Sedimentology (1995) 42, 147-160

Stable isotope evidence for the origin of diagenetic carbonate

minerals from the Lower Jurassic Inmar Formation, southern
Israel
AVNER AYALON" and FRED J . L O N G S T A F F E t
*Geological Survey of Israel, 30 Malkhe Yisrael Street, Jerusalem 95501, Israel
?Department of Earth Sciences, University of Western Ontario, London, Ontario, Canada N6A 5B7

ABSTRACT
The oxygen isotope compositions of diagenetic carbonate minerals from the Lower
Jurassic Inmar Formation, southern Israel, have been used to identify porewater
types during diagenesis. Changes in porewater composition can be related to major
geological events within southern Israel. In particular, saline brines played an
important role in late (Pliocene-Pleistocene) dolomitization of these rocks.
Diagenetic carbonates included early siderite (6180,Mow= + 24.4 to + 26-5%0;
613CpD13= - 1-1to +0.8%0),late dolomite, ferroan dolomite and ankerite
(6180sMOW=+18.4 to +25.8%,,;613CpDB= - 2 - 1 to +o.z%~),and calcite
(6180sM,w=+21~3 to +32.6%0; S13CpDB=- 4.2 to +3.2%0). The petrographic and
isotopic results suggest that siderite formed early in the diagenetic history at
shallow depths. The dolomitic phases formed at greater depths late in diagenesis.
Crystallization of secondary calcite spans early to late diagenesis, consistent with
its large range in isotopic values.
A strong negative correlation exists between burial depth (temperature) and the
oxygen isotopic compositions of the dolomitic cements. In addition, the 6l80 values
of the dolomitic phases in the northern Negev and Judea Mountains are in isotopic
equilibrium with present formation waters. This behaviour suggests that formation
of secondary dolomite post-dates the tectonic activity responsible for the present
relief of southern Israel (Upper Miocene to Pliocene) and that the dolomite
crystallized from present formation waters. Such is not the case in the Central
Negev. In that locality, present formation waters have much lower salinities and
6 l 8 0 values, indicating invasion of freshwater, and are out of isotopic equilibrium
with secondary dolomite. Recharge of the Inmar Formation by meteoric water in the
Central Negev occurred in the Pleistocene, and halted formation of dolomite.

INTRODUCTION Diagenetic minerals normally acquire oxygen

This paper presents mineralogical, petrographic
and oxygen and carbon isotope data for diagenetic
carbonate minerals from the Lower Jurassic Inmar
Formation in southern Israel, and interprets these
results in terms of the burial history and pore-
water evolution experienced by these rocks. In
particular, we address the origin and evolution of
secondary dolomite, which is the most pervasive
and abundant carbonate cement in subsurface
sandstones of the Inmar Formation.
isotope compositions that reflect the temperature
and porewater involved in their crystallization.
At temperatures typical of sedimentary environ-
ments, most minerals retain this isotopic signa-
ture because significant post-crystallization,
isotopic exchange with water is uncommon
(Longstaffe, 1983; O'Neil, 1987). However, be-
cause of its greater susceptibility to recrystalliza-
tion, calcite [and, to a lesser extent, dolomite) can
be affected by post-formational isotopic exchange
at lower temperatures than silicate minerals
147
148 A. Ayulon and F. J. Longstaffe
I I
m
m 1
m
I I
I
II
34O 34030' 35O
(Clayton, 1959). Nevertheless, in most sedimen-
tary systems, diagenetic carbonate minerals still
retain a valuable isotopic record of the porewater
origin, the source of carbon and the temperature at
that stage of diagenesis, all of which are useful
insights into the geological and hydrogeological
history of the basin.
GEOLOGICAL B A C K G R O U N D
Stratigraphy and sedimentology
The Lower Jurassic (Middle Liassic to Early
Bajocian) Inmar Formation occurs in outcrops in
the northern Sinai (Gebel Maghara) and the
Central Negev (Makhtesh Ramon), and subsurface
sections in southern Israel (Negev region)
(Goldberg, 1970; Fig. I). It overlies the Upper
Carbonate Member of the Ardon Formation
(Lower Liassic) and is overlain by the Daya
Formation (Bajocian; Fig. 2). The Inmar For-
mation consists of three members: the Lower
Member (mostly clastic sedimentary rocks up to
1 4 0 m thick); the Qeren Member (mostly lime-
stone up to 157 m thick) and the Upper Member
- 31 30'
, 31
- 3030'
I
I
I Fig. 1. Map of sampling locations
35O30' and study area.
(mostly clastic sedimentary rocks up to 337 m
thick; Goldberg, 1970). The formation thickens
towards the north-western Negev Desert, and
wedges out eastward. Near the Dead Sea, the
Inmar Formation is absent, either as a result of
non-deposition or because of later erosion
(Goldberg & Friedman, 1974).
The Lower and Upper members consist of inter-
bedded sandstone, siltstone, shale, limestone and
dolomite. Sandstone, ranging in grain size from
very fine sand to fine gravel, is the dominant rock
type. On the whole, the Lower Member tends to
be finer grained than the Upper Member. Organic
matter and carbonaceous plant remains can be
abundant. Pyrite and siderite are ubiquitous, and
are particularly abundant where associated with
shaley portions of the Inmar Formation. Besides
the abundant diagenetic carbonate minerals that
are the focus of this paper, sandstones from both
the Upper and Lower members contain many
other diagenetic phases, including clay minerals,
silica, evaporites, oxides and hydroxides (Ayalon
& Longstaffe, in prep.).
The Qeren Member, which separates the Lower
and Upper members, is composed mostly of lime-
stones (low-energy pelmicrites). Dolomites and

