Chemical Geology 160 Ž1999.

19–38

Trace metals and organic geochemistry of the Machiques Member

žAptian–Albian / and La Luna Formation
žCenomanian–Campanian /, Venezuela
Margarita Alberdi-Genolet ) , Rafael Tocco
PDVSA-INTEVEP S.A. Apdo. 76343, Caracas, 1070 A, Venezuela
Received 14 January 1998; accepted 23 February 1999

Abstract

Two proposed source-rock sequences in the Lower ŽAptian–Albian. and the Upper ŽCenomanian–Campanian. Creta-
ceous sediments of the Perija´ Range, Maracaibo Basin, were geochemically analyzed in order to find environmentally
controlled characteristic fingerprints. Trace metals and sulfur concentrations were found to be closely related with the
physicochemical conditions during deposition of the rocks. Based on trace metal analyses and sulfur relationships with TOC,
the Aptian–Albian sequence ŽMachiques Member. shows alternate oxic and anoxic episodes close to the bottom-water
surface where mixed marine and terrestrial organic matter were deposited. The Cenomanian–Campanian sequence ŽLa Luna
Formation. persistently shows anoxic–euxinic conditions that allowed the preservation of marine organic matter. Ratios of
trace metals ŽV, Mo and Zn. characterize both Cretaceous sedimentary columns, however, some limitations are visualized in
using trace metals as correlation tools in further geochemical studies. Biomarker ratios are related to the organic matter type
and lithology. Some specific ratios and individual compounds allow a clear differentiation between these two sequences and
offer, in the context of d13C, an excellent tool for further oil-source rock correlation studies. q 1999 Elsevier Science B.V.
All rights reserved.

Keywords: Apon formation; La Luna Formation; Machiques Member; Trace metals; Biomarkers; Cretaceous anoxic events; Maracaibo Lake
Basin

1. Introduction 1982; Dill et al., 1988; Telnaes et al., 1991;

Trace metals, especially the elements in the first
transition series ŽV, Cr, Mn, Fe, Co, Ni, Cu, Zn.,
have been used as geochemical tools to understand
anoxic deposition of recent sediments and ancient
source rocks ŽErnst, 1970; Lewan and Maynard,
)
Corresponding author. M. Alberdi-Genolet, Ciencias de la
Tierra, Edf. Sur-1, PDVSA-INTEVEP, Urb. El Tambor, Los
Teques, Edo. Miranda, Venezuela.
Alberdi-Genolet and Lafargue, 1993; Mongenot et
al., 1996.. Trace metal concentrations, VrNi ratios
and nickel and vanadyl porphyrins have been exten-
sively used for oil–oil correlation studies ŽFilby,
1994.. A few studies on oil-source rock correlations
have been made ŽFilby, 1994. and also a few de-
tailed analyses of trace metals on source rocks show
an integration with the biomarker compounds in the
bitumens ŽOdermatt and Curiale, 1991; Telnaes et
al., 1991., whose significance is widely accepted to

0009-2541r99r$ - see front matter q 1999 Elsevier Science B.V. All rights reserved.
PII: S 0 0 0 9 - 2 5 4 1 Ž 9 9 . 0 0 0 4 4 - 3
20 M. Alberdi-Genolet, R. Toccor Chemical Geology 160 (1999) 19–38

assess paleoenvironmental information and oil-source
correlations ŽPeters and Moldowan, 1993..
In the present work, a group of trace metals and
biomarker compounds have been analyzed in two
Cretaceous sedimentary sequences proposed as
source rock of the Maracaibo Basin, the most impor-
tant oil producing area of Venezuela which accounts
for about 76% of the cumulative production Ž48,625
MMSTB, 1914–1996..
Most of the oils analyzed in Maracaibo Basin can
be correlated with the La Luna Formation based on
biomarker fingerprints ŽTalukdar et al., 1986; Gal-
lango and Tocco, 1994.. La Luna Formation, dated
as Cenomanian–Campanian, composed of carbonate
mudstones and cherts, has been recognized as the
principal source rock of Maracaibo Basin ŽHedberg,
1931; Gonzalez de Juana et al., 1980; Blaser and
White, 1984; Talukdar and Marcano, 1994; Talukdar
et al., 1985; Perez et al., 1996..
In the western limit of Maracaibo Basin, sec-
ondary volumes of hydrocarbons could have been
generated by the Lower Cretaceous sedimentary sec-
tions outcropping in Perija area ŽFig. 1.. The
Machiques Member ŽApon Formation. dated as Ap-
tian–Albian ŽGonzalez de Juana et al., 1980. is
composed by limestones and shales with abundant
organic matter and good potential for oil generation
ŽEscandon et al., 1993; Perez, 1996.. Nevertheless,
no geochemical oil-source rock correlation has been
firmly established.
In the present work, a group of trace metals and
traditional organic geochemical parameters ŽTOC,

