Geochimica et Cosmochimica Acta, Vol. 59, No. 17, pp.

3525-3533, 1995
Pergamon Copyright © 1995 Elsevier Science Ltd
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0016-7037( 95 ) 00229-4

Mechanisms of sulfate removal from subsurface calcium chloride brines:

Heletz-Kokhav oilfields, Israel
ITTAI GAVRIEL1, ~ AVRAHAM STARINSKY, 2 BARUCH SPIRO, 3 ZEEV AIZENSHTAT, 4 and HEIMO NIELSEN 5
~GeologicalSurvey of Israel, 30 Malkhe Street, Jerusalem 95501, Israel
~-Departmentof Geology, Institute of Earth Sciences, The Hebrew University, Jerusalem 91904, Israel
3NERC Isotope Geosciences Laboratory, Keyworth, NottinghamshireNGI2 5GG, UK
4School of Applied Sciences, The Hebrew University, Jerusalem 91904, Israel
5Stable Isotope Laboratory, Geochemical Institute, University of Gtttingen, Gtttingen, Germany

(Received July 26, 1994; accepted in revisedform May 28, 1995)

Abstract--The evolution of the Ca-chloride brines in the Heletz Formation, Lower Cretaceous, in the
southern coastal plain of Israel was reconstructed through the study of its sulfate concentration and isotopic
composition. Particular emphasis was given to the brine-oil interaction in the oilfields and to the sulfate
depletion and lower 5 0 4 / C 1 ratio in brines in contact with hydrocarbons (oil brines) relative to "oil-free"
from dry wells in the same oilfields.
A method is presented for a calculation of the amount of sulfate removed from the original seawater in
the various stages of its evolution to Ca-chloride brine. These stages include evaporation, dolomitization,
and sulfate reduction in different stages of its evolution, from early diagenetic processes to the contact with
crude oil. In the present study, based on the ~345so 4 and SO4/C1 ratio, it was found that in the Heletz brines
most of the sulfate ( 8 0 - 9 4 % ) was removed from the original seawater prior to their interaction with the
hydrocarbons and only a negligible fraction of few percent of the sulfate was removed during the crude
oil-water contact.
The Ca-chloride brines evolved from Messinian (Upper Miocene) seawater that underwent evaporation
during the desiccation of the Mediterranean. Sulfate was removed from Messinian lagoon(s) during gyp-
sum precipitation due to evaporation and dolomitization. Bacterial sulfate reduction further depleted the
brine in sulfate and changed its isotopic composition, from its original Miocene seawater composition of
634Sso, ~ 20%o, to 26%0. Overall, some 50% of the original sulfate, as normalized to chloride, was removed
from the original lagoon through the above processes, mostly by gypsum precipitation. Eastward migration
of the Messinian Ca-Chloride brine into the Heletz Formation was accompanied by dolomitization of the
country rock.
Final depletion of sulfate from the brines took place, and possibly still occurs, in the presence of
crude oil in the oilfields. The two oil-producing fields, Heletz and Kokhav, occupy different areas on
a Rayleigh distillation diagram. Sulfate depletion in both fields is accompanied by an increase in
~345SO4, which reaches a maximum value of 59%0. The above correlation is explained by bacterial
sulfate reduction facilitated by the contact with the crude. Samples collected from the same boreholes
at time intervals of several months show two opposing trends: sulfate concentration decrease accom-
panied by increase in 634Sso,, and vice versa. While the first can be explained as in situ bacterial sul-
fate reduction, the latter attest to subsurface brine migration, as would be expected in oil-producing
fields.

