Book Chapter On Oil Field Water

Chapter 8.
CLASSIFICATION OF OILFIELD WATERS
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 devel-
oped t o 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. Sur-
face 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 classified as fresh water, while water in an ocean will
contain about 35,000 mg/l dissolved minerals and is classified as saline.
Waters found in rivers connecting the mountain stream t o 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 stoichiometric 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 t o the water
since entering the subsurface environment. For example, some subsurface
waters found in deep sediments were trapped during sedimentation, while
other subsurface waters have 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 Some waters have been replaced by infiltration water.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, which
dissolve in the waters or contain chemicals which will exchange with chemi-
cals 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 t o more than 350,000 mg/L This
salinity distribution is dependent upon several factors, including hydraulic
gradients, depth of occurrence, distance from outcrops, mobility of the
dissolved chemical elements, soluble material in the associated rocks, and the
exchange reactions.
254 CLASSIFICATION OF OILFIELD WATERS
Portions of three classification systems (Palmer, 1911; Sulin, 1946;

Schoeller, 1955) and Bojarski’s (1970) modification of Sulin’s system were
applied to about 4,000 formation waters (U.S. Bureau of Mines, 1965). The
waters were analyzed by standard methods (American Petroleum Institute,
1968). The results indicated that the classifications are useful in exploration
and production problems.
Palmer’s classification
Palmer (1911) observed that the basic characteristics of natural waters are
dependent upon their salinity (salts of strong acids) and alkalinity (salts of
weak acids). Salts that cause salinity are those that are not hydrolyzed, while
alkalinity is caused by free alkaline bases produced by the easily hydrolyz-
able salts of weak bases.
All positive ions (cations) including hydrogen can cause salinity, but of
the negative ions (anions), only the strong acids, (e.g., chloride, sulfate, and
nitrate) can cause salinity. Because salinity is dependent upon the combined
activity of the cations and anions and is limited by the reacting values of the
strong acids, its value is determined by multiplying the total value of the
strong acids by two.
Alkalinity is caused by free alkaline bases as a result of the hydrolytic
action of water on dissolved bicarbonates and other weak acid salts. The
alkalinity value is calculated by doubling the reacting values of the bases
which exceed the reacting values of the strong acids.
The ions that commonly are found in waters comprise three groups: (a)
alkalies (sodium, potassium, lithium), whose salts are easily soluble in water
and do not cause hardness; (b) alkaline earths (magnesium, calcium, stron-
tium, barium), whose salts cause hardness and many of which are sparingly
soluble; and (c) hydrogen, whose salts are acids and cause acidity.
Geologists know what “strong alkalies”, “alkaline earths”, “strong acid
radicles”, “weak acid radicles”, “ions”, and “reacting values” mean general-
ly. To compare several analyses it usually is easier if they are made on a
chemical basis. The. proportions of the various ions do not react in propor-
tion t o the various weights given in milligrams per liter but rather in propor-
tion to their “capacity for reaction”, or “reaction value”. The reacting value
of each ion is determined by multiplying the amount of each radicle by
weight (mg/l) by its “reaction coefficient”, which is the valence of a radicle
divided by its atomic weight.
The groups of the ions are determined by summing the reacting values of
their members, and according to the predominance of reacting values of the
groups, five special properties were designated by Palmer. To determine the
special properties, the reacting values of a group of cations or anions are
doubled so that the full value of a given special property is considered. The
terms “primary” and “secondary” were used t o qualify the general proper-
PALMER’S CLASSIFICATION 25 5
ties of the water; e.g., the principal soluble decomposition products of the
oldest rock formations are the alkalies (primary), while more recent rock
formations are the principal source of the alkaline earths (secondary), This
theory of Palmer’s that the terms primary and secondary are associated with
the age of the rock should not necessarily be considered undisputably true,
because primary salinity certainly can be acquired from other soluble
material than that derived directly from decomposition products of the
oldest rock formations.
The five special properties of water are:
(1) Primary salinity (alkali salinity); that is, salinity not t o exceed twice
the sum of the reacting values of the radicles of the alkalies.
(2) Secondary salinity (permanent hardness); that is, the excess (if any) of
salinity over primary salinity, not t o exceed twice the sum of the reacting
values of the radicles of the alkaline earths group.
(3) Tertiary salinity (acidity); that is, the excess (if any) of salinity over
primary and secondary salinity.
(4) Primary alkalinity (permanent alkalinity); that is, the excess (if any) of
twice the sum of the reacting values of the alkalies over salinity.
(5) Secondary alkalinity (temporary alkalinity); that is, the excess (if any)
of twice the sum of the reacting values of the radicles of the alkaline earths
group over secondary salinity.
Reacting values in percent are used in this system. The percentage values
are determined by summing the milliequivalents of all the ions, dividing the
milliequivalents of a given ion by the sum of the total milliequivalents, and
multiplying by 100. Waters are classified by numerical values of the relation-
ships of anions to the cations, where a , b , and d represent the percentage
values of the alkali cations, alkaline earth cations, and strong acid anions,
respectively. Any one of the following five conditions may exist: d may be
equal t o or less than a , greater than a and less than a + b y equal to a + b y or
greater than a + b . Using these conditions, waters are classified into five
classes:
Classl: d < a
2d = primary salinity
2(a - d ) = primary alkalinity
2b = secondary alkalinity
Class 2: d = a
2u or 2d = primary salinity
2b = secondary alkalinity
Class 3 : d > a ; d < (a + b )

2a = primary salinity
2(d - a ) = secondary salinity
2(a + b - d ) = secondary alkalinity
Class 4: d = (a + b )
2a = primary salinity
2b = secondary salinity
Class 5: d > ( a + b )
2u = primary salinity
2b = secondary salinity
2(d - a - b ) = tertiary salinity (acidity)
These five classes of water are found in nature. Examples of the first three
classes are various surface waters, sea water and brines represent class 4,
while mine drainage waters and waters of volcanic origin fall in class 5
(Palmer, 1911).
Rogers (1917, 1919) studied oilfield waters of the San Joaquin Valley,
California, and used the classification system of Palmer (1911). He found
that generally the surface waters of the San Joaquin Valley possess second-
ary salinity rather than primary alkalinity, contain more sulfate than
chloride, and contain low amounts of bicarbonate. With increasing depth,
the subsurface waters decrease in secondary salinity until primary alkalinity
becomes evident. Waters above an oil zone often contained hydrogen sulfide,
which was attributed t o reduction of sulfates by hydrocarbons, thus de-
creasing the amounts of sulfate and increasing the bicarbonate in the water,
which Rogers called an altered water. Further he found that, in these altered
waters in close proximity to hydrocarbon accumulations, chloride becomes
relatively and absolutely important because of the residual chloride from the
original (ancient) sea water chlorides as compared to waters above the oil
zone which often are freshened because of a more hydrodynamic situation.
Altered waters, according t o his definition, can have either primary alkalinity
or secondary salinity depending upon their amounts of carbonate and chlo-
ride, but normal waters have only secondary salinity.
Elliott (1953) used the Palmer system t o determine the chemical charac-
teristics of some Paleozoic age formation waters in Texas. He found that all
of the waters in the group that he studied (about 70) contained predomi-
nant, primary salinity. Many of these waters contained appreciable concen-
trations of sulfate; one contained 5,800 mg/l sulfate, and many contained
more than 2,000 mg/l. The calcium concentration ranged up to 13,000 mg/l
while the bicarbonate concentrations ranged up t o 800 mg/l.
Ostroff (1967) used the Palmer classification to classify waters from
several basins and t o compare this classification system with two other
systems. He found that the Palmer system groups some of the constituents
together that are not closely related chemically. Furthermore the system
does not consider ionic concentrations or saturation conditions related t o
sulfate or bicarbonate.
SULIN’S CLASSIFICATION 257
Sulin’s classification
Sulin (1946), a Russian geochemist, proposed a classification system based

upon various combinations of dissolved salts in the waters. The waters are
described according to chemical type, subdivided into group, subgroup, and
class. He found four basic environments of natural water distribution:
(1) Continental (terrestrial) conditions which promote the formation of
sulfate waters. Such conditions supply soluble sulfate constituents t o the
water and the genetic type of such a water is “sulfate-sodium”.
(2) Continental conditions which promote the formation of sodium bicar-
bonate waters. The genetic type is “bicarbonate-sodium”.
( 3 ) Marine conditions and the formation of a “chloride-magnesium ” type
of water.
(4) Deep subsurface conditions within the earth’s crust and the formation
of a “chloride-calcium ” type of water.
The first two types are characteristic of meteoric and/or artesian waters,
the third of marine environments and evaporite sequences, and the fourth of
deep stagnant conditions.
Types, groups, and subgroups
Water composition is expressed in milligram-equivalents of the separable

ions, and the composition is calculated per 100 g of water. The percent of
the sum of the equivalents is used t o exclude the degree of water mineraliza-
tion, and t o compare waters containing different amounts of dissolved solids.
The ratio Na/Cl expressed in the percent equivalent form determines the
genetic water type. If the value is greater than one, sodium predominates
over chloride and the excess sodium can be combined with sulfate or bicar-
bonate. Therefore waters with a Na/Cl ratio greater than one belong to the
bicarbonate-sodium or the sulfate-sodium types. Sulin calculated sodium as
the sum of all the alkalies (Li, K, Na etc.) and chloride as the sum of all the
halides (Cl, Br, I).
The ratio (Na - C1)/S04, if greater than one, indicates that the water is
the bicarbonate-sodium type, while if it is less than one it is the sulfate-
sodium type. Similarly the ratio (Cl- Na)/Na if less than one indicates the
chloride-magnesium type, but if greater than one it indicates the chloride-
calcium type.
Water classes
Subdivision of the groups of waters were made by Sulin (1946) using the
Palmer (1911) characteristics, because these characteristics express the dis-
solved constituents in the waters in a generalized format. For example, the
sum of the alkali chlorides and sulfates corresponds t o primary salinity, and
the sum of the alkaline earth chlorides and sulfates corresponds to secondary
salinity and the sodium bicarbonate-calcium stage. N o sodium bicarbonate is

