Chapter 24

Properties of Produced Waters

A. Gene Collins,* U S. DOE Bartlesville Energy Technology Center**
Introduction and History
Early U.S. settlements commonly were located close to
salt licks that supplied salt to the population. Often these
salt springs were contaminated with petroleum. and
many of the early efforts to acquire salt by digging wells
were rewarded by finding unwanted increased amounts
of oil and gas associated with the saline waters. In the
Appalachian Mts.. many saline water springs occurred
along the crests of anticlines.
In 1855 it was found that distillation of petroleum pro-
duced a light oil that was similar to coal oil and better
than whale oil as an illuminant. This knowledge
spurred the search for saline waters that contained oil.
Using the methods of the salt producers, Col. Edward
Drake drilled a well on Oil Creek, near Titusville. PA. in
1859, He struck oil at a depth of 70 ft, and this first oil
well produced about 3.5 B/D.
The early oil producers did not realize the significance
of the oil and saline waters occurring together. In fact, it
was not until 1938 that the existence of interstitial water
in oil reservoirs was generally recognized. 4 Torrey was
convinced as early as 1928 that dispersed interstitial
water existed in oil reservoirs, but his belief was rejected
by his colleagues because most of the producing wells
did not produce any water upon completion. Occur-
rences of mixtures of oil and gas with water were
recognized by Griswold and Munn,6 but they believed
that there was a definite separation of the oil and water,
and that oil, gas, and water mixtures did not occur in the
sand before a well tapped the reservoir.
It was not until 1928 that the first commercial
laboratory for the analysis of rock cores was established,
and the first core tested was from the Bradford third sand
(from the Bradford field. McKcan County. PA). The
Now with the Natl Ins1 of Petroleum and Energy Research Eartlesv~lle OK
The author of the or!gmal chapter on this topic I the 1962 edlllon was J Wade
W2fk,<
percent saturation and percent porosity of this core were
plotted vs. depth to construct a graphic representation of
the oil and water saturation. The soluble mineral salts
that were extracted from the core led Torrey to suspect
that water was indigenous to the oil-productive sand.
Shortly thereafter a test well was drilled near Custer Ci-
ty, PA, that encountered higher than average oil satura-
tion in the lower part of the Bradford sand. This high oil
saturation resulted from the action of an unsuspected
flood. the existence of which was not known when the
location for the test well had been selected. The upper
part of the sand was not cored. Toward the end of the
cutting of the first core with a cable tool core barrel. oil
began to come into the hole so fast that it was not
necessary to add water for the cutting of the second sec-
tion of the sand. Therefore, the lower 3 ft of the Bradford
sand was cut with oil in a hole free from water. Two
samples from this section were preserved in sealed con-
tainers for saturation tests, and both of them, when
analyzed, had a water content of about 2O%PV. This
well made about IO BOPD and no water after being shot
with nitroglycerine. Thus, the evidence developed by the
core analysis and the productivity test after completion
provided a satisfactory indication of the existence of im-
mobile water, indigenous to the Bradford sand oil reser-
voir, which was held in its pore system and could not be
produced by conventional pumping methods.
Fettke was the first to report the presence of water in
an oil-producing sand. However, he thought that it might
have been introduced by the drilling process.
Munn* recognized that moving underground water
might be the primary cause of migration and accumula-
tion of oil and gas. However, this theory had little ex-
perimental data to back it until Mills conducted several
laboratory experiments on the effect of moving water
and gas on water/oil/gas/sand and water/oil/sand
systems. Mills concluded that the up-dip migration of
24-2 PETROLEUM ENGINEERING HANDBOOK
oil and gas under the propulsive force of their buoyancy
in water, as well as the migration of oil, either up or
down dip, caused by hydraulic currents, are among the
primary factors influencing both the accumulation and
the recovery of oil and gas. This theory was seriously
questioned and completely rejected by many of his
contemporaries.
Rich I assumed that hydraulic currents, rather than
buoyancy, are effective in causing accumulation of oil or
its retention. He did not believe that the hydraulic ac-
cumulation and flushing of oil required a rapid move-
ment of water but rather that the oil was an integral con-
stituent of the rock fluids and that it could be carried
along with them whether the movement was very slow or
relatively rapid.
The effect of water displacing oil during production
was not recognized in the early days of the petroleum in
dustty in Pennsylvania. Laws were passed, however, to
prevent operators from injecting water into the oil reser-
voir sands through unplugged wells. In spite of these
laws, some operators at Bradford secretly opened the
well casing opposite shallow groundwater sands to start a
watertlood in the oil sands. Effect of artificial
watertloods were noted in the Bradford field in 1907,
and became evident about 5 years later in the nearby oil
fields of New York. Volumetric calculations of the
oil-reservoir volume that were made for engineering
studies of these waterflood operations proved that in-
terstitial water was generally present in the oil sands.
Garrison and Schilthuis gave detailed information
concerning the distribution of water and oil in porous
rocks, and of the origin and occurrence of connate
water with information concerning the relationship of
water saturation to formation permeability.
The word connate was first used by Lane and Gor-
don to mean interstitial water that was deposited with
the sediments. The processes of rock compaction and
mineral diagenesis result in the expulsion of large
amounts of water from sediments and movement out of
the deposit through the more permeable rocks. It is
therefore highly unlikely that the water now in any pore
is the same as that which was there when the particles
that surround it were deposited. White redefined con-
nate water as fossil water because it has been out of
contact with the atmosphere for an appreciable part of a
gcnlogic time period. Thus. connate water is distin-
cruished from meteoric
2
water, which has entered the
rocks in geologically recent times, and from juvenile
water. which has come from deep in the earths crust and
has never been in contact with the atmosphere.
Meanwhile. petroleum engineers and geologists had
learned that waters associated with petroleum could be
identified with regard to the reservoir in which they oc-
curred by a knowledge of their chemical characteristics.
Commonlv, the waters from different strata differ con-
siderably In their dissolved chemical constituents. mak-
ing the identification of a water from a particular stratutn
easy. Howjcvcr. in some areas the concentrations of
dissolved constituents in waters from different strata do
not ditfcr significantly, and the identification of such
waters is difficult or impossible.
The amount of water produced with the oil often in-
creases as the amount of oil produced decreases. lfthis is
edge water. nothing can be done about it. If it is botton-
water, the well can be plugged back. However, it often is
intrusive water from a shallow sand gaining access to the
well from a leaky casing or faulty completion and this
can be repaired.
Enormous quantities of water are produced with the oil
in some fields, and it is necessary to separate the oil from
the water. Most of the oil can be removed by settling.
Often, however, an oil-in-water emulsion forms, which
is very difficult to break. In such cases, the oil is heated
and various surface-active chemicals are added to induce
separation.
In the early days, the water was dumped on the
ground, where it seeped below the land surface. Until
about 1930, the oilfield waters were disposed into local
drainage, frequently killing fish and even surface vegeta-
tion. After 1930, it became common practice to
evaporate the water in earthen pits or inject it into the
producing sand or another deep aquifer. The primary
concern in such disposal practice is to remove all oil and
basic sediment from the waters before pumping them in-
to injection wells to prevent clogging of the pore spaces
in the formation receiving the waste water. Chemical
compatibility of waste water and host aquifer water also
must be ensured.
Waters produced with petroleum are growing in im-
portance. In years past, these waters were considered
waste and had to be disposed of in some manner. Injec-
tion of these waters into the petroleum reservoir rock
serves three purposes: it produces additional petroleum
(secondary recovery), it utilizes a potential pollutant.
and in some areas it controls land subsidence.
The volume of water produced with petroleum in the
U.S. is large. In 1981 domestic oil production was about
8.6~ IO B/D and the amount of water produced with
the oil ranges from 4 to 5 times the oil production.
Therefore, the water production, assuming a factor of
4.5, would be about 38.7~ IO BID.
Secondary and tertiary oil recovery processes that use
water injection usually result in the production of even
more water along with the oil. To inject these waters into
reservoir rocks, suspended solids and oil must be re-
moved from the waters to prevent plugging of the porous
formations. Water injection systems require xepardtors,
filters, and, in some areas, deoxygenating and bacteria
control equipment with chemical and physical methods
to minimize corrosion and plugging in the injection
system.
In waterflooding most petroleum reservoirs, the
volume of produced water is not sufficient to rccovcr the
additional petroleum efficiently. Therefore, supplemen-
tal water must be added to the petroleum reservoir. The
use of waters from the other sources requires that the
blending of produced water with supplemental water
must yield a chemically stable mixture so that plugging
solids will not be formed. For example, a produced
water containing considerable calcium should not be
mixed with a water containing considerable carbonate
because calcium carbonate may precipitate and prevent
injection of the tloodwater. The design and successful
operation of a secondary or tertiary recovery operation
requires a thorough knowledge of the composition of the
waters used.
Chemical analyses of waters produced with oil are
useful in oil production problems. such as identifying the
PROPERTIES OF PRODUCED WATERS
24.3
source of Intrusive water, planning watcrfood and
saltwater disposal projects. and treating to prevent corro-
sion problems in primary, secondary, and tertiary
recovery. Electrical well-lo g interpretation rcquircs a
knowlc$Fc of the dissolved solids concentration and
composltton of the interstitial water. Such information
also is useful in correlation of stratigraphic units and of
the aquifers within these units. and in studies of the
movcmcnt of xubsurfacc waters. It is impossible to
understand the processes that accumulate petroleum or
other minerals without insight into the nature of these
waters.
Sampling
The composition of subsurface water commonly changes
with depth and also laterally in the same aquifer.
Changes may be brought about by the intrusion of other
waters. and by discharge from and recharge to the
aquifer. It is thus difficult to obtain a representative sari--
pie of a given subsurface body of water. Any one sample
is a very small part of the total mass. which may vary
MJidely in composition. Therefore. it is generally
necessary to obtain and analyze many samples. Also. the
samples may change with time as gases come out of
solution and supersaturated solutions approach
saturation.
The sampling sites should be selected, if possible, to
fit into a comprehensive network to cover an oil-
productive geologic basin.
There is a tendency for some oilfield waters to become
more diluted as the oil reservoir is produced. Such dilu-
tion may result from the movement of dilute water from
adjacent compacting clay beds into the petroleum rescr-
voir as pressure declines with the continued removal of
oil and brine.
The composition of oilfield water varies with the posi-
tion within the geologic structure from which it is ob-
tained. In some cases the salinity will increase upstruc-
ture to a maximum at the point of oil/water contact.
Few of the samples collected by drillstem test (DST)
arc truly representative formation-water samples. During
drilling. the pressure in the wellbore is intentionally
maintained higher than that in the formations. Filtrate
from the drilling mud seeps into the permeable strata.
and this filtrate is the first liquid to enter the test tool.
The most truly representative formation-water sample
usually is obtained after the oil well has produced for a
period of time and all extraneous fluids adjacent to the
wellhore have been flushed out. Samples taken im-
mediately after the well is completed may be con-
taminated with drilling fluids and/or with well complc-
tion fluids. such as filtrate from cement, tracing fluids,
and acids. which contain many different chemicals.
Sampling methods are discussed in publications of the
American Petroleum Inst. (API), American Sot. for
Testing and Materials (ASTM), and the Natl. Assn. of
Corrosion Engineers (NACE). I8
Drillstem Test
The DST, if properly made, can provide a reliable for-
mation water sample. it is best to sample the water after
each stand of pipe is removed. Normally, the total
dissolved solids (TDS) content will increase downward
and become constant when pure formation water is ob-
tained. A test that ilows water will give even higher
assurance of an uncontaminated sample. If only one DST
water sample is taken for analysis. it should bc taken just
above the tool. since this is the last water to enter the tool
and is least likely to show contamination.