1. INTRODUCTION pertains to the mechanism of Ca-chloride evolution from

Subsurface aqueous fluids associated with crude oil and
gas pools belong mostly, according to their chemical com-
position, to the group of Ca-chloride brines, which make
up the bulk of the deep waters in sedimentary basins.
These brines are defined by their ionic equivalent ratios
of Na/C1 < 1 and (C1-Na)/Mg > 1 (Sulin, 1946), im-
plying that at least part of the chloride is balanced by Ca.
The above relationship may also be defined as Ca/(SO4
+ HCO3) > 1, thereby emphasizing the relative depletion
of these brines in sulfate and bicarbonate (Lerman, 1970;
Starinsky, 1974; Hardie, 1990). Several well-established
mechanisms for the evolution of Ca-chloride brines have
been identified, including evaporation, water-rock inter-
action, albitization, hydrothermal activities, membrane
filtration, and freezing (Carpenter, 1978; Hardie, 1990;
Land, 1992; Herut et al., 1990; Hanor, 1994). This study
3525
seawater.
At the beginning of the century it was already noted that
the "chemical analysis of waters associated with oil differ
widely from the composition of seawater." "The first notice-
able difference is the general absence of sulfates from oilfield
waters, but this has been explained satisfactorily through the
reduction of hydrocarbons and organic matter" (Washburne,
1914). The concentrations of SO4 in Ca-chloride brines, ei-
ther associated with oil or not, is in the range of few tens to
few hundreds mg/L, whereas their salinity ranges between
few tens to several hundreds g/L. It is widely accepted that
SOn depletion and low SO4/C1 ratio in seawater-derived Ca-
chloride brines has been caused by the following mechanisms:
(1) biological or chemical reduction or (2) precipitation of
gypsum as a result of either dolomitization or extensive evap-
oration, or both (Levorsen, 1958; Starinsky, 1974; Collins,
1975; Carpenter, 1978; Hanor, 1988). However, the condi-
3526 I. Gavrieli et al.
tions under which either of these processes took place and the
relative extent of SO4 depletion resulting from these different
processes, including the sulfate reduction in the presence of
hydrocarbons, have not yet been clarified.
In the present study, a method is presented, based on the
634Sso4 and S O J C 1 ratio, for a calculation of the amount of
sulfate removed from the original seawater in the various
stages of its evolution. The geochemical and sulfur isotopic
evolution of the brines in the Heletz Formation (Lower Cre-
taceous), in the southern part of the Israeli Coastal Plain, will
be reconstructed. Four oilfields, Heletz, Kokhav, Brur, and
Negba (Fig. 1 ), two of which (Heletz and Kokhav) still pro-
duce some crude oil from five to six wells, were considered.
Oil is produced mainly from Lower Cretaceous sandstones
and to a lesser extent from dolomites, from depths ranging
from 1.5 to 2.0 km. A distinction is made here between brines
associated with oil (oil brines) and brines pumped from dry
holes (oil-free brines). The water content in most of the
pumped brine-oil mixture increased with production and at
present most of the still active wells have water content above
90%. Most of the brines discussed in the present study were
sampled during the late 1950s to early 1960s, while the oil-
fields were developed. A few were sampled in the seventies
(Table 1 ). An additional brine was taken from Saad-1 bore-
hole, a few km due south from the oilfields (Fig. 1 ), and is
regarded as representative of the oil-free brines in the Heletz
Formation.
Geological and geochemical considerations suggest that the
brines now present in the Heletz Formation were derived
from evaporated seawater (Bentor, 1969; Starinsky, 1974;
Fleischer et al., 1977; Starinsky et al., 1983; Calvo, 1993;
Vengosh et al., 1994). Such saline marginal lagoons existed
FIG. 1. Location map.
in the area during the Messinian (Upper Miocene) when the
Mediterranean sea underwent nearly complete desiccation
(Hsu, 1972). Along the Israeli coastal plain this desiccation
is expressed by the Mavqiim Formation (Fig. 2), which is
composed mainly of anhydrite, dolomite, and clastics (Derin
and Reiss, 1973 ). Some of the evaporated brines were trapped
as interstitial waters in the sediments of the Mavqiim For-
mation. In the present study these brines are represented by
the Gaza-I Mavqiim brine. Other brines migrated eastward in
the subsurface along a front of 50 km on the coastal plain of
Israel, which includes the oilfields in the study area, and were
diluted to various degrees by subsurface freshwater (F'leischer
et al., 1977; Starinsky et al., 1983).
The source rock for the Heletz oil is either the Lower Cre-
taceous shales of the Gevar-Am Formation (Grader, 1960,
Amit, 1978) or the Jurassic fine-grained carbonates of the
Barnea Formation (Bein and Sofer, 1987). It appears that the
oil migrated into its present reservoirs during the Neogene
following major tectonic movements (Cohen, 1971; Gilboa
et al., 1990).
2. METHODS
Most brines discussed in the present study were sampled during
oil pumping tests (DST and swabs) at the time of drilling performed
in the late 1950s to the 1970s. Potential reservoirs or entire wells that
proved to be dry of hydrocarbons were either abandoned and/or test-
ing was performed at a different depth. Thus, dry wells or nonproduc-
ing reservoirs within oil-producing wells could not be resampled.
Samples were also collected from oil-producing wells, the depth of
sampling being determined by the reservoir being exploited.
Brines were separated from the crude oil in the field by gravita-
tional settling immediately after sampling. All samples were filtered
prior to analysis. The chemical analyses were carried out by the Me-
ii//// SHE~'
Ii
 Sulfate removal from subsurface brines 3527

Table 1. Geological and chemical data (mg/1) of the oil field brines.