present in sulfate-sodium, chloride-magnesium, or chloride-calcium types of
water; therefore, these types are classified as follows:
(1)Class A2 : secondary alkalinity predominates (alkaline earth carbonates
and bicarbonates).
(2) Class S2 : secondary salinity predominates (alkaline earth sulfates and
chlorides).
(3) Class S, : primary salinity predominates (alkali sulfates and chlorides).
(4) Class S,: tertiary salinity predominates (iron and aluminum sulfates
and chlorides and free strong acids).
Bicarbonate-sodium type waters contain sodium bicarbonate and are
classified as follows:
( 5 ) Class A2 : secondary alkalinity predominates (alkaline earth carbonates
and bicarbonates).
(6) Class A , : primary alkalinity predominates (alkali carbonates and bicar-
bonates).
(7) Class S, : primary salinity predominates (alkali chlorides and sulfates).
(8) Class A, : tertiary alkalinity predominates (iron and aluminum carbon-
ates and bicarbonates).
The water classification is expressed by use of a formula representing
decreasing values of the Palmer characteristics. For example, S, S2 A 2 indi-
cates that primary salinity is predominant and is followed by secondary
salinity and secondary alkalinity. Therefore, the classes are subdivided into
subclasses, and class S1 can include the subclass S, S2 A 2 , S1 A2 S2, S1 S2,
and S, . Table 8.1 outlines Sulin’s method of water characterization. Table
8.11 briefly outlines the relative values of the coefficients which determine
the four genetic types of waters.
The Palmer characteristics do not account for the interrelations between
chloride and sulfate and between calcium and magnesium. Therefore, Sulin
calculated the ratio SO4/C1 and Ca/Mg to establish additional subgroups. The
complete water characterization included the following: (a) water formula
given in Palmer characteristics; (b) coefficients in percent equivalents for
S04/C1 and Ca/Mg; (c) sum of the milligram equivalents per 100 g of water
(Z r ) t o illustrate the degree of water mineralization; and (d) the genetic
coefficients (Na - C1)/ SO4 and (Ca - Na)/Mg t o determine the water type,
and Na/C1 t o determine related genetic types of water.
Hydrochemical indicators of hydrocarbons
Sulin (1946) noted that certain properties of subsurface waters were

favorable indicators of hydrocarbon accumulations. The bicarbonate-sodium
and chloride-calcium types of waters are widely found in oilfields. However,
the chloride-calcium type is the more favorable indicator if it has the most
characteristic composition plus certain minor or micro constituents. In gen-
eral, he determined that hydrocarbon accumulations are most commonly
SULIN’S CLASSIFICATION 25 9
TABLE 8.1
Sulin’s method of water characterization

_____
Na/Cl >1
Sulfate-sodium type:
(Na+ - C1-)
<1 Bicarbonate-sodium type:
(Na+ - C1-) >
so,,-2 so4-2
Bicarbonate group Bicarbonate group
class A2 class A1
calcium subgroup sodium subgroup
magnesium subgroup class A2
Sulfate group calcium subgroup
class S1 magnesium subgroup
magnesium subgroup class S 1
sodium subgroup sodium subgroup
class Sp Sulfate group
calcium subgroup class S1
magnesium subgroup sodium subgroup
Chloride group Chloride group
class S 1 class S1
magnesium subgroup
sodium subgroup
Na/Cl <1
(C1-- Na+) - Na+) >
Chloride-magnesium type:
Mg+’
< 1 Chloride-calcium type: (Cl-Mg+2
Bicarbonate group Bicarbonate group

class Aq class A 2
calcium subgroup calcium subgroup
magnesium subgroup magnesium subgroup
Sulfate group Sulfate group
class s1 class S1
class S2 class s 2
Chloride group Chloride group
class S1 class S1
sodium subgroup sodium subgroup
class S2 class s 2
26 0 CLASSIFICATION OF OILFIELD WATERS
TABLE 8.11
Coefficients characterizing the genetic types of waters

~~
Type of water Na+/Cl- (Na’ - Cl-)/S04-2 (Cl-- Na+)/Mg+’
Chloride-calcium <1 <O >1

Chloride-magnesium <1 <O <1
Bicarbonate-sodium >1 >1 <O
Sulfate-sodium >1 <1 <O
related t o water types in this order: chloride-calcium > bicarbonate-sodium

> chloride-magnesium > sulfate-sodium. Most oilfield waters of the
chloride-calcium type belong to the S1 S2 A2 class with a few in the S2 S,
A2 class, while most oilfield bicarbonate-sodium waters belong to the S, A,
A2 and A , S1 A 2 classes.
Other significant indicators were grouped by Sulin; however, none of
them can assure the existence of a hydrocarbon deposit, and certainly they
cannot provide definite evidence of the size of the accumulation. The groups
are as follows:
Group I: direct hydrocarbon indicators; for example, naphthenic acid salts
and iodide. The naphthenic acids are more soluble in bicarbonate-sodium
type waters and are related t o the composition of the hydrocarbon accumu-
lation. Iodide is related to oil because it must have an organic origin. Sulin
also noted the dissolved gases in the waters and considered the heavier
hydrocarbons such as ethane and butane and the absence of oxygen as direct
indicators.
Group 11: highly mineralized chloride-calcium or bicarbonate-sodium
types of water containing reduced forms of sulfur are important indirect
indicators of oil. The sulfate content should be low to indicate interaction
with bituminous constituents and/or sulfate-reducing bacteria.
Group 111: in this group are constituents which have no genetic relation-
ship to hydrocarbons but appear characteristic of waters that are related t o
hydrocarbon accumulations. The constituents are bromide, boron, barium,
strontium, radium, and possibly fluoride.
Modification of Sulin’s system by Bojarski
Bojarski (1970) studied 400 water analyses and differentiated hydro-

chemical zones within basins in Poland that appear suitable for preservation
of hydrocarbon deposits. He distinguished the waters as follows:
(1) Waters of the bicarbonate-sodium type. Such waters occur in the
upper zone of a sedimentation basin, with “intense water exchange” (that is,
a hydrodynamic situation where the waters are moving at a relatively fast
geological rate), which promotes unfavorable conditions for the preservation
of petroleum and natural gas deposits. The waters are defined by the ratio
MODIFICATION OF SULIN’S SYSTEM 26 1
(Na-Cl)/SO, > l . As Sulin (1946) noted, if the ratio Na/Cl in epm is

greater than 1, the water contains more sodium than chloride and the excess
sodium can react with sulfate or bicarbonate ions. Therefore, such waters
belong to the bicarbonate-sodium or sulfate-sodium types. If the ratio
(Na - C1)/S04 is greater than 1,it indicates an excess of sodium with respect
t o both chloride and sulfate.
(2) Waters of the sulfate-sodium type with (Na - Cl)/S04 < 1. This ratio,
if less than 1, indicates that all of the sodium will react with chloride or
sulfate.
(3) Waters of the chloride-magnesium type with (Cl- Na)/Mg < 1. A ratio
of this type indicates that all of the chloride will react with sodium and
magnesiun. Such a water is characteristic of the transition zone between a
hydrodynamic area which is becoming more hydrostatic in the deeper part
of the basin, and the amount of dissolved bromide increases directly with the
(Cl- Na)/Mg ratio.
(4) Waters of the chloride-calcium type with (Cl- Na)/Mg > 1. This ratio
indicates an excess of chloride with respect t o sodium and magnesium, and
the excess will react with calcium. This type of water occurs in deeper zones
which are isolated from the influence of infiltration waters and are hydro-
static or almost hydrostatic.
Bojarski observed a large variation in the chemical composition in the
chloride-calcium type of water and subdivided this type as follows:
(a) The first class, chloride-calcium I with Na/Cl > 0.85 characterizes an
active hydrodynamic zone with considerable water movement. It is con-
sidered a zone of little prospect for the preservation of hydrocarbon
deposits.
(b) The second class, chloride-calcium I1 with Na/C1 = 0.85-0.75, charac-
terizes the transition zone between an active hydrodynamic zone and a more
stable hydrostatic zone of the sedimentation basin, which is generally con-
sidered a poor zone for hydrocarbon preservation.
(c) The third class, chloride-calcium I11 with Na/Cl = 0.75-0.65 (0.60),
characterizes favorable conditions for the preservation of hydrocarbon
deposits.It is designated as a fairly favorable environment for the preserva-
tion of hydrocarbons.
(d) The fourth class, chloride-calcium IV with Na/C1 = 0 . 6 5 4 . 5 0 , is
characterized by complete isolation of the hydrocarbon accumulations as
well as by the presence of residual waters. I t is considered a good zone for
the preservation of hydrocarbons.
(e) The fifth class, chloride-calcium V with Na/C1 < 0.50, is characterized
by the presence of ancient residual sea water which has been highly altered
since original deposition, both in the concentration of dissolved solids and in
the ratios of the dissolved constituents. Bojarski considers a zone of this type
to be one of the most likely areas where hydrocarbons are accumulated.
Additional characteristics of water associated with hydrocarbon accumula-
tions are as follows: (1) iodide > 1mg/l; (2)bromide > 300 mg/l (increasing
iodide and bromide concenbrations may point to a bitumen accumulation);

(3) ratio Cl/Br < 350; and (4) SO4 x lOO/Cl< 1.
In addition t o indicating the degree of alteration, bromide and iodide as
biophile constituents play a decisive role in the classification Bojarski
adopted. This followed because of the increased concentration of biophile
elements in the waters accompanying a petroleum deposit. The concen-
tration of iodide in the ground waters depends mainly on the organic sub-
stances, whereas the’concentration of bromide up t o a certain limit takes
place in an inorganic medium, but an increase in bromide must be evaluated
as a positive indication. In many waters accompanying petroleum deposits,
large amounts of bromide and smaller amounts of iodide were detected, or
vice versa. This probably is related t o the type of bituminous substances
which absorb the individual biophile elements in different amounts.
Chebotarev’s classification
Chebotarev (1955),an Australian geochemist, classifies waters on the basis

of dissolved bicarbonate, sulfate, and chloride, and he does not consider the
acid waters or those that contain free sulfuric or hydrochloric acid. His
fundamental assumption is that the anions are independent variables while
the cations are dependent.
The geochemical types of waters are related t o the products of weath-
ering. Table 8.111 illustrates the cycles and products that are produced by
weathering. During the first cycle the igneous rocks are weathered allowing
chloride, sulfate, calcium, sodium, silica, and magnesium to go into solution.
The second cycle is the weathering of sedimentary rocks with the solution of
more of the same products. The third cycle is the weathering of recent drift
and yields of the above constituents plus aluminum and iron.
Table 8.IV illustrates Chebotarev’s (1955) geochemical classification of
subsurface waters. The phase of weathering corresponds t o four phases of
the solution and redistribution of the chemical constituents in the earth’s
crust and correlates with their relative mobilities. He plotted the relative
mobilities of nine chemical constituents using the mobility of chloride as
100%. From this four phases were obtained, namely: (1)chloride and sulfate
100% t o about 58% mobility; (2) calcium, sodium, magnesium and potas-
sium 3% t o about 1.2% mobility; (3) silica about 0.20% mobility; and (4)
iron oxide and aluminum oxide, less than 0.05% mobility. The four phases
of weathering correspond to the products of weathering shown in Table 8.IV
and also to the cycles and products of weathering in Table 8.111. For
example the fourth phase in Table 8.IV corresponds with the first cycle in
Table 8.111.
The genetic types of water shown in the upper portion (A) of Table 8.IV
do not correspond directly with the weathering phases since the genetic
types overlap the phases. These genetic types are related t o the accumulation
products shown in Table 8.111. In the lower portion (B) of Table 8.IV are the
TABLE 8.111
Cycles and types of products of weathering (after Chebotarev, 1955)