Fig. 1. Geographical location of the sampling sites in Perija Range and generalized stratigraphic section.
 M. Alberdi-Genolet, R. Toccor Chemical Geology 160 (1999) 19–38
Rock–Eval, biomarkers. have been analyzed in these
two Cretaceous sections, outcropping in the Perija
area. The information derived from inorganic and
organic analyses has been compared in order to
search for diagnostic fingerprints, environmentally
controlled, which can be used for oil–oil and oil-
source rock correlations.
2. Geological setting
Deposition of the La Luna Formation under
anoxic–euxinic conditions was recognized by Hed-
berg Ž1931. and Galea Ž1989.. Macellari and De
Vries Ž1987. recognized that the La Luna Formation
in Colombia and Venezuela near the Colombian
border, contains numerous chert and phosphorite
horizons, which were attributed to the existence of
upwelling conditions at the time of deposition. More-
over, combinations of an oceanic anoxic event ŽOAE.
with geographically migrating upwelling, have been
proposed by Perez et al., 1996. Recently, Erlich et
al., 1997 concluded that restricted circulation and
stagnation of bottom waters were the reason for the
anoxic condition prevailing during deposition of the
La Luna Formation. A widely accepted model for the
origin of the La Luna Formation, therefore, does not
exist.
The Machiques Member is considered the sedi-
mentological response to a transgressive pulse
ŽMendez, 1989. correlated with a maximum flooding
surface dated around 111 m.a. ŽCanache et al., 1994..
It shows a very variable thickness around the Perijá
and Lake Maracaibo areas. The variable thickness
has been explained as a differential sedimentation
between these two areas, where a peneplaned-graben
of Jurassic age, controlled sedimentation by in-
creased subsidence in the Perija´ area ŽMendez, 1989..
There are very few sedimentary studies about
Machiques Member, however, Canache et al. Ž1994.
proposed a shallow water Ž1–60 m. depositional
environment.
3. Methodology
The La Luna Formation and the Machiques Mem-
ber sediments were sampled at Maraca creek, Perija
Range. Complementary core samples, also from Per-
21
ija area, were gathered in order to corroborate the
interpretations drawn up of inorganic and organic
parameters ŽFig. 1, Table 1..
The samples were dried and pulverized. The total
organic carbon ŽTOC. was determined in fifty-two
samples from the Machiques Member and fifty-three
samples from the La Luna Formation to determine
the quantity of organic matter in each sample. The
TOC was determined in carbonate-free samples, pre-
viously treated with HCl Ž2 N., using a LECO
CS-244 instrument.
The quality of the organic matter in all the sam-
ples Ž105. was evaluated using a common pro-
grammed temperature pyrolysis method, called
Rock–Eval pyrolysis. The Rock–Eval pyrolysis was
developed in each sample using an instrument
Rock–Eval II-Delsi. A flame ionization detector
ŽFID. measures organic compounds generated during
pyrolysis. The first peak Ž S1 . represents hydrocar-
bons that can be thermally distilled from a rock. The
second peak Ž S2 . represents hydrocarbons generated
by pyrolytic degradation of the kerogen in the rock.
The third peak Ž S3 . detects carbon dioxide generated
during temperature programming up to 3908C, and it
is analyzed using a thermal conductivity detector
ŽTCD.. The hydrogen index ŽHI. corresponds to the
quantity of pyrolyzable organic compounds from S2
relative to the TOC in the samples Žmg HCrg TOC.
and it can be successfully used to assess the oil
generation potential of the rock and the type of the
organic matter. The oxygen index ŽOI. is indirectly
related to the quantity of terrestrial organic matter in
the sample.
The temperature at which the maximum amount
of S2 hydrocarbons is generated is called Tmax . It is a
rough measurement of the thermal maturity of the
organic matter because of its dependency on the type
of organic matter. Thus, conclusions regarding ther-
mal maturity should be supported by other geochem-
ical measurements such as vitrinite reflectance and
biomarker parameters. In general terms, the begin-
ning of the oil window is located between 430 and
4358C.
Selected samples of the Machiques Member and
the La Luna Formation were extracted with
dichloromethane in a soxhlet extractor for 72 h. The
bitumen extract was quantified and separated by
silica–alumina column chromatography. Sequential
 22
Table 1
Biomarker ratios for the Machiques Member and La Luna Formation bitumens by GC–MS
Sample Formation %C 27 %C 28 %C 29 %20S %bb %22S TsrŽTsqTm. C 29TsrC 29 ab CU30 Diasteranes PrrPh C 29 ab rC 30 ab
Ž1. Ž1. Ž1. Ž2. Ž3. Ž4. Ž5. norhop Ž6. Ž7. Ž8.
UU UUU
MA-24 Machiques M. 37.2 20 42.8 50.9 63.4 53.5 0.93 0.38 1.40 1.30

M. Alberdi-Genolet, R. Toccor Chemical Geology 160 (1999) 19–38

UU UUU
MA-32 Machiques M. 35.7 26.2 38.1 55.9 56.6 n.d. 0.99 0.53 1.00 0.82
UU UUU
MA-50 Machiques M. 38.3 24.8 36.9 59.0 49.8 56 0.85 0.93 0.50 0.98
UU UUU
MA-65 Machiques M. 40.2 27 32.8 50.1 56.4 n.d. 0.99 0.72 0.80 0.57
UU UUU
MA-71 Machiques M. 37.7 28.2 34.1 51.9 59.9 56.9 0.99 0.7 0.70 0.58
UU UUU
MA-82 Machiques M. 41.4 30.5 28.1 53.3 58.9 n.d. 0.99 1.17 0.60 0.40
UU UUU
core sample Machiques M. 41 29 30 56 58 58 0.8 0.30 1.10 0.40
U
LU-100 La Luna 30 35.8 34.2 46.5 46.1 59.2 0.26 C 29 Ts not present not present 1.08
U
LU-106 La Luna 37.7 35.5 26.8 47.2 59.6 59.6 0.28 C 29 Ts not present not present 1.00 0.76
U
LU-124 La Luna 39.6 26.9 33.5 49.5 n.d. 48.7 0.26 C 29 Ts not present not present 0.94
U
LU-139 La Luna n.d. n.d. n.d. n.d. n.d. 49.5 0.17 C 29 Ts not present not present 0.80
U
LU-142 La Luna 41.1 29.7 29.2 49.8 46.9 57.2 0.29 C 29 Ts not present not present 0.96
U
LU-147 La Luna 37.4 28.2 34.4 n.d. 47.8 55.8 0.21 C 29 Ts not present not present 0.80
U
LU-154 La Luna 42.1 24 33.9 42.3 51.1 45.6 0.26 C 29 Ts not present not present 0.94
U
core sample La Luna 34 34 32 56 52 58 0.17 C 29 Ts not present not present 0.70 0.95
U
Low concentration.
UU
Middle concentration.
UUU
High concentration.
n.d.: Not determinate.
Ž1. %C 27 , %C 28 , %C 29 -steranes Ž m r z s 218. taking into account 5a Ž H ., 14bŽ H .,17bŽ H ., 20Sq20R.
Ž2. %20Ss 20SrŽ20Sq20R.=100 Ž m r z s 217., isomerization at C-20 in the C 29 5a Ž H ., 14a Ž H ., 17a Ž H .-steranes.
Ž3. %bbsbb rŽbbq a a ., m r z s 217, isomerization at the C-14 and C-17 positions in the 20S and 20R regular steranes.
Ž4. %22Ss 22SrŽ22Sq22R.=100 Ž m r z s191., isomerization at C-22 position in the C 31 17a Ž H .-hopane.
Ž5. TsrŽTsqTm. s18a Ž H .-22, 29, 30 Trisnorneohopaner18a Ž H .-22, 29, 30 Trisnorneohopaneq17a Ž H .-22, 29, 39-trisnorhopane.
Ž6. C 29 ab rC 29Ts sC 29 17a Ž H .-hopaner18a Ž H .-30-norneohopane.
Ž7.17a Ž H .diahopane.
Ž8.C 29 ab-30-nor-hopanerC 30 ab hopane.
 M. Alberdi-Genolet, R. Toccor Chemical Geology 160 (1999) 19–38
solvent changes Ž n-hexane, toluene and methanol.
allow separation of saturate, aromatic and polar frac-
tions.
Gas chromatographic analyses of the saturated
C15 q hydrocarbons were carried out with a HP-
5880 gas chromatograph using a 25 m-crosslinked
methylsilicone column. Temperature was program-
med from 115 to 2758C at 88Crmin.
Gas chromatographic–mass spectrometry analy-
ses were performed with a HP-5971 mass selective
detector ŽMSD., a quadrupole mass spectrometer,
coupled directly to a HP-5890 series II gas chro-
matograph. The GC–MS was equipped with DB-1
columns for saturated fractions analyses. The GC
temperature was kept at 1008C for 2 min then in-
creased from 100 to 2808C at 48Crmin and main-
tained at 2808C for 30 min. All biomarkers were
analyzed in a MID Žmultiple ion detection. mode for
MS data acquisition.
Biological markers or biomarkers are molecular
fossils, meaning that these compounds are chemical
fossils derived from former living organisms.
Biomarkers are complex organic compounds com-
posed of carbon, hydrogen, and other elements. They
are found in source rocks and oils with modest to
strong structural change from their parent organic
molecules in living organisms. Many biomarkers are
useful for establishing oil–oil relationships, oil-
source rock correlations and source rock depositional
environment. Other biomarkers allow us to differen-
tiate marine and terrestrial organic matter input. Ra-
tios of certain biomarkers are commonly applied as
thermal maturity indicators. The two most commonly
used ratios are those involving carbon atoms at the
C-22 position in the hopanes Ž%22S. and the C-20
position in the steranes Ž%20S..
Several specific biomarkers related with the type
of organic matter in the rocks were analyzed by
monitoring metastable reaction–gas chromatogra-
phy–mass spectrometry ŽMRM–GC–MS.. This spe-
cific analysis was developed by Moldowan Ž1997.
on two selected saturate fractions, coming from ex-
tracts of MA-32 rock sample ŽMachiques Member.
and LU-124 rock sample ŽLa Luna Formation..
Trace metal analysis was done on previously ex-
tracted whole rock samples to avoid migrated bitu-
men. A qualitative sweep, using X-ray fluorescence
ŽPhilips instrument, Rhodium anode. showed the
23
presence of Na, Al, Si, Ca, S, K, Ti, Fe, Sr, Zn, V,
Ni, Cr, Mo, As, U, Co and Ba, and allowed the
quantitation of Al Žaluminium. and Fe Žiron.. Trace
metals in low concentration Žppm. were analyzed by
ICP-OES Žoptical emission spectrometry coupled
with inductive coupled plasma.. Details of the
methodology have been published previously
ŽGonzalez et al., 1994..
Kerogen is a good substrate for analysis of vana-
dium and nickel contents where these elements are in
high concentration, the samples have low pyrite con-
centration and the only sulfide mineral is pyrite Že.g.,
carbonate-siliceous mudstones of Querecual Forma-
tion, Alberdi-Genolet and Lafargue, 1993.. However,
in clastic rocks with a large amount of pyrite, it is
difficult to obtain pure kerogens by flotation meth-
ods. In addition, the existence of pyrite and other
sulfide minerals, in the same sample, made it diffi-
cult to develop corrections of contaminant trace met-
als on pyrite ŽHuerta Diaz and Morse, 1990; Oder-
matt and Curiale, 1991..
The use of chromium reduction for the selective
removal of sulfur species ŽCanfield et al., 1986. has
proved to have a high degree of specificity. Unfortu-
nately, in our experiments, available commercial
reagents showed low concentrations of all the ele-
ments in the first transition series, which represent a
methodological difficulty. In consequence, trace met-
als were analyzed in whole rocks Žbitumen-free.. In
this paper, the relation of trace metals with organic
matter content ŽTOC. was searched in order to iden-
tify possible inorganic elements associated with or-
ganic matter. On the other hand, trace metals in rock
samples have been extensively used as environmen-
tal indexes ŽBrumsack, 1980; Calvert and Price,
1983; Ten Haven et al., 1987; Leventhal, 1988;
Jones and Manning, 1994; Mongenot et al., 1996.
with very good results.
4. Results and discussion
4.1. Organic geochemistry of Machiques Member
(Aptian–Albian)
The TOC Žtotal organic carbon. in Maraca Ravine
outcrops of the Machiques Member is good to excel-
lent Ž1–5.5%. in most samples ŽFig. 2.. The organic
matter is mature as shown by the Tmax Ž4458C of the
24 M. Alberdi-Genolet, R. Toccor Chemical Geology 160 (1999) 19–38