lil/iiNNi|i
r¢,~,~u m n ~ mu-~.cmm~ ~ U ~ l~--~m urn'ram m u ~ i l ~ ¥ ~

~ ~ i-mr~lm ~ ~ U l~.~mm l ~ Z . m nr~'~nm n'w-~m l t ~

.,-e~,,iulm ~ mu-~--telm~ ~ U il~:n mm~nm m.-t!~nnnm,L,a-,~amunm~-.~n
~ ~ mu-~.~mm~ i U mmw'~m l ~ a n m.r;~m m u~-~ml ~ W
..e.~.~umm~ i-~-~-.mm ~ ~ U 1¥~'-¢1 nr'~am nm~.~n m ~ m l r ~ - ~
..-~.~Fe~um n ~ im~mi ~ ~ U ~ ~l~'r~n l ~ - r . m i ' . ~ l l~r~'a

..-emnrmmnmmn~lnn mu~--~amn~ mrnn U ~ l~m mt, r.......~mi u ~ m n l m ~

.,-~,~nn'lm ~ mu~-~Wl ~ nu,~n~ln U mu~n~i m~-.m l~-m l-~-m lm~
12 4.51 0.91 1.97
67 0.22 0.86 1.27
247 0.69 0.81 1.52
128 1.51 0.92 2.30
79 0.74 0.87 2.19
238 0.36 0.87 1.24
.mer.~:mn ~ nu~-~,mm~ ~ U ir.~nm n~'~n ~ Harem ~ 195 0.86 0.88 2.77
226 0.71 0.89 1.52
165 5.86 0.86 1.63
229 1.37 0.86 1.63
273 0.94 0.78 2.88
~ m~n~.~in nu-~-mn nuu ~ - ~ l n j U n'r.~n ~ l~'~l i'.~l m~,'~. 1.55 0.80 1.47
..e~.n~'lm ~ nu-~nlm ~ m U ~ mw~-I i"~"~l n ~ mm~ 217 2.27 0.89 1.21
n.~,e~z ~ n / mr~-~mm ~ m~.nt,~.~lU m.~r.......~mnm-.rm m ~ m ~ ~ 146 18.55 0.86 2.25
18.96 0.82 2.46
146 12.40 0.82 2.27
.,~,v~V~ulm~ mu~--~,~mm~ j U ~ l z : ~ n n m - . ~ - i m - r , ~ l m~-.~z,,~ 172 4.99 0.89 1.34
..e~mmm ~ nun-mini ~ j U n v n ~ i mm~mm1 , ~ ' l i r~.~um~ 299 1.42 0.83 2.35
678 15.28 0.78 2.22
144 8.11 0.80 1.48
127 167 7.51 0.93 0.90
,w~m ~ m~mm ~ ~ U m~m m~m ma~m ma~m m ~ 166 364 9.55 0.75 1.15
19 500 1.07 0.87 1.48
21 719 0.96 0.89 1.18
576 204 19.96 0.85 1.10
86 220 1.70 0.84 1.85
117 695 5.57 0.87 1.65
1058 488 37.10 0.82 2.38
132 500 6.78 0.87 1.85
7 445 0.32 0.88 1.49
483 17.61 0.83 1.58
32 88 0.66 0.84 1.52
394 155 14.22 0.90 1.39
551 366 13.40 0.83 2.57
76 437 3.31 0.82 1.78
80 1253 4.01 0.88 1.53
981 212 46.27 0.87 1.68
890 457 43.31 0.90 2.70
1470 295 39.73 0.82 4.60
2114 53.64 0.87 2.76

luu /nil lUilmiB

a." +: oil brine, - : oil-free brine
b." weight ratio.
c: molar ratio.
sst: sandstone, lst: limestone; dol: dolomite; gyp: gypsum