b
rn
Cycles of
weathering:
First cycle (orthoeluvium)
from igneous and highly metamorphosed rocks
Second cycle (paraeluvium)
from sedimentary rocks
Third cycle (Neoluvium)
from Recent Drift
zrrl
is
residual products accumulative products residual products accumulative products residual products accumulative products b
=iJ
Types of (1) coarse detrital (1) chloride-sulphate (1) detrital (1) chloride-sulphate (1) solonez and (1) chloride-sulphate 0
products (chiefly alluvial) gypsum bearing z
of weathering (2) calcareous (2) calcareous (2) siallitic (2) calcareous (2) leached supra- (2) CaC03
(under vegetation (chiefly colluvial (supra-calcareous chloride-sulphate calcareous
cover) and proluvial) (siallitic)
(3)siallitic (3)siallitic (3) allitic (?) (3) unsaturated siallitic*2 (3) unsaturated siallitic (3) alumino- and ferri-
calcareous chloride- siallitic*’ siliceous system
sulphate
(4) a l l i t i ~ * ~
(lateritic crust of
weathering)
*’ A large quantity of silica and much of its calcium and sodium compounds are removed; the aluminosilicates pass gradually into residual aluminosilicic acids,
i.e., acids of the kaolin type.
*’ The action of carbonated atmospheric water is insufficient to replace the absorbed ions by hydrogen.
*3 The accumulation of sesquioxides at the expense of the leaching out of the alkalis, alkaline earth, and silica.
TABLE 8.IV
Geochemical classification of subsurface waters (after Chebotarev, 1955)
( A ) Relationship of the products of weathering to the genetic types of water
Presumable phase of weathering Products of weathering Genetic types of water
Fourth phase residual (orthoeluvium and detrital paraeluvium) bicarbonate (alkaline)

bicarbonate-chloride (alkaline-saline)
Third and partly second phases siallitic drift
chloride-bicarbonate (saline-alkaline)
Second and partly first phases calcareous accumulation
chloride-sulfate (saline)
First phase chloride-sulphate accumulation chloride (saline)
(B) Geochemical groups of Waters
Major group Class Genetic types of Reacting value in percent

of water water
H C 0 3 - + COB- Cl- SO4-’ Cl- + SO4-’ H C 0 , - + CI- HC03- + SOq-‘
Bicarbonate I bicarbonate >40 <lo - Na+ + K+ prevail in all types of

waters
C3+ and Mg” less than 2.5 in the
I1 bicarbonate-chloride 40-30 10-20 water of high saline facies and less
than 19.0 in low saline facies
111 chloride-bicarbonate 30-15 20-35
Sulphate IV sulphate-chloride 15-5 <25 >25 Na+ + K+ prevail in all types of

waters
sulphate - - >40 Ca+’ less than 4.5 in all waters
Mg” less than 4.0 in all waters
Chloride 111 chloride-bicarbonate 30-15 >20 - - Na+ + K+ prevail in all types of

waters
IV chloride-sulphate 15- 5 >20 - <2 5 Ca” less than 12.5 in the water
of high saline facies
V ch 1or ide < 5 >40 - <10 Mg+’ less than 6.0 in all types of
waters
CHEBOTAREV’S CLASSIFICATION 26 5
geochemical groups of waters. The three major groups of waters are divided
into genetic types, which are determined from the absolute concentrations
of the dissolved constituents expressed in reacting values in percent. The
bicarbonate group contains three genetic types of water, namely: (1)bicar-
bonate; (2) bicarbonate-chloride; and (3)chloride-bicarbonate. The amounts
of bicarbonate plus carbonate and chloride plus sulfate determines the
genetic type. The sulfate group is subdivided into two genetic types: (1)
sulfate-chloride; and (2) sulfate. The chloride group is divided into three
genetic types: (1)chloride-bicarbonate; (2) chloride-sulfate; and (3) chloride.
Chebotarev relates the genetic types to the products of weathering because
he believes that although the concentration of dissolved solids in subsurface
waters may vary substantially, the types of soluble salts remain largely
unchangeable .
The water classes are related to the products of weathering, rainfall, and
drainage conditions. Class I corresponds t o soluble products from the weath-
ering of orthoeluvium or igneous and highly metamorphosed rocks and their
silicate compounds. Class I1 waters are related t o products of weathering
from the same silicates and calcareous accumulations. Class I11 waters
primarily are related to weathered products from calcareous accumulations.
Class IV waters are related to weathering of alluvial, detrital, and gypsum
deposits. Class V waters are related to marine deposits plus weathering of the
products that derived the Class IV waters.
Table 8.IV shows the approximate reacting values in percent for waters
found in some oilfields (Chebotarev, 1955). For example, in such waters in
the bicarbonate group, the major cations are sodium plus potassium with the
reacting value percentage for calcium and magnesium less than 2.5 if the
saline facies are high. (The divisions between his saline facies are shown in
Table 8.V.)
Table 8.V shows the relationships of hydrodynamic zones t o the geo-
chemistry of the water and the geological environment. The zones are: (1)
recharge with active water exchange; (2) pressure with delayed water
exchange; and (3)accumulation with stagnant conditions.
The equilibrium of the chemical systems (those typical of the major geo-
chemical group of waters) is a criterion called the coefficient of water
exchange ( K e ) and is computed as:
Na(K)HC03 + (Ca,M&)(HC03)2
Ke =
Na(K)Cl + (Ca,Mg)C12 + Naz SO4 + (Ca,Mg)S04
The absolute and relative coefficients of water exchange for the three major
groups of waters are as follows:
Ke (absolute) Ke (relative)
Bicarbonate waters 1.55 96.9
Sulfate waters 0.11 6.9
Chloride waters 0.016 1.o
TABLE 8.V
Relationships of hydrodynamic zones to the geochemistry of water and the geological evironment (after Chebotarev, 1955)
Hydrodynamic zone Geochemistry of water Geological environment
recharge- water- class hydro-chemical approximate common structures relation to water depth examples
discharge exchange facies salinity terms for (ft)
cycle (ppm) water
Zone of active I and I1 low saline facies 180-2,400 fresh different intensive flush usually less everywhere
recharge exchange (some than 500
times
111)
transitional 2,400--11,400 brackish deep portions of delayed flush sometimes Great Artesian Basin,
(typical) facies structures with 5,000-7,000 Rocky Mountain oil-
peculiar geo- field and others
chemical en-
vironment
high saline facies 11,400-37.800 saline hampered flush
Zone of delayed 111 and low saline facies 400-2,500 fresh different inadequate flush usually less everywhere
pressure exchange IV than 1,000
trazs. Lional 2.500-7.400 brackish deeper portions circulation and sometimes precaucasian Basin,
(typical) facks of structures, drainage limited 3.000-4,000 South Dakota Basin,
folded zones some oilfield areas
high saline facies 7,400--19,300 saline
Zone of stagnant V low saline facies 1.500-20,000 fresh and different salt accumulation different chiefly in arid regions;
accumulation condition saline prevails upon deeper portions of many
leaching artesian basins: some
oilfields
transitional 20.000-90,000 saline and deeper portions sometimes

(typical) facies brines of structures, 8,000-1 3,000
highly folded
zones
high saline facies 90,000-300,000 brines water exchange many oilfield areas
manifests on geo- (Louisiana, Alberta, etc.)
loeical scale time
SCHOELLER’S SYSTEM 26 7
The absolute and relative coefficients were derived from assumed chemical
compositions of typical waters of the major geochemical groups. The abso-
lute value can be not lower for the group, but it can be relatively higher.
Several thousand analyses of waters associated with oil pools in the world
were used to formulate the typical waters. As the water-exchange conditions
deteriorate, the type of water changes, and the changes are related to altera-
tion or diagenesis of the waters (metamorphism). The data in Table 8.V give
hydrochemical facies, common names of various waters as related to
dissolved solids concentrations, geological structures, flush or water circula-
tion, depths, and examples where some of the water types are found.
The highly concentrated chloride waters are primarily associated with oil
occurrences; however, this is not always true. A prime determinant of the
chemical composition of oilfield waters is the hydrodynamic situation and
the type of trap. For example, an intensively flushed zone will contain a
different type of water from a zone with limited circulation. The type of
basin strongly influences the type of water that.is likely t o be found. For
example, an open basin probably will contain artesian waters of the bicar-
bonate group, a partly closed basin may contain artesian or subartesian
waters of the bicarbonate or sulfate groups, while a closed basin is more
likely t o contain bicarbonate waters on the flanks of the basin with sulfate
and chloride waters in the deeper areas.
Chebotarev (1955) applied his classification t o 917 subsurface waters in
oilfields in the world. The classification indicated that 73.7% of the waters
were of the chloride genetic type, 23.0% of the bicarbonate type, and 3.3%
of the sulfate type. Most of the sulfate and bicarbonate types were found in
the Rocky Mountain areas of the United States and probably were mixtures
containing infiltrating meteoric water.
Schoeller’s system
A French geochemist, Schoeller (1955),classified waters on the basis of

their dissolved constituents and in the following order of importance: (1)
chloride; (2) sulfate; (3) bicarbonate plus carbonate; (4) index of base
exchange (IBE); and (5) relationships of anions t o cations. This system
separates waters into six primary types based upon their amounts of dis-
solved chloride and four subgroups based on their concentrations of sulfate.
The amounts of bicarbonate and carbonate ions give additional differentia-
tion, and an index of base exchange indicates exchange of ions in the waters
with ions in associated clays. Table 8.VI outlines Schoeller’s classification.
As shown in Table 8.VI the chloride concentration separates waters into
six types. Waters from several oil-producing regions were classified and the
sequence C1> SO4 > HC03 was found to occur in very high chloride waters
and in sea waters, especially when they are saturated with CaS04. If the
waters are not saturated in CaS04, the sequence Cl- > HC0,- > S04-2 is
predominant, and in low-chloride waters the predominant sequence is
H C O ~ -> C T > S04-2.
26 8 CLASSIFICATION O F OILFIELD WATERS
TABLE 8.VI
Schoeller’s scheme for classifying petroleum reservoir waters*
Chloride concentration as Ci-
Very high if > 700

