EPA-660/2-74-010
APRIL 1974
Environmental Protection Technology Series
ine Groundwaters Produced with
Oil and Gas
^^Bjj
Office of Research and Development
U.S. Environmental Protection Agency
Washington, D.C. 20460
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RESEARCH REPORTING SERI2S
Research reports of the Office of Research and
Monitoring, Environmental Protection Agency, have
been grouped into five series. These five broad
categories were established to facilitate further
development and application of environmental
technology. Elimination of traditional grouping
was consciously planned to foster technology
transfer and a maximum interface in related
fields. The five series are:
1. Environmental Health Effects Research
2m Environmental Protection Technology
3. Ecological Research
4. Environmental Monitoring
5. Socioeconomic Environmental studies
This report has been assigned to the ENVIRONMENTAL
PROTECTION TECHNOLOGY series. This series
describes research performed to develop and
demonstrate instrumentation, equipment and
methodology to repair or prevent environmental
degradation from point and non-point sources of
pollution. This work provides the new or improved
technology required for the control and treatment
of pollution sources to meet environmental quality
standards.
EPA REVIEW NOTICE
This report has been reviewed by the Office of Research and
Development, EPA, and approved for publication. Approval
does not signify that the contents necessarily reflect the
views and policies of the Environmental Protection Agency,
nor does mention of trade names or commercial products consti-
tute endorsement or recommendation for use.
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EPA-660/2-74-010
April 1974
SALINE GROUNDWATERS PRODUCED WITH OIL AND GAS
By
A. Gene Collins
U.S. Department of the Interior
Bureau of Mines
Bartlesville Energy Research Center
Bartlesville, Oklahoma 74003
Project 16060EQQ
Program Element 1BA024
Project Officer
JackW. Keeley
Robert S. Kerr Environmental Research Laboratory
U.S. Environmental Protection Agency
Ada, Oklahoma 74820
Prepared for
OFFICE OF RESEARCH AND DEVELOPMENT
U.S. ENVIRONMENTAL PROTECTION AGENCY
WASHINGTON, D.C. 20460
For sale by the Superintendent of Documents, U.S. Government Printing Office, Washington, D.C. 20402 - Price $1.15
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ABSTRACT
More than 60,000 saline water analyses were collected by the U.S. Bureau
of Mines for entry into an automatic data processing system. Screening of the data
eliminated 30,000 analyses; 20,000 were entered into STORET, the data processing
system formulated by the Environmental Protection Agency; and 10,000 additional
analyses could be entered with additional funding.
The water analyses are used in studies related to identifying the source of a
brine, classification of groundwater for use in geochemistry, plotting local and
regional salinity maps, determining sources of pollution of freshwater and land by
brines, and studies of the use of saline water for desalination to produce fresh-
water and valuable minerals. Examples of each of these studies are given in this
report.
Irresponsible control of brines can seriously pollute fresh water and land.
The analyses now in STORET should be wisely used in pollution prevention programs,
Additional analyses should be entered into STORET to aid groundwater and land
pollution prevention programs.
This report was submitted in fulfillment of Contract 16060 EQQ under the
-.
sponsorship of the Office of Research and Monitoring, Environmental Protection
Agency.
ii
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CONTENTS
Page
Abstract ii
List of Figures iii
List of Tables v
t
Acknowledgments vi
Sections
I Conclusions 1
II Recommendations 2
III Introduction 3
IV Saline Water Analyses Stored in STORET 6
V Methods of Identifying a Water Source 9
VI Saline Water Classification 23
VII Plotting Salinity Maps for Use in Local or Regional Studies 29
VIII Pollution of Freshwater and Land by Brines 38
IX Use of Saline Waters for Desalination to Produce Freshwater
and Valuable Minerals 45
X References 61
XI Appendix I 63
XII Appendix II 68
iii
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FIGURES
No. Page
1 Tickell and modified Tickell diagram for Gulf Coast
water/ sample no. 1 14
2 Tickell and modified Tickell diagram for Anadarko Basin
water, sample no. 2 15
3 Tickell and modified Tickell diagram for Williston Basin
water, sample no. 3 16
4 Tickell and modified Tickell diagram for Gulf Coast and Anadarko
Basin waters, mixed 1 to 1 17
5 Tickell and modified Tickell diagram for Gulf Coast, Williston,
and Anadarko Basin waters, mixed 1:1:1 18
6 Water-analysis interpretation, Reistle system—sample numbers
correspond to those shown on figures 1-3 19
7 Water-analysis interpretation, Stiff method—sample numbers
correspond to those shown on figures 1-3 20
8 Concentrations of dissolved solids in the formation waters 30
9 Chloride concentration in the formation waters 31
10 Calcium concentration in the formation waters 32
11 Salinity variations in formation waters at the base of the Lower
Wilcox Formation located in portions of Texas, Louisiana,
Arkansas, Mississippi, and Alabama 35
12 Salinity variations in formation waters of the Lower Tuscaloosa
and Woodbine Formations located in portions of Oklahoma,
Texas, Arkansas, Louisiana, Mississippi, Georgia, South
Carolina, North Carolina, and Florida 36
13 Routes by which saltwater can enter freshwater wells from
faulty oil or disposal wells 42
14 Diagramatic flowsheet for producing freshwater and valuable
elements from brines 48
15 Diagramatic flowsheet for producing descaled seawater and
fertilizer 54
iv
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FIGURES
No. Page
16 Approximate geographic locations of brines containing high
concentrations of sodium 57
17 Approximate geographic locations of brines containing high
concentrations of calcium 58
18 Approximate geographic locations of brines containing high
concentrations of magnesium 59
19 Approximate geographic locations of brines containing high
concentrations of bromine 60
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TABLES
No. Page
1 Number pf Saline Water Analyses From Oil-Productive
States Entered Into STORE! 7
2 Reaction Coefficients 10
3 Reacting Values (R.V.) 10
4 Reacting Value Distribution 11
5 Combination factors 12
6 Hypothetical Combinations 13
7 Classification of Some Saline Groundwaters From 10 Formations
in Eight Sedimentary Basins 25
8 Chemicals Used in Scale Inhibitors 38
9 Dollar Value of Dissolved Cherrvcals a Brine Should Contain
Per Million Kilograms of Brine Produced From a Given Depth 49
10 Amount of Element Necessary in a Million Kilograms of
Brine to Produce a Chemical Worth $550 at the Market 50
vi
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ACKNOWLEDGMENTS
The interest and support of Mr. Jack W. Keeley, Program Element Director,
and Mr. Arnold B. Joseph, Program Element Manager, is especially noteworthy.
Mr. Joseph was instrumental in approving the project and revising the objectives.
Mr. Keeley also served as project officer and provided necessary recommendations
to guide the project.
Mr. Michael E. Crocker, Bureau of Mines, placed all of the oilfield brine
data in the correct format for entry into STORET. Other Bureau of Mines employees
who aided in the project included Ms. Katie Towers, Ms. Carolyn Jones, Ms. Bertha
Paine, Ms. Cynthia Pearson, Ms. Sherry Bishop, Ms. Debbie Williams, Ms. Carol
Parsons, Ms. Carolyn Cloe, and Mr, Fred Burrow.
vii
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SECTION I
CONCLUSIONS
The 20,000 saline water analyses that were entered into STORET will be
useful in preventing pollution of freshwater and land by brines. These analyses
can be used in identifying the source of a saline water that is polluting a fresh-
water. Salinity maps of local or regional areas can be plotted with the analyses
and used to determine potential waste disposal zones and potential pollution
areas, such as possible brine intrusion horizons. The maps also will be useful
in locating saline waters that can be desalinated for the production of fresh-
water and/or valuable minerals. Additional saline water analyses should be
added to STORET to aid these study areas.
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SECTION II
RECOMMENDATIONS
It is recommended that EPA add additional saline water analyses to STORET,
especially analyses that include minor and trace constituent data in addition to the
macroconstituents. Local and regional maps should be prepared from the saline
water analyses and used in groundwater, surface water, and land pollution studies.
Once a groundwater is polluted by a brine it can take several hundred years
before the polluted area is once again useful as a freshwater source. Therefore/
stringent regulations should be formulated and enforced. A saline groundwater
monitoring program should be established.
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SECTION 111
INTRODUCTION
GENERAL
In the early days of the oil industry, oilfield brines were allowed to flow by
natural drainage into streams until it was noted that some of the once-good fishing
streams contained less fish, that fur-bearing animals had disappeared in these areas,
and dead trees and barren soils now bordered these same streams that once had
luxurious vegetation. A few years prior to 1935, litigation pertaining to pollution
of freshwater was taking a heavy toll from oil operators. In certain older oil-
producing areas, extensive plots of ground still are barren, with no living vegeta-
tion. The litigations against oil operators combined with legislation for freshwater
protection to force better disposal techniques.
At first, evaporation ponds were employed; however, usually more brine
drained into freshwater aquifers than evaporated. Until recently, a widely
employed practice for disposal was the dumping of oil brines into freshwater bodies
when they existed nearby. This disposal method was practiced along the Gulf of
Mexico and in California. Authorities in these areas insisted that oil separation
be highly efficient to prevent damage to fish and oyster populations. Recently
the state pollution boards have ruled that oilfield brines can no longer be dumped
into surface saltwater bodies. In California, excess oilfield waters now are being
injected into porous subsurface formations as rapidly as the injection systems can
be constructed.
The plains states not only are situated in a hard water belt, but seldom have
had an overabundance of usable or surface groundwater. For this reason, State
legislatures passed laws for the protection of freshwater supplies, allowing the
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return of oilfield brines to subsurface formations and allowing the repressuring or
waterflood of oil properties with saltwater. Subsurface brine disposal has since
become the common practice. Since the laws were passed to allow subsurface
disposal, legislation has forced such disposal and set up tight controls for it. A
survey of cost data on subsurface injection in 1968 showed that subsurface disposal
costs ranged from 6.6 to 19.8 cents per cubic meter. These figures were based
on operating costs plus 5-year amortization.
Costs vary with the amount of treatment necessary before injection, the
number of production wells per injection well, and the costs of drilling injection
wells or the depth of the injection formation. The depths of disposal wells normally
encountered required no injection pressure. The brines normally flow readily into
the receiving formations under the gravity head alone.
The annual production of 1.23 billion cubic meters of saline water in associ-
ation with petroleum in the United States is an expense to oil producers even
i ..,'•
though some of these waters contain salts yielding valuable elements that might
be economically recovered. Elements found in some brines in economic concen-
trations are magnesium, calcium, potassium, lithium, boron, bromine, and iodine.
Many of them are recovered by chemical companies from seawater, salt lakes, and
subsurface saline waters.
The recovery of minerals from saline waters dates back to the first time that
someone precipitated a compound from a salt solution. Precipitation is the most
used separation process employed in separating minerals from seawater or subsurface
brines. Research continues on the separation methods which show economic
promise in mineral separation from saline waters.
Commonly the waters from different strata differ considerably in their dissolved
chemical constituents, making the identification of a water from a particular strata
easy. However, in some areas, the concentrations of dissolved constituents in waters
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from different strata do-not differ significantly, and the identification of such waters
is difficult or impossible.
The amount of brine produced with the oil often increases as the amount of
oil produced decreases. If this is edge water, nothing can be done about it. If
it is bottom water, the well can be plugged back. However, it often is intrusive
water from a shallow sand gaining access to the well from a leaky casing or faulty
completion,and this can be repaired.
OBJECTIVE
The project objective was to establish an automatic data processing reference
system for subsurface saline waters in the STORET format and to show its use in
determining the sources of ground water and surface water pollution resulting from
oil and gas production and deep well disposal. (STORET is the central computer-
oriented U.S. Environmental Protection Agency Water Quality Control System for
storing and retrieving water data and water-related data.) In addition, this saline
water reference system can be used to plot water analyses diagrams for use in saline
water intrusion studies, plot cross-section or contour salinity maps to study large
areas of possible pollutants, and to determine areas where desalination to produce
freshwater and valuable byproduct minerals might be feasible.
Scope
Brine analyses from most of the oil and gas producing sedimentary basins of
the United States were collected from government agencies and oil companies
and entered into the STORET system. This report examines the following areas:
1. Saline water analyses stored in STORET.
2. Methods of identifying a water source.
3. Saline water classification.
4. Plotting salinity maps for use in local or regional studies.
»
5. Pollution of freshwater and land by brines.
6. Use of brines for desalination to produce freshwater and valuable minerals.
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SECTION IV
SALINE WATER ANALYSES STORED IN STORET
More than 60,000 saline water analyses were collected from various
governmental and industrial sources. The primary method of collection was
microfilming of the original documents. The microfilmed data then were
restored to their original size with a Xerox microfilm printer. The data
were examined to insure that they were usable and complete.