korot Water Co. Ltd. Most samples were analysed within few weeks
after sampling, few were analysed within several months. The brines
associated with oils on which sulfur isotope analyses were carried
out were sampled in 1 9 7 9 - 1 9 8 0 from oil-producing wells. These
samples were analysed and BaSO4 was precipitated from them in the
Geological Survey of Israel and the Department of Geology at the
Hebrew University soon after sampling.
The full chemical analyses of the waters were carried out by the
following methods: Na and K by atomic absorption ( A A ) or flame
photometry; C a a n d Mg by EDTA or AA; and Chloride and bicar-
bonate by titration. Sulfate was analysed gravimetrically. The reac-
tion error in the analyses of more than 95% of the samples is less
than 3.2%. The lack of H2S odor when the bottles were reopened is
taken as an indicator that no reduction took place after sampling.
A serious problem in brine sampling during oil production test-
ing is the reliability of the brine as representatives of the forma-
tion water, because the water at this stage are often contaminated
by the drilling fluids, or m i x e d with other formation water. For
the Heletz Formation brines this problem has been addressed by
Starinsky ( 1 9 7 4 ) . The analyses presented in the study include
only the most reliable samples, chosen from a m o n g several hun-
dred samples taken mostly during oil p u m p i n g tests. Most of the
3528 I. Gavrieli et al.
I
-W-
I---- Oil fields
- .,~,*-'.'~I<urkor'.L.L-'~-~..'i~.~-. " . ~
oI ~ _ ~ _
"
, e " ."
kml
t i
Cloy ~ Limestone
~ ] Petroleum [ ' ~ Mor,
FIG. 2. Schematic west-east geological cross sections across the oilfields.
chemical analyses have been published previously (Bentor, 1969;
Starinsky, 1974; Fleischer et al., 1977; Starinsky et al., 1983).
Wells that were resampled were only oil producing wells in
which the question of contamination by drilling fluid does not
exist.
Most sulfur isotopic analyses were carried out on samples collected
during 1979-1980. For the sulfur isotopic analysis, the brines were
filtered and sulfate was precipitated from acidified brine samples as
BaSt4 using 5% BaC12 solution. The precipitate was filtered and
subsequently heated to 800°C to remove organic contaminants. The
preparation of SO2 gas for mass spectrometric analysis followed the
method of Coleman and Moore (1978). Mass spectrometric analyses
were carried out on a Finnigan MAT 251 at the Gottingen Laboratory
and on a VG SIRA 10 at the NERC Isotope Geosciences Laboratory.
Results are given as %0 deviation from the CDT standard with an
overall analytical precision of _0.2%0.
3. RESULTS
The chemical compositions and some ionic ratios of fifty-
one brine samples from thirty-four wells from the oilfields are
presented in Table 1. The brines are characterized by Na/C1
ratios similar to those of normal seawater (0.86), but show
higher ratios of C a / M g ( m a r i n e C a / M g = 0.19). The range
of C1 concentrations is from 17 to 53 g / L and that of SO4 is
from 6 to 1470 m g / L (Fig. 3). The SO4/C1 ratios (expressed
in weight units) show a large range, between 0.2 × 10 -3 and
46 × 10 3 ( m a r i n e SO4/C1 = 0.144). No correlation was
found between sulfate and chloride concentrations and SO4/
C1 ratios, and the lithology of the Formation, either sandstone
or dolomite. The oil brines have the same general major solute
composition as brines obtained from dry wells in the same
field. However, nine samples out of fourteen dry boreholes
have sulfate concentrations above 550 m g / L , whereas only
two out of thirty-two oil brines fall in this range. Thus, the
SO4/C1 ratios in the oil brines are generally lower than those
of the oil-free brines (Table 1). The Gaza-1 and Saad-1
brines, south and south-east of the oilfields, have ionic ratios
similar to those of the oilfield brines except for their higher
SO4/C1 ratios (Fig. 3 ) , which are due to higher SO4 concen-
trations.
Table 2 shows the sulfur isotopic composition of sulfate
from eleven brines collected from oil-producing wells and
E
t
~ ~ .
Juaea Grp. "
~ Dolomite ~ Gypsum
[ - ~ Chalk ~Sond
from the two dry reference boreholes of Gaza-1 and Saad-1.
The 634Sso, of the oil brines cover a wide range between 33.8
and 59.0%0, while that of the two latter boreholes is 2 6 . 3 -
26.4%~. Three oil-producing boreholes were sampled from the
same horizon more than once (Heletz 11, Heletz 35, and Kok-
hav 3). Whereas chloride concentrations in the consecutive
samples were constant within analytical error, the sulfate con-
centrations and 634Sso 4 varied between 1 0 - 2 5 % and 4.5-7%~,
respectively (Tables 1, 2). The changes in sulfate concentra-
tion ( a n d consequently SO4/C1 ratio) and 634Sso4 composition
within each borehole were consistent, whereby increases in
sulfate concentration were accompanied by decreases in
6345so4, or vice versa (Tables 1, 2).
4. DISCUSSION
Most oil brines in the studied area are depleted in sulfate
as compared to the oil-free brines, and both groups are de-
pleted with respect to normal seawater and with respect to the
Heletz brine in Saad- 1 and the M a v q i i m brine in Gaza- 1 bore-
holes (Fig. 3). Since the oil-free brines and oil brines are
closely located in the same lithostratigraphic units, and have
a similar chemical composition, they must have formed at the
same time and from the same original seawater masses. There-
fore, the advanced depletion in sulfate in the oil brines must
be due to processes which have occurred in conjunction with
the crude oil. The low SO4/C1 in some of the oil-free brines
can be explained by a previous contact between the brines
and crude. Such an association could be disrupted by migra-
tion of either the waters or the oil to different sites. It should
be remembered that crude oil is found in relatively close prox-
imity to the oil-free brines as is the case of sample BT-23
from Kokhav 9 borehole, which is located about 400 m above
an oil-producing horizon. Although the p h e n o m e n o n of de-
pletion in sulfate in interstitial waters associated with organic
matter in anaerobic environment is well known, only little
data on sulfate in oil brines have been published (Washburue,
1914; Kartsev et al., 1959;.London, 1964).
 Sulfate removal from subsurface brines 3529