Ž5a , 17bŽ H ., 20S q 20R. in most of the samples

Fig. 2. TOC distribution for the Machiques Member and La Luna
Formation.
ŽMA-50, 65, 71, 41, Table 1. indicates marine or-
ganic matter during sedimentation ŽHuang and Mein-
schein, 1979.. This deduction is proved by the pres-
ence of C 30 -steranes, immediate indicators of plank-
tonic Žalgal. contributions to the organic matter
ŽMoldowan et al., 1990, Table 2..
The oleanane index Ž17%., a pentacyclic triter-
pane derived from angiosperms ŽMoldowan et al.,
1994., indicates secondary inputs of plant debris in
the organic matter ŽTables 1 and 2., which is also
supported by isotopic analyses results.
The ratio 13 Cr12 C, in selected kerogens ŽMA-24,
MA-38, MA-65 and MA-82., was measured by mass
spectrometry after converting the carbon to CO 2 .
Distinctive values of d13 C were found in the

Rock–Eval pyrolysis. and 1.0–1.08% R o Žreflec-

tance of vitrinite..
Maturity parameters from biomarker ratios as
%20S Ž%20Sr20S q 20R in the C 29 5a ,14a ,
17a Ž H .-steranes. with values ranging from 50 to
59% and %22S Žisomerization at the C-22 position
in the C 31 17a Ž H .-hopanes. with values of 53–56%,
show, in both cases, values very close to the equilib-
rium Ž%20S s 52–55%, %22Ss 55–62%, Peters
and Moldowan, 1993..
The values for the % bb as maturity parameter
Žisomerization at the C-14 and C-17 positions in the
20S and 20R C 29 regular steranes., measured by
GC–MS, are lower Ž50–63%. with respect to equi-
librium values Ž71%, Peters and Moldowan, 1993..
However, more selective analyses ŽMRM–GC–MS.
can eliminate most interference by coeluting GC
peaks, showing a bb percentage of 72%.
A plot of S2 Žhydrocarbons generated in Rock–
Eval pyrolysis. vs. TOC shows a predominantly type
II kerogen ŽFig. 3.. Petrographic analysis of the
kerogens shows undifferentiated amorphous material
Ž57%. with a mixture of herbaceous Ž13%. and
woody Ž15%. macerals. Biomarker analyses Žsee be-
low. allow us to infer a relationship between amor-
phous material in the petrographic analyses of kero-
gens and residual marine organic matter of bacterial
and algal origin.
The relative abundance of C 27 regular sterane Fig. 3. S 2 vs. TOC plots for the Machiques Member and La Luna
Ž5a , 17 = Ž H ., 20S q 20R. over C 29 regular sterane Formation.
 M. Alberdi-Genolet, R. Toccor Chemical Geology 160 (1999) 19–38 25