This screening process eliminated about 30,000 analyses because of
incomplete sample description, incomplete analyses of the macro constituents
(sodium, calcium, magnesium, bicarbonate, chloride, and su I fate), or an
obviously poor sample or poor analysis. Funding of the project permitted the
entry of 20,000 analyses into STORET. At least 10,000 good additional
analyses could be entered into STORET with additional funds. Table 1 shows
the number from each oil-producing state.
The STORET saline groundwater data format shows the location in latitude
and longitude, the major river basin, the major geologic province, geologic era,
geologic system, and geologic formation, together with the depth of the well,
date sampled, and the chemical and physical analyses of the sample.
Problems previously encountered with coding were eliminated by the use
of standard codes obtained for the parameters that were not previously in the
STORET system; the geologicsystem, series, and formation for a particular sample
are coded from data obtained from the Bulletin of Standard Stratigraphic Codes
adopted by the American Association of Petroleum Geologists. The use of these
codes eliminates duplicity of coding because each formation has a specific
alphanumeric listing.
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Table 1. NUMBER OF SALINE WATER ANALYSES FROM OIL-PRODUCTIVE
STATES ENTERED INTO STORET
State
Alabama
Alaska
Arizona
Arkansas
California
Colorado
Illinois
Indiana
Kansas
Louisiana
Michigan
Mississippi
Montana '
Nebraska
New Mexico
New York
North Dakota
Oklahoma
Pennsylvania
South Dakota
Texas
Utah
Wyoming
Total
^^BABVWHVAV^^^^^^^^b^h^^*H^H4^^v^^BHH^^H^^^^^MM^M^^^^H^HMVMMMIMIIWMM«^^
Number of samples
90
112
15
573
109
1,032
543
443
2,350
1,695
347
320
1,083
325
388
2
301
1,769
90
73
2,820
489
5,000
19,969
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Appendix I illustrates the format used for coding of the data that is entered
into the STORE! system. A retrieval of the data entered into STORE! for the
State of !exas was completed to determine if the material was properly formated.
Appendix II is an example of a retrieval for the same sample illustrated in
Appendix I.
8
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SECTION V
METHODS OF IDENTIFYING A WATER SOURCE
Water analyses may be used to identify the source of a water. In the oilfield
one of the prime uses of these analyses is to determine the source of extraneous
water in an oil well. A leak may develop in the casing or cement, and water analyses
are used to identify the water-bearing horizon so that the water zone can be squeeze
cemented to prevent water from flooding the oil or gas horizon. With the present
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 commonly used for positive, rapid identification. A number
of systems have been developed, all of which have some merit. ' ' '
CALCULATING PROBABLE COMPOUNDS
The hypothetical combinations of dissolved constituents found in waters are
commonly calculated by combining the positive and negative radicals in the
following order:
Cation,
positive
Calcium
Magnesium
Sodium
Potassium
Anion,
negative
Bicarbonate
Sulfate
Chloride
Nitrate
Calcium is combined with bicarbonate, and if more calcium is available than that
consumed by bicarbonate, it is combined with sulfate, chloride, and nitrate until
exhausted. Conversely, any excess bicarbonate is combined with magnesium,
sodium, and potassium until consumed. Other radicals can and should be added
-------
for most petroleum reservoir waters. These include lithium, strontium, barium,
iron, borate, phosphate, bromide, and iodide. They can be grouped in the
appropriate column and then in the calculation; as each positive and negative
radical is totally combined, the next following radical is combined until both
the cations and onions are exhaused. If the analysis is correct, the cations and
onions will be present in approximately equivalent amounts.
To calculate the hypothetical combinations, the reacting values of the
positive and negative radicals or ions are calculated as follows: Reacting values
(R.V.) or equivalents per million (epm) = mg/l, ion x (valence of ion)/(m.w. of ion),
The term (valence of ion)/(m.w. of ion) is called "reaction coefficient"
and the positive and negative ions have values as shown in Table 2. Table 3
indicates how the results of a water analysis are converted to reacting values.
Table 2. REACTION COEFFICIENTS
Cation
Calcium
Magnesium
Iron
Sodium
0.0499
0.0823
0,0358
0.0435
Anion
Bicarbonate
Sulfate
Chloride
0.0164
0.0208
0.0282
Table 3. REACTING VALUES (R.V.)
Cation,
Ca
Mg
Fe
Na
4,
3,
9,
000
000
100
400
m
X
X
X
X
9/1
0.
0.
0.
0.
0499 =
0823 =
0358 =
0435 =
i
R.V
199.
246.
3.
408.
•MHMMfeiieVHa
858.
*
6
8
6
9
9
HC03
so4
Cl
••'• 1
Anion, mg/l
500x0.0164 =
200x0.0208 =
30,000x0.0282 =
R.V
8.
, <4-
846.
V^WMBMfl
858.
«
2
2
3
••MB
7
10
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The reacting values are a measure of the cations and onions dissolved in the
water. With a reacting value of 199.6, the 4,000 mg/l of calcium in the example
shown in Table3 can combine with all the bicarbonate, all the sulfate, and 187.2 epm
of the chloride. Magnesium will combine with 246.8 epm of chloride/ iron with 3.6,
and sodium with 408.9. Thus the reacting values can be considered to be distributed
as shown in Table 4.
Table 4. REACTING VALUE DISTRIBUTION
Ca as calcium bicarbonate 8.2
Ca as calcium sulfate 4.2
Ca as calcium chloride 187.2
Mg as magnesium chloride 246.8
Fe as iron chloride 3.6
Na as sodium chloride 408.9
858.9
A charge balance should be determined on the brine analysis. This can be
done using the equation: (x - y)/(x + y) x 100 = % CB
where x = total positive ions (epm)
y = total negative ions (epm)
CB = charge balance error and it should always be less than
2% for a brine.
DETERMINING A SOUGHT COMPOUND
It is necessary to multiply the reacting value of an anion or a cation by a
combination factor to determine a hypothetical compound. This factor is necessary
to convert the reported radical into the desired compound. For example, the factor
11
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for converting Ca to CaCCX is CaCOVCa or 2.50 and the reaction coefficient for
Ca is l/(Ca/2) or 0.0499. Therefore, the combination factor to convert the reacting
value for Ca to CaCCL is 2.50 f 0.0499= 50.1. Table 5 illustrates some combination
factors.
TableS. COMBINATION FACTORS
Reaction values
given
Ca or COg
Ca or SO.
Ca or Cl
Mg or CO3
Mg or SO.
Mg or Cl
Fe or CO3
Fe or SO.
4
Fe or Cl
Na or CO3
Na or SO4
Na or Cl
Compound
sought
CaC03
CaSO,
4
CaCI2
MgCO.
o
MgS04
MgCl2
FeC03
FeSO,
4
FeCI2
Na2C03
Na2S04
NaCI
Combination
factor
50.1
68.1
55.5
42.2
60.1
47.6
57.8
76.0
63.4
53.1
71.0
58.4
The combination factors given in Table 5 can be used to calculate the
hypothetical combinations shown in Table 6, using the analysis shown in Table 4.
12
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Table 6. HYPOTHETICAL COMBINATIONS
Ca(HCO_) to CaCO_ 8.2 x 50.1 = 411 mg/l CaCO_
o o 3
CaSO4 4.2 x 68.1 = 286 mg/l CaSO4
CaCI2 187.2 x 55.5 = 10,390 mg/l CaCl2
MgCL 246.8 x 47.6 = 11,748 mg/l MgCI2
FeCL 3.6 x 63.4 = 228 mg/l feC\2
NaCI 858.9 x 58.4 = 50,160 mg/l NaCI
GRAPHIC PLOTS
Graphic plots of the reacting values can be made to illustrate the relative
amounts of each radical present. The graphical presentation is an aid to rapid
identification of a water, and classification as to its type, and there are several
methods that have been developed.
Tickell Diagram
4
The Tickell diagram was developed by using a six-axis system or star diagram.
Percentage reaction values of the ions are plotted on the axes. The percentage
values are calculated by summing the epm's of all the ions, dividing the epm of a
given ion by the sum of the total epm's, and multiplying by 100.
The Tickell diagram uses reaction values in percentage while total reaction
values are used in the modified Tickell, Figure 1. 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.
13
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Co 4 Mg
C<>3+
I I I I I I I
1892 meq / liter
Cl \ S04
Cl RV = 49.92 percent
TICKELL METHOD
MODIFIED TICKELL
Figure 1. Tickell and modified Tickell diagram for Gulf Coast water, sample no. 1.
-------
Ca + Mg
Ca + Mg
HC03
MINIM
50 Percent
Cl 1 S04
Cl RV = 49.29 percent
1607 meq / liter
TICKELL METHOD
MODIFIED TICKELL
Figure 2. Tickell and modified Tickell diagram for Anadarko Basin water, sample no. 2.
-------
Co +Mg
Ca 4- Mg
+ HC03
I I I I I
50 Percent
Cl I S04
Cl RV = 49.92 percent
5708 meq/ liter
TICKELL METHOD
MODIFIED TICKELL
Figure 3. Tickell and modified Tickell diagram for Williston Basin water, sample no. 3.
-------
Ca + Mg
1769 meq / liter
Cl
Cl RV= 49.69 percent
TICKELL METHOD
MODIFIED TICKELL
Figure 4. Tickell and modified Tickell diagram for Gulf Coast and Anadarko Basin waters, mixed 1 to 1
-------
Ca + Mg
Na
Ca + Mg
00
C03 4- HCOs
I I I I I I-
50 Percent
S04
Cl RV= 49.82 percent
2870 meq / liter
TICKELL 'METHOD
MODIFIED TICKELL
Figure 5. Tickell and modified Tickell diagram for Gulf Coast, Willisten, and Anadarko Basin
waters, mixed 1:1:1.
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I 20,000
80,000 -
40,000 -
o>
E
CO
I-
jfj 40,000
CO
O
o
80,000 -
<
H 120,000
bJ
O
160,000 -
200,000 -
240,000
HC03
Mixture of
no. I a 2
Sample
no. 2
Sample
no. I
Mixture of
no. 1,2,83
S04
HCOs
Sample no. 3
REISTLE SYSTEM
Figure 6. Water-analysis interpretation, Reistle system—sample numbers
correspond to those shown on figures 1-3.
19
-------
Na +
1000
Mg+2
100
KE^
cr
1000
S04-2
10
f
Ca+2
100
Fe+2
100
HC03-
10
CO 3- 2
10
Sample number I
Sample number 2
Sample number 3
Mixture of I ft 2
Mixture of 1,2,83
-^f?«^^^miSii^
^X^v^V^T^Fpi*'«'r?^r^^*^^* • v'^^TT*^5!^-^--'^"^
STIFF METHOD
I I I I I
26 24 22 20 !8 16 14 12 10 8 6 4 20 24 6
Figure 7. Water-analysis interpretation, Stiff method—sample numbers correspond
to those shown on figures 1-3.
20
-------
To illustrate differences in patterns for different waters, Figures 1-5 were
prepared using the Tickell and modified Tickell methods. Figure 1 represents a
water from the Gulf Coast Basin, taken from the Wilcox Formation of Eocene Age.
Figure 2 is of a sample from the Meramec Formation of Mississippian Age in the
Anadarko Basin. Figure 3 is of a sample from a Devonian Age Formation in the
Williston Basin. Figure 4 represents a 1-to-l mixture of waters of the Gulf Coast
and Anadarko Basins, and Figure 5 is a 1-to-l mixture of all three waters.
Reistle Diagram
2~
Reistle devised a method of plotting water analyses using the ion concen-
trations as shown in Figure 6. The data are plotted on a vertical diagram, with
the cations plotted above the central zero line and the onions below. This type
of diagram often is useful in making regional correlations or studying lateral
variations in the water of a single formation, because several analyses can be
plotted on a large sheet of paper.
Stiff Diagram
3
Stiff plotted the reaction values of the ions on a system of rectangular
coordinates as illustrated in Figure 7. The cations are plotted to the left and
the onions to the right of a vertical zero line. The end points then are connected
by straight lines to form a closed diagram, sometimes called a "butterfly" diagram.
To emphasize a constituent that may be a key to interpretation, the scales may be
varied by changing the denominator of the ion fraction usually in multiples of 10.
However, when looking at a group of waters all must be plotted on the same scale.
Many investigators believe that this is the best method of comparing oilfield
water analyses. The method is simple, and nontechnical personnel can be easily
trained to construct the diagrams.
Automated Methods
1 3
The Piper diagram and the Stiff diagram were adapted to automatic data
processing by Morgan, et al , and Morgan and McNellis . The Piper diagram
21
-------
uses a multiple trilinear plot to depict the water anal/sis, and this quaternary
diagram shows the chemical composition of the water in terms of cations and
7 31.
anions. Angino and Morgan applied the automated Stiff and Piper diagrams
to some oilfield brines and obtained good results.