LITHOLOGY
IMMISHHoR F'.Ih
h h h h h h h h h h h h h h h h L h h h
h h h h h h h k h h Lh 4 h h L h h L
-
a 1 1 MOHILA F M .
K
L I A h h A h A h h h A h A h A h h A h h A
A h A h h h A A A h A h A h h h h A h h
Fig. 2. Schematic section of the Jurassic in southern
Israel (modified after Goldberg & Friedman, 1974).
Legend: 1, limestone; 2 , dolostone; 3, evaporites; 4 ,
shale; 5, sandstone; 6, palaeosol.
terrigenous sediments (mainly sandstones) are
uncommon within this unit.
Deep weathering of Triassic evaporites and
dolomites that had formed in a broad, sea-
marginal flat began in the Jurassic. During subse-
quent subsidence, the ensuing shallow shelf
conditions allowed widespread development of
sabkhas and, in places, deposition of lagoonal
sediments (Ardon Formation; Fig. 2) under arid,
tropical conditions (Goldberg & Friedman, 1974).
Inmar sedimentation was initiated by a marked
progradation during which the shallow shelf
deposits of the Ardon Formation were buried
beneath a continental, fluvial-deltaic complex.
These sands were derived from the Arabo-Nubian
shield, south of the Negev. Despite minor fluctua-
tions in sea level during deposition, the rocks of
the Lower Member were deposited almost exclu-
sively under fluvial conditions. The occurrence of
large tree trunks, the widespread distribution of
plant remains and carbonaceous organic matter,
and the cycles of alternating shale and sandstone
beds suggest that swamps and small lakes were
part of this fluvial system, and that humid, tropi-
cal conditions prevailed at that time (Goldberg
& Friedman, 1974). Deposition of the Qeren
Carbonate minerals, southern Israel 149
Member limestone, and in particular the pelmi-
crite that dominates this unit, has been inter-
preted as a transgressive event during which
shallow-shelf carbonates were deposited in a low-
energy environment on top of the fluvial-deltaic
clastic sequence. Subsequent deposition of the
clastic rocks of the Upper Member represents a
return to dominantly fluvial-deltaic conditions
(Goldberg & Friedman, 1974). Post-Inmar For-
mation deposition was dominated by limestones,
intercalated with lesser amounts of sandstones
and shale (Fig. 2).
Tectonic and thermal history
During the Jurassic, the continental margin of the
Tethyan Sea (including the study area) was
1 affected by block faulting and tensional tectonic
movements that were probably related to active
rifting and spreading of the central portions of the
Tethys Sea (Bernoulli, 1972). Freund et al. (1975)
suggested that this extensional structural regime
persisted until the Late Cretaceous. Extensional
regimes are commonly associated with high heat
flow (e.g. Spohn & Schubert, 1982), perhaps
explaining the high geothermal gradients reported
for the study area at that time. For example,
Jurassic and Cretaceous 'thermal events' of short
duration (5-25 Myr), characterized by a high
thermal gradient (45-55"C km l), were postu-
~
lated for the study area by Feinstein (1985),based
on vitrinite-reflectance measurements.
Orogenic activity responsible for uplift and
folding in the study area began in the Late
Cretaceous and culminated during the Late
Tertiary (Bentor & Vroman, 1954; Picard, 1959;
Freund et al., 1975). This transition from a
regional, extensional regime to a compressional
regime led to the development of the Syrian Arc,
and was also manifested by a change from high to
low geothermal gradients (max. 22C km ') ~
within the study area (De Sitter, 1962; Freund et
al., 1975; Erickson et al., 1977; Garfunkel, 1981;
Feinstein, 1985). Vitrinite reflectance and fission
track data suggest that this gradient persisted
throughout the Tertiary to the present time
(Feinstein, 1985). Such values are characteristic
of present-day southern Israel and the eastern
Mediterranean in general (Erickson et al., 1977).
Erosion has variably reduced the thickness of
the sedimentary section since post-Jurassic time.
The Jurassic-Cretaceous unconformity represents
erosion of several hundreds of metres of Jurassic
through Cambrian sediments in some localities
(Zak, 1957; Bentor, 1960; Druckman, 1974).
150 A. Ayalon and F. J. Longstaffe
Garfunkel & Derin (1988) reported that Early
Cretaceous erosion removed at least 500-700 m
of section in Makhtesh Ramon (Fig. l),a c. 15-km-
wide domal uplift associated with Early
Cretaceous intrusive magmatism in the Negev
Desert. Miocene or post-Miocene erosion varying
from 600m at the Northern Negev to 2400m at
the Central Negev has been suggested by Petersen
( 1980).
Chemistry of formation waters in Jurassic
units
The chemistry and Sr, H and 0 isotopic composi-
tions of formation waters contained in Jurassic
rocks of southern Israel (the 'Jurassic aquifer')
have been studied by Bentor (1969), Starinsky
(1974), Fleischer et al. (1977), Starinsky &
Katz (1978), Sass & Starinsky (1979), Issar (1979,
1981), Starinsky et al. (1983) and Nativ (1984).
These formation waters are characterized by
Ca/(HCO,- +SO,2 - ) > I and Na/C1<1 (equiva-
lents), and can be classified as Ca-chloride brines
(Lerman, 1970; Levy, 1972). Chemical, isotopic
and temperature data available for waters from
boreholes studied in the present work are sum-
marized in Table 1 from Starinsky (1974),
Fleischer et al. (1977), Starinsky & Katz (1978)
and Nativ (1984).
Starinsky (1974) defined two major groups of
these Ca-chloride brines, C and R, in southern
Israel. Group C has an mNalmC1 ratio similar to
seawater (c. 0.86) and is present to depths of
about 1-2 km. Group R, the deeper formation
waters, consists of brines whose mNalmC1 ratio is
lower than that of seawater. Starinsky (1974)
suggested that the Ca-chloride brines developed
in three stages: (i) surface evaporation of seawater
(the Na/Cl ratio was used to assume that evapora-
tion of group R exceeded halite saturation
whereas group C remained below halite satura-
tion); (ii) brine-sediment reactions, migration of
brine into surrounding rocks and dolomitization
of calcite and aragonite (see also Sass 8 Starinsky,
1979); and (iii) dilution of the brines by fresh-
water and(or) seawater. Starinksy & Katz (1978)
proposed that Group R brines evolved from
Pliocene seawater (in the vicinity of the Dead
Sea). Prior to Pliocene-Pleistocene tectonic uplift,
they migrated into deeper portions of the geologi-
cal section in a westerly direction, at least as far
as the present coast of the Mediterranean Sea.
This stage of fluid migration was driven by the
Messinian dessication of the Mediterranean Sea.
It is reasonable to assume that these Ca-chloride
brines are saturated with respect to dolomite
(Starinsky, 1974). However, because critical data
for the brines are lacking (e.g. pCO,, alkalinity),
this cannot be properly tested using geochemical
modelling.
Nativ (1984) found no correlations among salin-
ity, isotopic composition of formation water,
depth, lithology or formation within the Jurassic
aquifer. Instead, the prevailing factor dictating
water composition was geographical location.
Ca-chloride brines (30 000-130 000 mg C11- ')
enriched in l80are present in the Negev to the
west; fresher water (800-10 000 mg C11- I),
depleted of '*O, is present to the east.
ANALYTICAL METHODS
Fifteen outcrop samples from the Gebel Maghara
area (northern Sinai) and 31 core-samples from
Negev boreholes have been examined (Fig. 1).
Subsurface material has been analysed from the
following boreholes: Qeren 1,Hazerim 1 and Beer
Sheva 1 in the northern Negev; Dabeshet 1 and
Tsia 1 in the Judea Mountains; Daya 1 and Barbur
1in the Central Negev; and Makhtesh Qatan 1 and
Makhtesh Qatan 2 in the South-Central Negev
(Fig. 1). The mineralogy and petrology of the
samples were studied using optical microscopy,
scanning electron microscopy, energy-dispersive
spectrometry and X-ray diffraction (XRD). Oxygen
and carbon isotope analyses of the carbonate
minerals were also completed.
The carbonate mineralogy is summarized in
Table 2. Carbonate mineral abundances were cal-
culated using CO,, Mg and XRD measurements.
Carbon (and total CO,) contents were determined
for c. 250-mg powder samples using a LECO
carbon analyser furnace with 0, flow and an
infra-red (IR) detector, calibrated using a CaCO,
standard. Mg content was determined by atomic
absorption spectrometry (AAS) following dissolu-
tion in hot 1:1 HC1. Given the value for total
carbonate, XRD calibration curves for calcite and
dolomite/ankerite were then used to determine
the relative abundance of each phase.
The stable isotope data are presented in Table 3
using the normal &notation relative to SMOW for
oxygen (Craig, 1961) and PDB for carbon (Craig,
1957). An oxygen isotope C0,-H,O fractionation
factor of 1-0412 at 25C was used to calibrate the
mass-spectrometer working gas. To calculate the
oxygen isotope results for calcite and dolomite,
values of 1.01025 and 1.01110, respectively, were
employed for the total carbonate C0,-phosphoric
Table 1. Composition of waters in Jurassic formations.
Depth Na K Ca c1 SO, HCO, Br TDS 6D 6'*O Tem erature Refer-
~ ~ ~ ~ ~ I)
Well (m) Stratigraphy (mg 1 '1 (mg 1 - '1 ( m p '1 (mg 1 '1 (mg 1 ') (mg 1 '1 (mg 1 - ') (mg 1 (g 1 I ) (%o)* (%)* ?C)t enceS