Table 2 Machiques Member ŽMA-24, 42, 71. show, respec-

Specific biomarker analyses of LU-124 and MA-32 bitumens by tively, 52, 22 and 25% of clays in the lithology,
MRM–GC–MS
which support the relationship between a clastic
MA-32 LU-124
component in the rocks Žshales. and diasteranes
Diterpane peak measurements by abundance. Nevertheless, diasteranersterane ratios
MRM – GC – MS (ppm) of compounds
increase with the maturity of the samples, then other
Rimuane 0.114 0.0685
Isopimarane 0.0944 0.178 biomarkers have been used to support this interpreta-
Beyerane 0.0322 0.0349 tion, such as, the presence of C 29 Ts.
Norisopimarene-1 1.14 3.85 The C 29 Ts Ž18a Ž H .-30-noneohopane. as well as
Norisopimarene-2 0.864 0.552 C30 ŽU .-17a Ž H .-diahopane were only registered in
Labdane-1 0.334 0.441
the Machiques Member samples. They have been
Labdane-2 0.302 1.53
used as organic indicators of oxic–suboxic condi-
Sterane ratios by MRM – GC – MS tions during sedimentation of clastic rocks. C 29 Ts is
4a Methylstigmastaner 0.214 0.425 supposed to be related to bacterial hopanoids precur-
stigmastane
sors that have undergone oxidation by clay-mediated
C 30 rC 27 qC 28 qC 29 q 0.04 0.07
C 30 -steranes acidic catalysis ŽPeters and Moldowan, 1993..
20SrŽ20Sq20R. C 29 Ž%. 58% 59% The isoprenoid ratio PrrPh, defined as redox
21-rŽ21-q27-. 41% 25% index ŽDidyk et al., 1978. shows similar values close
norcholestane Ž%. to units ŽTable 1. and more specific information
Triterpane ratio by MRM – GC – MS from sulfur content and trace metal was obtained to
Oleananeroleananeqhopane Ž%. 17% 1.5% understand the physicochemical conditions of depo-
sition.

Machiques Member Žy21.7 to y24.5‰ PDB. in
comparison to La Luna Formation kerogens Žy26.3
to y27.1‰ PDB.. Similar values to those observed
in the Machiques Member have been found in the
AptianrAlbian source rocks from the Sergipe Basin
in Brazil Žy23 to y27‰ PDB, Mello et al., 1988.
and other Aptian–Albian sequences ŽHofmann et al.,
1997.. The most accepted explanation for the enrich-
ments of values in the Lower Cretaceous sequences
with respect to Upper Cretaceous sequences is re-
lated to increased input of terrestrial organic matter
ŽArthur et al., 1985; Dean et al., 1986..
Rock lithology can be directly determined by
sedimentological description or indirectly inferred by
biomarkers rearrangements. An important contribu-
tion of diasteranes is characteristic of the Machiques
Member ŽTable 1, Fig. 4.. Diasteranersterane ratios,
measured on the saturated fraction of bitumens and
rock extracts, may be used to distinguish the
petroleum generated from carbonate as opposed to
clastic source rocks. The conversion of sterols to
diasteranes during diagenesis is believed to be cat-
alyzed by acidic sites of clays ŽSieskind et al., 1979..
A mineralogical analysis ŽX-RD. of three samples of
4.2. Inorganic geochemistry of Machiques Member
At least three populations of samples could be
differentiated in analyses of %S vs. TOC for
Machiques Member. One population shows a
pseudo-linear relationship between %S and TOC, the
second group is impoverished in sulfur content and
the third group of samples shows a clear enrichment
in sulfur content ŽFig. 5..
In the first population, the samples show a propor-
tionality of %S vs. TOC with Y-axis intercepts be-
tween 0 and 0,27. Linear relationships between these
two parameters have been used to identify sediments
deposited under oxygenated environments Ž Y-axis
intercept around 0%, Berner, 1970; Berner and
Raiswell, 1984. or euxinic conditions of sedimenta-
tion Ž Y-axis intercept around 1% to 2%, Leventhal,
1983.. When a comparison is done between Y-axis
intercept of the Machiques Member Ž0–0.27%. and
the intercept values reported for Black Sea sediments
Ž1% to 2%; in Leventhal, 1983., it is possible to
infer very weak euxinic conditions for the Machiques
Member. Perhaps anoxic conditions were established
in some episodes ŽwO 2 x - 0 mlrl H 2 O, Wignall,
 26
M. Alberdi-Genolet, R. Toccor Chemical Geology 160 (1999) 19–38
Fig. 4. Biomarker distribution for the Machiques Member and La Luna Formation bitumens.
 M. Alberdi-Genolet, R. Toccor Chemical Geology 160 (1999) 19–38
Fig. 5. %Sulphur vs. TOC plot for the Machiques Member.
1994., but with only a weak concentration of free
H 2 S Žeuxinic, Wignall, 1994..
Pyrite formation during early diagenesis is con-
trolled by pore-water concentration of sulfide, Eh,
availability of reactive iron and organic matter avail-
able in the environment. Other factors like sedimen-
tation rate, bioturbation and reactivity of the organic
matter are considered by Hieshima Ž1992.. Pyrite
formation during early diagenesis in some sampling
sites ŽFig. 5, group II. seems to be restricted. Avail-
ability of reactive iron seems to be a good reason for
the limestone samples with low TOC Ž25, 46. but
some other geological controls could be important
during sedimentation in sampling site 35 and 53.
Meanwhile, the third group of samples ŽFig. 5,
III. has enrichment in %S, indicating sulfide fixation
without a corresponding residual organic component.
This has been interpreted by Berner Ž1985. and Van
der Weijden Ž1993. as related to sedimentation under
euxinic conditions. Trace metal distribution supports
this kind of interpretation for the samples MA-79,
39, and 72. However, in oxygenated environments
similar distributions have been found when pyrite
formation continues during the diagenetic step, in
closed-pores with the abundance of Fe and carbon
being limited ŽCalvert and Karlin, 1991.. Trace metal
analyses support this conclusion for samples MA-29,
31, 28.
27
The absolute concentrations of major, minor and
trace elements is shown in Table 3, whereas normal-
ized concentrations of these elements, using Al as
detritus index and the standard black-shale, are shown
in Table 4 and Fig. 6 ŽVine and Tourtelot, 1970;
Mongenot et al., 1996..
Shale normalized trace-elements contents
Ž Trace-element contentrAl content. sample
s
Ž Trace-element contentrAl content. shales
Ž 1.
Mo normalized concentrations reveal major en-
richments in the trace metal distribution ŽFig. 6.. The
oceanic behavior of Mo in recent sediments has
potential as a proxy indicator of physicochemical
conditions ŽEmerson and Huested, 1991.. Concentra-
tions of Mo increase with increasing anoxic condi-
tions at the water-bottom surface. Several workers
reported Mo associated with humic acids in the
organic matter ŽNissebaum and Swaine, 1976; Calvert
and Price, 1983.. Other authors have reported associ-
ations with sulfur ŽGlikson et al., 1985. and they
consider a selective removal in solution as thyo-
molybdate during FeS precipitation ŽKorolev, 1958;
Bertine, 1972..
 28
Table 3
Concentration of trace, minor, major elements and interelementalic ratios for selected rock samples
Sample Zn Žppm. Ba Žppm. Mo Žppm. Cu Žppm. Ni Žppm. V Žppm. Co Žppm. %Al %Fe VrNi VrMo VrZn MorNi MorCu ZnrMo
MA-24 1400 n.d. 95 77 141 152 -1 6.9 3.00 1.08 1.60 0.11 0.67 1.23 14.74
MA-26 909 922 186 121 228 318 -1 2.87 1.28 1.39 1.71 0.35 0.82 1.54 4.89
MA-31 66 203 n.d. n.d. n.d. n.d. -1 1.4 1.2 n.d. n.d. n.d. n.d. n.d. n.d.
MA-32 3300 n.d. 828 108 810 1135 -1 3.7 1.9 1.40 1.37 0.34 1.02 7.67 3.99
MA-39 870 579 240 127 288 459 -1 6.34 3.04 1.59 1.91 0.53 0.83 1.89 3.63
MA-42 392 n.d. 47 19 79 469 -1 3.7 0.9 5.94 9.98 1.20 0.59 2.47 8.34

