeps in the search of oil and gas. Surface geochemical prospecting methods are most effective as part of an
integrated program that includes geological and geophysical methods. Surface geochemical prospecting is a good complement to seismic. The
acceptance of geochemical prospecting as an exploration tool lies in the fact that surface geochemical anomaly. as a product of leakage from the
petroleum accumulationr does exist:.

SW !',IE
Sea
Feet
1000 30

2000
ITCHEGOIN
3000

4000

5000
15

0000
18

7000
2.100
8000 Lost HIia
oll field
2-400
9000

11

200 I
I
I
I
I ' Propane
I
I
I Methame
i H;ydrogen
22
I
•
I

II
!ii: I
'
n. I
I 1.200
::i
'
C: I
IJ> I ll.
I ll.
I

e
(ll
c c C:
C) nll. . I ' l l
"O w
:r>:
C:
m
.. . .:
. c
(ll

a. ::i
:. e
a.

/from JonesW1d Drmd, 1:983; courtasy AAPG)

FIGURE 2

An increase in detectable gases is apparent across the Lost Hills field. The sample profile was obtained by soil-gas sampling in which gas was drawn
from augered and packed holes). (Jones and Droid. 1983).

Prospecting for leakage and microseeps is done by looking directly for hydrocarbon enrichment and associated increases (e.g., methane-consuming
bacteria, see Brooks et al., 1986). Traverse or grid sampling is commonly carried out in the prospecting area so that background levels can be
established and anomalies determined.
Concepts
A reservoired petroleum pool Es an active mass of hydrocaribon molecules. No seaI rock is comp etely impermeable. A network of microfr-actures exists
in the sedimentary layers above the petroleum pool. Small size hydrncarlbon molecules like C through Cs move vertically through the microfiracture
system and ..-each to the earth's sulrface. A colloidal mechanism is responsible for the migiration of microseeps. A 1microseep is defined as the
migration of,Ct -,Cs hydroc.a rbon from a subsurface accumulation by a process of vertical ascerit of coUoidal size particles through a microfracture
system overlying a petroleum deposmt. Microseeps generate positive hydrocarbon anomalies on the surface that tend to overlie all or a large part of
the petroleum deposit tr-om which they 01rEginate. Microseeping hydirocalrlbons are pr-esent in soils which are sampled. Ider'!tification of the areas wEth
high concentration of hydrocarbo11s in the surface soil are mapped and related to the subsurface accumuilatio11.

Interpretation
Adsorbed gas surveys are used as both as reconnaissance surveys and as a detailed survey tools.

Reconnaissance Survey
The objectives of a reconnaissance survey are:

., To identify interesting areas,

• To select most valuable concessions .

•, To differentiate between oil-prone and gas-prone areas.

e, To diffeire11tiate between therimally immature a11d mature areas.

Detaill Survey
The objectives of a detail survey are:

• To identify drilling prospects.

• , To rank and prioritize drilling prospects,

., To assist in deciding which prospects need not to be drilled .

• , To define the areal extent of an oil and gas accumulation to assist orderly field development.

Sampling1Techniique
The soil samples are generally collected from a depth of 3 to 10m. The sample in this case is a soil/ sediment core. The soil core samples are
collected from holes dri lied by hand augers or power augers with the help of a sample catcher at the base of the pipe.

Sample Analysis
The adsorbed gases are desorbed from the soil sample (2-3g) with the action of orthopohsphoric acid under vacuum in a preparation system called
desorber and then analyzed by a gas chromatograph to get the chemica I com position of the microseeps. A typical gas chromatogram of microseep
analysis shows the presence of methane to pentanes hydrocarbons.

Advantages
Petroliferol!Js Nature of Microseeps

The composition of gases desoribed from soU samples Es ir'ldicative of the petroliferous nature. If the gas contair'!s on y methane or methane and some
negligEble ethane., the microseep is not of petrolmfelious nature. If the microseep sample contains the entire spectrum of hydrocarbons from methane to
pentanes, this indicates the petroliferous nature of the microseep. The hydrocarbon composition trend C1 > C2 > C3 > C4 > Cs.
Catagenetic OrEgin of Microseeps

A ratio of methane and ethane (

. , )1less ttian 16 and a ratio ,c. less than 10 indicate ttie catagenetic origin of miciroseeps .

Type of Petroleum +s.c,

A ratio of f:, less than l.3 and a ratio of : less than 0.8 indicate association of microseeps with liquid hydrocarbons.
Genetic Conrelation of Hydrocarbon Constituents

The concentratEon values of methane and ethane., ettiane and propane.,. p1ropane and n-butane and n-butane and n-pentane are cross plotted. A lir'lear
relation between the two hydrocarbons indkat:es that these hyd1rocarbons are genetic.ally corr-elated, emanating from same petroleum depositi and not
altered by any type of secondary processes like separation migration or biodegradation. This ensures high reliabUity of microseep anomalEes.

Dellineation and Ranking of Surface Hyd1rocarbon Anomalies

In ordeir to identify the areas of anomalously hEgh concentration of surface adsorbed (microseep) hydrocairbonsr the concentrations of methane,
ethane, propane, butanes and pentanes are contoured separately. In on:iier to define meaningful anomalies, background mean (m) and standard
dev ation (u) are computed by using availab e methods. Contour maps are the iso-concentration maps of methane to pentanes. In the iso
concent1ration maps, the startEng contour is generally equal to ttie background mean plus one stc1nda1id deviatEon (m + a) of that particular
hydrocarbon and the contour interval is the standard deviatEon (o-).. Most investigators define values as anomalous if t:rley have conce11trations gre.ater
than m plus some multiples (usually 2 or 3) of a-. This is the anomaly threshold value. Although m 2o- or m + +
3a- ace considered good indicators
of petroleum.,. still better criteria (> m +
3u) may be employed to resolve the surface hydliocarbon anomalies with increasing levels of confidence irn
predicting subsurface accumulation. The greater the va ue of m, ttie stronger the anomaly. The evaluation criteria may vary with basin, block, field,
objective of survey and will be guided by the experience of the skilled interpreter. Ethane, propane and butane anomaly maps are generally used for
evaluation purpose.