22
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SECTION VI
SALINE WATER CLASSIFICATION
Classification of waters provides a basis for grouping closely related waters.
Because the grouping is chemical, it is dependent upon the dissolved constituents
found in the waters. Most of the classification systems developed to date have
considered only the dissolved major inorganic constituents and have ignored the
organic and the minor and trace inorganic constituents.
Waters as related to the earth are meteoric, surface, and subsurface. Surface
waters can be fresh or saline if the amounts of dissolved constituents in the waters
are used to classify them. For example, water from melting snow on a mountain
top usually will contain small amounts of dissolved mineral matter and can be
i
classified as freshwater, while water in an ocean will contain about 35,000
milligrams per liter (ma/1) dissolved minerals and is classified as saline. Waters
found in rivers connecting the mountain stream to the ocean may contain varying
amounts of dissolved constituents and depending upon the amounts can be classified
as fresh or saline. In a similar manner, subsurface waters are classified as fresh or
saline. Merely classifying a water as either fresh or saline does not provide a very
useful classification. The dissolved constituents that are used in many classification
systems depend upon the amounts or ratios of sodium, magnesium, calcium, carbonate,
bicarbonate, sulfate, and chloride found in the water. The reason for this is that
these are the ions that usually are determined or calculated in a water. (Sodium
often is calculated from the difference found in the stotchiometric balance of the
determined anions and cations.)
The amounts and ratios of these constituents in subsurface waters are dependent
upon the origin of the water and what has occurred to the water since entering the
subsurface environment. For example, some subsurface waters found in deep
23
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sediments were trapped during sedimentation while other subsurface waters have
been diluted by infiltration of surface waters through outcrops. Some waters have
been replaced by infiltration water. Also, rocks containing the waters often
contain soluble constituents that dissolve in the waters or contain chemicals
that will exchange with chemicals dissolved in the waters/ causing alterations
of the dissolved constituents.
The amounts of dissolved constituents found in subsurface waters can range
from a few milligrams per liter to more than 350,000 mg/l. This salinity dis-
tribution is dependent upon several factors, including hydraulic gradients, depth
of occurrence, distance from outcrops, mobility of the dissolved chemical ele-
i
ments, soluble material in the associated rocks, and the exchange reactions.
Several thousand saline waters were classified using automatic data
processing. Table 7 illustrates some of the classification data for some of the
samples from the Arbuckle and Lansing Kansas City Formations in the Central
Kansas Basin; the Wilcox Formation in the Cherokee Basin; the Nacatoch, Paluxy,
Rodessa, and Woodbine Formations in the East Texas Basin; the Eutaw Formation
in the Interior Salt Basin; the Smackover Formation in the North Louisiana Basin;
and the Wilcox Formation in the Western Gulf Basin. The majority of these waters
o
fall in the S.S.A- class and are of the chloride-calcium type; Collins explained
these classes and types.
Most of the samples of the bicarbonate-sodium and su If ate-sodium types were
found at relatively shallow depths. This indicates that the waters contain infiltrating
meteoric water. The mafority of the oilfield waters classified were very high-
chloride waters (where chloride epm is equal to or greater than 700). The sulfate
concentration of these waters according to this classification was not as consistent.
Many of them were normal with sulfate epm less than 6. However, in several
waters the sulfate epm was higher than 24. Few waters contained sulfate in excess
of 58 epm. The ^Ca x SO. in epm units exceeded 70 in some waters, indicating
24
-------
Table 7. CLASSIFICATION OF SOME SALINE GROUNDWATKS FROM 10 FORMATIONS IN EIGHT SEDIMENTARY BASINS
ISJ
Ol
No.
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
State
Kans.
Da.
Do.
Do.
Do.
Do.
Do.
Do.
Do.
Do.
Do.
Do.
Do.
Do.
Do.
Do.
Do.
Do.
Do.
Do.
Okla.
Do.
Do.
Do.
Do.
Do.
Do.
Do.
Do.
Do.
Ark.
Do.
Do.
Tex.
Do.
Do.
Do.
Do.
Do.
Do.
Formation
Arbockle
do.
do.
do.
do.
do.
do.
do.
do.
do.
Lansing
do.
do.
do.
do.
do.
do.
do.
do.
do.
Wilcox
da.
do.
do.
do.
do.
do.
do.
do.
do.
Nacatoch
do.
do.
do.
do.
do.
do.
do.
do.
do.
Basin
Cent. Kans.
do.
do.
do.
do.
do.
do.
do.
do.
do.
do.
do.
do.
do.
do.
do.
do.
do.
do.
do.
Cherokee
do.
do.
do.
do.
do.
do.
do.
do.
do.
E. Texas
do.
do.
do.
do.
do.
do.
do.
do.
do.
Depth,
meters
1,050
1,091
1,023
1,102
992
1,152
1,174
949
1,195
1,104
928
1,075
966
999
902
1,009
1,063
1,148
1,172
853
1,228
1,731
904
1,539
1,106
1.020
582
1,432
1,972
1,865
360
465
373
905
701
242
650
283
191
181
Concentration, EPM
No
634.6
581.6
282.0
639.9
430.3
458.7
473.2
356.4
446.4
577.4
1759.6
570.4
1899.9
1728.2
1903.8
2514.8
1854.7
2087.2
2414.5
1898.4
2366.5
2188.4
2161.5
2365.3
1997.1
1990.0
1587.2
2459.0
2701.4
2635.5
233.4
463.4
300.4
788.2
481.8
274.0
492.7
295.4
451.5
490.6
Mg
60.6
58.4
24.8
56.6
38.8
34.4
53.1
57.4
35.4
49.4
266.6
117.4
266.4
232.0
274.5
309.3
225.2
223.6
251.0
210. 8
193.3
209.5
163.2
200.8
140.4
161.3
151.2
174.5
153.1
180.6
9.0
39.5
25.9
9.4
7.8
8.1
10.4
8.1
17.6
3.6
Co
133.0
121.8
40.2
13.0
65.4
81.3
119.4
100.4
71.2
112.1
373.9
174.6
442.1
512.4
478.8
532.7
449.8
384.8
519.0
416.7
810.1
529.4
530.3
445.6
457.3
513.7
287.5
511.6
606.0
629.6
22.4
59.5
36.8
28.7
17.3
14.7
16.5
14.7
44.7
7.8
HCO3
7.7
6.5
9.5
2.2
8.5
3.4
5.1
12.8
9.0
35.9
1.8
2.4
0'.3
1.7
1.1
0.4
0.5
1.4
0.7
0.8
1.1
0.3
0.4
1.1
0.9
0.7
1.8
1.1
0.7
1.1
3.7
1.4
4.3
3.1
3.3
2.5
18.9
2.4
7.1
2.8
S04
49.0
22.7
22.1
46.6
17.5
45.9
36.0
39.9
30.0
45.5
0.0
34.9
0.8
2.5
0.0
1.5
1.1
1.0
2.4
0.7
7.7
9.8
7.3
15.9
7.8
13.3
1.4
6.0
8.4
8.6
0.0
0.0
1.0
0.0
0.0
0.8
0.1
0.9
0.4
0.6
a
773.8
732.3
313.9
827.0
510.9
523.2
705.0
456.7
512.7
685.8
2398.9
826.6
2605.0
2469.4
2655.6
3353.6
2529.5
2706.1
3179.9
2515.5
3360.6
2917.2
2847.4
2992.0
2584.3
2650.8
2021.6
3138,8
3449.1
3436.6
261.1
559.5
357.7
824.6
503.5
294.2
498.4
313.6
506.2
498.4
SEPM
1659.0
1523.6
692.6
1585.4
1071.6
1147.2
1492.0
1024.0
1105.0
1506.4
4800.9
1726.6
5214.7
4946.5
5314.0
6712.5
5061.1
5404.4
6367.7
5013.1
6739.4
5854.9
5710.4
6021.0
5188.0
5330.0
4051.1
6291.3
6918.8
6892.3
529.8
1123.5
726.2
1654.2
1013.8
594.5
1037.4
635.2
1027 8
1004.0
Sulin
Type
Cl-Ca
Cl-Ca
Cl-Ca
Cl-Ca
Cl-Ca
Cl-Ca
Cl-Ca
Cl-Ca
Cl-Ca
a-Ca
Cl-Ca
Cl-Ca
Cl-Ca
Cl-Ca
Cl-Ca
CI-Co
Cl-Ca
Cl-Ca
Cl-Ca
Cl-Ca
Cl-Ca
Cl-Ca
CI-Co
Cl-Ca
Cl-Ca
Cl-Ca
Cl-Ca
Cl-Ca
CI-Co
Cl-Ca
Cl-Ca
Cl-Ca
Cl-Ca
Cl-Ca
Cl-Ca
ClrCa
CI-Mg
CI-Co
Cl-Ca
Cl-Ca
Class
**2*i
slsjAj
ss^
S^Sj
*1*2*2
*1*2*2
¥2*2
S SjA^
SjSjAj
'1*2*2
siVz
'1*2*2
5l*2*i
S1S2*2
SlV2
*1*2*3
*iVs
S,Y2
SlV2
SjSjAj
Sl*2*2
S1S2*2
S1S2*2
*1*2*2
*l'2*2
S1S2*2
*1S2*2
S1S2*2
*1*2*2
S1S2*2
S,S2A2
'1*2*2
*1*2*2
*1*2*2
S1S2*2
'1*2*2
'l*2*2
*l'2*2
',*2*2
Schoeller
Cl°
(VH)C
(VH)C
(H)C
«VH)C
(M)C
(M)C
(VH)C
(M)C
(M)C
(M)C
-------
Table 7 (continued). CLASSIFICATION OF SOME SALINE GROUNDWATERS t-ROM 10 FORMATIONS IN EIGHT SEDIMENTARY BASINS
No.
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
61
62
63
64
65
66
67
68
69
70
71
72
73
74
75
76
77
78
79
80
Slote
Ark.
Do.
Do.
Do.
Do.
Tex.
Do.
Do.
Do.
Do.
Ark.
Do.
Do.
Do.
Tex.
Do.
Do.
Do.
Do.
Do.
Do.
Do.
Do.
Do.
Do.
Do.
Do.
Do.
Do.
Do.
Alo.
Do.
Do.
Miss.
Do.
Do.
Do.
Do.
Do.
Do.
Formation
Paluxy
do.
do.
do.
do.
do.
do.
do.
do.
do.
Rodessa
do.
do.
do.
do.
do.
do.
do.
do.
do.
Woodbine
do.
do.
do.
do.
do.
do.
do.
do.
do.
Eutaw
do.
do.
do.
do.
do.
do.
do.
do.
do.
Basin
E. Texas
do.
do.
do.
do.
do.
do.
do.
do.
do.
6. Texas
do.
do.
do.
do.
do.
do.
do.
do.
do.
do.
do.
do.
do.
do.
do.
do.
do.
do.
do.
Interior Sal .
do.
do.
do.
do.
do.
do.
do.
do.
do.
