CHEMICAL

GEOLOGY
rwcr_uLvNc
ISOTOPE GEOSCIENCE
ELSEVIER Chemical Geology 130 ( 1996) 271-288

Global and local controls influencing the deposition of the La

Luna Formation ( Cenomanian-Carnpanian) , western Venezuela
Julio Perez-Infante a71,Paul Farrimond a7*, Max Furrer b
a Newcastle Research Group in Fossil Fuels and Environmental Geochemistry, Drummond Building, University ofNewcastle, Newcastle
upon Tyne, NE1 7RlJ, UK
b Lagouen, S.A., Filial Petroleos de Venezuela, Apartado 889, Caracas 1010 A, Venezuela

Received 12 April 1995; accepted 30 January 1996

Abstract

Bulk and molecular geochemical, micropalaeontological, and carbon-isotopic data are used to address the different local
and global factors influencing the environment of sedimentation of the La Luna Formation (Cenomanian-Campanian,
approximate palaeolatitude IS’N) in a single section in western Venezuela. Based on the constructed chronostratigraphic
framework, oxygen-depleted bottom-water conditions and black-shale deposition started in western Venezuela well before
the widespread occurrence of organic-rich sediments in higher palaeolatitude regions such as the Tethys and the North
Atlantic near or at the Cenomanian-Turonian boundary. In the La Luna Formation, palaeoenvironmental conditions that
allowed the preservation of organic matter (mainly of marine origin), prevailed until Santonian times in a distal platform
facies with very low siliciclastic input. Changes in lithology appear to reflect the local response to eustatic sea-level
variations and the presence of a migrating upwelling belt affecting the bioproductivity of silica and carbonate. A marked
8’3COrg isotopic excursion is recognised in the middle part of the section, and is apparently unrelated to local palaeoenviron-
mental changes in bioproductivity and oxygen depletion. Biological marker dam show no variations in association with the
isotopic excursion, being mainly controlled by local fluctuations in organic-matter input and preservation.

1. Introduction Ocean Drilling Program, and their correlation with

many exposed sections on land show that organic-
The Mid-Late Cretaceous age represents one of carbon-rich sediments of this age are confined to
the periods of more extensive distribution of particular stratigraphic horizons (for a review see
organic-rich sediments in both deep- and shallow- Arthur et al., 1990), leading to the conclusion that,
marine environments, throughout the world. Strati- within relatively narrow time envelopes (‘Oceanic
graphic data from the Deep Sea Drilling Project and Anoxic Events’), global oceanic conditions allowed
the preservation of large amounts of organic carbon
(Schlanger and Jenkyns, 1976; Jenkyns, 1980).
Scholle and Arthur (1980) have shown that temporal
* Corresponding author.
’Present address: Venezuelan Petroleum Research Institute, variations in 613C values correlate with these events.
Intevep, apartado 76343, Caracas 1070 A, Venezuela. Positive excursions in 613C of both organic matter

0009.2541/96/$15.00 Copyright 0 1996 Elsevier Science B.V. All rights reserved.

PII SOOOS-2541(96)00019-8
272 J. Perez-Infunre et al./Chemical Geology 130 (19961271-288