The variations in S O 4 content in Ca-chloride brines as a Table 2.6345 of sulfate in brines from the Heletz Fm.
function of sulfate reduction and precipitation of sulfate min- (L. Cretaceous) and Mavqiim Fro. (Gaza-1, Miocene).
erals (gypsum and anhydrite) is discussed in the present
study. The model for the evolution of Ca-chloride brines from
Sample Well 634Sso4 F* F#red
seawater includes three stages (Starinsky, 1974; Carpenter,
1978): D-704 Heletz 11 39.2 0.021 0.039
D-724 Heletz 11 45.2 0.017 0.043
1 ) A restricted sea or lagoonal water body where gypsum is D-730 Heletz 11 43.5 0.018 0.042
deposited due to surface evaporation. D-723 Heletz 22 59.0 0.0048 0.055
2) Interstitial water at the bottom sediments of the lagoon, D-720 Heletz 35 51.6 0.0065 0.053
where dolomitization takes place accompanied by gypsum D-731 Heletz 35 44.8 0.011 0.049
precipitation (Eqn. 1 ), and bacterial sulfate reduction ac- D-711 Heletz 37 39.4 0.016 0.044
companied by CaCO3 precipitation (Eqn. 2). D-706 Kokhav 3 45.2 0.052 0.148
D-721 Kokhav 3 40.7 0.066 0.134
2CACO3 + Mg 2÷ + SOn2- + 2H20 = D-729 Kokhav ll 33.8 0.121 0.079
D-705 Kokhav 14 35.4 0.099 0.101
CalVlg(CO3)2 + CaSO4"2H20. (1)
D-203 Gaza-1 26.4 0.50
2CH20 + SOn2 = H2S + 2HCO3 . (2) D-170 Saad-1 26.3 0.37

3) Migration into the surrounding rocks where mixing
and epigenetic reactions may occur.
In the present study we evaluate quantitatively each of the
above processes in the evolution of the Heletz Formation
brines. In addition we present geochemical and isotopic evi-
dence for sulfate reduction during brine-oil interaction.
Figure 4 presents 6345so4 data from Table 2 on a Rayleigh
distillation diagram which is based on the Rayleigh distilla-
tion equation (after Goldhaber and Kaplan, 1974):
(~345f = 634Si --~ 1 0 0 0 ( a ' - 1) In F,
where:
6 3 4 S f, 6345i : final and initial 6 34Sso4, respectively.
o/t:
Fractionation factor, a~6s = 1 / a
F: Fraction of the sulfate remaining in the brine.
The solid lines in the diagram thus follow the theoretical ev-
olutionary paths of the remaining sulfate in a solution in a
closed system under various sulfate fractionation factors ( a ) .
*: F: Fraction of sulfate remaining in solution.
#: Fred: Fraction of sulfate removed by sulfate reduction during
water-oil interaction assuming that 94 and 80% were removed
from the Heletz and Kokhav oilfields brines, respectively, during
their earlier evolution.
The F value of the oil brines from Gaza- 1 and Saad- 1 bore-
holes as presented on the diagram were calculated by nor-
malizing the SO4/C1 ratio in the brines to the marine SO4/C1
ratio (0.14). We assume that the SO4 and C1 concentrations
(3) of the Miocene seawater were similar to the present-day sea-
water (Holland et al., 1986). Since the Na/C1 ratio of the
brines is about 0.86 (marine value), it was concluded that the
studied water did not precipitate halite. The diagram illus-
trates the strong sulfate depletion in the oil brines, in which
generally over 90% and locally over 99% of the sulfate has
been removed. The largest depletions are reported from the
Heletz oilfield. The two different areas occupied on the Ray-
leigh diagram by the fluids from Heletz and Kokhav oilfields
indicate that ( 1 ) the brines in the two oilfields had somewhat

Heletz Formation Brines

55-

50-
+
+

45 - ~ -I-

"~" 40" Ir- [] Saad-1

"~ 35' ~+
-4-
• []
Gaza-1
+ + • ~Messlnlan~

25-
-h-
A A
202 ++ seawater []