Marine if 420 - 700
High if 140 - 420
Average if 40 - 140
Low if 10 - 40
N o r m a l i f < 10
Sulfate concentration as s04-’
Very high if >

58
High if 24 - 58
Average if 6 24 -
Normalif< 6
Near saturation when J(S04-’) (Ca+’) > 70
Bicarbonate plus carbonate concentmtion as H C 0 3 - + c03-’
High if 7>
Normal if 2 7-
Low if 2<
However, he recommends using q ( H C 0 3 - + CO3-’ )‘(Ca+’ ) rather
than HC03- + C03-’
Index o f base exchange (IBE)
If Cl- > Na+ then IBE = (Cl- - Na+)/Cl-

If Na+ > Cl- then IBE = ( C T - Na+)/(S04-’ + HCO3- + C03-2)
Importance o f anions and cations
c1- > SO^' > co3-’

c1- > .co~-‘> so4-’
co3-’ > c1-> so4-2
co3-’ > so4-’ > C T
Na+ > Mg” > Ca+’
Na+ > Ca+ ’ > Mg+’
* All constituents are calculated in epm.
SCHOELLER’S SYSTEM 26 9
Also, in very high chloride waters only the sequence Na+ > Ca+’ > Mg+2
is found. As the C1- decreases, the sequence Na+ > Mg+’ > Ca+’ becomes
more frequent. In very high chloride waters SO4-’ > Ca+’, but in less
concentrated waters the opposite may occur. The sequence HC03-< Ca+’
always is found in very high chloride waters. In less concentrated chloride
waters, either HCO,- < Ca+’ or HC03- > Ca+’ may be found, while in
low chloride waters HC03- > Ca+’ is predominant.
Schoeller used an arbitrary value of 70 for JSO4- x Ca+’ to indicate
that a water is saturated with CaS04. (This is not necessarily true because
some waters, depending upon their other dissolved constituents, can contain
smaller or larger amounts.) He divided waters into four additional types
depending upon their amounts of sulfate.
Saturation with CaS04 was found to occur only in very high chloride
waters. The calcium concentration always is very high - ranging from 150 to
1,100 epm - in high chloride waters which have SO4-’ > 58 epm and
usually is less than 150 epm in high chloride waters where SO4-’ < 58 epm.
All petroleum waters even if saturated in CaS04 have a low S04/C1 ratio
which is attributed t o reduction of sulfates and high concentrations of
chloride. The ratio never exceeds one except in low or normal chloride
waters.
The third subgroup contains three additional types depending upon the
amounts of bicarbonate and carbonate in the waters. The preferred formula
for this calculation is Y(HCO,- + C03-’ )’ (Ca+’ ) which is proportional to
the gaseous pressure of C 0 2 in equilibrium with CaCO, in the water. As the
Cl- increases, the tendency is for Ca+’ t o increase and HC03- to decrease;
however, because the Ca+’ increases, the product of y(HCO,- + C03-’ )’
(Ca+’ ) does not vary greatly.
As the waters move in their subsurface environment their dissolved ions
’have a tendency to exchange with those in the rocks. Two extreme types of
adsorption can be noted in addition to intermediate types of adsorption. The
extreme types are a physical adsorption or the Van der Waals adsorption with
weak bonding between the adsorbent and the constituent adsorbed and a
chemical adsorption with strong valence bonds. Both of these adsorptions
can act simultaneously.
Cations can be fixed at the surface and in the interior of the associated
minerals. These fixed cations can exchange with the cations in the water.
When the exchange occurs, there is an exchange of bases. With the right
physical conditions of the adsorbent, similar exchange can occur with the
anions. Some of the formation constituents that are capable of exchange and
adsorption are argillaceous minerals, zeolites, ferric hydroxide, and certain
organic compounds.
Particle size influences rates and capacities, if the solids are clays such as
illite and kaolinite. The.rate increases with decreasing particle size. However,
if a larger mineral has a lattice, the exchange can easily occur on the plates.
The concentration of exchangeable ions in the adsorbent and in the water is

important. More exchange will occur when the solution is highly concen-
trated.
Schoeller (1955) used the formula:
1
(a-x)=K -
( a E x ) IP
to indicate the relationship that exists between the initial concentration, a ,
of the cations in milliequivalents in the unreacted water, and x , which equals
the final concentration of the cations in milliequivalents in the water after
equilibrium or reaction with the rocks. The amounts of cations exchanged
by passing from the liquid t o the rock or clay is a - x and the index of base
exchange (IBE) = (a - x ) / a . By substitution:
The IBE is used to indicate the ratio between the exchanged ions and the
same ions as they originally existed. For example, assume that in the original
water there were as many equivalents of C1- as (Na+ + K , and that when
'
)
the Na+ and K+ of the water exchanged with the alkaline earths in the rocks
alkaline exchange occurred, then:
IBE =
C1- - (Na+ + K+)
c1-
and this value is positive if the equivalents are Cl- > (Na' + K . Theoret-
'
)
ically all the halides should be included as C1- and all the alkalies as Na+ or
(Na+ + K '
)
.
However, when the alkaline earth ions in the water exchange for alkali
metal ions on the rocks then:
Cl- - (Na+ + K + )
IBE =
SO4- + HC03- + NO3-
and this value is negative if the equivalents are Cl- < (Na+ + K+).The lack
of equilibrium between the halides and the alkalies is not always a charac-
teristic of base exchange because sea water has a positive value without the
occurrence of base exchange. Negative values usually are observed for water
coming from altered crystalline rocks. Waters with an IBE equal t o or greater
than 0.129 can be true connate petroleum reservoir waters. Waters with a
negative IBE are waters of meteoric origin that have infiltrated into marine
sediments.
Comparison of petroleum-reservoir waters with other types of subsurface
waters revealed that the other waters have most of the same characteristics
a much higher SO4- concentration and a lower
or Kr. Waters that are in contact with organic matter
SCHOELLER’S SYSTEM 271
(other than petroleum), such as bitumens, lignites, and coals, resemble petro-
leum reservoir water, but the frequency of a Kr above normal is greater in
petroleum associated waters. Waters related - to magmatic reactions com-
monly possess high concentrations of HC03 .
Schoeller’s (1955) study of petroleum reservoir waters indicated that a
positive IBE is more frequent as the C1- increases. A negative IBE is more
frequent as the C1- decreases, and a negative value is predominant in low
and normal chloride waters associated with petroleum. In fact, this charac-
teristic appears specific for petroleum reservoir waters since in other subsur-
face waters a positive index occurs as frequently as a negative index.
Ancient sea water (connate water) deposited with the sediments usually
has an IBE > 0.129 and a Cl/Na > 1.17. Intruding meteoric water in sedi-
mentary marine rock has an IBE < 0.129 and Cl/Na < 1.17. Petroleum-
reservoir waters with an IBE greater than sea water 0.129 also have the
characteristics Cl/Na > 1.17, Cl/Ca < 26.8, Cl/Mg > 5.13, Mg/Ca < 5.24; a
very high value for $(HCO,-)’ (Ca+*) indicating sulfate reduction; low con-
centrations of HC03-; and frequent high concentrations of NH4 +.
Petroleum-reservoir waters containing infiltrating meteoric water mixed
with ancient sea water have an IBE less than sea water, 0.129, and the
characteristics Cl/Na < 1.17, the ratio Mg/Ca increases and approaches but
never equals 5.24, and the ratios Na/Ca and Na/Mg decrease as the dissolved
solids increase.
Gases in petroleum-reservoir waters
Schoeller (1955) noted that there should be equilibrium between the free
petroleum gases and those dissolved in the water. Considering the solubility
of the gases, those in the water should reflect the composition of the petro-
leum. Components characteristic of petroleum accumulations are ethane,
propane, butane, pentane, ethylene, and propylene. Associated components,
which may also be present in volcanic waters and in waters in contact with
other organic matter such as coal, peat, and lignite as well as in petroleum-
associated waters, are favorable components. These are methane, carbon
dioxide, organic nitrogen, hydrogen sulfide, helium, radon, and the absence
of oxygen. Other components or universal components found in all types of
waters are nitrogen and argon.
The top waters can contain gases such as Hz S, C 0 2 , and CH4 but because
they do not contact the petroleum deposit they are not similar in com-
position t o the bottom waters. The edge waters are in contact with the
petroleum and are characterized by higher amounts of HC03, sulfate reduc-
tion, and the presence of H2S , NH4, and small amounts of dissolved hydro-
carbons.
Oilfield brine analyses
About 4,000 oilfield brine analyses were classified. All of these analyses
are now in the U.S. Bureau of Mines (1965) open-file report on oilfield
brines. The data are on automatic data processing magnetic tape as well as in
a file of computer printout sheets listed by State, county, sedimentary basin,
formation, etc.
These brine data were collected by the Bureau of Mines because the value
of oilfield brine analyses in the study of various petroleum-related problems
was recognized early in the history of petroleum and natural gas. Before
1928 the Bureau of Mines had indicated in several reports (Ambrose, 1921;
Swigart and Schwarzenbek, 1921; Collom, 1922; Mills, 1925; Reistle, 1927)
ways in which the analyses could be used. In earlier years, confusion existed
because of greatly varying methods of analysis that were used. A paper
presenting the methods used by the Bureau of Mines was published by
Reistle and Lane (1928). This system of determining the characteristic con-
stituents of oilfield waters and of calculating and reporting results was
widely adopted by the petroleum industry. Later the Bureau of Mines
cooperated with several interested agencies, and a more detailed report with
more modern methods of analyzing oilfield waters was published (American
Petroleum Institute, 1968).
The Bureau of Mines has an oilfield water analysis laboratory at the
Bartlesville Energy Research Center, Bartlesville, Oklahoma. These 4,000
samples were analyzed at this laboratory.
Analysis methods
The specific gravity of each sample is determined so that a correct aliquot