M. Alberdi-Genolet, R. Toccor Chemical Geology 160 (1999) 19–38

MA-46 79 227 n.d. n.d. n.d. 21 -1 n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d.
MA-48 63 123 n.d. n.d. n.d. 5.5 -1 0.3 1.9 n.d. n.d. n.d. n.d. n.d. n.d.
MA-53 161 136 1 64 60 151 50 1.00 0.34 2.52 n.d 0.94 n.d n.d n.d.
MA-61 73 292 n.d. n.d. n.d. n.d. -1 0.3 1.7 n.d. n.d. n.d. n.d. n.d. n.d.
MA-65 816 n.d. 136 52 238 892 -1 5.9 0.31 3.75 6.56 1.09 0.57 2.62 6.00
MA-68 730 493 72 76 247 300 -1 4.7 1.8 1.21 4.17 0.41 0.29 0.95 10.14
MA-72 1586 191 224 73 316 930 200 3.82 1.06 2.94 4.15 0.59 0.71 3.07 7.08
MA-79 835 240 194 118 532 1496 -1 9.4 493.00 2.81 7.71 1.79 0.36 1.64 4.30
LU-98 327 293 73 73 683 281 42 1.58 0.83 0.41 3.85 0.86 0.11 1.00 4.48
LU-100 33 n.d. 19 24 36 48 n.d 0.64 0.69 1.33 2.53 1.45 0.53 0.79 1.74
LU-106 880 n.d. 82 32 196 958 n.d 1.3 1.7 4.89 11.68 1.09 0.42 2.56 10.73
LU-108 1176 260 218 59 262 1765 n.d 3.5 1.12 6.74 8.1 1.5 0.83 3.69 5.39
LU-115 1313 201 89 44 185 1525 n.d 1.22 0.35 8.24 17.13 1.16 0.48 2.02 14.75
LU-119 1454 217 177 65 292 2112 n.d 1.13 0.43 7.23 11.93 1.45 0.61 2.72 8.21
LU-121 1573 297 126 128 425 4065 1 3.8 1.22 9.56 32.26 2.58 0.3 0.98 12.48
LU-125 1115 694 45 45 176 1497 119 3.1 0.84 8.51 33.27 1.34 0.26 1.00 24.78
LU-128 83 n.d. 44 28 60 232 n.d 1.3 0.66 3.87 5.27 2.8 0.73 1.57 1.89
LU-138 312 266 42 80 120 683 50 0.62 0.3 5.69 16.26 2.19 0.35 0.53 7.43
LU-141 1400 n.d. 126 42 209 1401 n.d 1.7 0.65 6.7 11.12 1.00 0.6 3.00 11.11
LU-145 360 238 30 38 109 462 n.d 1.23 0.43 4.24 15.4 1.28 0.28 0.79 12.00
LU-147 1910 775 62 100 393 1389 110 1.91 0.65 3.53 22.4 0.73 0.16 0.62 30.81
LU-151 974 654 192 57 174 1433 n.d 3.07 1.07 8.24 7.46 1.47 1.1 3.37 5.07
LU-153 590 940 56 100 1593 1085 n.d 2.61 0.97 0.68 19.38 1.84 0.04 0.56 10.54
X
9989 1118 2114 103 136 342 1108 27 1.98 0.79 3.24 10.76 0.99 0.3 0.76 10.85
X
10019 3085 309 127 109 303 1982 36 0.98 0.37 6.54 15.61 0.64 0.42 1.17 24.29
X
10049 679 386 83 64 204 1110 27 3.1 1.01 5.44 13.37 1.63 0.41 1.3 8.18
X
10100 97 190 -1 60 115 310 1093 1.07 0.21 2.7 n.d 3.2 n.d n.d n.d.
X
10128 296 325 42 67 1211 3899 n.d 0.31 0.32 3.22 92.83 13.17 0.03 0.63 7.05
X
10221 718 348 39 106 2137 1179 21 1.36 0.62 0.55 30.23 1.64 0.02 0.37 18.41

n.d.s No determination.
 M. Alberdi-Genolet, R. Toccor Chemical Geology 160 (1999) 19–38 29

Table 4
Normalized concentrations of trace metals for selected rock samples
Sample %TOC %Cmin %S Zn Ba Mo Cu Ni V Fe
MA-24 6.1 14 1.95 9.6 1 19.6 1 1.3 0.7 0.18
MA-26 5.7 46 1.52 15 2.45 93 4 4.9 3.7 0.18
MA-31 0.2 75 1.72 2.3 1.2 n.d. n.d. n.d 0.5 1.19
MA-32 10 57 2.88 42 1 320 2.9 14 10 0.21
MA-39 3.8 69 2.89 6.5 1 13 2 2.8 2.4 0.2
MA-42 2.6 79 1.01 5.04 1 18 0.5 1.3 4.2 0.1
MA-46 0.5 83 0.22 14 6.6 n.d. n.d. n.d 0.7 ) 1.19
MA-48 0.6 84 0.15 11 3.6 n.d. n.d. n.d 0.7 1.9
MA-61 0.7 88 0.3 11.7 7.6 n.d. n.d. n.d. 1.8 ) 1.7
MA-53 2.8 39 0.44 7.6 1 0.2 6.4 3.75 5 1.41
MA-65 5.4 33 1.86 6.6 1 32 0.8 2.5 5 0.02
MA-68 3.6 30 1.81 7.3 1.2 5.4 1.6 3.3 2.1 0.16
MA-72 4.2 31 1.24 19.7 0.6 20 1.9 5.2 8.1 0.11
MA-79 2.9 13 3.21 4.2 0.3 7 1.2 3.5 5.3 0.22
LU-98 3.8 49 1.07 9.8 1.4 6.8 4.6 27.8 5.9 0.21
LU-100 1.5 83 n.d 2.5 n.d. 44 3.7 3.6 2.5 0.44
LU-106 5.2 64 n.d 32 n.d. 93 2.5 9.7 25 0.5
LU-108 5.3 68 0.93 16 0.6 91 2 5 17 0.5
LU-115 5 54 0.54 51 1.2 107 3.6 9.7 42.4 0.5
LU-119 6.5 46 n.d 61 2 229 6 17 63 0.7
LU-121 4.5 55 0.82 20 0.6 49 3.4 7.2 36 0.13
LU-125 3.4 33 1.04 17 1.7 21 1.5 3.7 1.6 0.01
LU-128 1.3 73 n.d. 3 n.d. 50 2.2 2.98 6 0.21
LU-138 3.6 62 0.46 24 3.3 100 13 12.5 37 0.2
LU-141 5.1 59 1.17 39 n.d. 109 2.5 7.9 28 0.16
LU-145 5.4 41 n.d. 14 2 1 3 6 13 0.63
LU-147 7.2 51 0.53 48 3.1 48 5.2 13.2 25 0.14
LU-151 5.6 34 n.d. 15 2 94 2 4 16 0.61
LU-153 3.1 41 0.89 11 2.8 32 3.8 39.4 14 0.15
X
9989 6.3 62 1.3 27 8.2 77 6.9 11.1 19 0.17
X
10019 7.5 63 1.17 149 2.4 190 11.1 19.9 69 0.16
X
10049 5.3 44 n.d. 149 0.95 39 2 4.2 12 0.13
X
10221 2.53 77 1.01 25 1.9 42 7.8 101 29.3 0.19
X
10341 6.8 72 n.d. 37 3.9 146 14.2 28 39 0.002

