Or~!ani (ieochemi~trl. Vol I. pp. 237 Io 241 0146- 63~0' 79 1201-0237502.

00/0
,~5 Per gamon press Li d 1979. Pr i nt ed in Gr eat Br i l ai n
The role of kerogen constituents in oil generation
in the Gevar'am Formation (Lower Cretaceous), Israel
O. AMIT
Oil Research Division, Geological Survey of Israel, 30 Malkhe Yisrael St. Jerusalem~ Israel
and
Z . A I Z E N S H T A T and I. P I N S K I
Energy Research Center, Dcpartment of Organic Chemistry, Thc Hcbrcw University of Jcrusalcm,
Israel
(Recei red 22 Au~lust 1978 ; accept ed in reri sed, / orm 3 December 1978)
Abstrac! Kerogen from various samples of the Gcvar' am Formation (Early Cretaceous, Israel) were
analyzed for their elemental composition, and by I.R. and ESR spectroscopy. Thc results were compared
with other organochemical characteristics of the basin (Amit, 1978. Bull. Am. As,ww. Pet. Geol., V. 62~
p. 827 836). The types of organic material and their rolc in thc formation of oil were investigated.
It appears that the kerogen is mostly constituted of tcrrcstrially derived organic mattcr. A small amount
of marine-dcrived organic matter is also inferred. The kerogen of terrestrial origin is a poor oil produccr
and is expected to generate oil only at a higher stage of maturation than the Gevar' am Formation
has attained. Any hydrocarbons that have been gcncrated in this formation wcrc probably generated
from that part of the kerogen thought to be marine derived. Thus the Gevar' am Formation is considcrcd
as a potential sourcc rock which has gencratcd only a small amount of oil.
I NTRODUCTI ON
THI! GEOL(X;-ICAL associ at i on of t he gray-bl ack shales
of t he Ge va r ' a m For mat i on with sands and car-
bonat es of the Hel ez For mat i on in which oil was
found led t o the concept that this oil was deri ved
from the Ge va r ' a m shales (Cohen, 1971. 19761. Thc
high concent r at i on of gaseous hydr ocar bons in the
Ge va r ' a m shales also suppor t s this idea (Shenhav and
Shoresh. 1972).
A study carri ed out on somc or ganochemi cal
charact eri st i cs of the Ge va r ' a m For mat i on (Amit,
19781 suggested that the rat i os of total ext ract abl es/
or gani c car bon and t ot al hydr ocar bons / or gani c car-
bon change with depth. The ratios were descri bed as
being lowest in the sampl es taken from dept hs of
about 1500m, i ncreasi ng in the samples from the
1600 1900m i nt erval and decreasi ng agai n in the
samples from a 3100- 3800m depth. Howevcr, this
pattern, which appar ent l y follows the scheme of hy-
dr ocar bon gener at i on (Tissot et. al., 19741 and which
shoul d i mpl y a high degree of mat ur at i on (Albrecht
c t a l . , 19761 in the deepest samples, is not in accord
with the relatively low exper i ment al values of vitrinitc
reflectance. These values range from 0.45 to 0.55 in
the samples from the 1500 1900m i nt erval and from.
0.55 to 0.65 in the deepest samples (Amit, 1978).
The present study of t he geochemi cal charact er-
istics of the kerogen was pr ompt ed by the need to
clarify this di screpancy. It was also hoped that the
t ype of or gani c mat t er as well as t he intensity of dia-
genesis which later t ook place coul d be det ermi ned
from this study.
237
The study was carried out on core sampl es from
t he 1600-1900 and 3100- 3800m intervals. A detailed
descri pt i on of the f or mat i on and the geol ogi cal setting
was given by Cohen (1971, 19761. Sampl e l ocat i ons
and a bri ef summar y of the rel evant geol ogy arc de-
scribed by Ami t (1978).