Analyses of water obtained from a DST of Smackovcr
limestone water in Rains County. TX. show how errors
can be caused by improper sampling of DST water.
Analyses of top, middle. and bottom samples taken from
a SO-ft fluid recovery show an increase in salinity with
depth in the drillpipe. indicating that the first water wa\
contaminated by mud filtrate. I) Thus. the bottom sam-
ple was the most representative of Smackovcr water.
Sample Procedure
No single procedure is universally applicable for obtain-
ing a sample of oilfield water. For cxamplc. inthrmation
may bc desired concerning the dissolved gas or
hydrocarbons in the water or the reduced species present.
such as ferrous or manganous compounds. Sampling
procedures applicable to the desired infomlation must be
used.
Some of the special information and sample location
cases, with appropriate procedures or references cited for
proper sampling. follow.
Sample Containing Dissolved Gas. Knowlcdgc of ccr-
tain dissolved hydrocarbon gases is used in
exploration. OZ
Sampling at the Flowline. Another method of obtaining
a sample for analysis of dissolved gases is to place a
sampling device in a flowline. Fig. 24. I illustrates such
a device. The device is connected to the flowline. and
water is allowed to flow into and through the container.
which is held above the flowlinc. until 10 or more
volumes of water have flowed through. The lower valve
on the sample container is closed and the container
removed. If any bubbles are present in the sample, the
sample is discarded and a new one is obtained.
Sampling at the Wellhead. It is common practice in the
oil industry to obtain a sample of formation water from a
sampling valve at the wellhead. A plastic or rubber tube
can be used to transfer the sample from the sample valve
into the container (usually plastic). The source and sam-
ple container should be flushed to remove any foreign
material before a sample is taken. After flushing the
system. the end of the tube is placed in the bottom of the
container, and several volumes of fluid are displaced
bcforc the tube is removed slowly from the container and
the container is sealed. Fig. 24.2 illustrates a method of
obtalnmg a sample at the wellhead. An extension of this
method is to place the sample container in a larger con-
tainer. insert the tube to the bottom of the sample con-
tainer. allow the brine to overflow both containers. and
withdraw the tube and cap the sample under the fluid.
At pumping wellheads the brine will surge out in heads
and be mixed with oil. In such situations a larger con-
tainer equipped with a valve at the bottom can be used as
a surge tank or an oil-water separator or both. To use this
device, place the sample tube in the bottom of the large
container, open the wcllhead valve, rinse the large con-
tainer with the well fluid, allow the large container to
24-4 PETROLEUM ENGINEERING HANDBOOK
Valve
74
Sample
I-+
container
Fig. 24-l-Flowline sampler.
fill, and withdraw a sample through the valve at the bot-
tom of the large container. This method will serve to ob-
tain samples that are relatively oil-free.
Field Filtered Sample. In some studies it is necessary to
obtain a field filtered sample. The filtering system shown
in Fig. 24.3 was designed and has proved successful for
various applications.
Fig. 24.2-Example of the method used for obtaining a sample
at the wellhead.
This filtering system is simple and economical. It con-
sists of a SO-mL disposable syringe, two check valves.
and an inline-disk-filter holder. The filter holder takes
size 47-mm diameter, 0.45pm pore size filters, with the
option of a prefilter and depth prefilter.
After the oilfield brine is separated from the oil, the
brine is drawn from the separator into the syringe. With
the syringe, it is forced through the filter into the collec-
tion bottle. The check valves allow the syringe to be used
as a pump for filling the collection bottle. If the filter
becomes clogged, it can be replaced in a few minutes.
About 2 minutes are required to collect 250 mL of sam-
ple. Usually two samples are taken, with the one being
acidified to pH 3 or less with concentrated HCI or
HN03. The system can be cleaned easily or flushed with
brine to prevent contamination.
Sample for Stable-Isotope Analysis. Stable isotopes
have been used in several research studies to determine
the origin of oilfield brines. 22-24
Sample for Determining Unstable Properties or
Species. A mobile analyzer was designed to measure
pH, Eh (redox potential), Oz, resistivity, S=, HCOT,
CO,, and CO2 in oilfield water at the wellhead. When
oilfield brine samples are collected in the field and
transported to the laboratory for analysis, many of the
unstable constituents change in concentration. The
amount of change depends on the sampling method,
sample storage, ambient conditions, and the amounts of
the constituents in the original sample. Therefore an
analysis of the brine at the wellhead is necessary to ob-
tain reliable data.
Sample Containers. Containers that are used include
polyethylene, other plastics, hard rubber, metal cans,
and borosilicate glass. Glass will adsorb various ions
such as iron and manganese, and may contribute boron
or silica to the aqueous sample. Plastic and hard rubber
containers are not suitable if the sample is to be analyzed
to determine its organic content. A metal container is
used by some laboratories if the sample is to be analyzed
for dissolved hydrocarbons such as benzene.
The type of container selected depends on the planned
use of the analytical data. Probably the more satisfactory
container, if the sample is to be stored for some time
Fig. 24.3-Example of field filtering equipment.
PROPERTIES OF PRODUCED WATERS
24- 5
TABLE 24.1-DESCRIPTION NEEDED FOR EACH OILFIELD WATER SAMPLE
Sample Number Field
Farm or lease ~ Well No. ~ in the
of Section Townshlp Range
County State Operator
Operators address (main office)
Sample obtained by Date
Address Representing
Sample obtained from (lead line, separatory flow tank, etc.)
Completion date of well
Name of productive zone from which sample is produced
Sand Shale Lime Other
Name of productive Names of formations
formation well passes through
Depths: Top of formation Bottom of formation
Top of producing zone Bottom of producing zone
Top of depth drilled Present depth
Bottomhole pressure and date of pressure
Bottomhole temperature
Date of last workover Are any chemicals added to treat well If yes, what?
Well producti on I ni ti al Present Casing service record,
Oil, BID
Water, B/D
Gas, cu ft/D
Method of production (primary, secondary, or tertiary)
Remarks: (such as casing leaks, communication or other pay in same well, lease or field)
before analysis. is the polyethylene bottle. Not all
polyethylenes are satisfactory because some contain
relatively high amounts of metal contributed by catalysts
in their manufacture. The approximate metal content of
the plastic can bc determined by a qualitative emission
spectrographic technique. If the sample is transported
during freezing temperatures, the plastic container is less
likely to break than is glass.
Tabulation of Sample Description. Information such as
that in Table 24.1 should be obtained for each sample of
oilfield water.
Analysis Methods for Oilfield Waters
Analytical methods for analyzing oilfield waters are im-
proving with respect to precision, accuracy, and speed.
There have been at least two groups trying to standardize
methods of oilfield water analysis during the past 20
years. They are the API and ASTM. The API published
Recommended Practice 45 for Analysis of Oilfield
Waters.
The ASTMs Committee D-19 standardizes methods
of analyzing oilficld brines. Methods standardized by
rigorous round-robin testing by several laboratories and
subsequent ASTM committee balloting procedures are
found in Ref. 17.
Table 24.2 illustrates the analyses for various proper-
ties or constituents of oilfield water. Methods to deter-
mine most of these properties or constltucnts can bc
found in Refs. 16, 17, and 25 through 30.
Chemical Properties of Oilfield Waters
Oilfield waters are analyzed for various chemical and
physical properties. Most oilfield waters contain a varie-
ty of dissolved inorganic and organic compounds.
TABLE 24.2-GEOCHEMICAL WATER ANALYSES*
Steam
Produced I nj ecti on Generati on Di sposal
Water Water Water Water
PH
Eh
Speci i l c resi stwty
Speci i tc gravi ty
Bacteri a
Bari um
Bi carbonate
Boron
Bromi de
Calcium
Carbonate
Carbon di oxi de
Chl onde
Hydrogen sul f i de
I odi ne
IlOll
Magnesi um
Manganese
Oxygen
Potassi um
Resi dual hydrocarbons
Sodi um
Si l i ca
Stronti um
Sulfate
Suspended sol I ds
Total di ssol ved sol i ds
X =usual l y requesm
O=somel l mes requested
X
0
X
X
0
X
: :
0
X
: :
X
0
0
X
: :
0
0
X
0
0
X
X
X
X
X
X
;
X
X
::
0
X
::
X
0
24-6
PETROLEUM ENGINEERING HANDBOOK
TABLE 24.3-CHARACTERISTICS OF SOME WATERS PRODUCED FROM APPALACHIAN FIELDS
Number of
Analyses* System
KentuckyZ3,24
4 Devonian-Silurian
8 Mississippian
5
-
Ohi0 35.36
8 Mississippian
7 Ordovician
8 Mississrppian
10 Upper Devonian
12 Mississippian
Pennsylvania3 38
IO Devonian
7 Devono-
Mississippian
12 Devontan
West Virginia39
29 Mtssisstppian
6 Mississippian
21 Mississippian
44 Pennsylvanian
43 Devonian
Formation
Subsurface
Depth
(fl)
Corniferous 400 to 1,506
McClosky 1,390 to 2,618
Jett 939 to 1,534
Blue Lick
Sub Trenton
Second Water
Big Lime
First Water
Big Lime
Berea
1,843 to 3,263
3,820 to 5,815
2,175 to 3,270
5,175 to 5,300
401 to 1,592
Bradford
Venango
Bradford III
-
-
-
Big lnjun 1,390 to 3,215
Squaw 1,908 to 2,019
Maxton 1,287 to 3,259
Salt Sand 450 to 1,960
Oriskany 3,036 to 8,089
Constituents (mg/L)
Ca Mg Na
1,520 670 9,520
12,160 3,350 44,740
1,700 990 15,700
3,400 2,180 33,600
370 130 1,860
830 320 15,500
1,390 650 10,500
9,230 2,900 33,600
11,000 2,700 39,500
44,000 6,600 58,600
32,300 5,180 36,000
51,200 10,200 60,700
25,900 4.100 21.600
29,600 1O;OOO 861400
4,600 1,500 25,000
11,900 3,000 43,900
40 30 1,600
-
32,400 1,940 39,500
-
7,000 70 3,600
-
82,000 2,020 16,000
-
420 40 300
-
16,900 2,530 39,200
-
30 300 50
1,730 3,910 52,200
630 200 6,300
8,920 2,250 38,100
100 40 3,800
15,300 2,740 35,100
400 340 2,500
20,600 2,650 50,900
2,500 480 34,000
33,600 3,800 98,300
K
120
1,290
ND*
ND
ND
ND
150
1,510
0
2,890
1,950
2,330
270
2,370
120
220
IO
750
290
340
30
660
3,6::
200
6,900
However. oil producers usually are interested in only a
few of the macro properties. This is understandable
because oil producers wish to spend the least amount of
money possible. Therefore, they will look at only the
properties that are necessary to evaluate any treatment
for rcinjection to recover more oil or to dispose of the
oilfield waters.
Composition of Oilfield Waters
, ,,
The composition ot otltteld waters varies from relatively
dilute waters to heavy brines. Several thousand oilfield
water analyses are available on computerized files.
Tables 24.3 through 24. I4 show characteristics of pro
duced waters. and much of the text was taken from the
1962 edition of this book.
The tabulated data on water analyses following arc
lihted alphabetically in order of general oil-productive
areas of the U.S.. Canada. and Venezuela. rather than by
the smaller subdivisions of basins. geologic provinces.
or gcosynclines. An exception to this is the Illinois
basin, a large area not generally otherwise identifiable.
This division has been made arbitrarily for convenience
and because of the lack of a uniform system and is not in-
tended as a precedent for any system of classification.
The states or provinces from which reliable analyses
were available are listed alphabetically in the tables
under each area.
The reader is referred to the original indicated sources
of analytical data for more complete information.