Enhanced Mo and Zn enrichments in the
Machiques Formation samples ŽFig. 6. are related to
TOC ŽFig. 7.. However, logarithmic relationships
were found for the Machiques Member rather than
linear as previously reported ŽNissebaum and Swaine,
1976; Leventhal, 1988.. A possible explanation is
related to fixation mechanisms. At lower TOC under
suboxic–anoxic conditions and absence of H 2 S, Mo
and Zn, are weakly fixed by organic matter. Under
enhanced reducing conditions, with some H 2 S devel-
opment close to surface, organic matter is better
preserved. Mo and Zn are fixed onto organic matter
and, complementarily, Zn can form sulfur com-
pounds and Mo can be removed from solution as
thiosulfate, following Eq. Ž2. ŽKorolev, 1958;
Bertine, 1972..
FeS q MoO 2 S 2yq H 2 S q 2H q
™ FeS P Mo P S 3 Ž amorphous. q 2H 2 O
FeS P MoS 3 Ž amorphous. ™ FeS Ž tetr . q MoS 3 Ž 2.
Maximum enrichments of Mo and V in the MA-
32, 63–65 and 71–72 sampling sites coincide with
the highest TOC values ŽFig. 8. although vanadium
normalized contents Žas well as nickel. show a rough
relationship with TOC. Some intervals in the section
30 M. Alberdi-Genolet, R. Toccor Chemical Geology 160 (1999) 19–38

Fig. 6. Normalized concentrations of the trace metals and minor elements in the Machiques Member and La Luna Formation.

seem to have had anoxic Žeuxinic?. conditions dur- suggested based on TOC, HI, Mo and V normalized
ing their sedimentation ŽFig. 8. and cyclic events of distribution ŽFig. 8.. Previous geochemical studies
preservation of hydrogen-rich organic matter can be by Perez Ž1996., proposed a global OAE controlling
 M. Alberdi-Genolet, R. Toccor Chemical Geology 160 (1999) 19–38 31

Fig. 7. TOC vs. normalized concentrations of Mo and Zn in the Machiques Member.