Beer-Sheva 1 2740-2782 Inmar Fm. 41400 705 2190 14400 91194 530 214 690 151 - 10.6 0.47 75.6 1
Qeren 1 2463-2501 Inmar Fm. 40900 774 1890 14400 94100 464 102 153 67 1
Qeren 1 2503-2520 Inmar Fm. 44400 615 1732 15150 99264 500 115 756 162 79 1
Qeren 1 2520-2 534 Inmar Fm. 44400 598 1730 15050 98867 502 64 750 161 68 1
Qeren 1 2541-2 566 Inmar Fm. 42792 946 1462 15610 98210 515 158 802 160 69 1
Qeren 1 2566-2567 Inmar Fm. 39123 665 1338 14380 89582 624 61 146 - 4.5 0.49 2
Qeren 1 2689-2700 Inmar Fm. 41634 992 1585 15407 96327 494 152 745 157 1
Qeren 1 2700-2708 Inmar Fm. 41256 988 1587 15204 95414 491 131 719 155 84 1
Qeren 1 2708-2719 Inmar Fm. 41256 1012 1585 15407 95764 497 158 733 156 84 1
~
Qeren 1 2845-2846 Inmar Fm. 39928 805 1277 15560 92454 528 61 151 0.96 104 2
Qeren 1 291 9-2935 Inmar Fm. 42676 1080 2094 15570 99627 505 146 816 162 100 1
Qeren 1 2972-2992 Inmar Fm. 46199 2149 16580 105283 461 195 171 104 1
Hazerim 1 3146-3165 Inmar Fm. 21050 640 865 7830 53680 361 84 4
~
Tsia 1 1638 Zohar Fm. 12949 137 280 740 22050 1104 122 38 3.93
~
Tsia 1 1665 Zohar Fm. 10304 117 109 180 16484 1152 183 29 - 20.4 3.71
Tsia 1 1790 Sherif Fin. 6680 117 213 1127 11470 1609 210 21 1
Tsia 1 2441 Inmar Fm. 70
Daya 1 1080-1083 Zohar Fm. 10380 99 219 1600 18490 165 31 - 45.0 - 5.26
~
Daya 1 1 333-1 354 Sherif Fm. 2208 36 160 2198 1776 427 7 - 53.0 8.12
~
Daya 1 1422-1444 Sherif Fm. 2829 12 80 2162 2400 1037 8 - 45.8 8.45
Daya 1 1844-1856 Inmar Fm. 805 85 580 1170 1584 305 4 - 7.73 60 2
~
Barbur 1 1299-1335 Sherif Fm. 1794 47 24 20 2021 1056 366 5 4.76 46 2
Barbur 1 1407-1446 Sherif Fm. 1288 63 49 20 1276 1200 122 4 - 5.22 2
Barbur 1 1452-1482 Daya Fm. 1725 59 36 40 1489 1680 61 5 - 45.8 - 6.82 2
~
Barbur 1 1517-1562 Daya Fm. 1081 63 12 460 1347 1488 183 5 - 39.8 6.04 2
Barbur 1 1778-1780 Inmar Fm. 2100 56 3