Depth,
meters
1,115
737
1,297
884
1,417
2,340
2,174
1,943
1,512
1,943
1,897
1,241
1,033
711
2,844
2,519
2,722
2,115
2,289
3,062
1,047
1,750
898
841
1,809
1,144
925
1,442
1,596
1,332
1,061
972
1,060
1,444
2,263
1,312
2,443
1,690
1,315
2,469
Concentration, EPM
Na
1246.8
586.0
1310.3
934.9
1507.2
1642.1
1515.1
1495.4
205.3
1522.8
1971.8
1943.8
1060.3
538.6
1772.1
1861.9
2068.5
1950.3
2020.0
1877.5
1507.0
1263.0
341.8
1060.5
1271.9
809.1
478.8
1451.3
1447.3
1268.0
1124.4
1102.9
1186.7
1733.6
2009.8
1572.7
1721.3
1925.9
1579.6
2153.7
Mg
90.6
32.2
107.1
64.8
138.6
22.5
51.1
89.0
6.4
90.2
157.2
185.1
108.2
35.9
127.3
2T7.4
148.5
132.9
141. 2
92.7
44.3
33.4
4.4
32.4
59.6
12.7
12.4
26.7
38.3
30.2
45.0
25.6
59.6
82.7
75.9
88.9
256.7
61.6
60.6
87.7
Co
254.1
86.7
278.5
197.6
504.4
378.5
205.9
44B.9
10.0
448.1
669.7
563.6
289.8
75.0
878.8
1084.7
900.9
726.1
741.8
610.0
161.4
56.3
9.3
58.9
154.9
61.1
23.6
213.3
144.1
81.9
164.7
160.5
164.3
287.3
306.8
224.9
458.0
359.9
252.9
518.9
HCO3
0.4
2.8
2.7
1.5
0.5
0.0
4.7
2.7
14.9
1.8
0.0
0.9
0.0
3.0
1.5
1.1
0.6
1.8
0.8
1.0
4.2
8.2
11.3
0.0
1.0
7.3
7.0
3.9
1.6
8.3
2.7
2.0
2.9
0.9
5.2
0.9
0.0
3.9
2.3
0.0
so4
0.0
3.3
0.7
1.1
3.3
9.3
3.7
8.2
6.0
8.3
8.0
11.7
21.4
2.9
2.8
2.7
4.8
8.5
4.2
5.4
3.5
1.8
0.6
0.2
4.9
3.7
0.1
0.0
0.1
4.0
0.0
0.0
0.0
0.0
33.6
0.0
0.0
0.0
0.0
1.0
Cl
1594.4
699.0
1692.0
1194.9
2208.7
2033.8
1763.1
2022.2
202.4
2050.3
2789.9
2679.0
1436.5
643.4
2773.2
3165.1
3111.6
2802.4
2909.8
2576.9
1705.0
1342.2
343.5
1161.4
1478.2
873.3
507.7
1685.1
1629.4
1367.4
1330.1
1288.9
1411.8
2108.5
2358.5
J890.2
2433.4
2352.4
1893.5
2765.6
£EPM
3186.6
1410.3
3391.5
2395.0
4363.0
4086.4
3543.9
4066.7
445.2
4121.6
5596.8
5384.3
2916.3
1299.0
5556.0
6333.1
6235.2
5622.2
5818.1
5163.7
3425.6
2705.0
711.0
2313.7
2970.7
1767.3
1029.9
3379.5
3261.0
2760.0
2667.1
2580.1
2825.4
4213.1
4789.9
3777.7
4869.6
4704.8
3789.1
5527. 1
Su In
Type
Cl-Ca
a-Co
Cl-Ca
Cl-Ca
Cl-Ca
CI-Co
Cl-Ca
Cl-Ca
SO4-No
Cl-Ca
Cl-Ca
Cl-Ca
Cl-Ca
CI-Co
Cl-Ca
Cl-Ca
Cl-Ca
Cl-Ca
Cl-Ca
Cl-Ca
Cl-Ca
Cl-Ca
CI-Mg
Cl-Ca
Cl-Ca
Cl-Ca
Cl-Ca
Cl-Ca
Cl-Ca
Cl-Ca
Cl-Ca
Cl-Ca
Cl-Ca
Cl-Ca
Cl-Ca
Cl-Ca
Cl-Ca
Cl-Ca
Cl-Ca
Cl-Ca
Class
¥2S3
¥2*2
¥2*2
¥2*2
¥2*2
¥2*2
¥2*2
¥2*2
Sl*2%
¥2*2
¥2*2
¥2*2
¥2*2
¥2*2
¥2*2
¥2S3
¥2*2
¥2S3
¥2S3
¥2S3
¥2*2
¥2*2
S1A2%
¥2S3
¥2*2
¥2*2
¥2*2
¥2*2
¥2*2
¥2*2
¥2*2
¥2*2
¥2S3
¥2S3
¥2A2
¥2S3
¥2*2
¥2S3
¥2S3
1S2S3
Schoeller
a"
(VH)C
(M)C
(VH)C
(VH)C
(VH)C
(VH)C
(VH)C
(VH)C
(MIC
(VH)C
(VH)C
(VH)C
(VH)C
(M)C
(VH)C
-------
Toble 7 (continued). CLASSIFICATION OF SOME SALINE GROUNDWATERS FROM 10 FORMATIONS IN EIGHT SEDIMENTARY BASINS
NJ
XI
No.
81
82
83
84
85
86
87
88
89
90
91
92
93
94
95
96
97
98
99
100
101
102
103
104
105
106
107
108
109
110
111
State
Miss.
Do.
Do.
Do.
Do.
Do.
Do.
Do.
Do.
Do.
La.
Ark.
Do.
Do.
Do.
Do.
Do.
La.
Do.
Do.
Do.
Do.
Do.
Do.
Do.
Do.
Do.
Do.
Do.
Do.
N.Dak.
Formation
Wilcox
do.
do.
do.
do.
do.
do.
do.
do.
do.
Smackover
do.
do.
do.
do.
do.
do.
do.
do.
da.
Wilcox
do.
do.
do.
do.
do.
do.
do.
do.
do.
Silurian
Basin
Miocene
do.
do.
do.
do.
do.
do.
do.
do.
do.
N. Louis
do.
do.
do.
do.
do.
do.
do.
do.
do.
W. Gulf
do.
do.
do.
do.
do.
do.
do.
da.
do.
Wil listen
Depth,
meters
1,975
1,748
1,412
1,871
2,330
1,646
2,162
2,268
1,552
1,327
3,109
2,103
2,399
2,509
2,240
2,526
2,615
2,949
3,271
701
1,399
1,814
747
1,561
1,722
666
1,124
2,441
2,158
471
3,633
Concentration, EPM
Na
2031.8
1847.9
1362.9
2157.3
1972.2
1992.4
2043.7
2198.7
1280.8
1318.9
1589.7
2444.9
2518.1
2790.1
2418.0
2729.0
4277.5
2225.4
1971.2
681.8
1718.5
2035.8
1206.3
1874.2
2138.9
1057.5
1379.4
2119.4
2132.3
840.1
3431.2
Mg
36.8
48.4
15.0
54.1
65.8
38.0
25.5
83.8
36.7
20.9
86.7
275.9
280.4
222.2
279.5
218.6
10.0
149.7
173.5
35.2
44.9
46.5
43.6
40.9
41.9
26.6
41.8
43.7
15.3
26.8
100.6
Co
100.3
94.9
82.5
89.9
95.7
81.9
132.2
90.7
56.3
99.6
1256.8
1392.8
1622.1
1641.6
1470.8
1598.2
34.9
2282.1
1668.9
63.6
90.1
124.7
47.2
91.0
96.2
51.0
60.0
100.2
115.2
24.1
993.7
LHCO3
4.5
3.8
4.4
6.8
3.9
3.0
7.2
3.9
9.4
3.9
0.0
2.0
1.8
2.3
0.0
2.4
2.4
0.0
0.0
5.1
1.4
5.6
4.6
0.7
1.4
0.0
2.5
6.1
4.0
7.0
1.5
SO,
0.0
0.0
0.0
0.0
7.2
0.0
0.0
0.3
0.0
0.0
8.8
4.6
3.7
1.7
4.1
1.7
0.0
1.4
1.8
2.1
0.2
0.8
0,6
0.8
1.4
0.0
0.6
0.0
8.0
0.0
8.4
Cl
2163.3
1985.9
1455.8
2114.0
2122.3
2108.5
2194.5
2369.8
1364.3
1434.8
2940.8
4105.9
4413.8
4648.6
4163.0
4540.4
4312.9
4654.9
3810.9
778.6
1851.2
2199.9
1291.2
2003.8
2273.4
1058.4
1477.6
2263.8
2256.4
888.4
4305.3
E EPM
4336.9
3981.1
2920.8
4422.4
4267.3
4223.9
4403.4
4747.3
2747.7
2878.2
5883.0
8226.2
8840.1
9306.8
8335.6
4545.9
8637.9
9313.8
7626.5
1566.7
3706.6
4413.6
2593.7
4011.7
4553.5
2193.6
2962.2
4533.4
4531.3
1786.7
8840.7
Sulin
Type
Cl-Ca
Cl-Ca
Cl-Ca
HCOj-Na
Cl-Ca
Ci-Co
Cl-Ca
Cl-Ca
a-co
Cl-Ca
Cl-Ca
Cl-Ca
Cl-Ca
Cl-Ca
Cl-Ca
Cl-Ca
Cl-Ca
Cl-Ca
Cl-Ca
Cl-Ca
Cl-Ca
CI-Co
CKa
Cl-Ca
Cl-Ca
CI-Mg
Cl-Ca
Cl-Ca
Cl-Ca
Cl-Ca
Cl-Ca
Class
siVz
S1S2^
SjSjA^
SlM
SlV^
SlV^
SlV^
siVz
siV^
SjSjAj
S1S2S3
S,S2A,
VA
SIS2A2
S1S2^
SlVfe
siVz
S1S2A2
Sl%^
S1S2*2
S1S2^
S1S2A2
S1S2A2
SlV2
S1S2A2
S^Sj
SIS2A2
S1S2S3
W3
S1S2A2
W*
Schoeller
c,a
(VH)C
(VH)C
(VH)C
(VH)C
(VH)C
(VH)C
(VH)C
(VH)C
(VH)C
(VH)C
(VH)C
2(Ca)
12.7
11.2
11.8
16.1
11.4
9.0
18.9
11.1
17.0
11.5
0.0
17.7
17.9
21.1
0.6
21.3
5.9
0.7
0.6
11.6
5.6
15.8
10.1
3.6
5.9
0.0
7.3
15.2
12.1
9.9
13.0
IBE
0.06
0.07
0.06
0.0
0.7
0.06
0.07
0.07
0.06
0.08
0.46
0.40
0.43
0.40
0.42
0.40
0.01
0.52
0.48
0.12
0.07
0.07
0.07
0.06
0.06
0.0
0.07
0.06
0.05
0.05
0.20
epm Cl is > 700, (VH)C
epm Cl is 420 to 700, (M)C
epm Cl is 140 to 420, (H)C
epm Cl is 40 to 140, (A)C
epm Cl is 10 to 40, (L)C
epm Cl is < 10, (N)C
epm SO. is >58, (VH)
epm SO? is 24 to 58, (H)
epm Sol is 6 to 24, (A)
epm SO* is < 6, (N)
-------
that such waters were nearly saturated with calcium sulfate. The solubility of
calcium sulfate increases in the presence of certain other dissolved ions, therefore
the value of 70 may not always indicate saturation.
The v (HCCX + CO_) (Ca) in epm units is used to determine if a water is
saturated with calcium carbonate, and such a water should have a value greater
than 7. This is not entirely accurate, but the calculated value from the cubed
root expression does indicate the presence of an excess of calcium which decreases
the carbonate concentration. Many of the waters classified had values greater
than 7. A distilled water thus saturated would deposit precipitated calcium
carbonate, but the activities of other ions dissolved in a brine cause the solubility
product to be different in the brine.
The predominant cation sequence for the classified oilfield brines was
Na > Ca > Mg. The anion ratios of SO ,/CI ranged from 0.00 to 0.34. The ratio
0.34 found for a bicarbonate-sodium type of water strongly indicates infiltrating
surface water. None of the chloride-calcium type waters had a SO ,/CI ratio
greater than 0.17.
The index of base exchange (IBE), given in Table 7, indicates that exchange
o
of metal ions dissolved in the water has occurred with metal ions on the clays. If
the IBE is a positive number, the exchange was alkali metals such as sodium in the
water for alkaline earth metals such as calcium on the clays, and if the IBE is neg-
ative, the exchange was alkaline earth metals in the water for alkali metals on the
clays. Very few negative numbers were evident when the IBE was determined on
the oilfield water analyses. This indicates that most of these saline formation waters
have exchanged alkali metals for alkaline earth metals on the clays. The few sam-
ples that yielded the negative IBE numbers were sulfate-sodium and bicarbonate-
sodium type waters, which is indicative of terrestrial waters.
28
-------
SECTION VII
PLOTTING SALINITY MAPS FOR USE IN LOCAL OR REGIONAL STUDIES
A study of stratigraphic problems within a subsurface formation was made by
the use of saline formation waters. Over 300 samples of formation water were
collected and analyzed. The results were processed by computer techniques. Data
collected in this manner were posted on maps and machine contoured. Several
aspects of the waters (relative percentages of $04, Mg, Ca, and total solids) show
systematic variations in the basin. Variation in these parameters is related to
proximity to outcrop and the degree of transmissibility of the formation. The
highest sulfate content is near the outcrop belt to the west; the calcium and total
solids increase toward more impermeable rocks and areas of low circulation. In
the center of the basin the waters are characterized by very high salinities, high
calcium and low sulfate content, but in the porous and permeable fingers near the
outcrop, salinities are low and sulfate is high. All gradations between these two
extremes exist in the example formation. In areas where the sand fingers pinch
out very rapidly into low permeability sediments, the transition between these two
extremes of water composition may take place in a matter of a few well locations.
9
An excellent example of this is illustrated by Figures 8-10, where a range of waters
is evidenced in one homogeneous, continuous sand body. Note that the spot locations
are divided by 100, while the contour lines are not.
The reason for these rapid changes in formation water composition may be
explained by permeability changes within the subsurface formation. In areas of
low permeability there is less circulation, less dilution, and more chance for the
maintenance of an equilibrium relation between formation water and sediment.