Appalachian Area. The Appalachian area was the first
in the U.S. in which petroleum was produced commer-
cially and is one of the best known and studied geologic
features of North America. Table 24.3 gives the
characteristics of some waters produced from Ap-
palachian fields. F--~,
Petroleum and associated water are produced from
more than 50 strata in systems from the Cambrian to the
Permian. Most of the productive strata are sandstones,
although some limestones are productive. Many of the
PROPERTIESOF PRODUCED WATERS
24-7
TABLE24.3-CHARACTERISTICSOF SOMEWATERSPRODUCEDFROMAPPALACHIANFIELDS (continued)
Ba Sr
Constituents (mg/L)
HCO, SO, Cl
Specific
Gravity
I Br 60/600
TDS
O-ML)
- 0
- 630
- ND
- ND
ND
ND
628:
10 19,600 Trace 120
690 93,900 10 820
60 910 31,700 ND ND
230 3,320 61,000 ND ND
120 50 14,000 ND ND
250 3.200 26.000 ND ND
1.022
1.120
1.036
1.070
1.020
1.039
31,600
158,330
51,060
103,730
16,530
46,100
Trace 110 30 18,200 0 0 1.025 31,030
- 315 380 380 77,600 IO 570 1.089 125,180
- 0 20 150 113,500 10 150 1.150 167,030
- 900 510 490 189,400 30 600 1.224 304,020
- 0 60 30 113,000 ND 580 1.151 189,100
1,240 140 100 216,300 ND 1,900 1.240 344,110
- Trace 30 210 114,200 ND 1,230 1.125 167,540
Trace 230 550 193.100 ND 2,100 1.211 324,350
- 0 20 0 52,700 ND 320 1.063 84,260
- 1,800 20 60 93,400 ND 520 1.115 154,820
-
-
-
-
- -
-
30 30 1,100
- - -
560 1,080 83,200
- - -
0 260 30,900
-
0 1,270 75,300
- - -
0 0 490
- - -
40 1.080 97.600
2,790
158,680
41,830
176,590
1,260
157,350
Trace 10 IO 5 70 Trace Trace 1.001
300 830 70 320 121,000 20 1,750 1.149
0 0 0 0 11,330 2 80 1.010
540 70 40 10 81,130 10 700 1.101
IO 5 10 20 5.830 Trace Trace 1.007
1,500 220 1,680 530 89,900 10 500 1.115
10
2::
10 5 2,500 Trace 5 1.004
870 1,330 400 125.000 10 780 1.159
20 Trace Trace 10 44,300 2 40 1.059
760 1.570 270 900 170,000 30 2,500 1.219
475
191,580
18,832
132,110
9,825
148,090
5,810
206,430
51,552
318,630
sandstones are nonuniform and discontinuous. although
the Big In.jun and Berea sands have been traced across
wide areas. The oil-producing states included in the Ap-
palachian area from which analyses were available arc
Kentucky, Ohio. Pennsylvania. and West Virginia. The
concentrations ofdissolved salts in waters produced Gth
petroleum range from a few hundred to more than
300,000 IllgiL.
California. In different fields of California. oil is pro-
duced from many reservoirs, ranging in age from
Cretaceous to Pleistocene. Sandstones and sands are the
principal productive rocks. Many of the formations arc
of massive thickness. and much folding and faulting are
evident. In general. mineralized water produced with
petroleum from California reservoirs is by no means as
concentrated as that from reservoirs in many other areas.
especially the midcontincnt. Table 24.4 gives the
characteristics of some water produced from California
fields, JO.41
U.S. Gulf Coast. For many years since the Spindletop
dome was discovered in 1901, copious quantities of oil
have been produced from Tertiary and Quaternary for-
mations on the flanks, in the caprock, and in structures
abovle the capmck of massive salt domes. usually con-
sidered intrusive in nature. During recent years. offshore
drilling has focused attention on drilling oft the coasts of
Louisiana and Texas. Some waters produced from gulf
coast fields are quite fresh; others have concentrations of
dissolved salts as high as 170.000 nngit, (Table
24.5). 4L44
Illinois Basin. The Illinois basin. divided roughly into
halves by the LaSallc anticline. comprises much of II-
linois and southwestern Indiana. Oil is produced here
from many fields, principally from Pennsylvanian and
Mississippian sandstones and. to a smaller extent. from
limestones. TDS in the produced waters range from
about I.000 to more than 160,000 mg/L (Table 24.6).j5
24-a PETROLEUM ENGINEERING HANDBOOK
TABLE 24.4-CHARACTERISTICS OF SOME WATERS PRODUCED FROM CALIFORNIA FIELDS
Subsurface
Constituents (mg/L)
Depth
(fi)
Ca Mg Na a
--z- 10
HCO,
1,104 to 1,916 40 50 180
390 340 3,290 480 360
1,495 to 3,250 20 IO 910 0 180
2,890 690 13,250 360 360
2,270 to 3,550 60 20 3,650 0 50
1,280 570 11,650 90 4,270
400 to 3,000 10 10 50 0 20 20 1,550 390 7:
- 200 140 4,770 150 0
220 230 7,640 460 0
- 200 10 1,300 0 4
2,900 1,300 15,015 510 1,020
10 3 2,050 0 1,700
80 140 7,090 340 3,900
so,
190
TDS Number of
Analyses
17
10
System Formation
Tertiary Coalinga
Tertiary Midway
Tertiary Sunset
Tertiary Kern River
Tertiary Lost Hills
Tertiary Maricopa
Tertiary Zone A
Cl
90
2,520
1,010
23,550
4,360
21,420
10
60
FwU
580
7.260 14,640
2,140
42,120
8,145
39,320
80
2,130
13,020
21,120
10
1,380
5
40
5
4
2
26
18
0
20
20
630
2
110
7,740
11,950
1,170
27,100
1,300
9,560
2,686
47,995
5,064
21,200 90
' Upper l i gure i n each col umn I S m~n~murn val ue and l ower f i gure I S maxi mum val ue f or number of anal yses ndl cated ' +I '
Midcontinent Area. The midcontinent oil productive
area is the largest geographically of all oil-productive
areas in the U.S. For purposes of this section, it is con-
sidered to include Arkansas, Kansas. northern Loui-
siana, Missouri, Nebraska, Oklahoma. and all of Texas
except the gulf coast fields.
Oil and associated brines are produced from many
sandstones and limestones, as well as from other types of
formations, in geologic systems ranging from the Cam-
brian through the Upper Crctaceous. Waters produced
with petroleum from midcontinent fields have a wide
range of concentration of dissolved salts, from little
more than 1,000 to more than 350.000 mg/L. Tables
24.7 through 24.9 present the characteristics of some
produced waters from the midcontinent fields of Kansas,
Oklahoma, and Texas.36-
Rocky Mt. Area. Petroleum is produced in Colorado,
Montana. New Mexico, Utah, and Wyoming from many
fields in the Rocky Mt. area. The principal production is
from rocks of the Cretaceous system, although oil and
associated waters also are produced from Jurassic, Per-
mian, Pennsylvanian, and Mississippian rocks. Pro-
duced waters from Rocky Mt. fields have comparatively
low concentrations of dissolved salts and often are
characterized by comparatively high concentrations of
bicarbonate. Tables 24.10 and 24.11 give the
characteristics of some waters produced from Rocky Mt.
fields of Colorado, Montana, and Wyoming. 55m5y
Canada. The principal oil-productive areas in Canada
are the lower Ontario Peninsula, where oil is produced
from rocks ranging from Ordovician to Devonian age,
and the western provinces, principally Alberta, Sas-
katchewan, and the Northwest Territories. Reservoir
rocks in western Canada range in age from Devonian to
Cretaceous. Although many of the waters produced with
petroleum have quite low concentrations of dissolved
salts, others are quite concentrated. Tables 24.12 and
24. I3 present the characteristics of some waters from
Canadian fields in Alberta, Manitoba, and Saskatche-
wan, hObh5
TABLE 24.5-CHARACTERISTICS OF SOME WATERS PRODUCED FROM GULF COAST FIELDS (TEXAS)
Constituents ( mg/ L)
Subsurf ace
Depth
u9
2, 579 to 11 400
40610 1 100
1. 305 to 3. 296
FormatIon
or field
Mg
50
Cl
TDS
(m9L)
5 700
116900
353
4 500
10, 860
54480
10. 470
171. 300
18. 900
109. 990
570
1.710
11. 490
36400
Number of
Anal yses' System
42 Teri l ary
5
6 Ol i gocene
6 Upper Eocene
5 Oligocene
Ca Na
2.240
40.600
60
1. 330
3, 800
18, 200
3. 600
61. 000
6. 700
40. 800
340
30
4. 460
12. 730
HCO,
30
990
230
770
70
400
so,
0 3. 180
69. 100
20
2.130
6.300
33. 700
6. 100
105000
Fno
Norm Coastal
Goose Creek
Humbl e
Damon Mound
Barber HIII Dome
Powell-Mexla
1, 000
10
30
110
3
160
120
210
Trace
1. 750
270
3. 010
16
230
10
210
775 to
250to 11 300
63400
110
610
6. 700
21 600
4 Pliocene-Miocene 70
550
30
240
6
PROPERTIES OF PRODUCED WATERS
24-9
TABLE 24.6-CHARACTERISTICS OF SOME WATERS PRODUCED FROM ILLINOIS FIELDS
Number of Formatton
Subsurf ace
Depth
Anal yses System of f i el d
( N
12 Mi sswl ool an Wal l ersbura 1. 994
2 437
18 M~ss~ss~pp~an Tar Spri ngs 1. 125
2, 596
57 M~ss~ss~pp~an Cypress 1.045
2.960
17 Ordowcl an Trenton 672 to 4, 000
134 Mwssi ppl an St Geneweve 1.104 to 3. 519
Ca
1. 200
2. 970
960
6. 020
840
6. 600
50
7. 500
1. 900
16. 430
Consti tuents ( mg/ L)
MC!
Na
HCO_,
so,
640 22. 660 30 0
1. 020 32. 220 390 1 620
I O 240 20 0
1. 730 42. 810 1.050 980
510 3. 970 10 10
1, 660 47. 900 1. 660 3.840
40 340 20 30
1. 830 41. 830 960 1. 350
910 8.740 20 30
3. 460 47. 660 1.470 2. 990
Cl
38 300
56 700
700
76 000
25 800
83 200
200
82 400
14000
95 400
TDS
( mgl L)
62. 830
93 920
62 930
i 28 590
31 140
143.940
680
135870
25 600
167. 940
Upper figure in each column IS minimum value and lower llgure IS ma~~rnum value for number of analyses Indicated
Venezuela. The principal productive formations in
oilfield waters are sodium, calcium, and magnesium.
Venezuela are Tertiary sandstones and Cretaceous
The concentrations of these ions can range from less than
limestones. In general. the various waters produced with 10.000 mg/L for sodium, and from less than I .OOO mg/L
petroleum have low concentrations of dissolved salts
to more than 30,000 me/L for calcium and/or
(Table 24. 14).66m69 magnesium.
Inorganic Constituents
Petroleum companies often analyze oilfield waters to
determine their major dissolved inorganic constituents.
The major constituents usually are sodium, calcium,
magnesium, chloride, bicarbonate, and sulfate. The
analytical data are used in studies such as water iden-
tification. log evaluation, water treatment, environmen-
tal impact, geochemical exploration, and recovery of
valuable minerals. 26
Other cations that often are present in oilfield waters in
concentrations greater than 10 mg/L are potassium,
strontium, lithium, and barium. Some oilfield waters
contain concentrations in excess of IO mg/L of
aluminum, ammonium, iron, lead, manganese, silicon,
and zi nc, 26. 70. 71
Anions
Cations
The presence of various cations and anions in oilfield
waters can cause solubility, acidity, and redox (Eh)
potential changes as well as the precipitation and adsotp-
tion of some constituents. The major cations in most
The major anion in most oilfield waters is chloride. The
chloride concentration can range from less than 10,000
to more than 200,000 mg/L. There are exceptions to
this-e.g., some Venezuelan oilfield waters contain
more bicarbonate than chloride.