METHODS
Sampl es previ ousl y ext ract ed by benzene + met h-
anol were t reat ed with HC1 and subsequent l y with
HF: HCI 3:1 to el i mi nat e their car bonat e and silicate
minerals. The resi due of this t reat ment cont ai ned, in
addi t i on to the organi c mat t er, about 50",. pyrite. Thc
residues werc split: one batch was t reat ed with
LiAIH4 and the ot her with HNO 3 (see discussions
by McHugh et al., 1978, and Saxby, 1970). The ele-
ment al composi t i on and t he infrared {I.R.) spectra of
the bat ch treated with HNO 3 revealed a st rong oxi-
dat i on of the kerogen. Therefore, in the study of ele-
ment al composi t i on and I.R. spectra, only kerogens
t reat ed with LiAIH4 were consi dered. The dest ruct i on
of pyrite was checked t hr ough the di sappear ance of
its peaks in the X-ray analysis. The el ement al analysis
for C, H, N, S was carried out by mi croanal ysi s, Most
samples have a high ash cont ent which was deter-
mi ned as Ti O2 by X-ray analysis: therefore, oxygen
was cal cul at ed by difference on an ash-free basis. No
fluorides were det ect ed by X-ray analysis.
Stepwisc pyrolysis experi ment s werc carri ed out in
a ni t rogen at mospher e on t wo samples, from which
pyrite was el i mi nat ed by HNO3. Thc samplcs wcrc
heat ed to a maxi mum t empcr at ur c of 600 C, Loss
238 O. AM~T, Z. AIZENSHTAT and I. PINSKI
Table 1. Elemental composition of kerogen after LiAIH4
treatment lash-free)
Depth C H O
Sample ~m) (o) (,,) (!~,) H/C O/C
H22C3 1725 61.2 6.2 27.9 1.2 0. 34
B9 1845 65.0 6.6 23.7 1.2 0. 27
G V* 1980 64.1 6.4 25. 0 1.2 0.29
AS2CI 3180 68.6 6.2 22.3 1.1 0.24
AS2C2 3665 68.9 6.4 18.3 1.1 0.20
AS2C3 3840 70.6 6.4 17.9 1. I 0.19
* After Glattstein (1976L
of weight and ESR par amet er s were measur ed every
50' C, and el ement al analysis of solid resi due and the
amount of liquid ext ract abl es were measur ed after
300C.
ELEMENTAL COMPOSI TI ON
The analysis of C, H and O in kerogens cal cul at ed
on an ash-free basis is gi ven in Tabl e 1. The at omi c
rat i o H: C is about 1.2 in t he shal l ow samples and
1.1 in t he deep ones. The at omi c rat i o O: C is hi gher
in the shal l ow samples, about 0.3, and decreases to
about 0.2 in t he deepest ones.
When these rat i os are pl ot t ed on Tissot et al. (1974)
di agr am of kerogen evol ut i on paths, the fol l owi ng
concl usi ons can be dr awn:
1. The t ype of kerogen of t he Gevar ' am For mat i on
is somewher e bet ween Type II and Type III (Fig. 1).
2. All t he sampl es fall wi t hi n a range which indi-
cates i mmat ur i t y with respect to oil generat i on. It
shoul d be noted, t hough, that the vi t ri ni t e reflectances
for these sampl es do not agree with Dow' s (1977) rela-
t i onshi p of reflectance to el ement al composi t i on
(Fig. 2). On the basis of Fig, 2, the deepest Gevar ' am
sampl es (i.e., AS2 CI t hr ough AS2C3) woul d be
expect ed to have reflectance values less t han 0.4, but
the measur ed reflectances are between 0.55 and 0.65.
I . fl
/ IT A S 2 C 2
I Q ,
0 . 5
B 9 G V H 2 2 C 5
e A S 2 C I
I I A T O M I C O / C
o. f o . 2 0 . 3 0 . 4
Fig. 1. Evolution path of kerogens after Tissot (1974L
GV--aft er Glattstein (1976).
Infrared spect ra of all kerogen samples (Fig. 3)
reveal t wo st r ong bands, one at 2900cm 1, t he peak
of t he sat urat ed C - - H groups and one at 1600 cm- 1
which pr obabl y represent s the ar omat i c C ~ C bond.
It is i nt erest i ng to not e t hat at t he wavel engt h of
1700- ~cm, which is t he expressi on of C ~ O func-
t i onal groups, no peak was observed. The intensity
of the C~--C rel at ed band is st r onger t han that of
t he sat urat ed C - - H groups, but nei t her of t he bands
changes not i ceabl y with buri al depth. A change in
the I.R. spect ra as a funct i on of dept h was descri bed
for t he Doual a Basin by Dur and and Espitali6 (1976).