15
0 5bo lo'oo 15bo 2o'oo 2500 3ooo
S04 (mg/I)
FIG. 3. Chloride vs. sulfate concentrations in the oil brines (+) and oil-free brines (A) in the Heletz Formation. The
concentrations in Gaza-l, Saad-1 and seawater (squares) are given for comparison.
3530
70
65
60
0.0014
I
55
50
45
40
35
30
25
20 i I I I I I Ill
0.001 0.01
FIG. 4. /534Sso4 of the oil brines plotted on a Rayleigh diagram. F is the fraction of sulfate remaining in the solutions
and is calculated as (SOJCI)br~J(SOJC1) . . . . ,~r, assuming SOJCI in Miocene seawater was similar to the present day
ratio. The lines projecting from F = 1 and 6~4Sso~ = 20%o denote the evolutionary path of sulfate during closed system
sulfate reduction at various fractionation factors (a). Arrows are drawn between samples collected from the same
boreholes, their direction denoting the chemical changes with time.
different histories and (2) the brines in each field had similar
history.
Taking Gaza- 1 as a typical representative of the Messinian
interstitial waters or its in situ diagenetic derivative, it appears
that about 50% of the original seawater sulfate was removed
at an early stage, before migration and before interaction with
oil took place. The initial sulfur isotopic composition of the
Upper Miocene seawater sulfate can be estimated from the
634Sso4 of the anhydrite in the Mavqiim Formation which is
+21.7 to +22.7%0 (Nissenbaum, 1978). This range falls
within the global 634Sso4 composition of marine evaporite sul-
fate during the Miocene (Claypool et al., 1980). The sulfur
fractionation during gypsum precipitation from seawater has
been shown to be l - 2 % o (Raab and Spiro, 1991 ), implying
that the Messinian seawater from which the Mavqiim brines
evolved (and consequently the Heletz Formation brines ) had
a 634Sso4 ~ 2(F/00, similar to present-day oceanic composition.
Thus, the heavier value of 634Sso4 = 26.4%0 in the Gaza-1
Mavqiim brine indicates that some of its sulfate removal was
accompanied by sulfur isotope fractionation which enriched
the residual brine in 34S.
Sulfate reduction in seawater is accompanied by sulfur iso-
tope fractionation whereby the lighter isotope, 32S, is prefer-
entially reduced. Although it may appear as if the Gaza-1
Mavqiim brines have evolved from seawater composition
through sulfate reduction along the line of a = 1.01, this pos-
sibility must be rejected. As evident from the CaSO4 in the
Mavqiim Formation, these brines have lost part of their sulfate
through gypsum precipitation (Starinsky, 1974), and since
the latter process is accompanied by only minor fractionation
( 1-2%0, i.e., a ~ 1.001 - 1.002, see above), it cannot account
for the sulfur isotopic composition of the brine. Thus, it must
I. Gavrieli et al.
S 0 4 / CI
o;,o\\ 0.014
I
0~=1.04
0.14
Saad- 1
zx I
I I I I I I fll I I I I I I II
0.1
F
be concluded that the Messinian brines lost their sulfate
through both gypsum precipitation and sulfate reduction. Ap-
plying the Rayleigh distillation equation, the relative role of
each of the processes in removing sulfate from the Mavqiim
lagoon can be estimated. Two limiting cases must be consid-
ered (box in Fig. 5): (1) sulfate reduction preceded gypsum
precipitation (pathway a) and (2) gypsum precipitation pre-
ceded sulfate reduction (pathway b). In both cases a fraction-
ation factor of 1.030 is assumed, corresponding to average
values in anoxic lagoons and recent interstitial waters (Gold-
haber and Kaplan, 1974). In the first case, the ratio of sulfate
removal due to precipitation vs. that of reduction is about 3:2
(0.31:0.19), while in the second case the ratio is about 3:1
(0.38:0.12), the numbers being the displacement along the F
coordinate. In all other cases the two processes alternate or
occur simultaneously and the ratio will fall within these
ranges. Thus, it is evident that within the Messinian lagoonal
and interstitial water stages, more sulfate must have been re-
moved through precipitation than by bacterial reduction. Such
high percentage of sulfate removal through gypsum precipi-
tation can take place either through introduction of Ca by
dolomitization followed by gypsum precipitation (Eqn. 1 ) or
in a combination with surface evaporation. That dolomitiza-
tion occurred is confirmed by the relatively high Ca/Mg ratio
of the Mavqiim brine ( = 1.63, Table 1 ) and the presence of
dolostones in the Mavqiim Formation.
The next step in which sulfate was removed from the brine
was during the migration of the Mavqiim brines into the sur-
rounding country rocks. The process responsible for such sul-
fate removal is gypsum or anhydrite precipitation due to
subsurface epigenetic dolomitization (Eqn. 1 ). Since only
negligible fractionation takes place in this process, it is rep-
 Sulfate removal from subsurface brines 3531