This was substantiated by the distribution of magnesium in the formation waters.
A series of multiple-regression analyses were made to determine the relation
of the percent of various ions dissolved in the waters to the total solids dissolved
29
-------
CO
O
NEW MEXICO
TEXAS
50
«W xJPff^M /Mi \ °°
-
VU»?|M ^ I N^T //////M><38r30*4
^o^*- \ n I' ij&
• <* ^M**^MllMdfl /,
N
o
o
o
742/66^
//*^?
.25OI
Dissolved solids content in mg/1/IOO
Cl = 25,000 mg/l
ri?wy'
^
2484 \
'2477
•2447
i 2622 ;i/^;
VJ -2629V/
f ^-">~1 «2257
' /W
Figure 8. Concentrations of dissolved solids in the formation waters.?
-------
100,000
CO
Chloride content in mg/l/lOO
Cl = 25,000 mg/l
Figure 9. Chloride concentration in the formation waters.
-------
CO
CO
•3°* NEW MEXICO _
TEXAS
Calcium content in mg/l/IO
= 5,000 mg/1
Cl
Figure 10, Calcium concentration in the formation waters.'
-------
In the waters. First, all the waters were analyzed as a unit to determine the cor-
relation coefficients and the degree of variability explained by the ions chosen for
analysis. The second stage was the breakdown of the waters into three arbitrarily
defined groups (based principally on salinities) to see if there were any noticeable
changes in either correlation coefficients or degree of explained variance. The
only significant change was in the relation of magnesium to total solids; i.e., in
waters of relatively low salinity, there was a significant positive correlation to
total dissolved, sol ids, but in waters with high dissolved solids concentrations
there was a significant negative correlation. These correlations indicate that the
relative concentration of magnesium decreases in high-salinity waters. These waters
are precisely those that are found in low-permeability, fine-grained, argillaceous
rocks in which magnesium would most likely be taken out of the waters by diagenetic
alteration of clay mineral.
Maps of the dissolved solids content, Figure 8, the chloride content, Figure 9,
and the calcium content, Figure 10, of formation waters were prepared. It is
important to note on each of the constituent maps that the local variation of the
iso-mg/l contours are of greatest importance and not the precise value of the
contour. For example, on the dissolved solids map, Figure 8, note that the overall
appearance is a series of fingering expressions shown by the contour lines.
The chloride map, Figure 9, has a configuration similar to the total solids
map. Again it is not the precise iso-mg/l contour that is of prime concern, but
the variation in the limited area. This rate of change from higher to lower concen-
tration is important in studying zones for subsurface disposal of waste; i.e., the
lower concentration may indicate an outcrop.
The calcium content map, Figure 10, does not show the prominent fingering,
almost pseudodeltaic, effect that the total solids and chloride maps have. Perhaps
this is due to the smaller range of values mapped. Some of the high to lower con-
centration effect is present and in some of the locales, iso-mg/l closure is developed.
33
-------
This map is not as diagnostic as the others. However, considered in conjunction
with the other two maps, the coexistence of various salinity accumulations and the
transition zones, even strata closure is quite evident.
The formation water constituent maps are definitely of value. Consideration
of these with rock properties and hydrodynamic gradients permits the studying the
potential of a disposal zone more accurately and will also permit meaningful ex-
trapolation of inference with a minimum of data. The principal prerequisite for
mapping reservoir trends such as sand fingers is the development of a detailed
stratigraphic correlation. In deep subsurface water environments, as a rule,
correlations are excellent because there is little variability in sedimentary environ-
ments. This can be substantiated by specific recognizable gamma ray markers on
well logs.
Figure 11 is a map that illustrates the variation in salinity in the Lower Wilcox
Formation in portions of Texas, Louisiana, Arkansas, Mississippi, and Alabama.
The most saline brines occur in the deeper basin areas with the dilute brines
nearer outcrop areas. The low-salinity waters near the coast cannot easily be
attributed to intruding seawater because their salinity often is less than normal
seawater. Pressure data a re needed to determine if these waters are related to
abnormally pressured zones such as those found in certain areas of Louisiana and
elsewhere. Figure 12 is a similar map of the Lower Tuscaloosa and Woodbine
Formations with no differentiation being given between the two.
The saline water data entered into STORET will prove of immense value
in studies related to groundwater pollution and subsurface disposal of wastes.
As noted,diagrams useful in water identification have been adapted to automatic
data process ing, and the saline water data in STORET can be used for this type of
application. Water classification systems have been adapted to automatic data
processing and the saline water data in STORET can be classified and studied to
determine where certain types of saline waters are more prevalent. The class,
34
-------
co
en
Greater than 170,000 mg/l (as NaCI) gVvl 5,600 to 70,000 mg/l
70,000 to 170,000 mg/l E£J3 Less than 5,600 mg/l
Outcrop areas
Figure 11, Salinity variations in formation waters at the base of the Lower Wilcox Formation located
in portions of Texas, Louisiana, Arkansas, Mississippi, and Alabama.
-------
co
Os
Pv—I
l
-------
type, etc., of saline waters can be mapped, and in map form will be useful in
pollution research.
Maps of certain ions in saline waters should be constructed for all areas of
the United States and they should be drawn with a knowledge of the subsurface
pressure gradients. Such maps are important in studying areas where subsurface
injection of waste is contemplated or occurring. These maps can be drawn using
a computer-controlled plotter.
37
-------
SECTION VIII
POLLUTION OF FRESHWATER AND LAND BY BRINES
Waters associated with petroleum in subsurface formations usually contain
many dissolved ions. Those dissolved ions most commonly present in greater than
trace amounts are sodium, calcium, magnesium, potassium, barium, strontium,
ferrous iron, ferric iron, chloride, sulfate, sulfide, bromide, and bicarbonate.
Dissolved gases in these waters often include carbon dioxide, hydrogen sulfide,
and methane. The stability of petroleum-associated brine is related to the con-
stituents dissolved in it, the chemical composition of the surrounding rocks and
minerals, the temperature, the pressure, and the composition of any gases in
contact with the brine. A recent case study of a fresh water aquifer that was
polluted by oilfield brine indicated that the aquifer would remain polluted for
more than 250 years.
Scale inhibitors are added to waters and brines to prevent the precipitation
reactions. Some of the chemicals used in these inhibitors are listed in Table 8.
Table 8. CHEMICALS USED IN SCALE INHIBITORS
Ethylenediamine tetraacetic acid salts
Nitrilotriacetic acid salts
Sodium hexametaphosphate
Sodium tripolyphosphate '
Sodium carboxymethyl cellulose
Aminotrimethylene phosphate
38
-------
Knowledge of the oxidation state of dissolved iron in brines is important in
compatibility studies. Brines in contact with the air will dissolve oxygen, and
their oxidation-reduction potential (Eh) generally will be from 0.35 to 0.50 mv.
Brines in contact with petroleum in the formation normally will have an Eh lower
than 0.35 mv, as will waters in contact with reducible hydrocarbons. Any change
in the oxidation state of brine containing dissolved iron may result in the deposition
of dissolved iron compounds.
1 The sediments or precipitate formed from brines can cause environmental
pollution directly or indirectly. For example, if the produced brines are stored
in a pond, the sediments may cause soil pollution; if the brines are injected into
a disposal well, the sediments may plug the face of the disposal formation, resulting
in the necessity to increase infection pressures,which may rupture the input system.
The amount of saltwater or brine produced from oil wells varies considerably
with different wells and is dependent upon the producing formation and the location,
construction, and age of the well. Some oil wells produce little or no brine when
first produced, but as they are produced, they gradually produce more and more
brine. As some wells become older, the produced fluids may be more than 99
percent brine; or for each cubic meter of oil coming to the surface, ]QO cubic
meters or more of brine also is produced. The produced brines differ in concentration,
but usually consist primarily of sodium chloride in concentrations ranging from 5,000
to more than 200,000 ppm; the average probably is about 40,000 ppm. For com-
parison, note that seawater contains about 20,000 ppm of chlorides. One cubic
meter of brine containing 100,000 ppm of chloride will raise the chloride content
of 400 cubic meters of fresh water above the maximum recommended for drinking
water,which is 250 ppm of chloride. Petroleum-associated brines may escape and
contact freshwater or soil in different ways. For example, to protect the upper
freshwaters from the deeper mineralized waters that might rise in the drilled well,
the upper portion of the well is sealed by a string of cemented surface casing. If
39
-------
a well has insufficient surface casing, an avenue may be provided for the escape ,
of brines if they are under sufficient hydrostatic head to cause them to rise in the
hole to the surface or to the level of freshwater sands.
Handling the tremendous volume of brine produced simultaneously with
petroleum is hazardous. Basically, the problem is to handle and dispose of the
brine in such a manner that it does not contact soil or freshwater and cause
detrimental pollution.
Currently, some produced brines are being discharged into approved surface
ponds, whereas most brines are returned underground for disposal or to repressure
secondary oil or gas recovery wells. The discharge of brines to any surface drain-
age is strictly prohibited in most states. Potential water and soil pollution problems
are associated with both disposal methods. For example, if the surface pond is
faulty, the brine will contact the soil and various chemical reactions will occur
between the soil and the brine. Sometimes the brine will pass through the soil,
reappear at the surface, and produce scar areas, and sometimes it will pollute the
soil; leaching will pollute surface streams or shallow surface aquifiers.
RESIDUAL SALT CONCENTRATIONS BENEATH OR NEAR
ABANDONED UNSEALED DISPOSAL PONDS
Unsealed surface ponds used for the disposal of oilfield brines have polluted
fresh surface waters, potable groundwarers, and fertile land. Because of chemical
and physical phenomena and dispersion, the movement of soluble pollutants from
these ponds is complex. For example, the soluble pollutants move slowly in relation
to the soil water flow rate, and dispersion effects a displacement that causes the
contaminated zone to grow.
The Kansas State Department of Health studied the soils beneath and near an
old unsealed brine disposal pond that had been abandoned for 10 years. During its
use, the pond received more than 29,000 metric tons of salts, and most of those
soluble salts probably escaped by soil leaching and down-drainage and penetrated
40
-------
below the underlying limestone formation. Eleven test holes were drilled into the
soil and shale beneath and adjacent to the pond, both above and below the natural
drainage slope. Chemical analysis of the test hole core samples indicated that
more than 430 tons (about 1.4 percent of the original) of the soluble residual salt
still remained to be leached out of the soil and shale in the pond area. This amount
of soluble or teachable salt remaining in the area indicates that the return of the
subsurface water and soil to their prepollution level is a very slow process and
may take several decades. Network pollution zones appear to form where formation
fracture conjugates occur. Leaching appears to be entirely dependent upon the
flushing mechanism provided by meteoric water.
The cation concentrations in the clay minerals in the soils near the disposal
pond were evaluated by x-ray diffraction techniques to trace cation transportation
rates. Chloride analysis was selected as the most useful single means of detecting
the presence of oilfield brine pollution, but the associated cation concentration
should also be determined to formulate a more complete picture. Cation adsorption
studies are apparently useful in differentiating brine-polluted soil and shale; clay
mineral studies provide the information on the environmental characteristics of the
pollution media/ and cation exchange information aids in explaining the apparent
differential transportation rates of ions in brine seepage solutions.
SUBSURFACE DISPOSAL
A problem associated with subsurface brine disposal is casing leaks in the
disposal well, which could allow the brine to enter freshwater aquifers. Figure
13 shows how an improperly designed disposal well and a leaky oil well can pollute
a freshwater aquifer. Erroneous geologic knowledge of the subsurface formation
into which the brine is being pumped presents another problem. Brine usually is
pumped into a subsurface formation that contains similar brine; however, exact
knowledge of the faulting and fracturing of such a subsurface formation is difficult
to determine. Because the brine is pumped into the formation, bottomhole pressure
41
-------
River
Waste disposal
well
K>
Contamination
\viw .. •PI
*k • . .•:. m EI. . . . . • • .
f: •.•: : :: *J*r".".: .•: ::
, Leonardlan
Wolfcampian
Desmoinesian
Mississippian
Surface
Red beds.salt
Limestone
Shale
Limestone and shale
=^ Siltstone and shale
'•'•'•'•:S Sandstone
••»•*; Leak contamination
Figure 13. Routes by which salt water can enter freshwater wells from faulty oil or disposal wells.
-------
2
must not exceed 0.23 kg/cm /m of overburden, or the hydraulic pressure may cause
fracturing and in time, the wastes may migrate to a freshwater zone.