Most oilfield waters contain bromide and iodide. The
concentrations of these anions range from less than 50 to
more than 6.000 mg/L for bromide and from less than IO
TABLE 24.7-CHARACTERISTICS OF SOME WATERS PRODUCED FROM MID-CONTINENT FIELDS (KANSAS)
Subsurface
Constituents (nq/L)
Speclflc
Number01 Depth
~ Gravely TDS
Analyses System Formamn
tft) ca blq N.3 Ba HCO, so, Cl I Br (60160~) (mg,L)
-~ 87 Pennsylvanian Kansas C~fy Lansmg 1.228 lo 3.409 2 040 840 16940 4 5 0 34.100 2. 30 1040 53.959
16 DO0 3 950 77.000 70 450 2 160 158.800 15 400 1 159 256.830
8 Ordovlclan WllCOX 3.500 to 3 800 790 5.560 10800 0 20 80 10,870 Trace 80 1015 28.120
14400 68500 142,500 0 530 300 142600 3 x50- 1140 369.180
123 Ordowaan Arbuckle 2.750 lo 3 770 700 240 6 820 0 50 0 12.300 0 Trace ,014 20.180
19 BOO 10.900 34 450 0 640 2 700 79200 Trace 60 1091 145.060
76 Ordoviaan VIOla 2091 lo 4 14, 620 230 5240 0 IO 20 330 0 5 1012 6,455
11 000 3.110 52000 0 650 1180 112.700 10 90 1116 160.740
27 Pennsylvania Bartlesvllle 625 to 3 200 420 1EO 7550 0 10 1 12.600 2 20 1016 20.782
12 100 3,480 69.800 10 520 750 141 200 10 200 1 141 224.870
20 Mississippian Mississippian 1010 to 4 679 560 220 9 150 0 30 0 14.400 1 2 ,017 24.363
12 900 2.660 59300 20 670 3540 122000 60 3 1140 201.153
8 Basal Pennsylvaman Conglomerate 3320 to 3469 1000 360 11 600 0 0 0 20.700 0 200 1023 33.850
8 480 2.000 47.000 0 180 700 58,300 Trace 400 1 105 116.660
24 PWlSlWllX Chat 2697f0 3 365 3.120 640 24400 0 30 0 42,700 2 10 1088 70,902
13480 1.950 66,500 0 130 2.200 137700 3 420 1143 222,383
12 SllUrlan HlO 2 390 to 2 893 230 90 3610 0 70 100 5,300 0 10 1007 9.410
5 220 1.460 36600 3 480 1,230 68.400 2 70 1075 113.460
10 Basal Pennsylvanian Gorham 33ooto 3 854 920 280 6 560 0 160 40 11.300 0 5 1019 19.265
3 960 1.030 17100 10 840 3.010 36,000 0 10 ,045 58,940
9 Pennsylanlan PrUe 1032 to 2.400 2.310 720 14300 0 20 0 28.000 0 0 1033 45.350
11 300 2.610 68 700 10 330 50 138.900 0 0 1 139 221.900
12 Cambraan Reagan 3175f03609 1390 310 9 300 0 80 30 14,700 NO ND ,021 26.810
5 250 1.370 43000 0 410 2,570 76,900 ND ND 1088 126.930
Upper fqure I each column IS mlnimum value and lower hgure IS maximum value for number of analyses Ind~caled %+
24-10 PETROLEUM ENGINEERING HANDBOOK
TABLE 24.8-CHARACTERISTICS OF SOME WATERS PRODUCED FROM MID-CONTINENT FIELDS (OKLAHOMA)
Subsurl ace
Consti tuents ( mg/ L)
Specl f l c
Depth
~- - ~
_~ Grady TDS
ut1
- ~Ca Mg Na Ba HCO, SO, Cl ( 60/ 600) ( mg/ L)
4. 489 to 5, 524 1. 900 910 12, 100 0 0 0 24 100 1031
3, 436 to 7. 233
1, 240 10 4. 800
542 to 6. 094
1. 48070 5430
1, 800 to 2, 490
1, 837 l o 4. 872
3. 927 10 5. 977
1. 258 to 6. 025
1. 213 l o 6. 495
1, 030 to 4. 567
1. 876 to 2 300
3. 197 l o 5, 021
2. 403 to 4. 650
3. 458 to 5. 004
2. 267 to 3. 587
982 to 3. 163
2 417 to 3, 254
790 to 5. 000
1. 882 to 3. 218
2. 173 to 7, 569
83. 800 730
48. 300 0
80. 230 130
31. 300 0
79. 000 380
14, 000 0
63. 800 110
34. 600 1
51. 500 20
42. 500 1
57. 700 200
43, 600 2
72. 000 30
19000 2. 740
6. 800 1. 400
18500 3300
5. 300 1, 800
18900 4. 300
2. 200 900
18. 800 2, 700
4, 600 1. 400
11. 900 4. 300
5, 900 2. 000
13. 300 2. 600
6400 2000
22, 400 2, 500
4. 600 1. 100
18. 400 3. 200
1 700 600
15. 800 3. 100
5. 600 1. 200
17, 600 3, 000
6. 200 1. 500
18. 700 3. 200
6600 1, 500
12700 2. 500
300 80
28. 900 4, 300
9. 700 1. 700
19. 600 2. 600
200 60
16000 2, 400
8. 500 1. 300
11, 700 3. 100
740 230
7. 300 2, 900
14. 000 2. 200
17. 400 3. 100
10, 900 1, 800
300
20
160
10
80
0
850
0
29, 500 0
76. 000 10
17, 600 10
61. 300 280
310
15
120
10
80
30
24. 400 0
71, 900 2
31, 700 0
I 390 144. 000
0 91. 300
720 163. 000
0 34, 900
510 160. 000
0 33, 000
1. 880 127. 000
0 65, 000
1. 130 113. 500
0 81. 600
200 115. 000
24 84. 200
430 157. 000
60 55, 400
1. 920 156, 000
0 29. 800
2, 750 121. 000
0 50. 900
440 140. 000
30 64, 100
450 139. 000
0 90, 000
110
20
90
67, 400 I O
42, 500 0
56, 500 240
4. 000 0
0
110
I O
130
75. 900 170
42, 800 5
71. 700 220
2900 0
62, 000 10
43, 400 5
5
140
15
660
3
680 117, 000
0 8, 200
7. 010 142, 000
0 101. 000
72, 900 20
10800 0
20. 000 3. 500
5. 500 900
13. 900 2. 000
700 400
22. 400 3. 500
27, 900 50
23800 0
76400 5
43200 2
69, 000 40
32. 000 0
54700 10
11 500 10
80500 450
170
40
940
50
120
20
380
0
50
20
133
50
130
1 175
1 103
1170
1075
1179
1. 034
1 147
1073
1 130
1. 091
I 129
1095
1 173
1. 066
1 173
1. 039
1 134
1059
1. 159
1075
1157
1. 103
1. 131
1012
1155
1115
1 164
1005
1137
1 110
1 158
1022
1076
1 160
1 171
1 109
1 163
1073
1 122
1024
1 183
370 149, 000
0 4, 400
980 122, 000
30 86. 300
480 142. 000
2 18. 600
40 63, 600
130 132, 800
370 156. 200
15 99, 300
260 149. 000
40 45, 500
760 108. 000
0 19, 500
920 167, 000
39. 010
251 460
147. 820
266. 010
73. 310
263. 170
50, 100
214. 140
105 701
182, 660
132, 016
189, 120
136. 212
254440
90, 690
250, 640
49. 730
204. 320
82. 100
233. 042
103, 540
228. 890
141. 050
189. 760
11. 995
258. 948
155. 208
243. 660
7. 600
204. 330
139. 885
230, 320
30. 392
102, 170
172. 930
253, 525
155, 235
241. 930
86. 900
179, 500
32, 110
275, 270
Number of
Anal yses System Formaf l on
Bartl esvl l l e
Wl l COX
Layton
Atbuckl e
Cromwel l
Burgess
Mi ssi ssi ppi
Ml sener
Pennsyl vani an
Sl mpso"
Ski nner
Booth
Hunton
Red Fork
VI ol a
Prue
Heal di on
Tonkawa
Burbank
Dutcher
Bromi de
75 Pennsyl vanEl n
94 Ordovl cl an
25 Pennsyf vanl an
28 Ordovua"
I 9 Pennsyl vani an
12 Pennsyl vani an
22 M~ss~ss~pp~an
18 Ml ssi ssl ppl an
I 7 Pennsyl vaman
10 Ordowan
22 Pennsyl vani a"
22 Pennsylvama
22 Siluro-Devontan
27 Pennsylvania
12 Ordowcl an
20 Pennsyf van, an
13 Pennsyl vani an
15 Pennsyl vani an
24 Pennsyl vani an
15 Pennsyl vani an
14 Ordowuan
TABLE 24.9-CHARACTERISTICS OF SOME WATERS PRODUCED FROM MID-CONTINENT FIELDS (TEXAS)
Number of
Analyses System
Subsurface Specific
Depth
Constituents ( mg/ L)
TDS _ Grawty
Formation
(ft)
Ca Mg Na
so4 HCO,
Cl (60~160~)
(m9Q
North-Central Texas 50-52
33 Upper Pennsylvanian
El Upper Pennsylvaman
7 Upper Pennsyl vani an
13 Upper Cretaceous
20 5
10, 700 2. 450
1, 884 ! O2, 081 14, 400 2, 440
16. 700 2. 860
2. 540 to 2, 668 10. 200 2, 030
13, 800 2, 440
3. 844 to 4. 446 3. 100 370
7, 900 600
530
48. 200
58, 300
66, 800
52, 500
61, 000
32. 100
62, 900
61;
1
690
0 300
0 520
0 630
10 740
130 250
410 370
460
97, 900
122, 200
139, 800
106, 000
119, 000
57. 500
112, 500
ND
ND
ND
ND
ND
ND
ND
ND
1, 017
160, 550
197, 640
226. 680
171, 360
196, 990
93, 450
184. 680
160 6. 030 0 I O 10. 000 1. 015 16, 700
3, 000 60, 400 180 400 134, 000 1. 157 221, 080
640 15, 700 10 40 31, 400 1044 50, 010
2, 300 57, 100 650 4, 840 109, 500 1 145 188, 390
350 12, 000 4 20 25, 300 1. 035 39, 374
2, 850 55. 700 1, 840 2. 140 130, 500 1 173 214, 330
810 25, 500 2 2 82, 900 1. 105 112, 414
3, 500 74, 300 710 710 161, 800 1212 262, 320
310 4. 400 210 350 19, 000 1. 033 25, 010
7, 900 67. 000 1. 840 4, 900 140, 500 1 154 241, 940
200 210 0 160 890 ND 1, 710
3, 700 122, 500 0 8, 600 212, 000 ND 356. 600
Dyson
Landreth
Woodbine
North and West Texas5354
21 Pennsylvanian
35 Pennsylvanian
47 Cambro- Ordovci an
56 Pennsylvanian
50 Permian
42 Permian
Cisco
Canyon
Ellenberger
Straw
San Andres
Big Lime
700 I O 1. 950 500
23, 100
2. 200 I O7. 000 2. 200
14. 000
3, 800 to 8. 370 1. 700
22.300
1, 700 to 6, 900 3, 200
21. 300
740
19. 800
- 250
9. 800
PROPERTI ES OF PRODUCED WATERS 24- 11
TABLE 24.10-CHARACTERISTICS OF SOME WATERS PRODUCED FROM ROCKY MOUNTAIN FIELDS
(COLORADO AND MONTANA)
Constrtuents ( mg/ L)
System
Subsurf ace
Depth
( f t)
Cretaceous Dakota 2. 819 to 5. 830
Cretaceous Frontrer 1, 230 IO 3. 464