size can be taken for a specific ion analysis. Chloride is determined by
titration with silver nitrate, carbonate and bicarbonate are determined by
titration with a standard acid, and a pH meter is used to determine the end
points. This alkalinity determination should be completed at the time of
sampling for accur?te results. However, most of the data for the 4,000
samples were obtained by analysis in the laboratory and were completed
within 6 t o more than 48 hours after sampling. Therefore, the alkalinity data
cannot be considered absolute but only relative.
The calcium was determined by titration of calcium oxalate with perman-
ganate until about 1957, about which time it was determined by com-
plexometric titration such as with disodium ethylenediametetraacetic acid
(EDTA) until about 1969; since then, it has been determined by atomic
absorption. Magnesium determination has a similar history. I t was precipi-
tated as the pyrophosphate until about 1957, and titrated with EDTA until
1969, from then t o now it has been determined by atomic absorption.
Sulfate was determined by precipitation as barium sulfate, and this meth-
od still is used. Sodium was determined by calculation from the difference
OILFIELD BRINE ANALYSES 273
between the reacting values of the assumed total anions and cations until
about 1960, after which time it was determined by flame photometry or
atomic absorption.
Several other analyses for dissolved constituents in oilfield brines are now
made by the Bureau of Mines. For example, potassium, lithium, rubidium,
and cesium are determined by atomic absorption or flame photometry;
strontium and barium by atomic absorption; manganese, iron, and boron by
atomic absorption or titrimetric methods; and bromide and iodide by
titrimetric methods.
The precision of the methods is as follows: alkalinity, 2-3% of the
amount present; sodium, 2--5% of the amount present; calcium and magne-
sium, 4--5% of the amount present; sulfate, 1-2% of the amount present;
chloride, 1% of the amount present. If sodium is calculated, the precision
value reflects the sum of the precision data for the data from which it is
calculated plus the undetermined dissolved constituents. The significant
figures for the analytical data are all the certain digits and only the first
doubtful digit. This number usually is limited to three significant figures
except for specific gravity, where four or five are common.
It often is recognized that the sampling method is as important as the
analytical method. This certainly is true of oilfield brines.
Field sampling methods
Most of the 4,000 samples were obtained only from wells where reason-
able assurance was evident that the formation brine was not contaminated
by drilling fluids or by intrusion of water from other formations. Wells were
selected on the basis of age, type of completion, and production of fluids.
Samples were not taken from some gasfields because of the likelihood of
dilution by water condensed from vapor carried up the hole with the gas.
Some samples were taken from gas-condensate wells that produced large
volumes of brine.
In many cases the electrical resistivity measurement was made on the
sample at the time the sample was taken, and resulting values were compared
with measurements from other samples from the same formation within that
field or nearby fields. Obvious discrepancies were eliminated by sampling
additional wells.
Nearly all samples were withdrawn at production wellheads, and the water
was separated from the oil in portable separators. A few samples were taken
of brines from formations that did not produce enough water t o permit
taking samples at individual wellheads. Such samples were taken from gun-
barrels or oil-water separators.
Samples were taken in clean, 1-gallon glass jugs that were first rinsed
several times with the water sampled and then filled, capped, and labeled. In
a few instances samples were obtained by the producer from comparatively
isolated small pools or fields and shipped t o the laboratory in 1-gallon poly-
ethylene jugs.
Application of the classification systems
Several investigators have applied the classification systems t o determine

their usefulness in studies related t o exploration and production of petro-
leum. Ostroff (1967) concluded that Palmer’s system is less useful than the
systems of Sulin and Schoeller. Further he concluded that the Sulin system
is more applicable to petroleum formation waters because many such waters
contain more than 2,000 epm of dissolved solids, and the Schoeller system
tends to lump these highly concentrated waters together. The index of base
exchange (IBE) in Schoeller’s system, however, appears to have merit for
certain interpretations as does theJ Ca+* x SO4-*.
Dickey (1966) concluded that the Palmer system does not correlate very
well with the geology of oil reservoirs, that Schoeller’s nomograph is useful,
but that the Sulin system appears t o conform better with geology. He also
noted that relating water types to geology and flow patterns should be useful
in exploration and that distinguishing between a stagnant water and artesian
related waters should be highly significant in a new oilfield development
area.
The Sulin system appears t o be more generally applicable than the other
systems in studies of waters from petroleum reservoirs. Because of this and
because the Schoeller system appears t o have merit in studying certain types
of oilfield waters, it was decided t o apply portions of the Sulin system, the
Schoeller system, and Bojarski’s modification of the Sulin system t o a study
of brines from various sedimentary basins of the United States that are
known to be related to petroleum and natural gas.
Calculations
The analyses of most oilfield waters are reported in units of milligrams per
liter (mg/l). The conversion of mg/l to equivalents per million (epm) is done
using the following formula:
mg/l of ion
= epm ion
atomic weight of ion
specific gravity of brine x
valence of ion
Table 8.VII provides formulas for calculating the epm for many of the
common constituents found in oilfield brines. If the constituent is reported
in parts per million (ppm), it is not necessary t o divide by the specific gravity
of the brine.
The sum of the epm’s (Z epm) shown in Table 8.VII are converted to
Zr/100 g of water for the Sulin calculations by moving the decimal to the
left in the Z epm and calling this Zr. The term s is used t o indicate the
percent of equivalent of a given constituent. The percentage equivalent (s) of
each ion is determined by dividing the equivalents per 100 g of water by the
total equivalent in 100 g of water. For example, if the r for sodium equals
APPLICATION OF THE CLASSIFICATION SYSTEMS 27 5
TABLE 8.VII
Formulas for converting milligrams per liter to equivalents per million for constituents
commonly found in oilfield waters
Lithium mg/l Li+ x 0.1442/sp. gr.* = epm Li+

Potassium mg/l K+ x O.O256/sp. gr. = epm K+
Sodium mg/l Na+ x O.O435/sp. gr. = epm Na+
Magnesium mg/l Mg+’ x O.O823/sp. gr. = epm Mg+’
Calcium mg/l Ca+’ x O.O499/sp. gr. = epm Ca+’
Strontium mg/l Sr+’ x O.O228/sp. gr. = epm Sr+’
Barium mg/l Ba+’ x O.O146/sp. gr. = epm Ba+’
Carbonate mg/l co3-’ x O.O333/sp. gr. = epm c03-’
Bicarbonate mg/l HC03- x O.O164/sp. gr. = epm HC03-
Sulfate mg/l SO^+ x 0.0208/sp.gr. = eprnS04-’
Chloride mg/l C1- x O.O282/sp. gr. = epm C1-
Bromide mg/l Br- x O.O125/sp. gr. = epm Br-
Iodide mg/l I- x O.O079/sp. gr. = epm I-
Zepm =
* Specific gravity.
200.6 and the Zr for the total equivalents equals 518.8, then
200.6/518.8 x 100 = 38.7, or 38.7 percentage equivalents for sodium.
The Sulin classification considers only the macro constituents; if ions such
as potassium, lithium, strontium, barium, bromide, and iodide are deter-
mined, they should be added t o their associated macro constituents t o be
properly considered in the analysis report. For example, when sodium,
potassium, and lithium are determined by atomic absorption the total mg/l
of each is reported. Therefore, the epm Na + epm K + epm Li should be
added to obtain the correct r value for sodium:
epm Na epm K epm Li
rNa=
+ +
10 10
epmCa e p m S r + epmBa
rCa=
+
10 10
epm C1 epm Br epm I

rC1 =
+
10 10
The r values then are divided by the Zr and multipIied by 100 to obtain
the s value or percentage equivalents. The s values are used to determine the
type, class, and other Sulin values of the water as illustrated in Table 8.1,
where a = sNa, b = sCa + sMg, and d = sC1+ s S 0 , . The epm values are used
to determine the Schoeller characteristics such as the degree of chloridiza-
tion, the degree of sulfation, IBE, etc., illustrated in Table 8.VI.
27 6 CLASSIFICATION O F OILFIELD WATERS
TABLE 8.VIII
Classification of some oilfield waters from 1 0 formations in eight sedimentary basins
No. State Formation Basin Depth Concentration (e pm)
1 Kans. Arbuckle Cent .Kans. 1,050 634.6 60.6 133.0 7.7 49.0 773.8
3 Kans. Arbuckle Cent.Kans. 1,023 282.0 24.8 40.2 9.5 22.1 313.9
5 Kans. Arbuckle Cent.Kans. 992 430.3 38.8 65.4 8.5 17.5 510.9
6 Kans. Arbuckle Cant.Kans. 1,152 458.7 34.4 81.3 3.4 45.9 523.2
8 Kans. Arb u ck le Cent.Kans. 949 356.4 57.4 100.4 12.8 39.9 456.7
11 Kans. Lansing Cent. Kans. 928 1,759.6 266.6 373.9 1.8 0.0 2,398.9
12 Kans. Lansing Cent.Kans. 1,075 570.4 117.4 174.6 2.4 34.9 826.6
13 Kans. Lansing Cent.Kans. 966 1,899.9 266.4 442.1 0.3 0.8 2,605.0
14 Kans. Lansing Cent .Kans. 999 1,728.2 232.0 512.4 1.7 2.5 2,469.4
15 Kans. Lansing Cent. Kans. 902 1,903.8 274.5 478.8 1.1 0.0 2,655.6
16 Kans. Lansing Cent. Kans. 1,009 2,514.8 309.3 532.7 0.4 1.5 3,353.6
17 Kans. Lansing Cent .Kans. 1,063 1,854.7 225.2 449.8 0.5 1.1 2,529.6
18 Kans. Lansing Cent.Kans. 1,148 2,087.2 223.6 384.8 1.4 1.o 2,706.1
19 Kans. Lansing Cent.Kans. 1,172 2,414.5 251.0 519.0 0.7 2.4 3,17 9.9
20 Kans. Lansing Cent .Kans. 853 1,898.4 210.8 416.7 0.8 0.7 2,515.5
21 Okla. Wilcox Cherokee 1,228 2,366.5 193.3 810.1 1.1 7.7 3,360.6
23 Okla. Wilcox Cherokee 904 2,161.5 163.2 530.3 0.4 7.3 2,847.4
27 Okla. Wilcox Cherokee 582 1,587.2 151.2 287.5 1.8 1.4 2,021.6
29 Okla. Wilcox Cherokee 1,97 2 2,701.4 153.1 606.0 0.7 8.4 3,449.1
31 Ark. Nacatoch E.Texas 360 233.4 9.0 22.4 3.7 0.0 261.1
34 Texas Nacatoch E.Texas 905 788.2 9.4 28.7 3.1 0.0 824.6
35 Texas Nacatoch E.Texas 70 1 481.8 7.8 17.3 3.3 0.0 503.5
40 Texas Nacatoch E.Texas 181 490.6 3.6 7.8 2.8 0.6 498,4
>
* Chloride (epm): (VH)C = 700, (MC) = 420-700, (H)C = 140-420, (A)C = 40-140,
(L)C = 10-40, (N)C = <
10. Sulfate (epm): (VH) = > 58, ( H )
=: 24-58, (A ) = 6-24, (N )
=<6.
APPLICATION OF THE CLASSIFICATION SYSTEMS 277
Sulin Schoeller*
Zepm type class CT so4-’