*The isotopic compositions of the formation waters are taken from Fleischer et al. (1977).
tBorehole measurements of groundwater temperatures are unreliable, mainly because of thermal disequilibrium in the borehole durin the measurement, and the cooling effects of the
drilling mud and filtrate. Usually the measured temperatures are lower than those existing in the aquifer (Eckstein, 1975) and they siould be considered as minimum temperatures.
$1, Starinsky (1974); 2, Fleischer et al. (1977); 3, Nativ (1984); 4 , Starinsky L Katz (1978).
152 A. Ayalon and F. J. Longstaffe
Table 2. Percentage of carbonate minerals, Inmar Formation.
Dolomite
Sample Depth Rock Calcite + ankerite Siderite
No. Well (4 Member type (% 1 (%I (%I
Al-1 Barbur 1 1588 Upper Mbr. Csst 0.5 2-9
A1-2 Barbur 1 1589 Upper Mbr. Msst 0.7 4.2
A1-3 Barbur 1 1624 Upper Mbr. Csst 11.5
A1-4 Barbur 1 1625 Upper Mbr. Msst 7.9
Al-5 Barbur 1 1683 Upper Mbr. Msst <0.2 18.6
A1-6 Barbur 1 1695 Upper Mbr. Fsst 0.2 4.2
A1-7 Barbur 1 1786 Lower Mbr. Msst
A1-8 Qeren 1 2567 Upper Mbr. Msst 1.8
A1-9 Qeren 1 2571 Upper Mbr. Fsst, shale >5
A1-10 Qeren 1 2881 Qeren Msst 2.7
Al-11 Qeren 1 2986 Lower Mbr. Msst 7.9
A1-12 Qeren 1 3007 Lower Mbr. Csst 3.8
A1-13 Hazerim 1 2740 Upper Mbr. Msst 12.5
A1-14 Hazerim 1 2742 Upper Mbr. Shale 10 to 20 (?) >5
A]-15 Hazerim 1 2927 Qeren Marine Lst 84.0 8.0 (An)
A]-16 Hazerim 1 3068 Lower Mbr. Msst 1.3
A]-17 Daya 1 1644 Upper Mbr. Shale >5
A1-18 Daya 1 1653 Upper Mbr. Msst 3.4
A1-19 Daya 1 1735 Upper Mbr. Csst 1.1
A1-20 Daya 1 1827 Lower Mbr. Msst
A1-24 Beer-Sheva 1 2634 Upper Mbr. Fsst 0.5 9.5 (An)
A1-25 Beer-Sheva 1 2705 Upper Mbr. Shale >5
A1-26 Beer-Sheva 1 2750 Upper Mbr. Msst <0.5
A]-27 Beer-Sheva 1 2794 Upper Mbr. Msst 0.5 40.0 (An)
A1-28 Dabeshet 1 2049 Upper Mbr. Shale
A1-29 Dabeshet 1 2048 Upper Mbr. Fsst 10.0
A1-30 Tsia 1 2454 Qeren Msst 2.1
A1-31 Tsia 1 2466 Lower Mbr. Shale 2 20 -4.0 (An)
A1-32 Makhtesh Qatan 1 651 Qeren Msst 5.4
A1-33 Makhtesh Qatan 2 484 Upper Mbr. Msst 3.8
A1-34 Makhtesh Qatan 2 488 Upper Mbr. Shale
A]-35 Gebel Maghara Upper Mbr. Fsst
A1-36
AI-37
Gebel Maghara
Gebel Maghara
Upper Mbr.
Upper Mbr.
Msst
Fsst
--0.4
0.4
36-0
A1-38 Gebel Maghara Upper Mbr. Msst 3.1
A1-39 Gebel Maghara Upper Mbr. Csst 21.8 33.4 (An)
A1-40 Gebel Maghara Upper Mbr. Msst 11.4
A1-41 Gebel Maghara Upper Mbr. Msst 13.6
A]-42 Gebel Maghara Qeren Sslst 56.3
A]-43 Gebel Maghara Qeren Vfsslst 85.8
A]-44 Gebel Maghara Qeren Cmsst 23.3 10.9 [An)
A1-45 Gebel Maghara Lower Mbr. Csst 2.0
AI-46
A1-47
Gebel Maghara
Gebel Maghara
Lower Mbr.
Lower Mbr.
Csst
Csst
-5
0.7
- 27.0 (?)(An)
A]-49 Gebel Maghara Lower Mbr. Msst % 20.0