Eocene Wasatch 2, 230 to 5. 283
J urasw Morrtson 3, 020 to 4. 395
J urassrc Sundance 4, 564 l o 6, 263
Ca
Mg
0
NC3
co3 HCO3 so,
TDS
Cl
ml / L)
310 0 210 40 40 560
13, 000 160 3, 600 890 22, 100 41, 220
820 0 340 0 820 1, 980
8, 200 240 4. 900 90 12. 800 26. 490
1, 800 0 120 20 2, 000 3. 990
10, 600 150 2, 000 870 18, 900 33, 830
1, 400 0 540 160 260 2. 360
3, 600 120 3, 350 980 5, 000 13, 160
1, 070 0 200 0 260 1, 530
5, 250 0 3, 030 1, 040 8, 060 17. 840
3.900
220
710
6, 200
260
4. 670
1. 110
3, 140
30
1, 390
20
0 140 0 10 4, 050
0 2, 000 1, 850 5, 530 9, 770
0 260 0 280 1, 250
0 1, 400 250 8, 800 16, 900
0 500 0 10 790
0 4, 900 290 6. 000 16. 010
0 1, 670 0 370 3, 150
0 4, 040 820 2. 890 11, 060
0 150 1, 310 10 1. 560
0 400 5. 540 440 8, 470
0 220 trace 10 250
Number of
Anal yses
Col orado5ss6
7
6
6
4
3
Montana5s- s7
J urassi c
Upper Cretaceous
Lower Cretaceous
Upper J urasw
Pennsyl vani an
Upper MI ssI ssi ppi an
Lower Mi ssrssi ppi an
9
10
11
55
22
25
Montana
-
Col orado
-
Kootenar
-
HIS
Quadrant
Tensl eep
Madi son
-
0
1, 180
0
190
30
900
0
80
0
380
0
70
40
410
0
30
0
80
0
100
0
130
0
90
trace
90
60
680
0
0
70
0
120
0
60
0
80
trace
700
0
500 430 2, 330 0 4, 830 2, 110 2,790 12, 990
TABLE 24.11-CHARACTERISTICS OF SOME WATERS PRODUCED FROM ROCKY MT. FIELDS (WYOMING)
Constttuents ( mg/ L)
-
CO, HCO,
Na
410 trace 280
5, 560 230 1, 900
550 trace 1, 270
20, 000 1, 050 7, 800
200 trace 1, 000
5, 320 320 5. 460
1, 740 trace 890
7, 000 590 6. 950
1, 040 trace 110
6, 210 300 2, 290
180 trace 230
13, 000 280 6, 900
630 trace 1. 000
5. 560 380 3. 680
180 0 480
430 60 980
520 0 410
6, 800 330 6. 850
140 0 210
5, 170 0 1. 690
5 0 30
790 10 1, 000
20 trace 20
580 20 1, 080
630 0 190
1, 670 0 550
Subsurf ace
Depth
( 4
900 to 1, 300
1, 000 to 3. 080
TDS
Number of
Anal vses System Ca
Mg
10
330
so,
0
3, 710
trace
240
trace
60
trace
880
0
110
20
980
trace
60
60
820
40
5, 880
190
5, 790
10
2, 500
50
1, 940
1, 930
3, 870
Cl
@WLl
20 ~ 730
Formatron
Shannon
Fronti er
Fi rst Wal l Creek
Second Wal l Creek
Cl everl y
Dakota
Dakota
Greybul l
Sundance
Embar
Tensl eep
Madtson
Mmnel usa
10
250
24 Cretaceous
7, 670 19. 650
70 1, 890
27, 900 57. 340
220 1, 420
5, 940 17. 230
1, 170 3, 800
6, 600 22. 070
150 1, 300
7, 590 16, 630
20 450
19, 200 40, 750
110 1, 740
1, 930 11. 730
40 760
90 2. 420
140 1. 110
35 Cretaceous
45 Cretaceous
50 Cretaceous
14 J urassrc
22 J urasstc
24 J urasstc
5 J urassrc
60 J urassi c
20 Permi an
50 Pennsyl vaman
19 Mi ssi ssi ppi an
20 Tri assi c
trace trace
220 130
trace trace
30 100
trace trace
40 10
trace trace
110 20
trace trace
230 160
trace trace
60 60
i race trace
40 trace
0 0
400 60
140 30
630 220
40 10
720 250
20 trace
870 180
250 50
450 60
-
1, 400 to 1. 500
4, 050 to 4. 505
4, 353 to 8. 500
-
-
7, 700 28, 020
10 620
3, 930 17, 430
3 98
1, 080 6, 350
4 114
1, 070 5. 740
250 3, 300
610 7, 210
-
-
-
24- 12
PETROLEUM ENGI NEERI NG HANDBOOK
TABLE 24.12-CHARACTERISTICS OF SOME WATERS PRODUCED FROM CANADIAN FIELDS
Number of
AllalySeS System Formalton
Subsurface
Depth
ml
Specl l i c
Constltenls (mJ/L,
GLWy TDS
Ca Mg Na CO, HCO, SO, Cl I Br ~60/60l (mg/L)
215 10 1,890
1.670 10 2 072
2 706 102,744
10 10 660 0 320 5
50 10 3.000 80 790 600
70 20 6400 0 580 20
620 230 19.000 60 640 40 29.200
5 60 1030 0 180 0 670
1.250 190 9.100 410 1250 2500
- -
1.570 to 3 323
2.200 to 2 942
3.000 lo 3 422
870 to 2 060
1,322 lo 2 553
2516fO4604
1.698 to 3 717
980 850 0 100 1000
67 340 44.900 40 2.140 4,600
240 4.900 0 110 900
2.000 81.400 30 360 4.900
550 21.300 0 80 3900
1400 72.800 80 780 4.300
200
4.500
6.400
11.000
-
-
-
850
94,900
7.000
149.600
34 900
120 700
740
31 200
530
8.800
7.900
173.500
14.300
154 900
ND ND ND 1205
NO ND ND 9,030
10 10 1010 13.510
40 620 1060 64.160
ND ND 1006 2.145
ND ND 1032 25.700
0 10 - -
20 460 - -
2 20 - -
20 220 - -
3 90 ~ -
10 110 - -
2 200 - -
20 1.500 - -
- 1010 3.940
- ,089 150 380
- 1016 14.150
- 1157 248.990
~ 1031 62 930
- 1136 203 880
- 1004 3 150
- 1033 25 680
- 1002 1840
- 1025 25 780
- 1025 16.120
- 1180 290.070
~ 1026 26 760
- 1176 264,300
to more than 1,400 mg/L for iodide. 26 Bromide concen- Physical Properties of Oilfield Waters*
tration is important in determining the origin of an
oilfield brine and is an important geochemical marker
Compressibility
constituent. Bicarbonate and sulfate are present in
The compressibility of formation water at pressures
many oilfield waters. Their concentrations can range
above the bubblepoint is defined as the change in water
from none to several thousand milligrams per liter.
volume per unit water volume per psi change in pressure.
Other anions found in oilfield waters include arsenate,
This is expressed mathematically as
borate, carbonate, fluoride, hydroxide, organic acid
I av
(',,. = --
( >
-
salts, and phosphates. Boron concentrations in excess of
T, _. _. ( l a)
100 mg/L can affect electric log deflections. 26
v ap
This sechon. except for the pH and Eh, was writlen by Howard B Bradley
TABLE 24.13-CHARACTERISTICS OF SOME WATERS PRODUCED FROM CANADIAN FIELDS, PROVINCE OF SASKATCHEWAN
Subsurf ace
Number of Depth
Consti tuents ( mg/ L)
Spectf f c
Anal yses System Formatron
( W Ca Mg Na
Gravrty TDS
CO, HCO, SO, Cl ( 60/ 600) ( ma/ L)
27 Cretaceous Bl af rmore 998 to 3, 713 ~ ~ trace trace
2, 200x- - - -
190 - 2. 800
5
5
25
12
9
11
4
11
Shaunavon 3, 205 to 3. 413
Gravel bourg 3. 290 to 4. 175
Mf ssron Canyon 3, 700 to 5, 785
Ntsku 4, 682 to 6, 927
Duperow 2, 253 to 4, 024
Mi ssi ssi ppi an 4, 487 to 5, 665
Lodgepol e 2. 305 to 4, 470
80 1, 300
- 190
- 300
- 140
- 350
- 60
- 440
- 200
- 2, 350
- 100
- 860
- 120
110 850
- 480
- 600
- 70
- 2, 600
- 40
- 1, 580
- 290
- 1, 320
1 000 6, 190
8
a
Devoni an
Devoni an
Mi ssI ssi ppI an
Mi ssi ssi ppi an
Lower
Cretaceous
Devoni an
J urassi c
Vi ki ng 2, 395 to 3, 026
Devoni an 3, 356 to 6, 605
J urassf c shal e 3, 105 to 4, 325
2, 300 870 20, 300
170 100 8, 800
1, 850 230 t 2, 400
470 220 11, 700
620 370 t 2. 900
100 130 760
7. 100 3, 100 73. 700
740 190 1,000
14, 100 7. 150 73, 000
680 170 940
9, 000 900 17. 700
trace trace 4, 300
5, 600 1, 600 71, 000
730 90 1, 400
2. 800 610 27, 000
trace trace 1, 100
190 100 9, 300
0 0 0
1, 100 1, 200 69, 100
trace trace 4, 300
8, 100 160 10, 900
3, 500
2, 100
3, 100
270
2, 100
3, 200
Trace
2, 500
2, 200
5, 000
340
3, 900
3, 400
3, 900
38,900 1. 048 67, 250
890 1. 007 12. 250
t 3, 800 1. 014 31. 580
14, 500 1 022 27. 300
20, 100 1. 026 36. 440
280 1. 001 1. 330
155, 000 1 093 242. 540
640 1 002 2. 770
142, 800 1 186 242. 600
700 t , 002 4, 790
31, 100 1. 040 64, 560
5, 700 1. 004 10. 460
123, 800 1 150 206, 860
580 1. 004 6, 680
45, 700 1 061 80, 610
0 2, 100 1. 002 3, 270
790 12, 700 1. 014 25, 680
190 4, 800 1. 012 5, 030
2, 400 111. 000 1. 160 185, 380
0 2, 800 1. 002 7, 390
3, 600 15, 400 1. 029 39, 480
Upper ftgure tn each column IS mmmum value and lower figure is maxmum value far number of analyses mdlcafed 65
PROPERTI ES OF PRODUCED WATERS 24- l 3
TABLE 24.14-CHARACTERISTICS OF SOME WATERS PRODUCED FROM VENEZUELAN FIELDS
Number of
Anal yses
5
7
6
7
a
8
7
8
10
11
Consti tuents ( mg/ L)
TDS
System Formati on or Ftel d Ca Mg Na CO,
HCO, SO,
Cl
- -
~
( mgl L)
Terti ary Zeta ( Qui ri qui re) 170 100 1, 750 0 3, 050
330 270 5. 150 0 5. 400
Terti ary
Terti ary
Cretaceous
Terti ary
Terti ary
Terti ary
Cretaceous
Eta ( Qui ri qui re)
Cabtmas f i el d,
La Rosa f ormati on
Laguni l l as f i el d,
l ceota f ormatl on
Bachaquero f i el d,
Puebl o Vi ej o mai n sandstone
Mene Grande f i el d,
Pauj i and Mason- Truj i l l o range
La Concepti on f i el d.