1,659.0 Cl-Ca 80.7 20.0 0.18
1,523.6 Cl-Ca 52.6 17.4 0.21
692.6 Cl-Ca 29.8 15.4 0.10
1,585.4 C l - C a 77.8 8.7 0.23
1,071.6 C1-Ca 33.8 16.8 0.16
1,147.2 Cl-Ca 61.1 9.9 0.12
1,492.0 CI-Ca 65.6 14.6 0.19
1,024.0 Cl-Ca 62.3 25.2 0.22
1,105.0 CI-Ca 46.2 17.9 0.1 3
1,506.4 C1-Ca 71.4 52.5 0.16
4,800.9 CI-Ca 0.0 10.7 0.27
1,726.6 Cl-Ca 78.0 10.2 0.31
5,214.7 Cl-Ca 19.4 3.5 0.27
4,946.5 Cl-Ca 36.0 11.6 0.30
5,314.0 CI-Ca 0.0 8.5 0.28
6,712.5 Cl-Ca 28.7 4.4 0.25
5,061.1 Cl-Ca 22.5 5.1 0.27
5,404.4 Cl-Ca 20.4 9.1 0.23
6,367.7 Cl-Ca 35.9 6.3 0.24
5,043.1 Cl-Ca 17.8 6.6 0.25
6,739.4 Cl-Ca 79.1 9.9 0.30
5,854.9 Cl-Ca 72.3 3.6 0.25
5,710.4 Cl-Ca 62.3 4.7 0.24
6,021.0 Cl-Ca 84.3 8.5 0.21
5,188.0 C l - C a 59.9 7.1 0.23
5,330.0 Cl-Ca 82.7 6.4 0.25
4,051.1 Cl-Ca 20.5 9.9 0.21
6,291.3 C l - C a 55.7 8.7 0.22
6,918.8 Cl-Ca 71.4 7.1 0.22
6,892.3 Cl-Ca 73.6 9.4 0.23
529.8 CI-Ca 0.6 6.8 0.11
1,123.5 C l - C a 0.0 4.9 0.17
726.2 Cl-Ca 6.0 8.8 0.16
1,654.2 C k C a 0.0 6.5 0.04
1.013.8 Cl-Ca 0.0 5.7 0.04
594.5 Cl-Ca 3.6 4.6 0.07
1,037.4 Cl-Mg 1.6 18.1 0.01
635.2 C l - C a 3.6 4.4 0.06
1.027.8 Cl-Ca 4.5 13.2 0.1 1
1,004.0 C l - C a 2.2 4.0 0.02
TABLE 8.VIII (continued)
No. State Formation Basin Depth Concentration (epm)

(m)
Na+ Mg+’ Ca+’ HCOJ- S04-* Cl-
41 Ark. Paluxy E.Texas 1,115 1,246.8 90.6 254.1 0.4 0.0 1,594.4
42 Ark. Paluxy E.Texas 737 586.0 32.2 86.7 2.8 3.3 699.0
43 Ark. Paluxy E.Texas 1,297 1,310.3 107.1 278.5 2.7 .7 1,692.0
44 Ark. Paluxy E.Texas 884 934.9 64.8 197.6 1.5 1.1 1,194.9
45 Ark. Paluxy E.Texas 1,417 1,507.2 138.6 504.4 0.5 3.3 2,208.7
46 Texas Paluxy E.Texas 2,340 1,642.1 22.5 378.5 0.0 9.3 2,033.8
49 Texas Paluxy E.Texas 1,512 205.3 6.4 10.0 14.9 6.0 202.4
51 Ark. Rodessa E.Texas 1,897 1,971.8 157.2 669.7 0.0 8.0 2,789.9
54 Ark. Rodessa E.Texas 711 538.6 35.9 75.0 3.0 2.9 643.4
55 Texas Rodessa E.Texas 2,844 1,772.1 127.3 878.8 1.5 2.8 2,773.2
56 Texas Rodessa E.Texas 2,519 1,861.9 217.4 1,084.7 1.1 2.7 3,165.1
61 Texas Woodbine E.Texas 1,047 1,507.0 44.3 161.4 4.2 3.5 1,705.0
63 Texas Woodbine E.Texas 898 341.8 4.4 9.3 11.3 0.6 343.5
64 Texas Woodbine E.Texas 841 1,060.5 32.4 58.9 0.0 0.2 1,161.4
66 Texas Woodbine E.Texas 1,144 809.1 12.7 61.1 7.3 3.7 873.3
67 Texas Woodbine E.Texas 925 478.8 12.4 23.6 7.0 0.1 507.7
70 Texas Woodbrine E.Texas 1,332 1,268.0 30.2 81.9 8.3 4.0 1,367.4
71 Ala. Eutaw Interior Sal. 1,061 1,124.4 45.0 164.7 2.7 0.0 1,330.1
72 Ala. Eutaw Interior Sal. 972 1,102.9 25.6 160.5 2.0 0.0 1,288.9
73 Ala. Eutaw Interior Sal. 1,060 1,186.7 59.6 164.3 2.9 0.0 1,411.8
74 Miss. Eutaw Interior Sal. 1,444 1,733.6 82.7 287.3 0.9 0.0 2,108.5
77 Miss. Eutaw InteriorSal. 2,443 1,721.3 256.7 458.0 0.0 0.0 2,433.4
80 Miss. Eutaw InteriorSal. 2,469 2,153.7 87.7 518.9 0.0 1.0 2,765.6
* Chloride (epm): (VH)C =->700, (MC) = 420-700, (H)C = 140-420, (A)C = 40-140,
(L)C = 10-40, (N)C = < 10. Sulfate (epm): (VH) = > 58,(H) = 24-58, (A) = 6-24, (N)
- < 6.
_-
Sulin Schoeller* d c a + ' + so4-' V(HCO~-+ coz-2 ) ? ( ~ a +IBE
~)
Zepm type class CT SO^-'

3,186.6 CI-Ca 3.1 3.8 0.22
1,410.3 CI-Ca 17.1 8.8 0.16
3,391.5 Cl-Ca 14.1 12.8 0.23
2,395.0 CI-Ca 15.0 7.6 0.22
4,363.0 CI-Ca 41.0 5.4 0.29
4,086.4 Cl-Ca 59.5 0.0 0.19
3,543.9 Cl-Ca 27.9 16.6 0.14
4,066.7 Cl-Ca 60.9 13.6 0.26
445.2 SO4-N 7.7 13.1 0.0
4,121.6 CI-Ca 61.0 11.1 0.26
5,596.8 Cl-Ca 73.3 0.5 0.29
5,384.3 Cl-Ca 81.3 8.0 0.27
2,916.3 CI-Ca 78.7 0.4 0.26
1,299.0 CI-Ca 14.8 8.8 0.16
5,556.0 Cl-Ca 50.1 12.9 0.36
6,333.1 Cl-Ca 54.4 11.1 0.41
6,235.2 Cl-Ca 66.2 7.3 0.34
5,622.2 CI-Ca 79.0 13.5 0.30
5,818.1 CI-Ca 55.9 7.7 0.31
5,163.7 CI-Ca 57.4 8.4 0.27
3,425.6 Cl-Ca 23.9 14.2 0.12
2,705.0 CI-Ca 10.0 15.6 0.06
711.0 CI-Mg 2.4 10.6 0.oo
2,313.7 Cl-Ca 4.0 0.0 0.09
2,970.7 CI-Ca 27.6 5.4 0.14
1,767.3 C1-Ca 15.1 14.8 0.07
1,029.9 Cl-Ca 1.5 10.5 0.06
3,379.5 Cl-Ca 0.0 14.8 0.14
3,261.0 Cl-Ca 3.7 7.4 0.11
2,760.0 Cl-Ca 18.1 17.8 0.07
2,667.1 Cl-Ca 0.1 10.6 0.15
2,580.1 Cl-Ca 0.1 8.8 0.14
2,825.4 CI-Ca 0.1 11.1 0.16
4,213.1 Cl-Ca 0.1 6.2 0.18
4,789.9 Cl-Ca 101.6 20.3 0.15
3,777.7 Cl-Ca 0.0 5.7 0.1 7
4,869.6 Cl-Ca 0.0 0.0 0.29
4,704.8 Cl-Ca 0.0 17.8 0.18
3,789.1 Cl-Ca 0.0 11.0 0.17
5,527.1 Cl-Ca 22.7 0.0 0.22
TABLE 8.VIII (continued)
No. State Formation Basin Depth Concentration

(m)
Na+ Mg+2 Ca+2 c1-
-___
81 Miss. Wilcox Miocene 1,975 2,031.8 36.8 100.3 4.5 0.0 2,163.3
84 Miss, Wilcox Miocene 1,871 2,157.3 54.1 89.9 6.8 0.0 2,114.0
91 La. Smackover N .Louisiana 3,109 1,589.7 86.7 1,256.8 0.0 8.8 2,940.8
92 Ark. Smackover N.Louisiana 2,103 2,444.9 275.9 1,392.8 2.0 4.6 4,105.9
96 Ark. Smackover N. Louisiana 2,526 2,729.0 218.6 1,598.2 2.4 1.7 4,540.4
97 Ark. Smackover N.Louisiana 2,615 4,277.5 10.0 34.9 2.4 0.0 4,312.9
98 La. Smackover N.Louisiana 2,949 2,225.4 149.7 2,282.1 0.0 1.4 4,654.9
99 La. Smackover N.Louisiana 3,271 1,971.2 173.5 1,668.9 0.0 1.8 3,810.9
100 La. Smackover N.Louisiana 701 681.8 35.2 63.6 5.1 2.1 778.6
101 La. Wilcox W. Gulf 1,399 1,718.5 44.9 90.1 1.4 0.2 1,851.2
102 La. Wilcox W. Gulf 1,814 2,035.8 46.5 124.7 5.6 0.8 2,199.9
103 La. Wilcox W. Gulf 747 1,206.3 43.6 47.2 4.6 0.6 1,291.2
204 La. Wilcox W. Gulf 1,561 1,874.2 40.9 91.0 0.7 0.8 2,003.8
105 La. Wilcox W. Gulf 1,722 2,138.9 41.9 96.2 1.4 1.4 2,273.4
106 La. Wilcox W. Gulf 666 1,057.5 26.6 51.0 0.0 0.0 1,058.4
107 La. Wilcox W. Gulf 1,124 1,379.4 41.8 60.0 2.5 0.6 1,477.6
108 La. Wilcox W. Gulf 2,441 2,119.4 43.7 100.2 6.1 0.0 2,263.4
109 La. Wilcox W. Gulf 2,158 2,132.3 15.3 115.2 4.0 8.0 2,256.4
110 La. Wilcox W. Gulf 471 840.1 26.8 24.1 7.0 0.0 888.4
111 N.D. Silurian Williston 3,633 3,431.2 100.6 993.7 1.5 8.4 4,305.3
>
* Chloride (epm): (VH)C = 700, (MC) = 420-700, (H)C = 140-420, (A)C = 4040,
>
(L)C = 10-40, (N)C = < 10. Sulfate (epm): (VH) = 58, (H) = 24-58, (A) = 6-24, (N)
=<6.
APPLICATION OF T H E CLASSIFICATION SYSTEMS 281
Cepm type class ~ 1 - SO^-^