Petroleum-associated brines from two different formations may form precip-
itates if they are mixed. For example, with a well used for disposal of brines
produced from several producing oil wells, it is imperative that precautions be
taken in mixing and treating the brines before injection. If the brines are incom-
patible and inappropriate precautions are taken, there is a possibility that deposits
will form and filter out on the face of the injection formation, thus reducing the
permeability. The quantity of deposits formed from incompatible brines depends
on ions present. The more common deposits resulting from reactions of incompatible
brines are gypsum (CaSO. • 2 H.O), anhydrite (CaSCO, aragonite (CaCOJ,
calcite (CaCOg), celestite (SrSC>4), barite (BaSOJ, triolite (FeS), and siderite
(FeC03).
Subsurface brine disposal can be categorized as confinement or containment;
confinement is the placement of brines in a horizon where any movement can be
controlled or monitored, while containment is the placement that precludes the
movement of the brines out of a formation or zone. Containment cannot be used
for an unlimited supply of brine, but confinement necessitates the monitoring of
the migration of the brines. The necessary knowledge to define the hydrodynamics
of brines injected into subsurface environments is expensive to obtain, and much
of the necessary fundamental knowledge of subsurface formations is not available.
Formations into which brines are often pumped for disposal are called salaquifers,
and these zones consist of permeable sedimentary rock. Some information needed
before such a zone can be used for disposal operations is as follows: 1) How big is
the zone? 2) If the brine migrates in the zone, might it reappear in another zone
or perhaps migrate to the surface? 3) What mechanisms control movement in a
given salaquifer or perhaps out of it? 4) What steps are necessary to assure con-
tainment or confinement of the brine within the salaquifer? It is difficult, if not
43
-------
impossible/ to develop adequate prior knowledge concerning how or where escape
channels may occur from a salaquifer. Test drilling is the only known method that
can provide such knowledge, and such drilling is expensive/ as is the subsequent
evaluation.
44
-------
SECTION IX
USE OF SALINE WATERS FOR DESALINATION,
TO PRODUCE FRESHWATER AND VALUABLE MINERALS
Dwindling freshwater supplies and polluted supplies have increased research
on how to best obtain freshwater from saline water. Several plants throughout the
world produce freshwater from seawater. The price of water for municipal purposes
is a highly specific thing. The availability of freshwater and costs of obtaining it
vary from place to place. Conventional water supplies range in cost from a few
dollars per thousand cubic meters to over $260 per thousand cubic meters.
The average cost of conventional water supplies in the United States was
$100 per thousand cubic meters in 1952. This was chosen as the goal for saline
water conversion costs. Several authors have estimated ultimate costs of saline
12
water conversion based on thermodynamic considerations. Dodge and Eshaya
have examined the minimum expected costs for saline water conversion. Prior to
their calculations, other authors reported seawater conversion costs to be ultimately
12
less than $79 per thousand cubic meters. Dodge and Eshaya expanded earlier
work to look at departure from isothermal operation, finite product recovery,
differential as opposed to single-stage operation, and salt concentration in the
feed. They found that $90 per thousand cubic meters is the smallest cost for
desalination of seawater that contains about 31,300 ppm of sodium chloride.
Consider the case for converting brackish water with 5,000 ppm sodium
chloride. For converting 50 percent of the feed to freshwater, 187 kW-hr per
1,000 cubic meters was the power requirement. To convert seawater with 35,000
ppm of dissolved solids conversion, the power requirement was 1,530 kW-hr per
1,000 cubic meters. Both calculations were for 50 percent recovery of freshwater
from feed, where the average power costs used in determining conversion costs are
1.5 cents per kW-hr. At this rate, the difference in power costs for seawater over
brackish water is $20 per 1,000 cubic meters.
45
-------
Oilfield brines contain up to seven times the concentrations of dissolved
salts compared with seawater. Would the power be seven times again as expensive
per 1,000 cubic meters? At over $132 for power and $92 for other costs, the cost
of obtaining freshwater from oilfield brines probably would be prohibitive when
consideration is given to the other sources for feed to a conversion plant in the
same area. An additional factor is that most oilfield brines with their high con-
centrations are nearly saturated. Removing 50 percent of the water would in essence
leave a precipitated salt. Therefore, since no conversion processes under study
deal with saturated brine effluents, it is not technologically feasible to completely
desalt oilfield brines at this time.
RECOVERY OF VALUABLE MINERALS FROM SALINE WATERS
The "brine refinery" concept would require a process plant the size of a
13
large petroleum refinery. The market prices used in the concept were
for the recovery and sale of the pure elements. The $3 billion in sales from
0.95 billion cubic meters of brine is the highest sales income possible that would
result from recovering and selling the minerals in the form that gives the highest
unit price.
Consider a "brine refinery" system that would gather 22 million cubic meters
of brine per year. The cost of gathering and disposing of this brine would be
approximately 9.4 cents per cubic meter. The question is whether or not minerals
could be sold at a profit such that the disposal expense would be negated or a
profit made. First, the minerals to be sold must be determined. At 7 ppm lithium,
163 metric tons per year could be produced. This is a large fraction of present
consumption and probably would depress the sale price. The same holds true for
most other elements of such a refinery.
The assumptions lead to a brine refinery system that would process 22 million
cubic meters of brine per year and would yield minerals worth $35 million.
46
-------
Assuming a 15-percent return on Investment and a profit of 15 percent of sales,
the plant would require $35 million investment and yield 23.6 cents per cubic
meter of brine processed. The original disposal operation without mineral
recovery was such that only $6 million was invested. The "brine refinery" would
turn brine disposal into a profit. But the new investment is six times that for disposal
only.
Would a chemical company be interested in such an operation since they
operate at about a 15-percent return? Companies that currently remove minerals
from brines use brines that are more concentrated in the minerals desired. It is
doubtful that a process could combine several less economical operations into a
more economical one, and this would probably be true even if the brine were
supplied to a chemical company free of charge. Only in the special case where
an oilfield brine contained a concentration of dissolved minerals very near a proven
economic brine would the oilfield brine be a best alternate. Therefore, a tax
incentive for pollution abatement or some other economic incentive such as price
increase of recovered chemicals is probably necessary. Figure 14 illustrates a
flowsheet for producing freshwater and valuable minerals from brines.
Table 9 illustrates the approximate amount of valuable chemicals a million
kilograms of brine produced from a given depth should contain before it can be
considered of economic value at present market conditions. The values shown in
Table 9 should allow a profit if conventional or better recovery operations are
utilized. The marketed end product will influence the selection of the recovery
operation as well as the delivered price. The price information used to make the
14
approximations was taken from the Bureau of Mines.
47
-------
RAW BRINE
I
DESALINATION
PROCESS
CONCENTRATED
BRINE
SULFATE
PRECIPITATION
I
IODINE
RECOVERY
I
BROMINE-
RECOVERY
I
CALCIUM
RECOVERY
SODIUM CHLORIDE
RECOVERY
MAGNESIUM
RECOVERY
PRODUCT
FRESH WATER
PRODUCT
SULFUR AND
SULFUR COMPOUNDS
PRODUCT
IODINE AND
IODINE COMPOUNDS
PRODUCT
BROMINE AND
BROMINE COMPOUNDS
PRODUCT
CALCIUM COMPOUNDS
PRODUCT
SODIUM CHLORIDE
OR
SODA ASH
AND
CHLORINE
PRODUCT
MAGNESIUM AND
MAGNESIUM COMPOUNDS
SLUDGE CONTAINING CALCIUM, STRONTIUM,
BARIUM, MAGNESIUM AND OTHER ELEMENT
COMPOUNDS. THE SLUDGE CAN BE DISPOSED
AS A SOLID OR RECYCLED FOR CHEMICAL
RECOVERY
Figure 14. Diagramatic flowsheet for producing freshwater and valuable elements
from brines.
48
-------
Table 9. DOLLAR VALUE OF DISSOLVED CHEMICALS A BRINE SHOULD
CONTAIN PER MILLION KILOGRAMS OF BRINE
PRODUCED FROM A GIVEN DEPTH
Value of dissolved chemicals
per million kilograms of brine
for economic production
$ 462
$ 968
$1,430
Depth of well,
meters
760
2,130
3,050
Factors that must be considered in evaluating a saline water as an economic
ore are the cost of bringing it to the factory, the cost of the recovery process, and
the cost of transporting the recovered products to market. Assuming that a brine
is produced only for the purpose of recovering its dissolved chemicals, a prime
factor is the cost of pumping the brine. It will cost less to produce the brine from
a shallow well than from a deep well. Therefore, neglecting other factors, a brine
must contain a certain amount of recoverable chemicals before it can be considered
economically valuable, and the farther it must be pumped, the more chemicals it
must contain.
Today the possibility of recovering elements from brines that are pumped to
the surface is increasingly important because the brines present a pollution hazard
if their disposal is improper. One cubic meter of brine containing 100,000 ppm of
chloride is capable of polluting 400 cubic meters of freshwater so that it is
unfit for human consumption.
Table 10 illustrates the value that chemicals recovered from brines have at
the market; however, because the market fluctuates, these values are approximate.
The column on the left indicates the elements that are found in petroleum-associated
49
-------
brines, and the second column indicates the concentration that a given brine must
contain before it can be used to produce a given amount of chemical. For example,
a brine containing 50,000 ppm of sodium will contain sufficient sodium in a million
kilograms of brine to produce sodium chloride worth about $550.
Table 10. AMOUNT OF ELEMENT NECESSARY IN A MILLION KILOGRAMS
OF BRINE TO PRODUCE A CHEMICAL WORTH
$550 AT THE MARKET
Element in
the brine
Sodium
Potassium
Lithium
Magnesium
Calcium
Strontium
Boron
Bromine
Iodine
Sulfur
Concentration of
element in a million
kilograms of brine,
parts per million
50,000
14,000
170
8,000
11,000
4,000
1,400
1,700
250
5,300
Market product
Sodium chloride
Potassium chloride
LJthium chloride
Magnesium chloride
Calcium chloride
Strontium chloride
Sodium borate
Bromine
Iodine
Sodium sulfate
The data in Table 10 indicate that some petroleum-associated waters contain
sufficient sodium to establish them as economic for the production of sodium chloride.
This is not necessarily true, because factors such as market demand, ease of recovery,
and proximity to market may be discouraging in certain geographic areas. Such
factors must be fully considered before startup of a chemical from brine recovery
50
-------
operation. One important goal that should not be discounted or overlooked is
developing a means of ultimately disposing of these brines to eliminate any pollution
hazard. Coupling of this goal with the fact that many of these brines contain eco-
nomic concentrations of several elements should make such recovery operations more
attractive. Additionally, several important chemicals can be produced from these
elements instead of those shown in the market product column in Table 10. An ex-
ample is soda ash, which is a basic chemical in many manufacturing processes.
Furthermore, the figures shown in Table 9 are applicable only if the brine is
produced solely for the recovery of its dissolved chemicals.,v If the brines are
pooled from several petroleum production operations, the cost of pumping the
brine becomes less, and the necessary amounts of chemicals dissolved in a million
pounds of brine become less.
Mixed Salts
Mixed salts are precipitated by evaporation of seawater and brines to produce
crude salt separations. The costs of these separations are low compared to those of
highly purified compounds or metals. There are several drawbacks that prevent
greater use of this type of recovery. The product does not command a high price,
the plant must be at the brine source, there must be solar evaporation conditions,
and a local market must exist for the majority of the mixed salts. Uses that have
been suggested include heattreating salt baths in the steel industry, raw materials
for refractory or catalyst manufacture, and fertilizer components.
Precipitation other than by solar evaporation is accomplished by cooling or
adding chemical agents. Simple cooling may be all that is necessary for more
concentrated brines, but fractional crystallization is necessary for dilute brines
such as seawater. Again,local markets dictate whether cooling or freezing pro-
cesses will yield the correct products for a particular area. Adding chemicals to
precipitate a specific product is the most fruitful of the nonsolar evaporation
processes. Most of the processes have been aimed at the production of fertilizer.
51
-------
Potassium and magnesium are the minerals in seawater that are most valuable for
use in producing fertilizers. Salutsky and Dunseth report that metal ammonium
?
phosphates (MAP) containing magnesium, calcium, iron, manganese, copper, and
many other trace metals comprise high-analysis fertilizer.
W. R. Grace Company started U.S. production of MAP fertilizer on a
semicommercial scale in I960 through the use of their patent issued in 1962.
The fertilizers are nonburning, long-lasting sources of nitrogen, phosphorus, and
various trace metals. Because of their low solubility, MAP's will not cause salt
>
injury to seeds or plants.
In magnesium ammonium phosphate, practically all of the P^O,- is available,
and the size of the MAP granules applied to plants determines how long the nutrients
will be available. Thus, availability of nutrients can be controlled by granulation
and, since growing time varies from crop to crop, MAP's can be tailored to a
specific crop. Therefore, fewer applications are necessary with MAP's than with
fertilizers of higher solubility and high nitrification rates.