ESR P A R A M E T E R S
Measur ement s of ESR par amet er s were conduct ed
on kerogen samples which cont ai n pyrite as well as
on sampl es t reat ed with HNO3 and some t reat ed with
LiAIH4 (Table 2). The results ar e similar in pri nci pl e
to t hose of Gl at t st ei n (1976). The Ng values of the
differently t reat ed kerogens show limited variability.
Vari abi l i t y is al so smal l among samples which were
i l L I P T I N I T I C
o R
. ~ . K E R O G E N
1.9
1.0 /
/
o . . f - /
K E R O G E N
0 . 6 i / 1 7 / / I - \
0 . 4 [ I I
0.1 0 .2 0 .3 A T O M IC O / C
Fig. 2. Evolution path of kerogens after Dow (1977). GV--aft er Glattstein (1976).
Oil generation in the Gevar'am Formation 239
A r o m a l i c
C=C
H 2 2 C
AS 2 C3
WAVE ~ U U B E R (cu~
Fig. 3. I.R. spectra of Gevar'am kerogens; H22C3 represents the shallow samples, AS2C3 the deep
ones.
taken from the different depths. Although the Ng
values of the deepest samples appear to be slightly
higher, they are in the same order of magni t ude
(Aizenshtat e t a l . , in prep.).
Systematic changes in ESR paramet ers as a func-
tion of dept h or pal eot emperat ure are discussed by
Pusey (1973). The ESR parameters of the Gevar' am
samples show only small changes with depth, thus
indicating a similar and low degree of mat urat i on for
the Gevar' am Format i on over the whole basin.
Ng x 10 -18 spin/g
Depth With after
Sample (m) pyrite HNO3 LiAIH4 ~/-value
H31C2 1500 0.63 0.74 2.0036
H23C4 1555 0.7 0.8 2.0039
K 12 1725 1.4 1.6 2.0039
H22 1765 1.15 1.3 1.44 2.0039
B9 1845 1.0 1.1 2.0042
GV* 1980 1.25 2.0042
AS2CI 3180 2.6 2.2 2.0044
AS2C2 3665 2.2 2.35 2.0045
AS2C3 3840 1.4 1.7 2.0039
* After Glattstein (1976).
Table 3. ESR factors for kerogens in the stepwise pyrolysis experiments
Temp. Ng x 10 18 Linewidth Weight loss (Ag~)
Sample (C) spin/g g-value (G) H/C (o)
Ambient 1.7 2.0039 5.0 0.78
AS2C3 150 6.0 2.0037 5.5 6.3
200 4.4 2.0037 6.3 6.0
250 5.5 2.0037 5.8 5.7
300 34.7 2.0037 7.3 15.3
350 25.8 2.0037 7.2 12.0
400 22.1 2.0036 6.8 0.43 4.3
450 30.0 2.0034 7.5 7.5
500 14.0 2.0032 7.5 5.0
550 8.7 2.0036 10.2 0.28 5.4
600 1.7 1.3
Ambient 0.7 0.8
H23 150 2.4 2.0037 5.7 4.3
200 1. I 2.0037 6.3 6.7
250 7.0 2.0037 7.0 7.5
300 18.4 2.0037 7.5 11.5
350 10.5 2.0036 8.0 8.0
400 9.6 2.0034 8.0 0.55 8.0
450 25.6 2.0032 8.0 11.3
500 14.5 2.0032 7.7 2.4
550 12.5 2.0039 9.0 8.0
600 9.0 0.27 4.2
Table 2. ESR characteristics of kerogens
240 O. AMIT, Z. AIZENSHTAT and I. PINSKI
STEPWISE PYROLYSIS
Stepwise pyrolysis was carri ed out on t wo samples
of kerogen, one from a dept h of 1550m and the ot her
from 3800 m. Each sampl e was heat ed for 60 min. at
successively higher t emper at ur es (150, 200, 250, . . .
and 600' C). At the end of each heat i ng step, ESR
par amet er s and loss of weight were measured
(Table 3).