0.0014 S04/ CI 0.014 0.14

70 i I
%=,o, \o=,o,
60 X ~~
55
X
50
~o
45
Heletz x

~ - Kokhav
Ko
35 SO4 re

30
gYPsi~mta~ ~ '~ S
GaZa~ ~

200.001 I I I I I I 111
0.01
I I I I I I I I
0.1
I I I i~'=r =

F
FIG. 5. Sulfate evolution of the Gaza-1 Messinian brine through gypsum precipitation and bacterial sulfate reduction
plotted on a Rayleigh diagram. Horizontal arrows represent gypsum precipitation with no sulfur fractionation. Inclining
arrows follow the sulfate evolutionary path during bacterial sulfate reduction. Two possible pathways from original
seawater to Gaza-1 brines are shown: (a) bacterial sulfate reduction followed by sulfate precipitation and (b) sulfate
precipitation followed by bacterial sulfate reduction, ot = 1.03 is assumed for bacterial sulfate reduction in both paths.

resented on the Rayleigh diagram (Fig. 5) by an horizontal
arrow starting at Gaza-1 (6345SO4 = 26.4). It should be noted
that the arrow crosses the Saad-1 point at 63% removal of the
original seawater sulfate. This process took place somewhere
along the way between the Mavqiim and Heletz Formation,
probably in the Judea group carbonates (Fig. 2).
Sulfate depletion is accompanied by an increase in
6345so4 in each oilfield (Fig. 4). A similar correlation exists
between samples collected from the same borehole and same
depth on different dates. The arrows in Fig. 4 show the chem-
ical and isotopic changes with time. Such correlation is gen-
erally attributed to S fractionation during sulfate reduction.
Indirect evidence for such a reaction may be found by the
negative 613C values, up to -20.4%0 (Calvo, 1993), of sec-
ondary calcite veins in the Heletz reservoir rock. This contri-
bution of bicarbonate originates from organic sources, such
as would be released during the sulfate reduction process
(Eqn. 2).
Of the two known sulfate reduction mechanisms, thermo-
chemical and bacterial, the first requires temperatures of more
than 100-150°C (Orr, 1974; Krouse et al., 1988), though it
has been suggested that the process may occur at temperatures
as low as 70°C (McManus and Hanor, 1993). The present-
day temperature-depth relationship in the oilfields (Starinsky,
1974) shows maximum temperatures of 5 0 - 6 0 ° C at the depth
of the brines in question ( 1 5 0 0 - 1 8 0 0 m). There is no evi-
dence that the brines were ever exposed to higher tempera-
tures and it is therefore deduced that bacterial sulfate reduc-
tion is responsible for the observed trend.
The dynamic and heterogeneous nature of the sulfate sys-
tem of the oilfield brines may be observed by the change with
time in sulfate concentrations and isotopic compositions in
samples collected from the same boreholes at different times
(Heletz-11, Heletz-35, and Kokhav-3). Of the four time in-
tervals between samplings (arrows in Fig. 4), three show sul-
fate increases and 6345so4 decreases with time, and the fourth
shows the opposite trend. No significant change in the con-
centration of chloride was observed in any of the boreholes.
The 634Sso4 decrease-sulfate increase suggest that the more
recent brines are different parcels of essentially the same
brine, having the same chlorinity, which has experienced
lower degrees of sulfate reduction. The fourth time interval
could be explained by either present-day bacterial activity at
depth, or subsurface flow.
The S fractionation factors that accompanied the sulfate
reduction in the above brines was calculated by applying Eqn.
4: 6345i, 634S f are the lower and higher 6345SO4 values in each
borehole, respectively. (SO4/C1) are the corresponding ratios
and F = (S04[CI)f](S04]C1)i. The calculated values are oe
= 1.013 and o~ = 1.019 for Heletz-35 and Kokhav-3, respec-
tively, and t~ = 1.029 and a = 1.031 for the two time intervals
in Heletz- 11 borehole.
In addition to the above single borehole calculations, gen-
eral fractionation factors were calculated as best fit lines for
all the 6 34Sso 4 data points in each oilfield. The values obtained
are 1.012 and 1.014 for Heletz and Kokhav oilfields, respec-
tively. When drawn on the Rayleigh diagram the intercept of
the calculated lines with the horizontal arrow starting at Mav-
qiim Gaza-1 634S504 = 26.4%0 is at F = 0.06 and F = 0.20,
respectively (Fig. 5). These imply that approximately 94 and
80% of the original seawater sulfate was removed, respec-
tively, before the brine-oil interaction began. The Heletz brine
in Saad-1, outside the oilfields, thus represent only one stage
through which the Messinian brines evolved in the subsurface.
3532 I. Gavrieli et al.
The similar fractionation factors indicate that similar condi-
tions for sulfate reduction exist in both fields, while the dif-
ferent intercepts indicate different histories for the Heletz and
Kokhav brines before the onset of reduction.
It is now possible to determine the fraction of sulfate that
was removed during the bacterial sulfate reduction in the pres-
ence of the crude. This value is the difference between the