Fig. 8. Vertical trends of Total Organic Carbon, Hydrogen Index, Mo and V over lithological section of the Machiques Member.
32 M. Alberdi-Genolet, R. Toccor Chemical Geology 160 (1999) 19–38
the d13 C distributions on kerogens in the lower part
of this sequence.
Mo and V normalized concentrations correlate
with enrichment of organic matter, but lower enrich-
ments of Mo are observed in comparison with V,
possibly related with a thin layer of H 2 S ŽEq. Ž2..
and poor removal from sea water during sedimenta-
tion.
In contrast, V ŽIV. could be incorporated into the
sediments following two path ways: Ža. by reduction
with H 2 S in euxinic environments ŽEq. Ž3.., or Žb.
by absorption to organic particles in anoxic sedi-
ments following Eq. Ž4. ŽBreint and Wanty, 1991..
H 2VO4y1 q H 2 S™VOq2
™ organic complexes Ž euxinic sediments.
VOq2 q H 2 S™V Ž OH . 3
™ clays Ž euxinic sediments. Ž 3.
H 2VO4y1 q Corg™VOq2
™ organic complexes Ž anoxic sediments. Ž 4.
No detection of Mo, Cu, V and Ni, coupled with
an enrichment in Fe, are observed in the samples
MA-46, MA-61, MA-48 and MA-31 ŽFig. 6. as a
typical trace metal distribution of oxic intervals. The
massive carbonates beds Ž46, 61, 48, 31, Fig. 8.
analyzed in this work show depleted contents of
trace metals and low concentrations of TOC. Thus,
spatial shifts in bottom water chemistry from anoxic
to oxic environments are possible. Behaviors like
that favor trace metal accumulation and organic mat-
ter preservation only during anoxic episodes of sedi-
mentation.
The nickel and vanadium content, VrNi ratios
and the relative abundance of the nickel and vanadyl
porphyrins have been applied as anoxic indicators in
ancient sediments, and have been used for oil–oil
and oil-source rock correlation studies ŽLewan and
Maynard, 1982; Lewan, 1984; Filby, 1994.. The
ratio VrNi shows an increase with increasing reduc-
ing conditions. The analysis of VrNi in whole sam-
ples Žboth metals roughly related to TOC. from
Machiques Member show relatively low values
Ž1.2–3.0. in comparison to the La Luna Formation
Žsee Section 4.3.. These differences could be inter-
preted as corresponding to conditions that are more
oxic.
Low enrichments in Cu and a rough direct corre-
lation with the Machiques Member sulfur content
could be interpreted as a replacement of this element
by iron within the pyrite structure or the co-precipita-
tion of other sulfide species.
Cobalt ŽCo. shows very low values in both the
Machiques Member and La Luna Formation ŽTable
4.. Co is easily solubilized during weathering and
unlike Ni does not form residual silicate minerals
ŽWedepohl, 1969.. Otherwise, restricted mobility for
Cu, Zn, Mo and V is reported in weathering situa-
tions ŽWedepohl, 1969.. The similarity in the distri-
bution of these elements for outcrops and core sam-
ples from the La Luna Formation ŽTables 3 and 4.
confirm this conclusion.
4.3. Organic geochemistry in the La Luna Formation
The TOC of outcrop samples ŽMaraca creek. from
the La Luna Formation, is good to excellent, ranging
from 0.5 to 8.5% ŽFig. 2.. The samples contain
mature organic matter with an average Tmax of 4408C
and vitrinite reflectance measurements of 0.95% to
1.04% R o .
Maturity parameters from biomarker ratios as
%20S Žin the C 29 steranes. with values ranging from
42% to 49% ŽGC–MS. and 59% in the sample
LU-124 ŽMRM–GC–MS, Table 2. suggest mature
organic matter. %22S Žisomerization in the C-22
position in the C 31 hopanes. with values ranging
from 45% to 59% ŽTables 1 and 2. corroborate that
the organic matter of the La Luna Formation, in this
sequence, has reached the oil window of hydrocar-
bon generation.
S2 vs. TOC plot ŽFig. 3. shows a type II kerogen.
S2 values Žpotential for hydrocarbon generation. con-
spicuously higher in the La Luna Formation than for
the Machiques Member corroborate a better oil-gen-
eration capacity for the Upper Cretaceous section.
Petrographic analysis shows 90% to 100% of
amorphous marine organic matter, in agreement with
previous studies ŽTalukdar et al., 1985.. Biomarker
analyses show a relative abundance of C 27 over C 29
abbŽ5a , 14b, 17bŽ H ., 20S q 20R. regular steranes
and abundance of tricyclic terpanes, which is consis-
tent with marine Žalgal. organic matter content.
 M. Alberdi-Genolet, R. Toccor Chemical Geology 160 (1999) 19–38
The C 30 steranes Ž4-desmethyl, C 30 sterane index,
Table 2., as straightforward indicators of marine
organic matter ŽMoldowan et al., 1990., show higher
values for the La Luna sample ŽLU-124. in compari-
son to the Machiques Member sample ŽMA-32..
These ratios indicate high chrysophyte algae input
during sedimentation of the Upper Cretaceous se-
quence.
Higher values of 4a-methylstigmastane for the La
Luna Formation sample than Machiques Member
sample ŽTable 2. also support a clear contribution of
algae in the Upper Cretaceous. 4a-Methylstigmas-
tane has a possible relationship to dinoesterol as
precursor molecule ŽRubinstein and Albrecht, 1975.
and dinoflagellates are the only proven major source
of dinoesterol ŽSummons et al., 1992..
Ratios of TsrTsq Tm Ž18a Ž H .trisnorneohopane
and 17a Ž H . trisnorhopane. between 0.17 and 0.29
for the La Luna Formation are characteristic of
organic matter in carbonate muds ŽMcKirdy et al.,
1983.; these ratios are very different from the ratio
found in the Machiques Member, very close to the
unit ŽTable 1, Fig. 4.. Certainly, TsrTsq Tm ratio
could be dependent on maturity and it could be
controversial to characterize both Cretaceous se-
quences, moreover, the concentration of diasteranes
and the sedimentological descriptions are in agree-
ment with a lithological interpretation.
Additional differences can be addressed by means
of diterpane and C21-norcholestane ratios ŽTable 2..
Diterpane compounds, derived from diterpenoids, are
widely distributed in the plant kingdom ŽNoble et al.,
1986, Table 2.. They show clear differences in both
Cretaceous samples because the La Luna Formation
Žalthough it has marine organic matter. show more
Labdane and Isopimarane. The C21-norcholestane is
a C 26 -sterane previously identified by Moldowan et
al. Ž1991..
Stable carbon isotope ratios in selected kerogens
ŽLU-98, 106, 124, 142 and 147. are very similar
Ž d13 C s y27‰ y26.3‰, PDB.. Systematic records
in the same section of Maraca Ravine ŽPerez et al.,
1996. show isotopic values around y27‰ with an
isotopic excursion to heavier values around y25‰.
Again, the differences between the La Luna Forma-
tion and the Machiques Member isotope ratios sup-
port the interpretations based on biomarker ratios as
indicators of organic matter type.
33
4.4. Inorganic geochemistry of La Luna Formation
No samples show a positive correlation between
TOC and low sulfur percentages on a whole rock
basis. The scarcity of Fe, in calcareous muds, is a
limiting factor for pyrite formation. The scarcity of
clastic input as a source of Fe could be a conse-
quence of sedimentation associated with a maximum
transgressive event on a platform far from the coast
ŽCanache et al., 1994..
Since Hedberg Ž1931., paleoecological studies
recognize only planktonic fauna in the La Luna
Formation. Absence of benthic fauna in most of the
samples is interpreted as a consequence of anoxic
conditions at the bottom waters. Euxinic conditions
Žfree H 2 S. were inferred by Mongenot et al. Ž1996.
on the base of sulfur in kerogens and DOP index.
Biomarker distributions ŽFig. 4. indicate a slight
predominance of C 35 homohopanes over C 34 homo-
hopanes, which is an indication of euxinic conditions
ŽPeters and Moldowan, 1993..
The scarcity of Fe helps to promote an excess of
HS-rH 2 S in the bottom-water sediment interface. In
such an environment aliphatic organic matter begins
to react with free H 2 S forming inter-molecular links
which generate macromolecules more stable than
their precursors ŽSinninghe Damste´ and Leeuw,
1989.. These macromolecules protect the hydrogen
rich lipid compounds from microbacterial activity
and consequently increase the preservation factor.
Trace metals, minor and major element concentra-
tions are shown in Table 3. The normalized concen-
trations using Eq. Ž1. with the standard black shale
ŽVine and Tourtelot, 1970; Mongenot et al., 1996.,
allow calculating of enrichment factors which are
shown in Table 4 and Fig. 6.
In general terms, the trace metal distribution of V,
Ni, Zn ŽFig. 6. in the La Luna Formation show