~ ~~

An, mostly ankerite; Fsst, fine-grained sandstone; Msst, medium-grained sandstone; Csst, coarse-grained sandstone;
Lst, limestone; Sslst, sandy limestone - abundant fossil debris and faecal pellets; Vfsslst, very fine-grained sandy
limestone; Cmsst, calcareous, medium-grained sandstone.

acid extracted CO, fractionation factor (u) at
25C (after Sharma & Clayton, 1965). The calcite (I
was used in all calculations for siderite; the dolo-
mite Q was used in all calculations for ankerite.
Using the siderite and ankerite values for Q
reported by Rosenbaum & Sheppard (1986)would
slightly lower the values reported here, but would
not affect the discussion and conclusions that
follow.
Carbonate minerals were prepared for isotopic
analysis by reacting organic-free powdered rock
samples (<44-pm size fraction) in anhydrous
H,PO, at 25"C, following procedures described by
Walters et al. (1972), modified after McCrea
 Carbonate minerals, southern Israel 153
Table 3. Oxygen a n d carbon isotope compositions of diagenetic carbonate minerals, Inmar Formation.
Calcite Dolomitic phases" Siderite
Sample Depth d'80 61C P O 61C P O 613C
No. (4 (%o SMOW) (%o PDB) (%o SMOW) (%o PDB) (%o SMOW) (%oPDB)

Upper Mbr.
Al-1 1588 25.03 0.38 23.46 - 0.78
A1-2 1589 24.67 0.24 23.46 - 1.00
A1-3 1624 22.70 - 0.87
A1-4 1625 22.67 - 1.00
A1-5 1683 24.18 - 0.55 23.80 - 0.61
A1-6 1695 23.42 - 0.56
A1-8 2567 21.76 - 2.02
A1-9 2571 25.35 - 0.72
A1-13 2740 21.02 - 1.39
A1-14 2742 27.98 2.76 26.51 0.82
Al-17 1644
A1-18 1653 22.90 - 1.18
A1-19 1735 23.53 - 0.88
A1-24 2634 21.03 - 0.97
A1-25 2705 24.37 - 1.12
A1-26 2750 20.68 - 0.87
A1-27 2 794 21.46 - 1.23 20.37 - 1.37
A1-29 2048 21.78 0.20
A1-33 484 25.58 - 0.71
A1-35 29.23 0.00
A1-36 32.59 1-56
A1-3 7 24.09 - 0.64
A1-38 24.66 0.62
A1-39 26.80 - 0.91 21.08 - 0.92
A1-40 23.71 - 1.94
Al-41 22.30 - 4.21

Qeren Mbr.
Al-10 2881 19.80 0.06
A1-15 2927 23.07 1.12
A1-30 2454 21-07 - 0.68
A1-32 651 25.82 - 0.61
A1-42 23.13 - 1.31
A1-43 20.89 0.80
A]-44 23.54 - 0.04

Lower Mbr.
Al-11 2986 19.90 - 1.36
A1-12 3007 19.98 - 1.43
A1-16 3068 20.58 - 0.32
A1-31 2466 26.88 - 0-06
A1-45 32.10 2.53
A1-46 21.34 - 1.82 18.41 - 2.09
A1-4 7 29.96 3.18
A1-49 26.12 - 0.88

*Dolomite, ferroan dolomite and ankerite.

