WATER ANALYSIS METHODS

Portions of this page were contributed by Susan Johnson, www.opuspetroleum.com.

Laboratory water analysis is an essential measurement required for accurate water
saturation calculations from log data. Water samples are collected from drill stem tests or
produced fluids. In the case of produced fluids, the water should be captured from the flow
line and separated later from the oil. Samples from separators or treaters may not be
representative of formation water due to contamination. Samples from drill stem tests are
usually taken at the top, middle, and bottom of the test recovery. The bottom sample should
have the least contamination from drilling fluid invasion. The top sample will have the most
contamination.
Laboratories usually measure from 9 to 15 of the individual ions in a water sample, recorded
in milligrams/litre (mg/l) or grams/cubic meter (g/m
3
). These two sets of units are equivalent:
1 mg/l = 1 g/m
3.


The cations (positive ions) are measured by ion chromatograph. These are Sodium (Na),
Potassium (K), Calcium (Ca), Magnesium (Mg), Iron (Fe), and sometimes Barium (Ba),
Strontium (Sr), or Boron (Bo). The anions (negative ions) cannot be measured by ion
chromatograph so Chloride (Cl) and sometimes Iodide (I) and Bromide (B) are still measured
by titration. Bicarbonate (HCO
3
) and Carbonate (CO
3
) are calculated from the volume of acid
required to reduce the pH to 8.3 (for CO
3
) and 4.5 (for HCO
3
). Sulphate (SO
4
) is calculated by
adding a volume of Barium Chloride and then measuring the turbidity of the solution. The
sum of all of these measured ions becomes the calculated total dissolved solids (TDS).

They also measure, in a routine analysis, the pH, relative density, and resistivity (Rw) of the
water sample. The Rw is measured in ohm-m and they will record the temperature at which
it was measured. This temperature will be used to adjust the measured Rw to a common
"laboratory temperature", usually 25 Celcius or 77 Farenheit. Some labs use different
standard temperatures.

Some labs also calculate mmol/l (or moles/m
3
). Mg/l (or g/m
3
) divided by the molar mass of
the ion equals mmol/l (or moles/m
3
). Since mg/l is the same thing as g/m
3
, mmol/l is the same
thing as mol/m
3
. Molar mass is derived from the atomic weight of the ion on the Periodic
Table. For instance, the atomic weight of S is 32 and the atomic weight of O is 16, so the
molar mass of SO
4
= 32 + 4 * 16 = 96.

Most labs calculate milli-equivalents (MEQ). MEQ equals mmol/l or moles/m
3
multiplied by
the valence or charge of the ion. SO
4
has a negative charge of 2 so 1 mmol/l of SO
4
equals 2
MEQ of SO
4
. Sodium (Na) has a positive charge of 1, so 1 mmol/l of Na equals 1 MEQ of Na.

Usually when people use the terms ppm or parts per million with respect to the salinity of
water, they really mean mg/l. The difference is that ppm = mg/l divided by the density of the
water.

The logging company charts that convert ppm to Rw are based on ppm of pure NaCl. This is
because the most common formation waters found in the world are NaCl based. These
charts will give you the wrong Rw if the fluid is a mud filtrate which is mostly Na
2
SO
4
or if the
fluid is Sodium Bicarbonate type formation water.

The diagram at the bottom of the water analysis is called a Stiff Diagram. It is a graphical
representation of the different ions. The shape of the Stiff Diagram can become a
fingerprint which can allow us to distinguish whether the fluid is formation water or an
introduced fluid, and can often distinguish the zone from which the formation water was
produced.

SAMPLE WATER ANALYSIS REPORT

Water analysis report from a drill stem test recovery, showing chemical analysis, calculated
and measured water resistivity, and Stiff diagram of chemical analysis. This is a fairly salty
formation water with salinity of 146,000 parts per million (ppm) and a resistivity of 0.066 @
25C.

WATER SAMPLE CONTAMINATION
Contamination of water samples by drilling fluid invasion is common and the Stiff Diagram
helps to spot this problem. For instance, a typical gel-chem type mud filtrate recovery will
have Na in MEQ divided by Cl in MEQ of 5 or greater. Most contamination problems require
some experience and a supply of Stiff Diagram fingerprints that are reasonably consistent.
For more information on fingerprinting water recoveries, please contact Opus Petroleum
Engineering Ltd., www.opuspetroleum.com.