~
4,336.9 Cl-Ca 0.0 12.7 0.06

3,981.1 Cl-Ca Q.0 11.2 0.07
2,920.8 Cl-Ca 0.0 11.8 0.06
4,422.4 HCO, 0.0 16.1 0.0
-Na
4,267.3 Cl-Ca 26.2 11.4 0.7
4,223.9 Cl-Ca 0.0 9.0 0.06
4,403.4 Cl-Ca 0.1 18.9 0.07
4,747.3 Cl-Ca 5.4 11.1 0.07
2,747.7 Cl-Ca 0.0 17.0 0.06
2,878.2 Cl-Ca 0.0 11.5 0.08
5,883.0 Cl-Ca 103.6 0.0 0.46
8,226.2 Cl-Ca 80.0 17.7 0.40
8,840.1 Cl-Ca 78.0 17.9 0.43
9,306.8 Cl-Ca 53.5 21.1 0.40
8,335.6 Cl-Ca 78.0 0.6 0.42
4,454.9 Cl-Ca 53.4 21.3 0.40
8,637.9 Cl-Ca 0.0 5.9 0.01
9,313.8 Cl-Ca 57.5 0.7 0.52
7,626.5 Cl-Ca 55.5 0.6 0.48
1,566.7 Cl-Ca 11.4 11.6 0.12
3,706.6 Cl-Ca 5.1 5.6 0.07
4,413.6 Cl-Ca 10.2 15.8 0.07
2,593.7 C1-Ca 5.6 10.1 0.07
4,011.7 Cl-Ca 8.8 3.6 0.06
4,55 3.5 Cl-Ca 11.7 5.9 0.06
2,193.6 Cl-Mg 0.0 0.0 0.0
2,962.2 Cl-Ca 6.1 7.3 0.07
4,533.4 Cl-Ca 0.0 15.2 0.06
4,531.3 Cl-Ca 29.9 12.1 0.05
1,786.7 Cl-Ca 0.0 9.9 0.05
8,840.7 Cl-Ca 90.6 13.0 0.20
Interpretation o f the classification
The majority of the 4,000 oilfield waters that were classified fell in the S ,
S2 A2 class and were of the chloride-calcium type. Table 8.VIII illustrates
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.
Most of the samples of the bicarbonate-sodium and sulfate-sodium types
were found at relatively shallow depths. This could indicate that the waters
contained infiltrating water.
The Cl/Na ratio was determined for each sample as suggested by Bojarski.
This ratio was calculated from the epm values, and the ratios ranged from
0.33 to values greater than 1. Values greater than 0.85 are characteristic of
hydrodynamic waters, according t o Bojarski (1970),while the more altered
waters found in static environments have ratios of less than 0.50.
Schoeller's classification uses the chloride concentration t o separate the
waters into six types. The majority of the 4,000 oilfield waters analyzed for
this study were very high chloride waters (where the chloride epm is equal to
or greater than 700). The sulfate concentration of these waters according to
his 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 JCa+' x SO4-' exceeded 70 in some waters, indicating that such
waters were nearly saturated with calcium sulfate. Schoeller did not consider
that the solubility of calcium sulfate increases in the presence of certain
other dissolved ions; therefore the value of 70 may not always indicate
saturation. However, in primary and secondary recovery operations this
value should be considered.
The 4 ( H C 0 3 - + C03-' )' (Ca+' ) was used by Schoeller to determine if a
water was saturated with calcium carbonate, and such a water should have a
value greater than 7. This is not entirely accurate, but the formula does
indicate if the water contains an excess of calcium, which decreases the
carbonate concentration. Many of the 4,000 waters evaluated 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 t o be different in the brine.
The predominant cation sequence for these 4,000 oilfield brines was Na+
> Ca+? > Mg+'. The SO4/Cl ratio ranged from 0.00 to 0.34.The ratio 0.34
was found for a bicarbonate-sodium water sample, which may have con-
tained infiltrating water. None of the chloride-calcium type waters had a
S04/Cl ratio greater than 0.17, with many of them 0.00.
The IBE indicates that exchange of metal ions dissolved in the water have
exchanged with metal ions on the clays. (Schoeller made the arbitrary as-
sumption that the concentrations of sodium and chloride originally present
in the water were equal.) If the IBE is a positive number the exchange was
alkali metals in the water for alkaline earth metals on the clays, and if the
IBE is negative the exchange was alkaline earth metals in the water for alkali
metals on the clays. Very few negative numbers were evident when the IBE
was determined on the 4,000 oilfield water analyses. This indicates that most
of the formation waters associated with hydrocarbons had exchanged dis-
solved alkali metals for alkaline earth metals on the clays. The few samples
that yielded the negative IBE numbers were sulfate-sodium and bicarbonate-
sodium type waters which, according to Sulin, is indicative of terrestrial
derived waters.
Ratios
The ratios Na/(Ca + Mg) and Ca/Mg were calculated from the analytical
data for the 4,000 oilfield water samples. Fig.8.1 illustrates a plot of the
Na/(Ca + Mg) ratio versus dissolved solids for samples from the East Texas
Basin. The ratio tends to decrease with increasing dissolved solids concen-
tration. The depletion of sodium with respect to calcium + magnesium can
be attributed to diagenesis of the waters. This correlates with Schoeller's
IBE, indicating that the alkali metals in the water exchange with alkaline
I KEY
Tertiary
Upper Cretaceous
6 Lower Cretaceous
0 Jurassic
x Pennsylvanian
0
DISSOLVED SOLIDS, g / l
Fig. 8.1. Plot of the Na/(Ca + Mg) ratio versus the concentration of dissolved solids in
some formation waters taken from sedimentary rocks in the East Texas Basin.
-
0
7- 0
Fig. 8.2. Plot of the Na/(Ca + Mg) ratio versus the concentration of dissolved solids in
some formation waters taken from the Rodessa formation in the East Texas Basin. The
line is a least squares fit (y = a + bx + ex2 ) for the scattered data.
earth metals on the clays, decreasing the dissolved alkali metals and in-
creasing the dissolved alkaline earth metals.
Fig.8.2 shows the scattered data for the brines taken from the Rodessa
formation in the East Texas Basin. The scattered data were submitted t o
least squares analysis to determine with more certainty how the ratios varied
with depth and with dissolved solids concentrations. The least squares
formula used was y = a + bx + cx2or the approximation to a parabola. If the
best fit is a straight line, the solution will regress to it, and this occurred for
the data shown in Fig. 8.2. Also, if this occurs, the value for c i n the formula
is very small. The curve shown in Fig. 8.2 represents a fit of about 88%of
the sum of the mean, a fit of 100%would be ideal.
Preliminary plots of the scattered data indicated that a better fit could be
obtained with the parabolic least squares approximation than with the least
squares approximation for a straight line. A computer was used t o obtain the
fit.
The least squares curve indicates that the concentration of sodium
decreased with respect t o calcium plus magnesium until the dissolved solids
were about 210,000 mg/l and then increased. This could be attributed to
exchange of sodium in the water for alkaline earths on the minerals until the
concentration of dissolved solids reached 210,000 mg/l, at which point the
solubility products of the alkaline earths are such that they are unable to
stay in solution. This would correlate with Schoeller’s IBE. However, the
IBE does not consider the effect of other ions in solution upon the solubility
product of an ion.
30 - Tertiary
0 Upper Cretaceous
Lower Cretaceous
Jurassic
x Pennsylvanian-
-=2
0
20- 0
:Is
. .
0
.
n&
.n n
10- 0 0
a
n
0
0
315 7b 105 I40 I'l5 2;O

DISSOLVED SOLIDS, g / l
245 280 3;5 z 50
Fig. 8.3. Plot of the Ca/Mg ratio versus the concentration of dissolved solids in some
formation waters taken from sedimentary rocks in the East Texas Basin.
Fig. 8.3 illustrates a plot of. the Ca/Mg ratio versus dissolved solids. Here
the trends appear t o be that the Ca/Mg ratio increases as the dissolved solids
increase. This trend also is related to diagenesis of the waters. The calcium
increases as the magnesium decreases, and this may be related to the forma-
tion of dolomite and chlorite, or to reactions with argillaceous minerals.
Fig. 8.4 is a plot of Ca/Mg versus dissolved solids. The Ca/Mg ratios for
some brines from the Rodessa formation in the East Texas Basin were sub-
mitted t o least squares analysis, and the results were used to plot Fig. 8.4.
The scattered data in Fig. 8.4 did not yield as good a fit to the formula
y = a + bx + cx2 as did the data in Fig. 8.2, because the fit is about 35%of
the mean where 100% is ideal. The line indicates that the ratio increased as
the dissolved solids increased. This is the result of magnesium lost from the
brine by reactions t o form minerals, ion exchange, or shale membrane filtra-
tion. It is not a result of solubility product because most magnesium com-
pounds are more soluble than calcium compounds.
Fig. 8.5 is a plot of Na/(Ca + Mg) against depth from which the samples
were taken. The trend does not indicate a definite relationship for these
samples.
Fig. 8.6 is a plot of the least squares analysis data for Na/(Ca + Mg) versus
depth for some brines from the Rodessa formation in the East Texas Basin.
The plot indicates that the sodium concentration decreases with respect to
calcium plus magnesium until the depth is about 2,350 m and then it in-
creases. The curve in Fig. 8.6 represents a 45% mean fit of the scattered data
where an ideal fit is 100%.
Fig. 8.7 is a plot of Ca/Mg versus depth, and there appears to be an
increase of this ratio with depth which would indicate that magnesium is
depleted more with respect t o calcium in brines taken from deeper strata.
.
7t 0 .
21i
I1 I I 1 I
20 80 I40 200 260 3 10
DISSOLVED SOLIDS, g/l
Fig. 8.4. Plot of the Ca/Mg ratio versus dissolved solids for some formation waters taken
from the Rodessa formation in the East Texas Basin. The line is a least squares fit
(y = a + bx + cx') for the scattered data.
I "
KEY
6C - o Cretaceous gulf
A Cretaceous Comanche
o Jurassic
50 -
x Pennsylvanian
Tertiary
-
-
.. 0
2c -
A
0
0 A 0 0
IC
C
500 1,000 1,500 2,000 2,500 3,000
DEPTH, meters
Fig. 8.5. Plot of the Na/Ca + Mg) ratio versus depth for some formation waters taken
from sedimentary rocks in the East Texas Basin
I I I I I
0 500 1.000 1,500 2,000 2,500 100
DEPTH, meters
Fig. 8.6. Plot of the Na/(Ca + Mg) ratio versus depth for some formation waters taken
from the Rodessa formation in the East Texas Basin. The line is a least squares fit
(y = a + bx + cx2 ) for the scattered data.
KEY
3c - o Cretaceous gulf
A Cretaceous Comanche
. A Jurassic
x Pennsylvanian
0 Tertiary 0
2c
'F
e
I: r" A
0
m
A
A A
-
. ..
A 0
10 A P o
8 0
0 I
500
I
If300
.
1,500
I
2,000
I
I
2,500
**
3,( 30
DEPTH, meters
Fig. 8.7. Plot of the Ca/Mg ratio versus depth for some formation waters taken from
sedimentary rocks in the East Texas Basin.
This would indicate that magnesium is taken from the brine by reactions to
form minerals or absorbed by clays.
Fig. 8.8 is a plot of the least squares analysis data for Ca/Mg versus depth
for some brines from the Rodessa formation in the East Texas Basin. The
plot indicates that the concentration of calcium increases with depth with
I I I I I 10 L
0 500 I.000 1.500 2POO 2.500 3pOO
DEPTH, meters
Fig. 8.8. Plot of the Ca/Mg ratio versus depth for some formation waters taken from the
Rodessa formation in the East Texas Basin. The line is a least squares fit (y = a
+ bx + cxz ) for the scattered data.
respect t o magnesium. Reactions occurred between the brines and the