(1950) and Epstein et al. (1964), and using the
following reaction times: calcite, 1 h; dolomite
and ankerite, 10 days; siderite, 2 1 days. Because
of possible cross contamination of CO, gas pro-
duced from calcite and dolomite/ankerite, results
for calcite are presented only when the calcite/
dolomite-ankerite ratio in the sample was greater
than 0.5. Results for dolomite and ankerite are
reported only when the calcite/dolomite-ankerite
ratio was less than 0.7. NBS-20 gave an average
6180sMOW= +26.50%0 and 613CpDB=- 1-17%0
during these analyses.
154 A. Ayalon and F. J. Longstaffe

Fig. 3. SEM photomicrographs of diagenetic calcite cements from the Inmar Formation. (a) Late Mg- and Fe-rich
calcite (Gebel Maghara, Lower Member, A1-47). Such radiating aggregates of calcite crystals have partially filled
secondary porosity in earlier carbonate. Each calcite crystal is composed of fibrous crystallites, a texture typical of
Mg- and Fe-rich calcite. This is the last generation of secondary calcite observed in these rocks. (b) Dissolution of
early, massive calcite cement (Gebel Maghara, Lower Member, A1-49). The pitted surface of the calcite is not present
on later anhydrite (smooth crystal surfaces to the left and bottom of the photomicrograph, surrounding the calcite).
This episode of anhydrite crystallization post-dated calcite dissolution. (c) Massive, early, sparry calcite cementing
quartz grains (Gebel Maghara, Qeren Member, A1-44). Precompaction textures have been preserved among quartz
grains where this cement has persisted. (d) Later diagenetic, idiomorphic, low-Mg (and low-Fe) calcite piercing
earlier, fine-grained, calcite matrix (Hazerim 1, Qeren Member, A1-15). This calcite pre-dates the final calcite
generation illustrated in (a).

RESULTS (alunite, jarosite, anhydrite/gypsum, bassanite).

The Inmar Formation has experienced a complex
diagenetic history, producing a wide range of
minerals whose presence and abundance vary
widely depending on sample locality and burial
depth (Ayalon & Longstaffe, in prep.). Siderite,
pyrite, calcite, chlorite, anhydrite and ankerite
formed early in diagenesis, at shallow depths.
Later, burial diagenetic phases include kaolinite,
quartz, dolomite, calcite, smectite, halloysite,
illite and illitelsmectite. The latest diagenetic
minerals are calcite, ankerite, pyrite, Ti-, Fe- and
Mn-oxides and hydroxides, halite and sulphates
These minerals formed (or are forming) over the
wide range of temperatures, burial depths and
formation water compositions that now character-
ize different portions of the Inmar Formation.
Calcite and dolomite are the most abundant
carbonate cements in the Inmar Formation sand-
stones. Calcite is most common in outcrop
samples whereas dolomite, ferroan dolomite and
ankerite are most abundant in subsurface samples
(Table 2). In the sandstones, diagenetic calcite
commonly occurs as a partial to complete replace-
ment of detrital grains, and also fills fractures in
some clasts. Calcite also fills pores (Fig. 3a), in

many cases coating previously crystallized diage-
netic clay minerals. In some samples, calcite with
or without anhydrite are the final diagenetic
phases, and completely occlude remaining poros-
ity. In other samples, dissolution of diagenetic
calcite and creation of secondary porosity have
been observed (Fig. 3b). The 6l80 values of the
diagenetic calcite show considerable variation
and extend to significantly higher values than the
other carbonate minerals analysed (+21.3 to
+32-6%,; Table 3). The 613C values for these
samples range from - 4.2 to +3.2%0(Table 3).
The carbonates of the Qeren Member are domi-
nated by fine-grained calcite, although dolomite
can be important locally (e.g. sample A1-32, Table
2). Minor quantities of sparry (Fig. 3c) and
coarsely crystalline, late diagenetic (Fig. 3d) cal-
cite are also present in many samples. Compared
with diagenetic calcite from the sandstones, the
Qeren Member calcite has a relatively narrow
range of 6l80 (+20.9 to +23.5%0)and dI3C ( - 1.3
to +l.l%O)values (Table 3).
Diagenetic siderite is common only in shales of
the Inmar Formation, where it occurs together
with pyrite. Three samples from the northern
Negev have 6l80 and 6I3C values of +24.4 to
+26-5%0and - 1.1 to +0.8%", respectively (Table
3).
Dolomite and ferroan dolomite/ankerite are
very common late diagenetic cements in subsur-
face samples of the Inmar Formation sandstone,
occurring as pore-filling cement (Fig. 4a,b) and as
replacement of detrital grains (Fig. 4c) or pre-
existing calcite. The dolomitic cements are some-
times coated by later anhydrite (Fig. 4d) and
calcite. By comparison, dolomitic cement is rare
in outcrop samples from Gebel Maghara, and was
not observed in outcrop samples from Makhtesh
Ramon (Summers, pers. comm.). Moreover, the
ankeritic cement that is locally abundant at Gebel
Maghara is texturally very early, and unlike the
late massive dolomitization that characterizes
subsurface samples.
A narrow range of 613C values was obtained for
the dolomitic samples ( - 2 - 1 to +0.2%0; Table 3),
regardless of sample location. In contrast, the 6 l 8 0
values of the late dolomitic cements (+18.4 to
+25.8%0; Table 3) vary systematically with
present burial depth and borehole temperature
(Fig. 5): South-Central Negev (30-35"C), +25.6
to +25.8%0;Central Negev (55-65"C), + 2 2 - 7 to
+23.8'X0; Judea Mountains (65-75"C), +21.1 to
+21.8%0; northern Negev (80-100C), +19.8
to +21.8%0. Figure 5 shows that a near linear
decrease in the oxygen isotope composition of
Carbonate minerals. southern Israel 155
dolomite occurs with increasing burial depth and
temperature from south-eastern to north-western
Israel. Only the (early) ankerite from Gebel
Maghara does not fit this pattern (Fig. 5).
DISCUSSION
Marine carbonate rocks normally have 613C
compositions of about O f 3 % 0 , as do cements
derived by dissolution of pre-existing carbonate
(Longstaffe, 1983,1989;Lundegard & Land, 1986).
The 6C values of most carbonate minerals from
the Inmar Formation ( - 4.2 to +3.2%0, average
- 0.5%0for 47 samples, Table 3) suggest such an
origin, i.e. dominantly normal marine carbon res-
ervoirs were involved in carbonate precipitation,
especially for the marine calcite of the Qeren
Member ( - 1.3 to + l . l % ) , the dolomitic cements
( - 2 - 1 to +0-2"/,) and siderite [ - 1.1 to +0.8%0).
However, the larger range obtained for diagenetic
calcite from the Lower and Upper members of the
Inmar Formation ( - 4.2 to +3.2%0)suggests that a
variable contribution was also made by carbon
derived from degradation of organic matter during
burial.
The dl80 values of the siderite [+24.4 to
+26.5%0)from Inmar Formation shales are typical
of crystallization from evolved seawater at rela-
tively low temperatures, after pyrite, early in the
diagenetic history. By comparison, the wide range
in dl'O values of diagenetic calcite from both the
Upper and the Lower members requires a pro-
longed interval of crystallization, consistent with
the range in carbon isotope compositions
described earlier. Calcite formation began very
early and continued throughout diagenesis, both
before and after dolomite crystallization. The
highest values (up to +32.6%0)could reflect early
calcite formation from evaporated seawater at low
temperatures (e.g. 6 ' ' 0 ~ , , . , ~up
~ ~to +3.7%0 at
25C). The lowest 6l80 values (+21.3%0)are com-
patible with later calcite crystallization from
brines of similar composition at the maximum
temperatures recorded for current formation
waters in the Inmar Formation (e.g. 104"C, Table
1).Most calcite probably formed at intermediate
temperatures. For example, present formation
water at 2567 m depth in the Beer Sheva 1 bore-
-
hole has a temperature of 76C and a 6'*0 value
of 0.47% (Table 1). Calcite from near this interval
has a 6l80 value of +21.5"/00(sample A1-27, Table
3), consistent with oxygen isotopic equilibration
under similar conditions. The d l 8 0 values of cal-
cite from the limestones of the Qeren Member
156 A. Ayalon and F. J. Longstaffe