higher enrichments than the Machiques Member.
Interestingly, the La Luna Formation and the
Machiques Member show similar Mo enrichments
although the environment during the La Luna sedi-
mentation was principally euxinic.
Experiments by Korolev Ž1958. demonstrated that
Mo fixation in sediments required formation of thy-
omolybdate species ŽEq. Ž2... Direct fixation of Mo
onto organic matter could be carried out as an ineffi-
cient mechanism, but in euxinic conditions, Mo could
34 M. Alberdi-Genolet, R. Toccor Chemical Geology 160 (1999) 19–38
be better fixed as thyomolibdate ŽMoS 3 . by means of
FeS P MoS 3 ŽEq. Ž2... It is proposed that the scarcity
of Fe in the La Luna Formation inhibit FeS forma-
tion and MoS 3 .
Mo and Zn show logarithmic correlation with
TOC ŽFig. 9., similar to the Machiques Member.
These results could also be explained by taking into
account two types of fixation mechanisms during the
sedimentation.
The enrichment in V for some samples of the La
Luna Formation is significant ŽFig. 6.. Some samples
of La Luna bitumens show a six order of magnitude
increase in vanadium over the normal sea concentra-
tion of this metal ŽPremovic et al., 1986.. High
VrNi ratios are characteristic of La Luna Formation
rocks. The sample LU-121 shows the highest ratio
ŽVrNi s 9.6..
Fixation of V ŽIII. in clays could help to explain
high concentrations of vanadium in black shales,
however, high ratios of VrNi Ž6–11. in oils of
Maracaibo reservoirs, being well correlated with a
Fig. 9. TOC vs. normalized concentrations of Mo and Zn in the La Luna Formation.
La Luna Formation source, suggest V and Ni associ-
ation with organic matter in the kerogen. It is not
possible to discard fixation on clays during sedimen-
tation, but considering the low clastic content of La
Luna Formation, this may not be a consistent expla-
nation. Rather, the authors believe that low rates of
sedimentation could be a crucial factor to the vana-
dium enrichment found in the La Luna Formation in
association with abundant organic matter and high
levels of H 2 S.
One of the characteristics of the La Luna Forma-
tion, when compared with Machiques Member, is the
general relation between TOC and absolute concen-
trations of V and Cu ŽTable 4.. This tendency could
indicate that the two trace metals were fixed to
organic matter directly or the accumulation of or-
ganic matter and trace metals was controlled by the
same mechanism Že.g., fixation by means of H 2 S..
Cu fixation requires the formation of polysulfur
compounds, beginning with H 2 S as the starting com-
pound ŽCalvert and Pedersen, 1993., and vanadium
 M. Alberdi-Genolet, R. Toccor Chemical Geology 160 (1999) 19–38
was most likely incorporated into the sediments us-
ing H 2 S as a reducing agent according to the reac-
tions shown in Eq. Ž4. ŽBreint and Wanty, 1991..
The relationship between TOC, V and Cu suggest a
similar control of fixationrpreservation by means of
intermediate sulfur compounds.
On the other hand, the stratigraphic distribution of
trace metals in the La Luna Formation shows inter-
esting cyclic trends that should be discussed ŽFig.
10.. Enrichments in Mo, V and Zn are particularly
on LU-115 and LU-119 samples, over the middle
part of the section. These enrichments in Mo and V,
which suggest a maximum development of reducing
conditions at this point, are in agreement with the
beginning of an isotopic excursion Ž d13 C. previously
reported by Perez et al. Ž1996.. Perez et al. Ž1996.
correlated this isotopic excursion with an OAE
ŽArthur and Schlanger, 1979..
Furthermore, trace metals show cyclic excursions
in several parts of the sequence ŽFig. 10., likely
related to periodic decreases in the Eh values Žin-
Fig. 10. Vertical trends of Total Organic Carbon, Hydrogen Index, Mo and V over lithological section of the La Luna Formation.
35
creases in reducing conditions.. Trace metals could
be sensitive to specific shifts from anoxic to euxinic
conditions. Otherwise, systematic high values of
TOCrHI are recorded and they do not seem to
respond in the specific way as trace metals do. This
behavior can be explained by taking into account the
persistent reducing conditions during the whole sedi-
mentation, where organic matter is always well pre-
served and the bacterial population in the sediments
selectively degrade specific compounds ŽKrumbein,
1983..
With the trace metal distribution being indepen-
dent of the maturity level of the La Luna Formation
ŽMongenot et al., 1996., and being some of the trace
metals related with TOC of the source rock, the
differences in trace metal ratios and their enrich-
ments between the La Luna Formation and the
Machiques Member are a potential tool for source-
rock correlation purposes. Ratios of VrMo, MorZn,
VrZn, VrNi most likely associated with the organic
matter show different values for each sequence ŽTa-
36 M. Alberdi-Genolet, R. Toccor Chemical Geology 160 (1999) 19–38
bles 3 and 4.. They would be analyzed in oils in
order to discriminate families that might show
source-related genetic characteristics. However, the
following essential points should be addressed.
Ø The ratios of this paper have been determined
in whole source-rocks. Their specific values should
be different in the kerogens and oils.
Ø Trace metal concentrations are strongly con-
trolled by the environmental conditions of sedimen-
tation. Their sensitive concentrations to physico-
chemical conditions support their applicability to
paleoenvironmental studies. However, there is a high
variability in the trace metal ratios for each sequence
in contrast to the stability of biomarker ratios, and
the latter are more suitable for oil–oil and oil-source
rock correlations.
5. Conclusions
Biomarker parameters allow differentiation be-
tween the mixed organic matter of the Machiques
Member ŽAptian–Albian. and the marine organic
matter of the La Luna Formation ŽCenomanian–
Campanian.. These biomarker parameters are con-
trolled by the type of organic matter plus the litho-
logical composition of the source rock. Most of the
biomarker parameters do not show significant varia-
tions along the sedimentary sequences. Heavier d13 C
values for Machiques Member with respect to the La
Luna Formation are also notable and offer an addi-
tional tool for correlation studies.
Trace metal analyses allowed the assessment of
changes in the environment of deposition. Trace
metal analyses ŽMo, V, and Fe. for the Machiques
Member suggest that this sequence be deposited in
an alternating oxic–anoxic environment. Cyclic
anoxic events were suggested by means of TOC, HI
and trace metals enrichments.
Higher hydrocarbon generation potential for the
La Luna Formation, with respect to Machiques
Member, is demonstrated by means of Rock–Eval
pyrolysis. Cyclic events of increasing reductor condi-
tions Žanoxic–euxinic. in the water–sediment inter-
face are inferred from trace metals enrichment.
Distinctive trace metal ratios Že.g., MorV. related
to the organic matter content were found for both
Cretaceous sequences. This approach applied jointly
with biomarker ratios could be useful for oil–oil and
oil-source rock correlation purposes. However, the
ratios of this paper have been determined in whole
source rocks and their values could be different in
the bitumens and oils. Inorganic values change dur-
ing sedimentation and these changing values could
be a limitation when they are intended as oil-source
and oil–oil correlation parameters.
Inorganic parameters are an excellent tool for
following physicochemical changes during sedimen-
tation of organic matter. On the other hand, biomarker
parameters and d13 C values are more consistent
within each sequence to be applied in further oil-
source rock and oil–oil correlation studies.
Acknowledgements
We are indebted to J. Burwood, A. Borrego and
R. Sassen for their reviews and constructive criti-
cisms of the manuscript, and to Andres ´ Pilloud,
Oswaldo Gallango and Julio Perez for field assis-
tance and stimulating discussion. We are also grate-
ful to J. Leigh and J. Cheatelier for assistance and to
T. Drever and T. Horscroft. We appreciate the assis-
tance of the laboratory staff at Intevep: Ana Picon,´
Simon´ Gonzalez, Angel Fraile, Claudio Ceccarelli,
Carmen Rodriguez, Irenio Berrios and Carmen Toro.
The management of PDVSA-Intevep is thanked for
granting the permission to publish.
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