It was found that t he ESR par amet er s changed
sharpl y in bot h ker ogen sampl es after they were
heat ed to a t emper at ur e of 300C. The j ump in the
ESR values was accompani ed by a high loss of weight
(Fig. 4). The loss was about 15"/i, in t he deepest sampl e
and 12",, in t he shal l ower one. The composi t i on of
the volatiles was not det ermi ned. In addi t i on to the
volatiles, the ker ogen also generat ed a small amount
of l i qui d hydr ocar bon, 4.2~, in the shal l ow sampl e
and onl y 1.2~J,i in t he deeper one.
The changes in the ESR values dur i ng the stepwise
pyrolysis and the accompanyi ng loss of weight
(Table 3) i ndi cat e t hat the ker ogens of the ori gi nal
samples are still in or appr oachi ng the stage of hydro-
car bon generat i on. The gener at i on of mai nl y vol at i l es
above 3 0 0 C al so suppor t s the i nt er pr et at i on that the
kerogen of the Gevar ' am For mat i on was most l y de-
rived from a terrestrial source.
DISCUSSION
El ement al composi t i on of t he kerogen of the
Gevar ' am For mat i on indicates that t hough the
or gani c mat t er was mai nl y deri ved from a terrestrial
source, t here was also some mar i ne cont r i but i on.
A compar i son of vari ous indices which reflect the
influence of diagenesis on or gani c mat t er raises the
fol l owi ng pr obl ems:
1. Ther e is a di screpancy bet ween the vi t ri ni t e re-
flectance values and the el ement al composi t i on
regardi ng oil mat ur at i on. The kerogens of all the
sampl es cont ai n a high concent r at i on of oxygen rela-
tive to t hat predi ct ed from t hei r vi t ri ni t e reflectance
values in t he Dow di agr am (Fig. 2). The reason for
this di screpancy is not clear.
2, Ther e is a cont r adi ct i on bet ween t he i mmat ur i t y
inferred from the el ement al composi t i on as compar ed
with t he increase in t he amount of t he ext ract abl es
in the 1500-1900m interval.
The possibility that this increase reflects cont ami -
nat i on and not necessarily mat ur at i on was con-
sidered. It appears that t he rat i o bet ween the satu-
rated hydrocarbons, ar omat i cs and resins as well as
the pat t ern of the sat urat ed hydr ocar bons of the
Gevar ' am shales differ compl et el y from t hose of the
N Z x ~ 18
40-
H23
~ A S 2 C 3
/ ~ S T
; I A
, o - "..i ~ \ 1" ,-7--.I V ~ . ~ '
1oo 300 .50o l oo 3 ~ .500
T (e.) , T ( e )
Fig. 4. ESR analysis and weight loss of kerogens after heating to 600C by 50C increments: H23
represents the shallow interval, AS2C3 the deep one.
Oil generation in the Gevar' am Format i on 241
t wo pot ent i al sour ces of c ont a mi na t i on, i.e. t he diesel
oil whi ch is s omet i mes used i n dr i l l i ng and f r om t he
Hel ez oil f ound near t he Ge v a r ' a m basi n.
Leyt haeus er (1974) c ompa r e d t he condi t i ons necess-
ary for h y d r o c a r b o n gener at i on f r om di fferent t ypes
of ker ogen. He s howed t hat ker ogen i nt er pr et ed as
mar i ne- der i ved begi ns t o gener at e hydr oc a r bons at a
l ower level of di agenesi s t ha n does t er r est r i al mat t er .
On t hat basi s it is bel i eved t hat t he i ncr ease i n hydr o-
c a r bons and ot he r ext r act abl e bi t ume ns wi t h i ncreas-
i ng de pt h in t he Ge va r ' a m Fo r ma t i o n have been
gener at ed mai nl y f r om t he mar i ne- der i ved com-
pone nt s of ker ogen, whi l e t he t er r est r i al l y der i ved
ker ogen is still in t he i mma t ur e st age wi t h r espect
t o h y d r o c a r b o n gener at i on.
It seems t hat t he el ement al c ompos i t i on of t he
ker ogen mai nl y expr esses t he t erest ri al l y der i ved
or gani c mat t er whi l e t he mi nor c ont r i but i on of t he
mar i ne or gani c mat t er is mas ked by it.