The Canadian Water Resistivity Catalog is well screened, but field samples may be
contaminated. The following rules of thumb are useful in detecting mud filtrate
contamination or meteoric water recharge.
1. Mg/l and ppm are approximately the same thing except in very saline waters.
2. Most gel-chem mud filtrates are usually from 3000 to 8000 mg/l TDS.
3. When the log header says gel-chem mud, they might mean gyped-up mud. Gyped-up
mud usually has soda ash added to compensate for drilling through anhydrites. Gyped-up
mud filtrates are usually from 10,000 to 25,000 mg/l TDS.
4. KCl mud filtrates are usually from 30,000 to 50,000 mg/l TDS with lots of K and lots of Cl.
5. Potassium Sulphate mud filtrates are usually from 50,000 to 80,000 mg/l TDS with lots of
K and lots of SO4.
6. Salt-saturated mud filtrates are usually 300,000 mg/l or higher.
7. Generally speaking, formation waters increase in salinity with depth but see #12.
8. Each zone should have a unique formation water fingerprint or Stiff Diagram unless it
is hydraulically connected to another zone.
9. This formation water fingerprint may change with location in the basin.
10. Most formation waters have a milli-equivalent Na/Cl ratio of 0.6 to 1.2.
11. Many formation waters are fresher than expected as they are affected by fresh water
recharge from the surface. These recharge waters have a distinctive fingerprint which is
high in bicarbonates and the milli-equivalent Na/Cl ratio is usually between 2 and 3. These
fresh waters have been found in formations as deep as the Devonian and can under-run
more saline formation waters.
12. Never rely on one water analysis as being representative of the formation water in a
particular pool and field. Try to find at least three water samples in your pool that have
formation water characteristics, are close to the same TDS and have similar fingerprints.
Then compare the Rw on your samples to the ones in the catalog.

Agat Lab in Calgary uses a "Smart Chart", incorporating these rules, to help identify clean
water samples from those contaminated by mud filtrate or other chemicals.


This crossplot of TDS versus the Na/Cl ratio helps check for contamination. Data point 1 is in
the formation water catagory. Point 2 is either naturally high in bicarbonates or
contaminated by some gyp-based mud invasion. Point 3 is mostly gel-based mud filtrate.

WATER RESISTIVITY - SALINITY RELATIONSHIPS
The resistivity of a water sample can be calculated from its chemical analysis. To do this, an
equivalent NaCl concentration must be determined based on the ionic activity of each ion.

Enter chart with total dissolved solids (TDS) concentration of the sample in ppm (mg/kg) to
find weighting factors for each ion present. The concentration of each ion is multiplied by its
weighting factor, and the products for all ions are summed to obtain equivalent NaCl
concentration.
WSe - EQUIVALENT NaCl WATER SALINITY FROM WATER ANALYSIS
1: TDS = SUM (UINI)
2: WSe = SUM (IONi * FACTRi)
WHERE:
TDS = total dissolved solids (equivalent NaCl ppm)
IONi = ion concentration of ith component (ppm)
FACTRi = multiplier factor for ith component (ppm)
WSe = equivalent NaCl concentration (ppm)

NUMERICAL EXAMPLE:
Assume formation-water sample analysis
460 ppm Ca,
1400 ppm SO4
19,000 ppm Na plus Cl.

Total dissolved solids concentration is 460 + 1400 + 19,000 = 20,860 ppm.
Entering the chart above with this total solids concentration
Ca multiplier = 0.81
SO4 multiplier = 0.45
Na+CL multiplier = 1.00

Equivalent NaCl concentration
WSe = 460 0.81 + 1400 0.45 + 19,000 1.0 = 20,000 ppm.
RW@FT_1 - Water Resistivity from Salinity
After converting a water analysis to equivalent NaCl concentration, the RW can be
calculated:
2: FT1 = SUFT + (BHT - SUFT) / BHTDEP * DEPTH)
3: IF LOGUNITS$ = "METRIC"
4: THEN FT1 = 9 / 5 * FT1 + 32
5: RW@FT = (400000 / FT1 / WSe) ^ 0.88
WHERE:
BHT = bottom hole temperature (degrees Fahrenheit or Celcius)
BHTDEP = depth at which BHT was measured (feet or meters)
FT1 = formation temperature (degrees Fahrenheit)
RW@FT = water resistivity at formation temperatures (ohm-m)
SUFT = surface temperature (degrees Fahrenheit or Celcius)
WSe = water salinity (ppm NaCl)
COMMENTS:
Use this relation if salinity is known from laboratory measurements.
NUMERICAL EXAMPLE:
1. Salinity to water resistivity.
RW@FT = (400000 / 102'F / 200,000 ppm) ^ 0.88 = 0.031 ohm-m @ 102'F
(rounded to three significant digits)
2. Water resistivity to salinity.
WSe = 400,000 / 102'F / ((0.250 ohm-m) ^ 1.14) = 19,000 ppm NaCl
(rounded to three significant digits)

Water resistivity - Temperature - Salinity relationships
WSa - Water salinity from chloride content:
6: WSa = Cc1 * 1.645
WHERE:
Ccl = water salinity (ppm Cl)
WSa = water salinity (ppm NaCl)
COMMENTS:
Use this relationship when chloride content of the water sample is known. Usually Cl content
is derived approximately at the well site from a drill stem test recovery. It is useful as a first
approximation until the water sample is analyzed more accurately at a laboratory. The
relationship is for pure NaCl solutions and the factor may be higher or lower if other ions are
present.
NUMERICAL EXAMPLE:
1. Chloride concentration to salinity.
WS = 11,600 ppm Cl * 1.645 = 19,000 ppm NaCl


"META/RW" SPREADSHEET -- Water Resistivity Calculations
This spreadsheet calculates RW at formation temperature using 5 different methods.

Calculate RW at formation temperature. Metric and English Units


Sample of "META/RW" for calculating water resistivity from various methods.