enclosing rocks to deplete the magnesium or increase the calcium in these
brines. The curve in Fig. 8.8 represents a 35% mean fit of the scattered data
where an ideal fit is 100%.
Ternary diagram
Ternary or triangular diagrams are useful in studying the distribution of

the cations and anions in subsurface waters. The ions which often are used in
these diagrams are sodium, calcium, and magnesium or chloride, sulfate, and
bicarbonate. To plot these constituents, the equivalent weights of three
cation constituents or three anion constituents are determined and summed
t o equal 100%.The percentage of the three then are plotted. Dickey (1966)
used these types of plots fo study the composition of some deep subsurface
waters.
Fig. 8.9 is a ternary plot of the normalized values for sodium, calcium,
and magnesium concentrations of some brines taken from oil-productive
sedimentary basins. This diagram indicates that all of these brines contain
more calcium than magnesium. For these particular samples the diagram
seems to indicate that the calcium equivalents tend to increase with the age
of the rocks from which the brines were taken; this does not, however, apply
to all brines.
DISCUSSION 289
Fig. 8.9. Relative concentrations of sodium, calcium, and magnesium in some formation
waters taken from sedimentary rocks in oil-productive basins.
Discussion
Chebotarev (1955) postulated that most subsurface waters are altered by

meteoric water. The three hydrodynamic zones that he considers are: (1)
active exchange, where water is influenced by a relatively high degree of
hydrodynamic movement with flushing-out of most of the salt thus pro-
ducing a low salinity water; (2) delayed exchange, where the hydrodynamic
flow is less rapid, thus leaving a higher salinity water; and (3) stagnant
conditions, where there is little hydrodynamic movement, so that the
salinity accumulates and is higher.
This system was not applied to the 4,000 waters because it evaluates in a
rather complex manner the types and classes of waters from the constituent
compositions in reacting values in percent. The method appears useful in
certain general types of studies.
Palmer’s system does not consider ionic concentrations or possible con-
ditions of saturation of calcium carbonate or calcium sulfate. Some consti-
tuents such as the alkaline earths and chloride and sulfate are lumped togeth-
er. Calcium and magnesium should not be lumped together because even
though they are in the same chemical group in the Periodic Table, they often
behave quite differently in chemical reactions. For example, the solubilities
of many of their salts are considerably different. The same often is true of
the chlorides and sulfates.
The portion of the Palmer system applied t o the 4,000 brines was used
only because it is incorporated in Sulin’s system. The Palmer system by itself
appears to have little value in studying subsurface brines related t o hydrocar-
bon accumulations.
Schoeller separates the waters into six types solely on the basis of the
concentration of the chloride ion and into four additional types using the
concentration of the sulfate ion. Because of this, his classification of oilfield
waters gives considerably more variation in types than the Sulin system, and
thus it is more confusing in interpretation. Schoeller’s formula for deter-
mining relative saturations of sulfates and carbonates in the waters has value
in production problems. For example, knowledge that the sulfates or carbon-
ates may precipitate from a water under certain conditions is useful so that
correct treatment can be applied t o prevent well and/or formation damage.
The index of base exchange also is useful in evaluating diagenetic reactions
that may have occurred to change the water.
Sulin’s system considers some of the ions in determining the type of
water, and the class indicates the predominance of the anion groups. These
two characteristics of waters appear useful in studying waters that are likely
to be associated with hydrocarbon accumulations. For example, several in-
vestigators have determined that the chloride-calcium type in the S1 S2 A2
class of water is the most likely type to be associated with a hydrostatic
environment that promotes the accumulation of hydrocarbons. The next
most likely type is bicarbonate-sodium in the S1 A l A2 class and the least
likely types are chloride-magnesium and sulfate-sodium.
Knowledge of the type and class plus what Sulin describes as the signifi-
cant indicators (direct and indirect) appears useful in hydrocarbon explora-
tion studies. The Sulin system does not consider the degree of saturation of
the water with respect to sulfates and carbonates, which is a disadvantage in
production problems. Also, the system makes no provision for determining
the degree of base exchange which is useful in certain interpretations of
diagenesis.
Bojarski’s modification of the Sulin system appears t o have little value in
evaluating a water that is likely to be associated with petroleum. Many of the
values that were found for the Na/Cl ratio in the 4,000 samples were greater
than 0.85. This value in a chloride-calcium type water according to Bojarski
is not likely t o be found in a water associated with petroleum. It is possible
that the waters that Bojarski evaluated were consistently very concentrated
waters with respect to dissolved solids.
CONCLUSIONS 291
Conclusions
Classification of the subsurface waters aids in interpreting the type of

water that is more likely t o be associated with a hydrocarbon accumulation.
Application of water classification techniques t o 4,000 oilfield brine samples
revealed that the majority of the samples were chloride-calcium type of the
S1 S2 A2 class, had positive IBE values, had a predominant cation sequence
of Na > Ca > Mg, and were very highly concentrated with dissolved chloride.
Many of the 4,000 samples had values greater than 7 for q m
C 0 3)’ (Ca), and some had values greater than 70 for d m , indicating
that many of the waters were saturated or nearly saturated with respect to
carbonate and sulfate.
The Bojarski modification of the Sulin system appears to be of little value.
The ratio Na/(Ca + Mg) generally decreased with increasing dissolved solids
and depth. The ratio Ca/Mg generally increased with increasing dissolved
solids and depth.
Studies of the water characteristics and mapping of the more important
water properties in conjunction with other geological and geophysical data
appear useful in exploration. Maps of certain water characteristics such as
the JCa+’ x SO,,-’ and d ( H C 0 3 - + C03- )’ (Ca+’ ) are useful in solving
production problems.
References
Ambrose, A.W., 1921. Underground conditions in oilfields. US.Bur. Min. Bull., 195, 238
PP.
American Petroleum Institute, 1968. API Recommended Practice for Analysis o f Oilfield
waters. Subcommittee on Analysis of Oilfield Waters, API RP 45, 2nd ed., 49 pp.
Bojarski, L., 1970. Die Anwendung der hydrochemischen Klassifikation bei Sucharbeiten
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Chapter 8.

CLASSIFICATION OF OILFIELD WATERS

Classification of waters provides a basis for grouping closely related

Portions of three classification systems (Palmer, 1911; Sulin, 1946;

Class 3 : d > a ; d < (a + b )

Sulin (1946), a Russian geochemist, proposed a classification system based

Types, groups, and subgroups

Water composition is expressed in milligram-equivalents of the separable

salinity and the sodium bicarbonate-calcium stage. N o sodium bicarbonate is

Hydrochemical indicators of hydrocarbons

Sulin (1946) noted that certain properties of subsurface waters were

Sulin’s method of water characterization

Bicarbonate group Bicarbonate group

Coefficients characterizing the genetic types of waters

Type of water Na+/Cl- (Na’ - Cl-)/S04-2 (Cl-- Na+)/Mg+’

Chloride-calcium <1 <O >1

related t o water types in this order: chloride-calcium > bicarbonate-sodium

Modification of Sulin’s system by Bojarski

Bojarski (1970) studied 400 water analyses and differentiated hydro-

(Na-Cl)/SO, > l . As Sulin (1946) noted, if the ratio Na/Cl in epm is

iodide and bromide concenbrations may point to a bitumen accumulation);

Chebotarev (1955),an Australian geochemist, classifies waters on the basis

Cycles and types of products of weathering (after Chebotarev, 1955)

Geochemical classification of subsurface waters (after Chebotarev, 1955)

( A ) Relationship of the products of weathering to the genetic types of water

Presumable phase of weathering Products of weathering Genetic types of water

Fourth phase residual (orthoeluvium and detrital paraeluvium) bicarbonate (alkaline)

(B) Geochemical groups of Waters

Major group Class Genetic types of Reacting value in percent

Bicarbonate I bicarbonate >40 <lo - Na+ + K+ prevail in all types of

Sulphate IV sulphate-chloride 15-5 <25 >25 Na+ + K+ prevail in all types of

Chloride 111 chloride-bicarbonate 30-15 >20 - - Na+ + K+ prevail in all types of

Hydrodynamic zone Geochemistry of water Geological environment

high saline facies 11,400-37.800 saline hampered flush

high saline facies 7,400--19,300 saline

transitional 20.000-90,000 saline and deeper portions sometimes

A French geochemist, Schoeller (1955),classified waters on the basis of

Schoeller’s scheme for classifying petroleum reservoir waters*

Chloride concentration as Ci-

Very high if > 700

Sulfate concentration as s04-’

Very high if >

Bicarbonate plus carbonate concentmtion as H C 0 3 - + c03-’

Index o f base exchange (IBE)

If Cl- > Na+ then IBE = (Cl- - Na+)/Cl-

Importance o f anions and cations

c1- > SO^' > co3-’

The concentration of exchangeable ions in the adsorbent and in the water is

Gases in petroleum-reservoir waters

Oilfield brine analyses

The specific gravity of each sample is determined so that a correct aliquot

Field sampling methods

Application of the classification systems

Several investigators have applied the classification systems t o determine

Lithium mg/l Li+ x 0.1442/sp. gr.* = epm Li+

epm C1 epm Br epm I

Classification of some oilfield waters from 1 0 formations in eight sedimentary basins

No. State Formation Basin Depth Concentration (e pm)