3. The r el at i ve decr ease i n t he r at i o of t ot al ext r ac-
t abl es / or gani c c a r bon and of ext r act abl e h y d r o c a r b o n /
or gani c c a r bon in t he sampl es of t he 3100- 3800m
i nt er val was i nt er pr et ed earl i er as a f eat ur e r epr es ent -
ing an advanced st age of oil ge ne r a t i on (Ami t , 1978).
However , t he l ow vi t r i ni t e refl ect ance val ues whi ch
i ncr ease l i t t l e wi t h dept h, t he new da t a on t he si mi -
l ari t y in t he I.R. and ESR spect r al da t a r ecor ded for
ker ogens of t he shal l ow i nt er val and t hose of t he deep
ones, and t he el ement al compos i t i on, whi ch even i ndi -
cat es i mma t ur i t y for t he whol e sequence, do not sup-
por t an advanced level of di agenesi s in t he deeper
sampl es. Fur t he r mor e , it appear s t hat si nce 2000m
of t he ove r bur de n t hi ckness of t he deepest sampl es
are of Neogene age, most l y Pl i ocene and younger
(Ami t , 1978), t he l engt h of t i me dur i ng whi ch t he Neo-
gene ove r bur de n i nf l uenced h y d r o c a r b o n gener at i on
was r el at i vel y mi nor . On t he ot her hand, it mi ght
be t ha t under such a t hi ck ove r bur de n t he sedi ment s
become mor e c ompa c t e d and, as a consequence, mor e
hydr oc a r bons were expel l ed. Si nce t he advanced com-
pact i on was not a c c ompa ni e d by a f ur t her ma t ur -
at i on, t he r at i o t ot al ext r act abl es / or gani e c a r b o n de-
creases in t he deepest sampl es. Co mp a c t i o n of shal es
wi t h de pt h of bur i al is well known. However its rol e
on hydr oc a r bons expul s i on is not well under s t ood.
The mi nor i nfl uence of t he Neogene ove r bur de n
on ma t u r a t i o n i mpl i es t hat a s i t uat i on in whi ch t he
Ge va r ' a m Fo r ma t i o n is cover ed by a t hi cker sequence
of Cr et aceous s edi ment s woul d be mor e pr omi s i ng
as a pot ent i al s our ce rock. Si nce t he ker ogen of t he
Ge va r ' a m Fo r ma t i o n exhi bi t s a t er r est r i al c ont r i bu-
t i on, it is suggest ed t hat when exposed t o mor e
advanced degr ee of ma t ur a t i on, t hi s f or ma t i on will
gener at e most l y gases and not l i qui d hydr oc a r bons .
Thi s eval uat i on was conf i r med in t he st epwi se pyr o-
lysis exper i ment s.
CONCLUSI ONS
1. The ker ogen of t he Ge v a r ' a m For ma t i on, whi ch
was depos i t ed in a mar i ne e nvi r onme nt , is compos ed
mai nl y of t er r est r i al l y der i ved or gani c mat t er . A smal l
c ont r i but i on of ma r i ne mi c r oor ga ni s ms is al so i n-
ferred.
2. The changes in ma t u r a t i o n i ndi ces bet ween ker o-
gen sampl es of t he 1600- 1900m i nt er val and t hat of
311X)-3800m are r a t he r smal l and t hus do not sup-
por t t he pr evi ous i nt e r pr e t a t i on of an advanced st age
of ma t u r a t i o n i n t he deepest par t of t he Ge va r ' a m
For ma t i on. It is suggest ed t ha t t he r el at i ve decr ease
i n bi t umi nous ma t t e r in t he deep i nt er val pr oba bl y
mai nl y i ndi cat es t he expul si on of hydr oc a r bons as a
resul t of e nha nc e d c ompa c t i on a nd not necessari l y
advanced ma t ur a t i on. The pr esent i nt e r pr e t a t i on of
t he or i gi nal da t a i mpl i es t hat t he Ge va r ' a m For ma -
t i on has r eached onl y a r at her l ow st age of mat ur i t y
t h r o u g h o u t t he whol e basi n.
3. Onl y a smal l a mo u n t of oil has been gener at ed
i n t he Ge va r ' a m For ma t i on, and it pr oba bl y came
mai nl y f r om t he mar i ne- der i ved par t of t he ker ogen.
Ter r est r i al c ompone nt s are still i n t he i mma t ur e st age
wi t h respect t o oil gener at i on.
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