Punta Gorda sands and deeper sands
La Paz f i el d,
Guasare f ormati on
70 50
400 300
60 60
10 60
40 60
2: 040 0
12, 360 0
1, 740 0
2, 000 120
4, 610 0
1, 800 100
4, 700 1, 900
3; 050
7. 410
2, 010
5, 260
6, 250
30 20 3, 570
50 20 30
30 20 6, 000 80 1, 230
Cretaceous
Terti ary
S. El Mene f i el d,
El Sal to f ormati on
Of i cma and W. Guard f tel ds
OF, sand
AB, sand
D, sand
Du and Eu sands
F, sand
H sand
L, sand
M sand
P sand
S sand
U sand
30 50 2, 660 0 1, 130
30 40 3, 000 0 1, 130
150 50 9, 000 0 2, 440
50 20 1, 260 0 2, 330
40 30 1, 360 0 2, 780
40 30 3, 080 0 1, 100
40 60 4, 000 0 1, 430
140 70 7, 900 0 3, 500
70 70 8, 400 0 2, 050
160 100 7, 300 0 4, 420
110 30 7, 700 0 2, 100
140 80 7, 800 0 970
330 80 8, 600 0 1, 700
940 180 11, 800 0 1, 100
4 1, 910 7, 190
10 5, 420 16, 260
5 710 6, 900
30 11 , 170 36, 500
0 1, 780 5, 643
0 90 5, 260
5 3, 700 14, 657
0 690 6. 210
0 6, 250 12, 955
0 8, 550 15. 911
0 3, 450 7, 320
0 1, 260 5, 460
0 9, 000 20, 640
140 640 4, 424
60 560 4, 830
130 4, 230 8, 520
0 5, 500 11, 030
150 10, 500 22, 260
10 12, 090 22, 690
trace 9, 260 21, 240
20 10, 900 20, 860
0 11, 600 20, 590
100 13, 050 23, 860
0 19, 800 33, 820
Upper tlgure I each column 1s minimum value and lower figure IS maximum value for number ot analyses mdlcated -
or
1 v*--v,
T,=-
( >
v PI--P2
, . . . . . . . . . . . . . . . . . . . . .
01
Bw2 - B, I
c, . = -
B, . ( p, - p2) , . . . . . . . . . . . . . .
(lb)
where
CkV
= water compressibility at the given pressure
and temperature, bbl/bbl-psi,
-cw
= average water compressibility within the
given pressure and temperature interval,
bbl/bbl-psi,
V = water volume at the given pressure and
temperature, bbl,
V = average water volume within p and T inter-
vals, bbl,
PI and
p2 = pressure at conditions 1 and 2 with p r >pz,
psi,
B,,, and
B
4
= water FVF p I and ~2, bbl/bbl, and
B,. = average water FVF corresponding to V,
bbhbbl.
Eq. 2 was fit for pressures between 1,000 and 20,000
psi, salinities of 0 to 200 g NaClIL, and temperatures
from 200 to 270F. Compressibilities were independent
of dissolved gas.
In an oil reservoir, water compressibility also depends Where conditions overlap, the agreement with the
on the salinity. In contrast to the literature, laboratory resul ts reported by both Dorsey 75 and Dotson and Stand-
measurements by Osif 74 show that the effect of gas in ing 76 is very good. Results from the Rowe and Chou
solution on compressibility of water with NaCl concen-
trations up to 200 g/cm3 is essentially negligible. Osifs
results show no effect at gas/water ratios (GWRs) of 13
scf/bbl, at GWRs of 35 scf/bbl probably no effect, but
certainly no more than a 5% increase in the com-
pressibility of brine.
Laboratory measurements 74 of water compressibility
resulted in linear plots of the reciprocal of compressibili-
ty vs. pressure. The plots of l/c, vs. p have a slope of
m r , and intercepts linear in salinity and temperature.
Data points for the systems tested containing no gas in
solution resulted in Eq. 2.
l/c~,=m~p+m~C+m~T+m4, (2)
where
cw
= water compressibility, psi - ,
p = pressure, psi,
C = salinity, g/L of solution,
T = temperature, F,
ml
= 7.033,
m2
= 541.5,
lfl3
= -531, and
m4 = 403.3 X 103.
24-14 PETROLEUM ENGINEERING HANDBOOK
Fig. 24.4-Specific gravity of salt solutrons at 60F and 14.7
psia.
Fig. 24.5-Density of NaCl solutions at 14.7 psia vs.
temperature.
equation agree well up to 5.000 psi (their upper pressure
limit) but result in larger deviations with increasing
pressure. In almost all cases, the Rowe and Chou com-
pressibilities are less than that of Eq. 2.
Density
The density of formation water is a function of pressure,
temperature. and dissolved constituents. It is determined
most accurately in the laboratory on a representative
sample of formation water. I7 The formation water den-
sity is defined as the mass of the formation water per unit
volume of the formation water. For engineering pur-
posts, density in metric units (g/cm) is considered
equal to specific gravity. Therefore, for most engineer-
ing calculations density and specific gravity are
interchangeable. e
When laboratory data are not available, the density of
fomration water at reservoir conditions can be estimated
(usually to within & 10%) from correlations (Figs. 24.4
through 24.6). The only field data necessary are the den-
sity at standard conditions, which can be obtained from
the salt content by use of Fig. 24.4. The salt content can
be estimated from the formation resistivity (obtained
from electric log measurements) by use of Fig. 49.3 (see
Chap. 49). The density of formation water at reservoir
conditions can be calculated in four steps.
I. Using the temperature and density at atmospheric
pressure, obtain the equivalent weight percent NaCl
from Fig. 24.5.
2. Assuming the equivalent weight percent NaCl re-
mains constant. extrapolate the weight percent to reser-
voir temperature and read the new density.
3. Knowing the density at atmospheric pressure and
reservoir temperature, use Fig. 24.6 to find the increase
in specific gravity (density) when compressed to reser-
voir pressure. Note that for oil reservoirs below the bub-
blepoint, the saturated-with-gas curves should be
used; for water considered to have no solution gas, the
no-gas-in-solution curves should be used. These
curves were computed from data given by Ashby and
Hawkins.
4. The density of formation water (g/cm) at reservoir
conditions is the sum of the values read frotn Figs. 24.5
and 24.6. They can be added directly since the metric
PROPERTIES OF PRODUCED WATERS 24-15
units are referred to the common density base of water (1
g/cm3). The metric units can be changed to customary
units (1 bmicu ft) by multiplying by 62.37.
Also the specific gravity of formation water can be
estimated if the dissolved solids are known. The equa-
tion is
y,*>=1+c,~xo.695x10-6, . . . . . I.. . .(3)
where Csd is the concentration of dissolved solids
(mgfL).
For precise but very detailed calculations, the reader is
referred to a recent paper by Rogers and Pitzer. 79 They
tabulated a large number of values of compressibility,
expansivity and specific volume vs. molality ,
temperature, and pressure. A semiempirical equation of
the same type found to be effective in describing thermal
properties of NaCl (0.1 to 5 molality) was used to
reproduce the volumetric data from 0 to 300C and I to
1,000 bars.
Formation Volume Factor (FVF)
The water FVF, II,., is defined as the volume at reser-
voir conditions occupied by 1 STB of formation water
plus its dissolved gas. It represents the change in volume
of the formation water as it moves from reservoir condi-
tions to surface conditions. Three effects are involved:
the liberation of gas from water as pressure is reduced,
the expansion of water as pressure is reduced. and the
shrinkage of water as temperature is reduced.
The water FVF also depends on pressure. Fig. 24.7 is
a typical plot of water FVF as a function of pressure. As
the pressure is decreased to the bubblepoint, ph. the FVF
increases as the liquid expands. At pressures below the
bubblepoint. gas is liberated, but in most cases the FVF
still will increase because the shrinkage of the water
resulting from gas liberation is insufficient to counter-
balance the expansion of the liquid. This is the effect of
the small solubility of natural gas in water.
The most accurate method of obtaining the FVF is
from laboratory data. It also can be calculated from den-
sity correlations if the effects of solution gas have been
accounted for properly. The following equation is used
to estimate B,,. if solution gas is included in the
laboratory measurement or correlation of P,.~:
H,,=L,..
VW P r
. . (4)
where
V,. = volume occupied by a unit mass of water at
reservoir conditions (weight of gas
dissolved in water at reservoir or standard
conditions is negligible), cu ft,
V,,. = volume occupied by a unit mass of water at
standard conditions, cu ft,
p,(. = density of water at standard conditions,
lbmicu ft, and
prc. = density of water at reservoir conditions,
lbmicu ft.
Fig. 24.6--Specific gravity increase with pressure--salt water
pb
PRESSURE, PSI A
Fig. 24.7-Typical plot of water FVF vs. pressure
The density correlations and the methods of estimating
P,,~ and prc. were described previously.
24-16
PETROLEUM ENGINEERING HANDBOOK
The FVF of water can be less than one if the increase
in volume resulting from dissolved gas is not great
enough to overcome the decrease in volume caused by
increased pressure. The value of FVF is seldom higher
than I .06.
Resistivity
The resistivity of formation water is a measure of the
resistance offered by the water to an electrical current. It
can be measured directly or calculated. The direct-
measurement method is essentially the electrical
resistance through a 1 -m cross-sectional area of I m7
of formation water, The fomlation water resistivity,
R ,, $, is expressed in units of Q-m. The resistivity of for-
mation water is used in electric log interpretation and for
such use the value is adjusted to formation
temperature. i (See Chap. 49 for more information).
Surface (Interfacial) Tension (IFT)
Surface tension is a measure of the attractive force acting
at a boundary between two phases. If the phase boundary
separates a liquid and a gas or a liquid and a solid, the at-
tractive force at the boundary usually is called surface
tension; however. the attractive force at the interface
between two liquids is called IFT. IFT is an impor-
tant factor in enhanced recovery processes (see Chap.
47. Chemical Flooding, describing Low-1FT Proc-
CSSCS and Phase Behavior and IFT in the
Miccllar/Polymer Flooding section).
Surface tension is measured in the laboratory by a ten-
siometer. by the drop method, or by other methods.
Descriptions of these methods arc found in most physical
chemistry texts.
Viscosity
The viscosity of formation water, p,, , is a function of
pressure. temperature. and dissolved solids. In gcncral,
brine viscosity increases with increasing prcsaure, in-
creasing salinity. and decreasing tempcraturc.
Dissolved gas in the fomlation water at reservoir condi-
tions generally results in a negligible effect on hater
viscosity. There is little information on the actual
numerical cffcct of dissolved gas on water viscosity.
Gas in solution behaves entirely differently from gas in
hydrocarbons. * In water the presence of the gas actually
causes the water molecules to interact with each other
more strongly, thus increasing the rigidity and viscosity
of the water. However. this effect is very small and has
not been measured to date. In the physical chemistry
literature there is an enormous amount of indirect
evidence to support this concept.
For the best estimation of the viscosity of water. the
reader is referred to a paper by Kestin (11 (11. Their cor-
relating equations involve 32 parameters for calculating
the numerical effect of pressure, temperature. and con-
ccntration of aqueous NaCl solutions on the dynamic and
kinematic viscosity of water. Twenty-eight tables
gcncratcd from the correlating equations cover a
temperature range from 20 to 150C. a pressure range
from 0. I to 35 mPa. and a concentration range from 0 to
6 molal.