The W. R. Grace Co. developed the MAP process for two purposes. First,
it is useful to remove scale-forming materials from seawater before desalination.
Secondly, it would yield the valuable, high-analysis fertilizer, magnesium ammon-
ium phosphate. In 1962, W. R. Grace Co. reported that the process was ready for
the pilot plant. The process is based on phosphate precipitation. To descale
seawater and produce high-analysis fertilizer at the same time, wet-process phos-
phoric acid and anhydrous ammonia are added continuously to raw seawater. This
precipitates the scale-forming elements—calcium, magnesium, iron, and other
metals—as metal ammonium phosphates and other phosphates. The precipitated
solids (MAP's) are removed by settling, and the descaled seawater is pumped to the
saline water conversion plant. The descaled water holds only 1 percent of the orig-
inal magnesium and 5 percent of the original calcium, thus representing a more
optimum water for desalination. The slurry of MAP's is dewatered to about 35 to
40 percent solids by continuous centrifuges and then it is heated to 90° C. This
52
-------
converts MAP hexahydrate to mono hydrate. The slurry is filtered, washed, mixed
with recycle fines, and granulated. Figure 15 shows a process flowsheet for pro-
ducing descaled oilfield brine and fertilizer.
Several questions surround the economics of the process. For a plant descal-
ing 3,800 cubic meters of seawater per day (output about 10,000 metric tons per
year of fertilizer), the fertilizer would have to command a price higher than that
of conventional farm fertilizers. The estimate assumes 1962 market prices for raw
materials (phosphoric acid and ammonia) and does not take credit for the increased
value of the descaled seawater. Because of its premium quality, MAP can go to
the market as a speciality product.
In the phosphoric acid-ammonia process, 2 moles of ammonia per mole of
MAP are lost to ammonium chloride in neutralizing the phosphoric acid. Using
disodium phosphate in place of the acid loses no ammonia, and using monosodium
phosphate only loses 1 mole of ammonia. If a cheap method were developed for
producing the sodium phosphates, ammonia waste would be reduced. The simplest
method for producing sodium phosphates involves the neutralization of phosphoric
acid with either dilute sodium hydroxide or soda ash. Caustic soda and chlorine
can both be produced from sodium chloride brines.
At the present time, many petroleum-associated brines are injected into sub-
surface strata, and it is assumed that they are thus disposed of permanently.
However, this method of disposal appears subject to question, because in some
instances, freshwaters apparently have been polluted by disposal of brines. Sub-
surface disposal operations are suspected in certain areas as possibly contributing
.. , , 18,19
to increased earthquakes and ground tremors.
The storage of brines in earthen pits is known to cause pollution of nearby
soils and streams. Such ponds that have been abandoned for 10 years still con-
tribute to soil pollution. Sound conservation should favor the recovery of
53
-------
Anhydrous Phosphoric
Ammonia Acid
1
r v
Raw oilfield
brine
Wnrh ,1,1 »
r -if- "i
1 Sodium 1 | Soda
1 Hydroxide 1 1 Ash
L J L_ ,- -1
~T —
1
X J
Settling and
thickening
Dehydration
u
Filtration and
washing
Descaled
oilfield brir
i
i
*
r
ie
^
Fresh
water
I
Granulation
Undersize
Drying
I
Screening
Crushing
Oversize
Finished product
to storage
Figure 15. Diagramatic flowsheet for producing descaled seawater and fertil
izer.
54
-------
valuable elements from brines, and with proper planning, the recovery processes
should aid in the ultimate disposal of unwanted brines. Conservation of this type
not only will develop new resources, but will benefit the oil producer and the
national economy and will aid in abating pollution of soils, potable waters, and
streams.
WORK NECESSARY FOR AN EXACT PRELIMINARY EVALUATION
20
Aries spells out the marketing research techniques employed in the chemical
industry. There are ways to determine quickly where a market for a product is.
Usually these places are currently served by some producer or another. If the
competition is located far from the market, then an evaluation of a closer area
source is readily made. To find product users, the following methods and approaches
are utilized: advertising, company analysis, product analysis, industry analysis,
use analysis, and other miscellaneous methods. If new markets must be found,
7'': ''
the following types of work are utilized: personal interview, questionnaire, trade
analysis, company records, and published sources. Before an economic analysis
can be made for a given area, probably several man-months of the above-listed
methods would be required. The product of this type of market study would be a
list of elements and compounds that could be sold from a given place. The quantities
and prices obtained would then allow an economic calculation of the production
costs.
With the quantities, prices, and production costs in hand, it is still not a
simple matter to determine what type of plant to operate. Regardless of who
the investor might be, he will want to know what return on investment he will
get, what risk is involved, and what payout period exists for the project. Depending
on the investor, he may want to limit the plant size by the amount of money he
can invest. This does not simply scale down the plant. It may rearrange various
55
-------
ratios of certain products produced in order to give the investor the combination
of profits/ return on investment, risk, and actual size of investment that he desires.
LOCATIONS OF VALUABLE BRINES
Figures 16, 17, 18, and 19 are maps showing areas in the United States where
brines containing high concentrations of sodium, calcium, magnesium, and bromine,
respectively, are found.
56
-------
SODIUM
en
XI
LEGEND
• 75,000-80,000 mg/l
o 80,000-95,000
A > 95,000
Figure 16. Approximate geographic locations of brines containing high concentrations of sodium.
-------
CALCIUM
Oi
00
Figure 17. Approximate geographic locations of brines containing high concentrations of calcium.
-------
MAGNESIUM
Cn
•O
A >30,000
Figure 18. Approximate geographic locations of brines containing high concentrations of magnesium.
-------
BROMINE
• 1,500-2,000 mg/l
o 2,000-3,000
A > 3,000
Figure 19. Approximate geographic locations of brines containing high concentrations of bromine
-------
SECTION X
REFERENCES
1. Piper, A. M. A Graphic Procedure in the Geochemical Interpretation of
Water Analyses. U.S. Geol. Survey Ground Water Note 12, 14 pp. (1953).
2. Reistle, C. E. Identification of Oil-Field Waters by Chemical Analysis.
U.S. BuMines Tech. Paper 404, 25 pp. (1927).
3. Stiff, H. A. The Interpretation of Chemical Water Analysis by Means of
Patterns. J. Petrol. Tech., 3, pp. 15-17 (1950).
4. Tickell, F. G. A Method for Graphical Interpretation of Water Analysis.
Calif. State Oil and Gas Supervisor, 6, pp. 5-11 (1921).
5. Morgan, C. E., R. J. Dingman, and J. M. McNellis. Digital Computer
Methods for Water-Quality Data. Ground Water, 4, pp. 35-42 (1966).
6. Morgan, C. O., and J. M. McNellis. Stiff Diagrams of Water-Quality
Data Programmed for the Digital Computer. Kans. State Geol. Survey.
Special Distribution Pub. 43, 27 pp. (1969).
7. Angino, E. E., and C. O. Morgan. Application of Pattern Analysis to the
Classification of Oil-Field Brines. Kans. State Geol. Survey. Computer
Contribution 7, pp. 53-56 (1966).
8. Collins, A. G. Geochemical Classification of Formation Waters for Use in
Hydrocarbon Exploration and Production. M.S. Thesis. University of
Tulsa, Tulsa, Okla., 63 pp. (1972). AlsoChapter 8 of Book, Geochemistry of
Oilfield Waters, Authored by Collins, Elsevier Publishing Company, In
Press.
9. Visher, G. S. 1961 Unpublished Report, Sinclair Oil Company, Now at
the University of Tulsa, Tulsa, Okla.
10. Fryberger, J. S. Rehabilitation of a Brine-Polluted Aquifer. Environmental
Protection Agency Report, EPA-R2-72-014, 61 pp. (1972).
61
-------
11. Bryson, W. R., G. W. Schmidt, and R. E. O'Connors. Residual Salt of
Brine Affected Soil and Shale, Potwin Areas, Butler Co., Kansas. Kansas
State Dept. of Health Bull. 3-1, 28 pp. (1966).
12. Dodge, B. F., and A. M. Eshaya. Thermodynamics of Some Desalting Pro-
cesses. Advan. Chem. Ser., No. 27, American Chemical Society, Wash-
i
ington, D. C., 246 pp. (I960).
13. Collins. A. G. Here's How Producers Can Turn Brine Disposal Into Profit.
Oil and Gas J., 64, pp. 112-113 (1966).
14. Bureau of Mines. Metals, Minerals, and Fuels. Minerals Yearbook. Vol.
l-ll, 1208 pp. (1968).
15. Salutsky, M. L, and M. G. Dunseth. Recovery of Minerals from Sea Water
by Phosphate Precipitation. Advan. Chem. Ser., No. 38, American Chem-
ical Society, Washington, D.C. 199 pp. (1962).
16. Anonymous. Descaling: Route to MAP. Chem. Eng. News, 40, pp. 52-53
(1962).
17. Crouch, R. L. Investigation of Alleged Ground-Water Contamination, Tri-
Rue and Ride Oil Fields, Scurry County, Texas. Texas Water Commission
Rept. LD-0464-MR, 16pp. (1964).
18. Evans, D. M. The Denver Area Earthquakes and the Rocky Mountain
Arsenal Disposal Well. The Mountain Geologist, 3, pp. 23-26 (1966).
19. Bardwell, G. E. Some Statistical Features of the Relationship Between
Rocky Mountain Arsenal Waste Disposal and Frequency of Earthquakes.
The Mountain Geologist, 3, pp. 37-42 (1966).
20. Aries, R. S. Marketing Research in the Chemical Industry. Chemonomics,
New York, N. Y., 220 pp. (1954).
62
-------
SECTION XI
APPENDIX I
USER INFORMATION & STATION DATA
(FWPCA'Storet System)
•U.S. DEPARTMENT OF THE INTERIOR
FEDERAL WATER POLLUTION CONTROL ADMINISTRATION
AGENCY (USER) CODE
2i1 iO iK i 1 i 1 ,R ,S
UNLOCKING KEY
9 ,9 ,9 ,9 ,9 ,9 ,9 ,9
9 - 16
17
24
USER NAME, LOCATION,
U, ,S , ,B , ,M, ,A,
PROJECT, ETC.
,G, ,0,0, L ,L ,1 ,N
25
USER NAME, LOCATION, PROJECT, ETC. (Cant.)
St ,9 ,1 18 |5 ,8 |4 |2 ,2 18|2
43
61
STATION TYPE
0 .2i4 i 1 iT i2 il .0
66 73
CONTROL
CODE
62
t_
65
(F) - FEET
(M) - METERS
74 75 76 77
78 79
PRIME STATION CODE
(Left Justify)
4 ,8 ,0 ,
0 ,2,6, , ,
i i i
i i i
19-33
(1) SECONDARY STATION CODE
(Lett Justify)
I I I
I I I
(2) SECONDARY STATION CODE
(Left Justify)
I I I I
J I
34
45
46
57
(3) SECONDARY STATION CODE
(Lett Justify)
I I I I I I
FWPCA ASSIGNED CODES
STATE
4 ,8
COUNTY
2 ,7 ,0
CITY
1 1 1
1
CONTROL
CODE
N,S
67
68 69 70
72 73
77
78 79
63
FWPCA 2H (11-69)
-------
DEPARTMENT OF HEALTH, EDUCATION, AND WELFARE
FEDERAL WATER POLLUTION CONTROL ADMINISTRATION
STORE! II - LOCATION DATA
HEADER CARD I (Required)
CARD SORTING NUMBER
1-3
4-6 BLANK
LATITUDE (Degrees, Minutes, 0. J Seconds) -
LONGITUDE (Degrees, Minutes, 0. J Seconds)
2 |7 ||3 |0 I |0 I 7j 9
7-13
0
9
8
0
1
2
1 ,
4
14-21
AGENCY CODE
22-27
PRECISION CODE (Use for original storage only)
UNITS CODE FOR DEPTH (F (or Feet ond M for Meters) .
TOTAL DEPTH OF WATER OR WELL (Use for ordinal storage only).
STATE CODE (Use for original storage only)
TYPE OF STATION CODE (Use for original sforoge only) .