Fig. 4.Diagenetic dolomitic cements from the Inmar Formation. (a) Pore-filling, sparry, ferroan dolomite cementing
detrital quartz (Barbur 1,Upper Member, A1-5). The SEM photomicrograph illustrates the highly corroded surface of
quartz grains (lower left) in contact with dolomite cement, a feature that is typical of subsurface samples. (b) SEM
photomicrograph of sparry, massive, ferroan dolomite/ankerite (Qeren 1, Upper Member, A1-8). This dolomitic
cement typically fills pores and/or replaces earlier carbonates (both calcite and dolomite). (c) Thin-section
photomicrograph (cross-polarized light) of dolomite (Do) replacing quartz (Qz) (Barbur 1, Upper Member, A1-5). The
surfaces of detrital quartz grains have been highly corroded. Dolomitizing fluids also have penetrated grain centres
along microfractures (centre of photomicrograph). Quartz overgrowths (lowermost left hand corner) also have been
partially dissolved and replaced by secondary dolomite. Width of view=5 mm. (d) SEM photomicrograph of a
complex mixture of diagenetic cements replacing grains and filling pores (Barbur 1,Upper Member, A1-4): kaolinite,
upper right hand corner: ferroan dolomite (DO) overlying earlier mat of illite/smectite, centre; anhydrite (AN),centre
and left. This generation of anhydrite coats the secondary dolomite.

(+20.9 to +23.5'XU) are far too low to reflect pri-
mary crystallization from seawater. Instead, these
results indicate that re-equilibration of calcite has
occurred at higher temperatures during burial,
and that substantial erosion has occurred to
expose Qeren Member limestones at Gebel
Maghara (Fig. 1).
The inverse relationship between burial depth
and 6l80 value of the late dolomitic cements (Fig.
5) is explored further in Fig. 6 by a comparison
between present formation water 6l80 values and
those that can be calculated using the spread of
secondary dolomite 6' '0values, current subsur-
face temperatures and the dolomite-water oxygen
isotope geothermometer of Land (1983). Figure 6
shows that in the northern Negev (boreholes
Qeren 1, Hazerim 1, Beer-Sheva 1)and the Judea
Mountains (boreholes Dabeshet 1, Tsia l ) , the
diagenetic dolomites are in oxygen isotopic equi-
librium with existing formation waters. The mod-
erately high Ca/Mg ratios of formation waters in
southern Israel (Table 1) have been previously
attributed to dolomitization (Bentor, 1961;
Starinsky, 1974; Starinsky et al., 1983). Together,
these isotopic and chemical data provide strong
evidence that the dolomite crystallized from these
 Carbonate minerals, southern Israel 157

South-Central
Nezev
30-G"C
(boreholes 1 & 2)