Figs. 24.X through 24. IO may be used to approximate
water viscosity for engineering purposes. These figures
show the effects of pressure, temperature, and NaCl con-
tent on the viscosity of water. They may be used when
the primary contaminant is sodium chloride.
Some engineers assume that reservoir brine viscosity
is equal to that of distilled water at atmospheric pressure
and reservoir temperature. In this case it is assumed that
the viscosity of brine is essentially independent of
pressure (a valid premise for the pressure ranges usually
encountered).
The pH
The pH of oilfield waters usually is controlled by the
COfibicarbonate system. Because the solubility of CO?
is directly proportional to temperature and prcssurc, the
pH measurement should be made in the field if a close-
to-natural-conditions value is desired. The pH of the
water is not used for water identification or correlation
purposes. but it does indicate possible scale-forming or
corrosion tendencies of a water. The pH also may in-
dicate the presence of drilling-mud filtrate or well-
trcatmcnt chemicals.
The pH of concentrated brines usually is less than 7.0.
and the pH will rise during laboratory storage. indicating
that the pH of the water in the reservoir probably is ap-
preciably lower than many published values. Addition of
the carbonate ion to sodium chloride solutions will raise
the pH. If calcium is present, calcium carbonate
precipitates. The reason the pH of most oilficld waters
rises during storage in the laboratory is because of the
fomlation of carbonate ions as a result of bicarbonate
decomposition.
The Redox Potential (Eh)
The redox potential often is abbreviated Eh, and also
may be referred to as oxidation potential. oxidation-
reduction potential, or pE. It is expressed in volts. and at
equilibrium it is related to the proportions of oxidized
and reduced species present. Standard equations of
chemical thermodynamics express the relationships.
Knowledge of the redox potential is useful in studies
of how compounds such as uranium. iron. sulfur. and
other minerals are transported in aqueous systems. The
solubility of some elements and compounds depends on
the redox potential and the pH of their environment.
Some water associated with petroleum is interstitial
(connate) water, and has a negative Eh: this has been
proved in various field studies. Knowledge of the Eh is
useful in determining how to treat a water before it is
rein.jected into a subsurface formation. For example. the
Eh of the water will be oxidizing if the water is open to
the atmosphere, but if it is kept in a closed system in an
oil-production operation the Eh should not change ap-
preciably as it is brought to the surface and then rein-
jetted. In such a situation. the Eh value is useful in deter-
mining how much iron will stay in solution and not
deposit in the wellbore.
Organisms that consume oxygen cause a lowering of
the Eh. In buried scdimcnts, it is the aerobic bacteria that
attract organic constituents, which remove the free oxy-
gen from the interstitial water. Sediments laid down in a
shoreline environment will differ in degree of oxidation
PROPERTIES OF PRODUCED WATERS
24-17
I I191111 I I
1000 10,000
PRESSURE, PSILI
Fig. 24.8-Effect of pressure on the viscosity of water
compared with those laid down in a deepwater environ-
ment. For example, the Eh of the shoreline sediments
may range from -50 to 0 mV, but the Eh of deepwater
sediments may range from - 150 to - 100 mV.
The aerobic bacteria die when the free oxygen is total-
ly consumed; the anaerobic bacteria attack the sulfate
ion, which is the second most important anion in the
seawater. During this attack. the sulfate reduces to
sulfite and then to sulfide; the Eh drops to -600 mV,
H 2 S is liberated, and CaCO 3 precipitates as the pH rises
above 8.5.
Dissolved Gases
Large quantities of dissolved gases are contained in
oilfield brines. Most of these gases are hydrocarbons;
however, other gases such as CO2 , N?. and HzS often
are present. The solubility of the gases generally
decreases with increased water salinity, and increases
with pressure.
Hundreds of drillstem samples of brine from water-
bearing subsurface formations in the U.S. gulf coast area
were analyzed to determine their amounts and kinds of
hydrocarbons. 2o The chief constituent of the dissolved
gases usually was methane, with measurable amounts of
ethane, propane, and butane. The concentration of the
dissolved hydrocarbons generally increased with depth
in a given formation and also increased basinward with
regional and local variations. In close proximity to some
oiltields, the waters were enriched in dissolved
hydrocarbons, and up to I4 scf dissolved gasibbl water
was observed in some locations. A more detailed discus-
sion of this topic is given in Chap. 22.
Organic Constituents
In addition to the simple hydrocarbons, a large number
of organic constituents in colloidal, ionic, and molecular
form occur in oilfield brines. In recent years, some of
these organic constituents have been measured quan-
titatively. However, many organic constituents are pre-
sent that have not been determined in some oilfield
TEMPERATURE , .F
Fig. 24.9-Viscosity of sodium chloride solutions as a function
of temperature and concentration at 14.7 psia.
brines primarily because the analytical problems are dif-
ficult and very time-consuming.
Knowledge of the dissolved organic constituents is im-
portant because these constituents are related to the
origin and/or migration of an oil accumulation, as well
as to the disintegration or degradation of an accumula-
tion. The concentrations of organic constituents in
oilfield brines vary widely. In general, the more alkaline
the water, the more likely that it will contain higher con-
centrations of organic constituents. The bulk of the
organic matter consists of anions and salts of organic
acids: however, other compounds also are present.
; 0.611
I I / I 1
i-
m
0 0.5.
,o
\
TEMPERATURE, F
Fig. 24.10-Effect of temperature on viscosity of water.
24-18
PETROLEUM ENGINEERING HANDBOOK
Knowledge of the concentrations of benzcnc. toluene,
and other components in oilfield brines is used in ex-
ploration. The solubilities of some of these compounds
in water at ambient conditions and in saline waters at
elevated tern eraturex
determined. x3.
f:

and pressures have been
However. the actual concentrations of these and other
organic constituents in subsurface oilfield brines is
another matter. It has been shown experimentally that
the solubilities of some organic compounds found in
crude oil increase with temperature and pressure if
pressure is maintained on the system. The increased
solubilitiea become significant above 150C. The
solubilities decrease with increasing water salinity.
Waters associated with paraffinic oils are likely to con-
tain fatty acids. while those associated with asphaltic oils
more likely contain naphthenic acids.
Quantitative recovery of organic constituents from
oilfield brines is difficult. Temperature and pressure
changes. bacterial actions. adsorption. and the high
inorganic/organic-constituents ratio in most oilfield
brines are some reasons why quantitative recovery is
difficult.
Interpretation of Chemical Analyses
Oilfield waters include all waters or brines found in
oilfields. Such waters have certain distinct chemical
characteristics.
About 70% of the world petroleum reserves are
associated with waters containing more than 100 g/L
dissolved solids. A water containing dissolved solids in
excess of 100 g/L can be classified as a brine. Waters
associated with the other 30% of petroleum reserves con-
tain less than 100 g/L dissolved solids. Some of these
waters are almost fresh. However, the presence of
fresher waters usually is attributed to invasion after the
petroleum accumulated in the reservoir trap.
Examples of some of the low-salinity waters can be
found in the Rocky Mt. areas in Wyoming fields such as
Enos Creek, South Sunshine. and Cottonwood Creek.
The Douleb oil field in Tunisia is another example.
The composition of dissolved solids found in oilfield
waters depends on several factors. Some of these factors
are the composition of the water in the depositional en-
vironment of the sedimentary rock, subsequent changes
by rock/water interaction during sediment compaction.
changes by rock/water interaction during water migra-
tion (if migration occurs), and changes by mixing with
other waters, including infiltrating younger waters such
as meteoric waters. The following are definitions of
some types of water.
Types of Water
Meteoric Water. This is water that recently was in-
volved in atmospheric circulation: furthermore, the age
of meteoric groundwater is slight when compared with
the age of the enclosing rocks and is not more than a
small part of a geologic period. I
Seawater. The composition of seawater varies
somewhat, but in general will have a composition
relative to the following (in mg/L): chloride--19.375,
bromide-67, sulfate-2,712. potassium-387. sodium
- 10,760, magnesium- 1,294, calcium-4 13, and stron-
tium-8.
Interstitial Water. Interstitial water is the water con
mined in the small pores or spaces between the minute
grains or units of rock. Interstitial waters are . snl , yc, , t r r i c'
(formed at the same time as the enclosing rocks) or
cyi gcr wr i c (originated by subsequent infiltration into
rocks).
Connate Water. The term connate implies born.
produced. or originated together-connascent. There-
fore. connate water probably should bc considered an in-
terstitial water of syngenetic origin. Connate water of
this definition is fossil water that has been out of contact
with the atmosphere for at least a large part of a geologic
period. The implication that connate waters are only
those born with the enclosing rocks is an undesirable
restriction.
Diagenetic Water. Diagenetic waters are those that have
changed chemically and physically, before. during, and
after sediment consolidation. Some of the reactions that
occur in or to diagenetic waters include bacterial. ion ex-
change, replacement (dolomitization). infiltration by
permeation, and membrane filtration.
Formation Water. Formation water. as defined here, is
water that occurs naturally in the rocks and is present in
them immediately before drilling.
Juvenile Water. Water that is in primary magma or
derived from primary magma is juvenile water.
Condensate Water. Water associated with gas
sometimes is carried as vapor to the surface of the well
where it condenses and precipitates because of
temperature and pressure changes. More of this water
occurs in the winter and in colder climates and only in
gas-producing wells. This water is easy to recognize
because it contains a relatively small amount of dis-
solved solids, mostly derived from reactions with
chemicals in or on the well casing or tubing.
Water analyses may be used to identify the water
source. In the oil field one of the prime uses of these
analyses is to determine the source of extraneous water
in an oil well so that casing can be set and cemented to
prevent such water from flooding the oil or gas horizons.
In some wells a leak may develop in the casing or ce-
ment, and water analyses are used to identify the water-
bearing horizon so that the leaking area can be repaired.
With the current emphasis on water pollution prevention.
it is very important to locate the source of a polluting
brine so that remedial action can be taken.
Comparisons of water-analysis data are tedious and
time-consuming; therefore. graphical methods are com-
monly used for positive, rapid identification. A number
of systems have been developed. all of which have some
merit.
Graphic Plots
Graphic plots of the reacting values can be made to il-
lustrate the relative amount of each radical present. The
graphical presentation is an aid to rapid identification of
a water and classification as to its type. Several methods
have been developed.
PROPERTIES OF PRODUCED WATERS 24-19
Tickell Diagram. The Tickell diagram was developed
using a six-axis system or star diagram. X5 Percentage
reaction values of the ions are plotted on the axes. The
percentage values are calculated by summing the
equivalent proton masses (EPMs) of all the ions.
dividing the EPM of a given ion by the sum of the total
EPMs, and multiplying by 100.
The plots of total reaction values, rather than of
percentage reaction values, are often more useful in
water identification because the percentage values do not
take into account the actual ion concentrations. Water
differing only in concentrations of dissolved constituents
cannot be distinguished.
However, with time and tectonic events plus transgres-
sion and regression of oceans and seas, even these
sediments probably were subjected to marine waters by
infiltration.
In any event. the petroleum, which formed from
organic matter deposited with the sediments, migrated
from what usually is called the source rock into more
porous and permeable sedimentary rock. Petroleum
(i.e., oil and gas) is less dense than water; therefore, it
tends to float to the top of a water body regardless of
whether the water is on the sutiace or in the subsurface.
is an oilfield water.