29
30-32
33-34
35-42
43-€7 BLANK
STATION CODE (Optional, Left Justify)
68-79
80
HEADER CARD III (Optional and Used for Original Storage Only)
CARD SORTING NUMBER (Some os Co/. J-3 on Cord /)
1-3
4-12 BLANK
STATE NAME (13-28):
i T . EiX .A iS i
J I
J I
MAJOR BASIN NAME (29-52):
• W.E ,S ,7 ,E ,R ,N,
G,U,L ,Fi j ( il ,2 .)
i i i
j i
MINOR BASIN NAME (53-79):
,G ,R ,A ,N,D ,E
B ,E ,L ^.W.P ,E ,C ,0,5
| | I 80
HEADER CARD IV (Optional and Used for Original Storage Only)
CARD SORTING NUMBER (Some as Co/. J-3 on Cords / and III)
1-3
4-6 BLANK
MINOR BASIN NAME - CONT. FROM CARD III (7-19):
I ( I 1 I 0 I ) I I I I I I I I I I
LOCATION NAME (20-51):
. P|R .O.P.U.C, I ,N,G, ,W,E ,L ,L
LOCATION NAME -CONT.:
I I I I I I I I
I I I I
52-79 BLANK
FWPCA - 2e
2-66
64
-------
STORE! I - LOCATION CARD V
DEPARTMENT OF HEALTH, EDUCATION, AND WELFARE
FEDERAL WATER POLLUTION CONTROL ADMINISTRATION
4
8
0
0
2
6
GiE iOiL ,0,Gi 1 iCiA.L i iP iR iO i V i 1 , N iC i E . i- , ,3,5i5i , i , , , i i .
STATION CODE (1-6) DESCRIPTION (7-78)
I i i . i i . . A,A ,P ,G. -C.O.D.E, , I i i i i i , I I ,- i ,1,2,3, iFIRll-O, I
58
66
75
LINE
4
8
0
0
L
2
6
F ,1 ,E, L,D, .N.A.M.E , , ,
1 ,N,T ,E ,R ,V,A,L , ,S ,A|M,P ,L ,E,D, ,
, i ,- , ,B ,O,R ,R , E ,G,O,S , ,
1 ,- , ,5 ,7,5 ,4, 1- 1 ,5 ,715
7
5
4
1
1
8
0
1 l
0
2
1 i
6
t l L i t i V i A i 1 i 1 | Ui Nl , I i i | i i i
S ,A ,M,P ,L ,E , ,S ,O,U ,R ,C,E i , , , ,
i i i i i i i i i i 1 i i i i i i
i i i i i i i i i i - i i i i i i i
i i i i i i i i i i 1 i i i i i i
> i i i i i i i i i i i i i i i i
i i i i i i i i i i 1 i i i i i i
i i i i i i i i i i i i i i i i i
i i i i i i i i i i 1 i i i i i i
i i i i i i i i i i i i i i i i i
i i i i i i i i i i 1 i i i i i l
i i i i i i i i i i i i i i i i i
i i i i i i i i i i 1 i i i i i i
i i i i i i i i i i i i i i i i i
i i i i i i i i i i 1 i i f i i i
i i i i i i i i i i i i
i i i 1 i i i i i i
|
|
|
i
|
i
|
l
i- 1 i 1 i3 lU i i
, l- i iW.E ,L ,L ,
i i i i i i i
i i i i i i i i
i i i i i i i
i i i i i i i
i i i i i i i
i i i i i i i
i i i i i i i
i i i i i i i
1 i i t i l i
,
l i i i i i i
i i l i i i i
1 1 1 1 1 1 i
ii i i i i i
ii
,H
1 i i
|E ,A ,D
1 i ,
i i i
i i
i i i
i i
i i i
, ,
i i
i i
i i
J i
i i
i i
i i
i i
|
1
|
|
1
|
1
5
5
5
5
|
5'
5
5
5»
8J
FOR LINE
FWPCA -
2-66
11 ONLY
2d
: 41-57 RESERVED, S8-64 LATITUDE, 65 BLANK, 66-73 LONGITUDE, 74 BLANK, 75-77 DEPTH, 78 F OR M FOR FT. OR METERS. 79 J
-------
U. S. DEPARTMENT OF THE INTERIOR
FEDERAL WATER POLLUTION CONTROL ADMINISTRATION
STORE! SYSTEM -WATER QUALITY DATA
LABORATORY BENCH DATA
STATION
DESIGNATION DATE OF SAMPLE
YR. MO. DAY
HOUR » MINUTE Or SAMPLE OR LAST
DATE OF COMPOSITE SAMPLE
ITEM
1 1
ITEM ....
1 1
IT Eh
1 1
8 7
ITFM
1 1
ITEM
1 1
ITEM
PH UNIT SU
111 1 110000000
1
Bicarbonate UN,T ma/I
1111110000000
'
Total Solids UN,T mg/l
Calcium UNIT- mS/l
HI
Magnesium UNIT ma/I
1 11 1 11 0000000
Sodium UNIT mg/l
1 11 11 11 1 0000000
ITEM
1 1
,
1
a 7
ITEM
1 1
8 7
ITEM
1 1
1 1
• 7
4- -
Chloride UNIT mg/l
J , -
Sulfate UNIT mg/l
t 11 111 0000000
Fe (total) UNIT Ua/l
11 11 11 0000000
Resistivity UNIT
1 11111 0000000
884*321 012346*
COMPUTER CODED DATA
STATION CODE SERIAL YR.
48002
1-8
\ 6 1 6 !a
1
1
PARAMETER CODE VALUE
00400
19-23
00440
31-38
| 6 6 0 0
24-27
] [T 9 5 0
36-3B
MO.
1 ll
7-12
!
13-18
EXPON
M
28
h 1
40
DAY ~
0\7
I
ENT RMKS
0D :
20 30
an
41 42
00530
43-47
00915
58-50
00925
87-71
3034
48-51
7350
(0-63
2500
72-79
ll 1
82
1 1 1 1
84
C
111
7e
NEXT CARD . REPEAT COLUMNS 1-18 ABOVE
00930
10-ZS
0 |0 9 4 0
SI-S8
0 |o 9 4 5
41-47
JIT 1 0 2
24-27
1 fl 8 1 |5
S6-3B
111 ll 0 0
46-61
0 |l 0 4 5
B8-8»
72010
67-71
2300
60-63
J [2 2 2 0
72-7S
ll I I
23
HI
40
ll I
82
•-
hi
84
C
lol
76 '
5
S3 54 ,
eg sa
OLUMN 80 (BLANK)
CHG.
3DD
77 78 7»
3D
2B 30
3D
41 42
3D
83 84
an ,
«« 8«
OLUMN 80 (BLANK)
CHG.
HDD
77 78 7»
FWPCA 2b (9-66) (Fomvrly PHS 4718-2)
66
-------
U. S. DEPARTMENT OF THE INTERIOR
FEDERAL WATER POLLUTION CONTROL ADMINISTRATION
STORE! SYSTEM -WATER QUALITY DATA
LABORATORY BENCH DATA
STATION DESIGNATION DATI
YR.
OF SAMPLE
MO. 1 DAY
Houn a MINUTE OF SAMPLE OR LAST
OATE OF COMPOSITE SAMPLE
ITEM Resistivity Temperature UNIT
°c
I 1
B 7 ' S 3 4 ' 3 2 1 0 ! 2 3 408
,TEM Specific Gravity UMIT
J ' i
ITEM Specific Gravity Temperature UNIT °C
1 'I
ITEM UNIT
.
ITEM UNIT
11111 1110000
000
ITEM UNIT
111111110000
1 J
0
0 0
ITEM UNIT
-T •- •
ITEM UtftT
III 111110000
000
ITEM UNIT
1II11II10000
1 -
0
0 0
ITVU UNIT
111111110000
0
0 0
COMPUTER CODED DATA
STATION CODE SERIAL YR. MO.
480026 o J 3 ill
1-8 7-12
DAY
0|7
18-18
PARAMETER CODE VALUE EXPONENT P.MKS
7 2 0 1 4 IJ2 2 7 0 ll_|
19-23 24-27 28
72013 1021 ll 1
31-3B 38-38 40
ma
29 30
41 42
72012 2270 |l|
43-47 48-81 82
a
BB-B9 80-83 84
JJ
S3 34
an
88 88
COLUMN 80 (BLAN
CHS.
D
87-71 72-78 78
NEXT CARD - REPEAT COLUMNS LIB ABOVE
a
19-23 24-27 28
a
If ">0 S6«3tt 40
DGC a
43-47 48-81 82
a
•8-88 80-83 84
1
1 1
77 7B 7»
an
29 90
DD
4f 42
an
S3 84
na
BB BB
COLUMN BO (BLAMH
CMC-
a
67*71 72*78 76
L
77 7
J
8 74
PWPCA 2b (*-«6) (Fotmnly PUS 4711-2)
67
-------
STORE! DATE 72/02/15
SECTION XII
APPENDIX II
480026
27 30 07.9 098 0! 21.4 1
PRODUCING WELL
48 TEXAS
WESTERN GULF (12)
RIO GRANDE LOWER BELOW PECOS RIVER (10)
210K11RS 02412210
0999
00
PARAMETER
00400
00440
00530
00915
00925
00930
00940
00945
01045
72010
72012
72013
72014
PH
HCO3 ION
RESIDUE
CALCIUM
MGNSIUM
SODIUM
CHLORIDE
SULFATE
IRON
RESISTIV
SP GR
SPECIFIC
RESISTIV
HCO3
TOT NFLT
CA,DISS
MG,DISS
NA,DISS
CL
S04
TOTAL
TEMP
GRAVITY
TEMP
SU
MG/L
MG/L
MG/L
MG/L
MG/L
MG/L
MG/L
UG/L
BM
CELSIUS
BM
CELSIUS
NUMBER
MEAN
6.60000
395.000
30340.0
735.000
25.0000
11020.0
18150.0
11.0000
23.0000
.222000
22.7000
1.02100
22.7000
VARIANCE STAN DEV
MAXIMUM
6.60000
395.000
30340.0
735.000
25.0000
11020.0
18150.0
1 1 .0000
23.0000
.222000
22.7000
1.02100
22.7000
MINIMUM
6.60000
395.000
30340.0
735.000
25.0000
11020.0
18150.0
11.0000
23.0000
.222000
22.7000
1.02100
22.7000
BEG DATE
63/11/07
63/11/07
63/1 1/07
63/1 1/07
63/11/07
63/1 1/07
63/1 1/07
63/11/07
63/1 1/07
63/1 1/07
63/1 1/07
63/1 1/07
63/11/07
END DATE
63/11/07
63/11/07
63/11/07
63/1 1/07
63/11/07
63/1 1/07
63/11/07
63/11/07
63/1 1/07
63/11/07
63/1 1/07
63/11/07
63/1 1/07
-------
SELECTED WATER
RESOURCES ABSTRACTS
INPUT TRANSACTION FORM
/. Repcrtffo,
F
7_
4. Title
SALINE GROUNDWATERS PRODUCED WITH OIL AND GAS
7. Author(s)
A. Gene Collins
9. Organization U.S. Department of the Interior
Bureau or Mines
Barrlesville Energy Research Center
fcSrJ!!ffii38L 74003 '
3. Accession No.
w
5, R<.-?ort DistTed
y jS>
Protection
IS. Supplementary Notes
U. S. Environmental Protection Agency Report EPA-660/2-74-010,
April 1974.
IS. Abstract
More than 60,000 saline water analyses were collected by the U.S. Bureau of Mines for entry into
an automatic data processing system. Screening of the data eliminated 30,000 analyses; 20,000 were
entered into STORET, the data processing system formulated by the Environmental Protection Agency.
The water analyses are used in studies related to identifying the source of a brine, classification of
groundwater for use in geochemistry, plotting local and regional salinity maps, determining sources of
pollution of freshwater and land by brines, and studies of the use of saline water for desalination to
produce freshwater and valuable minerals. Examples of each of these studies are given in this report.
Irresponsible control of brines can seriously pollute freshwater and land. The analyses now in
STORET should be wisely used in pollution prevention programs. Additional analyses should be
entered into STORET to aid groundwater and land pollution prevention programs.
The most important factors are the potentials that exist for using the data in studies related to
pollution abatement and exploration for minerals. (Collins - USBM)
17a. Descriptors
*Saline water, *Brines, *Connate water, Desalination, Descaling, Saline water systems, Water
pollution sources, Encroachment, *Oil wells, Saline water intrusion, Aquifers, Groundwater,
Subsurface waters, Water chemistry, Water reuse, *Salts, *Mapping, Subsurface mapping,
Distribution patterns, *Brine disposal injection wells, *Pollutant identification.
776. Identifiers '
'Recovery of valuable minerals from brine, Locations of valuable brines, Economics of recovering
minerals from brines.
17c. COWRR Field & Group 1QA
18. Availability
J9. " Security Wagi;
(Report)
20. Security Cl&ts. " .
,<£«*>
iti tlfk.-o/
Pages
• tit. Pfisa
Send To:
WATER RESOURCES SCIENTIFIC INFORMATION CENTER
U.S. DEPARTMENT OF THE INTERIOR
WASHINGTON. D. C. 2O240
Abstractor A. Gene Collins | institution U.S. Bureau of Mines
WRS1C 102 (REV. JUNE I97T
4U.S. GOVERNMENT PRINTING OFFICE: 1974 546-318/356 1-3
------- |