Fig. 5. Burial depth versus 8'0

-- E 1500 Central Negev
55-65C
values of dolomite, ferroan 5n (boreholes 3 & 4
dolomite and ankerite, Inmar a" 2000
Formation. Sample localities are Judea Mountains
also given: boreholes 1 & 65-75OC
2=Makhtesh Qatan 1 & 2; (boreholes 5 & 6)
boreholes 3 & 4=Daya 1 & Barbar 1;
boreholes 5 & 6=Tsia 1 & Dabeshet Northern Negev
1;boreholes 7, 8 & 9=Qeren 1, 3000 80-1000c
(boreholes 7, 8 & 9)
Hazerim 1 & Beer Sheva 1. The
range of borehole temperatures
(calculated from downhole electric 3500 I . " ' I " " I " . ' I ' ' . a I . ' . ' I " ' -

logs) at sample depths for these 18 20 21 22 23 24 25 6

localities is also given. &I *O Ro (SMOW) of Dolomite

0-
Fig. 6. Comparison between the
oxygen isotope composition of
present formation water and the
fluid involved in dolomitization. 20 -
The shaded areas show the
measured range of formation water
6'"O values and the spread of
temperatures for the Inmar
-
E 40 -
Formation in the Northern Negev, E
the Judea Mountains and the *
Central Negev (from Fleischer et 2 Central Negev
a]., 1977; Nativ, 1984). The areas
enclosed by heavy lines indicate,
z
G
60-
+23.8) Judea
for current borehole temperatures, Mountains
the range of formation water P O 80 -
values calculated using the
maximum and minimum oxygen
isotope values obtained for
secondary dolomite (shown in 100 -
parentheses) from each locality.
The P O values for the
dolomitizing fluid were calculated 120 I 1 I
using the dolomite-water equation -10 -5 0 5
of Land (1983):
1000 lna=3.14 x (10'T ") - 2.0. 6' '0 760 (SMOW) of Formation Water

brines at or near current burial temperatures;
hence dolomitization must have occurred after
the Upper Miocene to Pliocene culmination of
orogenic activity. More specifically, because late
dolomite is virtually absent from outcrop in
the Gebel Maghara and Makhtesh Ramon areas
(Fig. I), it seems that the present topography of
southern Israel and northern Sinai was largely
established prior to dolomitization. All of these
conclusions are consistent with the petrographic
observations that most dolomite formed late.
Figure 6 also illustrates that formation waters in
the Central Negev (boreholes Daya 1 and Barbur
I) have P O values that are 3 4 % " lower than
those predicted for dolomitization at these sites at
present subsurface temperatures. The formation
waters also contain much lower total dissolved
solids than the brines sampled at the Qeren 1,
158 A. Ayalon and F. J. Longstaffe
Hazerim 1 and Beer-Sheva 1 boreholes (Table 1).
These data indicate a significant contribution of
meteoric water to the Inmar Formation after the
post-Upper Miocene to Pliocene dolomitization.
However, the secondary dolomite has retained the
oxygen isotope signature of the brine from which
it formed; isotopic exchange with later fluids has
not been important.
A Pleistocene timing for the influx of meteoric
water has been previously indicated by Starinsky
& Katz (1978) and Ilani et al. (1988). Outflow of
pressurized brines from the Jurassic aquifer first
occurred during the Late Miocene because of the
opening of the Dead Sea Graben (Steinitz et al.,
1978; Ilani et al., 1988). However, brine discharge
again was activated in the Pleistocene because of
the downfaulting of the Dead Sea Rift (Ilani et a].,
1988). In the latter case, substantial infiltration of
meteoric water into the Jurassic aquifer was made
possible by the long periods of humid climate that
characterized the Pleistocene in this area (Issar,
1979, 1981).
It is conceivable that the lack of agreement
between calculated and measured formation
water 6l80 values in the Central Negev resulted
from a significant change in temperature, rather
than water composition, since dolomitization.
However, we consider this possibility to be
unlikely. The present geothermal gradient has
prevailed in the area since the Early Tertiary, and
gradients before that time were higher, not lower
(Feinstein, 1985).
SUMMARY
Late diagenetic, dolomitic cements from Lower
Jurassic sandstones of the Inmar Formation are in
isotopic equilibrium with present brines in sev-
eral deep boreholes situated in the northern
Negev and Judea Mountains of southern Israel.
The 6l80 values of the secondary dolomite
decrease systematically with increasing tempera-
ture (and depth in the borehole). This behaviour
suggests that dolomitization post-dated the main
tectonic activity (Late Miocene-Pliocene) in
southern Israel. Because of the scarcity of late
dolomite in outcrops of the Inmar Formation, we
also conclude that the present topography of
southern Israel and northern Sinai was estab-
lished prior to dolomitization. We can further
speculate that the westward (Pliocene?) migration
of the brines responsible for the late dolomitiza-
tion displaced any liquid hydrocarbons that
might have been present in the Negev.
In contrast to the Northern Negev and the Judea
Mountains, Inmar Formation waters from bore-
holes in the Central Negev region are substantially
depleted of l80relative to values predicted for
isotopic equilibrium with the secondary dolo-
mite. This change in composition reflects post-
Pliocene (Pleistocene?) influx of meteoric water.
This water mixed with, and(or) partially flushed,
pre-existing brines from the Inmar sandstones
in this region, and is probably responsible for
halting dolomitization.
ACKNOWLEDGMENTS
We thank M. Goldberg for outcrop samples used
in this study, D. Caird for her assistance in the
laboratory and M. Dvorachek for his technical
assistance with the SEM. Special thanks go to M.
Matthews and I. Perath for their critical reading of
the manuscript. Portions of this research were
made possible through the financial support of
the Natural Sciences and Engineering Research
Council of Canada (F.J.L.). We also thank Drs
Christoph Spot1 and Mark Wilkinson for their
reviews of an earlier version of this paper.
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