The question of the origin of oilfield brines is difficult
to answer in a general manner. The water involved and
the constituents dissolved in the water to form the brine
can involve divergent histories. Subsurface water is there
either because it originally was there or because it in-
Therefore, water associated with petroleum in a sub-
surface reservoir is called an oilfield water. By this
definition, any water associated with a petroleum deposit
filtrated to the subsurface from the surface. If it was
there originally, it would be endogenetic, whereas if it
infiltrated from the surface and/or penetrated with sedi-
Stiff Diagram. Stiff plotted the reaction values of the
Reistle Diagram. Reistle devised a method of plotting
ions on a system of rectangular coordinates. 87 The cat-
water analyses by using the ion concentrations. * The
ions are plotted to the left and the anions to the right of a
vertical zero line. The endpoints then are connected by
data are plotted on a vertical diagram. with the cations
straight lines to form a closed diagram, sometimes called
a butterfly diagram. To emphasize a constituent that
plotted above the central zero line and the anions below.
may be a key to interpretation, the scales may be varied
by changing the denominator of the ion fraction. usually
This type of diagram often is useful in making regional
in multiples of 10. However, when a group of waters is
being considered, all must be plotted on the same scale.
correlations or studying lateral variations in the water of
a single formation because several analyses can be plot-
ted on a large sheet of paper.
ment accumulations, it would be exogenetic.
Obviously these two types of waters could meet and
mix in the subsurface and thus the mixture would contain
water of two separate origins. The problem could multi-
ply if more than one exogenetic water were involved.
The chemical composition of an oilfield brine is an end
product of several variables. These variables include (I)
dissolved ions, salts, gases, and organic matter, (2) reac-
tions between these dissolved constituents, and (3) in-
teraction of the brine with the surrounding rocks,
petroleum, etc. There are a number of pertinent reactions
that could cause the composition of a subsurface oilfield
brine to change in composition, including leaching of the
rocks, ion exchange between water and rock, redox,
mineral hydration, mineral formation and/or dissolution,
ion diffusion, gravitational segregation of ions, and
membrane filtration, or other osmotic effects.
Many investigators believe that this is the best method
of comparing oilfield water analyses. The method is sim-
ple. and nontechnical personnel can be easily trained to
construct the diagrams.
Other Methods. Several other water identification
diagrams have been developed, primarily for use with
fresh waters, and they are not discussed here. The Stiff
and Piper diagrams, 87~88 were ada ted to automatic data
processing by Morgan et al .
*B
and Morgan and
McNellis. * The Piper diagram uses a multiple trilinear
plot to depict the water analysis. and this quaternary
diagram shows the chemical composition of the water in
terms of cations and anions.88 Angino and Morgan ap-
plied the automated Stiff and Piper diagrams to some
oilfield brines and obtained good results.
Occurrence, Origin, and Evolution of
Oilfield Waters
The sedimentary rocks that now consist of stratified
deposits originally were laid down as sediments in
oceans, seas. lakes. and streams. Naturally. these
sediments were filled with water. This water is still pres-
ent in the stratified sediments and millions of years later
would be considered truly connate water.
Many large sedimentary strata originally were
associated with oceans and seas. The original associated
water. therefore. was marine in such sediments.
Sediments laid down by lakes and streams would not
contain a marine water during their initial deposition.
It is rather difficult to rank the factors that might be
more important for general consideration. However. two
of the more important factors probably are the original
composition of the water and interaction of that water
with the rocks. If one assumes that the original water was
a marine water and that the associated sediments (subse-
quently sedimentary rocks) were marine, then the
original composition of the marine water could be an im-
portant factor.
However, even the salinity in the various oceans and
seas is not constant. For example. the salinity of the
waters in the major oceans ranges from 33,000 to 38,000
mg/L, about 40,000 mg/L in the Mediterranean Sea, up
to 70,000 mg/L in the Red Sea. about 18,000 to 22,000
mg/L in the Black Sea, and only about I .OOO mg/L in the
Baltic Sea. Some land-locked waters. such as the Dead
Sea. Great Salt Lake, etc., contain waters that are nearly
saturated with dissolved solids.
Studies of formation waters in the western Canada
sedimentary basin indicate that 85% of the strata were
deposited under marine conditions, while 15% were
deposited under brackish-water and possibly under
freshwater conditions. y2 These investigators estimated
that 80% of all the sedimentary strata in Alberta were
24-20 PETROLEUM ENGINEERING HANDBOOK
deposited under marine conditions. This led to the con-
clusion that one could assume with negligible error that
all sedimentary strata originally contained seawater.
Further, the study indicated that evaporites form an
important volumetric part of several of the stratigraphic
units. Some of the stratigraphic units possibly contain
bitterns subsequent to halite precipitation but preceding
precipitation of potassium salts. They calculated an
average formation water salinity of about 46,000 mg/L
TDS. which indicated a net gain of dissolved salts. Of
the major and some minor components, all showed a net
gain with the exception of Mg and SOa.
Factor analysis was used in interpretation of the
analyses. and the following factors were considered to be
major controls: composition of the original seawater,
dilution by freshwater recharge, membrane filtration,
solution of halite. dolomitization, bacterial reduction of
sulfate. formation of chlorite. cation exchange on clays,
contribution from organic matter, and solubility
relationships.
It was concluded that (I) the formation waters of
western Canada are ancient seawaters in which the
deuterium concentration was changed because of mixing
with infiltrating fresh water, (2) oxygen-18 was ex-
changed with carbonates in the rocks, and (3) dissolved
salts are in equilibrium with the rock matrix subsequent
to their redistribution by membrane filtration and/or dilu-
tion by freshwater recharge. Equilibrium was attained by
such processes as dissolution of evaporates, new mineral
formation. cation exchange on clays. desorption of ions
from clays and organic matter, and mineral solubilities.
The majority of the published research studies seem to
agree that all these controls and/or reactions are involved
in establishing the composition of oilfield brines. Fur-
ther. most investigators agree with the assumption that
marine water usually is a part of the original material
from which formation waters evolve. Opinions,
however, are not unanimous with respect to how they
evolved. The major disagreements are related to the
membrane filtration theory and to other modes of con-
ccntrating the dissolved solids such as seawater
evaporation.
It is possible to reconstruct the evolution of some
oilfield brines in sedimentary basins if one reasons that
they are genetically related to evaporites. For example.
geochemical and geological studies of some very con-
centrated brines indicate that in deep quiescent bodies of
water. strong bitterns can persist for long periods of time
under a layer of near-normal seawater. As a result, car-
bonates can precipitate from the less saline water and fall
through the bittern at the bottom, and. as compaction
proceeds. the pore spaces remain filled with bitterns.
Some fossil brines once trapped have not moved very far
or very fast.
A geochemical model can be built to represent the
origin and evolution of this type of brine by using the
relatively simple operations and processes of (I)
evaporation. (2) precipitation, (3) sulfate reduction, (4)
mineral fomlation and diagenesis. (5) ion exchange. (6)
leaching. and (7) expulsion of interstitial fluids from
evaporites during compaction.
Experimental work indicated that about 14% of the
bromide in seawater precipitates with the halite as
seawater evaporates. The average concentration of
bromide in the Smackover brines is 3,100 mg/L.
Therefore. the average degree of concentration of these
brines compared to seawater is 3,100+65 =48. Assum-
ing that seawater is concentrated 50-fold, the approx-
imate composition of a brine can be calculated. 26
Shale Compaction and Membrane Filtration
Some investigators believe that the salinity variations
found in oilfield waters are the result of filtration of
water through shale. The membrane filtration theory
first was suggested by De Sitter. Laboratory ex-
periments indicated that natural shales can act as
semipermeable membranes. ys.y6 This system working in
nature should cause a water to be more saline on one side
of the shale membrane and almost fresh or less saline on
the other side. This follows because the shale membrane
should filter out the dissolved ions on the upflow side.
causing the water on the downflow side to contain few or
no dissolved ions.
Quantities of Produced Water
An analysis was made of the approximate amount of
water produced with crude oil in I4 states. The states and
their percent of total U.S. crude oil production in 1981
are: Alabama, 0.3%; Alaska, 19.9%; California,
I I .7%; Colorado, I .O%; Florida, I .4%; Louisiana.
13.4%; Montana, 1.0%; Mississippi, 1.2%; Nebraska,
0.2%; New Mexico, 2.3%; North Dakota, 1.4%;
Texas, 31.2%; Utah, 0.8%: and Wyoming, 4.2%.
Fig. 24.1 I indicates the crude oil and water production
from wells in the 14 states. The figure indicates produc-
tion of about 4.3 bbl water/bbl oil. Fig. 24.12 is a
similar graph for 13 states excluding Alaska. This figure
indicates production of about 5.2 bbl wateribbl oil. Fur-
ther. it can be shown that oil wells produce more water
as cumulative oil production increases. In other words,
the older the well, the higher the WOR.
Recovery of Minerals From Brines
Extraction of minerals from oilfield brines should be
considered in production planning (I) to recoup explora-
tion and development costs, (2) to prevent environmental
damage from brine, (3) to produce potable water. and (4)
to conserve all valuable minerals and energy.
Precipitation is the most common separation process
used in separating minerals from any type of brine.
Minerals recovered from brines in the U.S. include com-
pounds of iodine, bromine. chlorine, sodium. lithium.
potassium, magnesium, and calcium.
Evaporation of a saline water or brine will cause the
precipitation of calcium carbonate. calcium sulfate,
sodium chloride, magnesium sulfate, potassium
chloride, and finally magnesium chloride. These are the
major chemicals in most brines, and this is the sequence
order in which these compounds will precipitate. Mere
preclpltation will not produce a very pure chemical from
a brine; therefore, other chemical or physical processes
arc used.
For example. iodine, which is in the foml of iodide in
a brine. is recovered by these steps: (I) the iodide is ox-
idized to iodine, (2) the iodine is stripped from the brine,
(3) the iodine then is reduced back to iodide, (4) the
iodide is oxidized again to iodine, (5) the iodine is
PROPERTIES OF PRODUCED WATERS 24-21
D 2700C
2
6
6
2 2600C
E
ZSOOC
BOO<
700(
6OOt
H---L,-
--4
,/ Crude
I I I I
1975 76 77 78 73 80
YEAR
Fig. 24.1 I-Crude oil and water produced ( x 1,000 B/D) from
wells in 14 states including Alaska.
crystallized and filtered, and (6) the iodine crystals are
purified further.
Bromine is recovered by a similar though, of course,
different process. It is present in a brine as bromide. The
U.S. Bureau ofMines Yearbook9 contains information
on general recovery technology, domestic production,
consumption and uses, prices, stocks, etc., of minerals
recovered from brines as well as minerals recovered
from other sources.
The first plant in the U.S. in more than 40 years built
solely to produce iodine from brine went on stream in
1977 near Woodward, OK. It has a design capacity of 2
million lbm iodineiyr or about 30% of the annual U.S.
demand. Some smaller-scale operations to recover
iodine started in 1982 near Kingfisher, OK.
Several plants recover bromine and other constituents
from brine near El Dorado, AR. The brine is produced
from the Smackover formation.
Magnesium and other chemicals are recovered from
lake brines, well brines, and seawater in plants located
near Ogden, UT; Ludington, MI: Freeport, TX; and
Port St. Joe, FL. Lithium is recovered from brine near
Clayton Valley, NV. 98
Economic Evaluation
It is true that market demand fluctuates with supply;
therefore, any company considering an enterprise to
30000
29000
27000
g
o 26000
z
I
25000
c
7000
6000
5000
I!
13 Stclcs (ercludlng Aiasio)
5 76 77 70 79
YEAR
80
Fig. 24.1 P-Crude oil and water produced ( x 1,000 B/D) from
wells in 13 states excluding Alaska.
recover minerals from brines should make an in-depth
study of the current and potential economics. Some of
the factors that must be determined are (1) concentm-
tions of valuable minerals in a brine, (2) amount of brine
available, (3) costs of gathering the brine, (4) costs of
recovering the minerals from the brine, (5) present and
potential market demand for the recovered minerals, and
(6) costs of delivering the minerals to the market. 26
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