above calculated value of sulfate remaining in the oilfield
brine prior to its contact with the crude and F, the fraction of
sulfate presently found in each sample. The values obtained
(Table 2) indicate that 8 - 1 5 % of the original sulfate were
removed from the Kokhav oilfield brines during this stage
while only 4 - 6 % were removed from the Heletz oilfield
brines. Thus, despite the extreme depletion of sulfate in the
studied Heletz Formation Ca-chloride brines, only a relatively
small fraction of it was removed as a result of the contact with
the hydrocarbons. However, due to the low concentration of
sulfate at the onset of the reduction, it significantly altered the
isotopic composition of the remaining sulfate.
5. SUMMARY AND CONCLUSIONS
The behaviour of sulfate was studied in the Ca-chloride
brines from productive oilfields of the Heletz Formation in
the Israeli Mediterranean coastal plain. The two identified wa-
ter groups, the oil brines, associated with oil and the oil-free
brines from dry wells, were found to be similar in their major
chemical components. Both are depleted in SO4 compared to
evaporated seawater with the same salinity. However, the oil
brines were found to be low in sulfate in comparison with oil-
free brines from the same oil-producing field. The 634S values
of the sulfate in the oil brines are in the range of +30%o to
+60°/oo while that of the sulfate in Heletz Formation brine of
the Saad-I borehole, outside the oilfield, is 26.3%0. The latter
value is similar to that of the Gaza-1 brines in the Miocene
Mavqiim Formation, and is heavier than the 634Sso4 = 20°/oo
of the original Miocene seawater from which the oilfield
brines are believed to have evolved.
The SOa/Cl ratios and 634S of the sulfate in the Mavqiim
brines and in the Heletz Formation brines suggest the follow-
ing evolutionary path:
1 ) Evaporitic lagoons which existed in the Upper Miocene,
at the onset of the Mediterranean desiccation, are the
source of the Ca-chloride brines in the Heletz Formation.
Sulfate was removed from the brines of these Mavqiim
lagoon (s) through both gypsum precipitation and bacte-
rial sulfate reduction. In the Gaza-1 Mavqiim brines some
50% of the sulfate were removed, mostly through precip-
itation, while the sulfate reduction resulted in a change in
634Sso4, from an original seawater composition of 2 0 -
26.4%0. Part, if not all, of the gypsum precipitation was
due to dolomitization of the young carbonate sediments.
Bacterial sulfate reduction occurred either within the evap-
orating lagoon (s) or in the interstitial brines of its sedi-
ments.
2) Migration of evolved Mavqiim brines into the Heletz For-
mation was accompanied by dolomitization and gypsum
precipitation which further depleted the sulfate concentra-
tion in the brines though without significantly changing
their sulfur isotopic compositions.
3 ) Dilution of the brines to various degrees occurred by mix-
ing with fresh groundwater. This dilution did not signifi-
cantly change the chemical ratios among the major sol-
utes.
4) Contact occurred between the diluted brines and crude oil.
However, there are no geochemical indications nor un-
equivocal geological controls to suggest whether the crude
oil in the Heletz Formation migrated with the brines or the
brines came into contact with the oil as they migrated to
their present location.
5) The contact with the crude enabled S-reducing microor-
ganisms to flourish. The sulfate reduction was accompa-
nied by sulfur isotope fractionation. This process enriched
the remaining sulfate in the oil brines with 345, reaching
values as high as 634Sso4 = 59.0%0 in Heletz-22 borehole.
6) In the Kokhav oilfield brines, the bacterial sulfate reduc-
tion removed 8 - 1 5 % of the original seawater sulfate,
whereas in the Heletz oilfield brines it accounts for no
more than 6%. However, due to the low concentration of
sulfate at the onset of the reduction, it significantly altered
the isotopic composition of the remaining sulfate.
7) The oil-brine system in the oilfield is dynamic and parcels
of brines of different chemical and isotopic characteristics
were sampled within periods of months. The chemical and
isotopic compositions of brines can therefore be used not
only as indications for sedimentary and diagenetic pro-
cesses but also to help identify brines which are or have
previously been spatially associated with hydrocarbons.
Acknowledgments We would like to thank E. Kashai and G. Gvirtz-
man for permission to use information from oil boreholes and water
samples. Special thanks are due to M. Leng for assistance with the
analyses of sulfur isotopes and to A. Bein and M. Goldberg for fruit-
ful discussions. Chemical analyses were carried out by R. Bilu-
Greenblat, R. Binshtuk, N. Dalman, and R. Nisan. We also thank
A. M. Stueber and J. S. Hanor and an anonymous reviewer for sig-
nificantly improving the paper.
Editorial handling: E. J. Reardon
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