and primary carbonates have been widely observed ate-rich facies towards the Andes (southeast),
in many North American and European sections at or Colombia (west), and to the east.
near the Cenomanian/Turonian boundary (e.g. The La Luna Formation has often been quoted as
Arthur et al., 1987; Bralower, 1988; Gale et al., an example of C/T black shale deposition (i.e.
1993; Jenkyns et al., 1994). Although this isotopic Schlanger et al., 1987; Kuhnt et al., 1990). It is
excursion is commonly related to the presence of considered that dysaerobic to anoxic conditions pre-
black shales, at many localities the signal (measured vailed, and that these were probably linked to a
on primary carbonate) is found within Cenomaniar- regional anoxic event and seasonal upwelling along
Turonian shallow-water limestones lacking black the coast of South America (Tribovillard et al., 1991;
shales and deposited under oxic conditions (Schlanger Martinez and Hemandez, 1992). Macellari and De
et al., 1987). Therefore, this isotopic excursion is Vries (1987) proposed that the La Luna’s anoxic
considered a global event that resulted from a change sediments in northwestern South America are dis-
in the carbon-isotopic composition of the hydro- tributed on a Trough Sub-province (Colombia and
sphere and atmosphere (Scholle and Arthur, 1980; southwestern Venezuela), affected by dynamic up-
Popp et al., 1989). This has been explained through welling, and a Platform Sub-province (northwestern
widespread accumulation of organic matter (enriched Venezuela), ‘reflecting a global anoxic event’. Turo-
in 12C) in oceanic sediments leaving the oceanic nian-Coniacian organic-rich sediments are also found
carbon pool enriched in 13C and causing subsequent in Deep Sea Drilling Project sites in the Venezuela
carbonate or organic carbon deposits to be also Basin (Hay, 19851, and James (1990) argues that it is
enriched in 13C. This interval of extensive black ‘unreal’ to imagine that upwelling would have af-
shale deposition has been called the fected such a large area of northern South America
Cenomanian/Turonian Oceanic Anoxic Event and the southern Caribbean.
(‘OAE-2’; Schlanger and Jenkyns, 1976; Schlanger In this paper we present bulk and molecular geo-
et al., 1987) or the Cenomanian/Turonian Boundary chemical, micropalaeontological, and carbon-isotopic
Event (CTBE). It has been suggested that the anoxic data to address the occurrence of different local and
event is related to a major global sea-level rise. global events during the sedimentation of the La
However, the highest sea-level peak in the Late Luna Formation. In addition to defining the Cenoma-
Cretaceous appears to occur some time later in the nian/Turonian Boundary Event in the La Luna,
middle Turonian (between 91.5 and 90.3 million stratigraphic variability represented by lithofacies
years ago; Haq et al., 19871, as is pointed out by changes, biomarker composition and micropalaeonto
Hancock (1993) based on the stratigraphical position logical assemblages were considered in detail at a
of hardgrounds and ammonoid zones of the Tethyan single but representative location, to investigate tem-
region. poral relationships between eustatic changes and lo-
In western Mediterranean and North Atlantic re- cal bioproductivity of silica, carbonate and organic
gions the development of black shales is often re- matter.
stricted to the CTBE, but in low-latitude shelf basins
along the African continental margin, deposition of
black shales took place from as early as middle 2. Experimental
Cenomanian to late Turonian (Einsele and Wied-
mann, 1982; Kuhnt et al., 19901, suggesting that 2.1. Geologic setting and sampling information
local mechanisms contributed to their origin. In this
study, we consider another low-latitude occurrence Samples for this study were collected from Maraca
of mid-Cretaceous black shales: the La Luna Forma- Ravine (20 km southwest of Machiques City; Fig. l),
tion of Venezuela (Cenomaniar-Campaniann; palaeo- in the Perija Foothills. The La Luna here lies within
latitude of approximately 15”N). In ‘he western area an area of rain forest and although well exposed
of the Maracaibo Basin, the La Luna Formation during the dry season (November to March), some
mainly comprises alternating beds of marls and segments of the section are covered by dense vegeta-
pelagic limestones, changing laterally to less carbon- tion or stone blocks, producing gaps in sampling.
 J. Perez-Infante et d/Chemical Geology 130 (1996) 271-288 273

The section was measured from the base of the La atomic absorbtion spectrometry using a Varian AA-
Luna Fm. This contact is abrupt and clearly distinc- 300 spectrometer, following digestion for 12 h at
tive as a lithological change between the massive 110°C with hydrochloric and hydrofluoric acids in
and organic-lean limestone of the Maraca Formation closed Teflon liners placed in stainless-steel cases.
and the first occurrence of organic-rich, laminated Total carbon and organic carbon (after acid dissolu-
marls of the La Luna Formation. A set of 90 samples tion of carbonate minerals) were determined using a
were collected from an estimated 160 m vertical Leco CS-244 Carbon-Sulphur Analyser. Carbonate
interval. Micropalaeontological analyses were per- content was determined by the difference between
formed on thin sections of selected samples placing the two measurements.
emphasis on radiolaria and planktic and benthic
foraminifers. 2.3. Sediment extraction and fractionation

2.2. Bulk geochemistry Approximately 25 g of powdered rock were ex-

Samples were crushed to powder in a rotary disc
mill (Terna@) and aliquots analysed by Rock-Eva1
pyrolysis, and for their total organic carbon (TOC)
and carbonate contents. Free bitumen (S l), kerogen
pyrolysis yields (S2) and maximum temperature of
pyrolysis CT,,,) were determined using a Leco
THA200 Thermolytic Hydrocarbon Analyser. The
elements silicon and aluminium were determined by
tracted in a soxhlet apparatus using cellulose thim-
bles for 48 h with dichloromethane (DCM)/methanol
(230 ml/20 ml) as solvent. Activated copper was
added to the extraction flask to remove any elemen-
tal suiphur. After extraction, excess solvent was
removed by rotary evaporation and the dried extracts
were weighed in order to calculate the total ex-
tractable organic matter (EOM). The extracts were
fractionated by column chromatography using pre-

!
\
I
i
‘,
lo”, /
!
\
0 15km \
I I /’
? ?Field section studied
i

i
9”4O’N
I;

72”H
I
Fig. I. Sampling site of the La Luna Formation in the western Maracaibo Basin.
274 J. Perez-Infuntr et al./Chemical
extracted silica and alumina. Aliphatic hydrocarbons
were obtained by eluting with petroleum ether. An
aromatic hydrocarbon fraction was obtained by elu-
tion with 1: 1 petroleum ether:DCM, and the final
fraction (polar compounds) with 1: 1 DCM:methanol.
2.4. Analysis of aliphatic hydrocarbons
Capillary gas chromatography was performed us-
ing a Carlo Erba Mega Series 5160, fitted with an
OV-1 fused silica capillary column (30 m X 0.32
mm id.; 0.25 km film thickness) and an on-column
injector. Analyses were performed using hydrogen as
the carrier gas, with an oven temperature of 50°C for
2 min then ramped up at 4”C/min to a final tempera-
ture of 3OO“C, which was held for 20 min. Data were
acquired and processed using a VG Multichrom lab-
oratory data system. Subsequent analyses by gas
chromatography-mass spectrometry (GC-MS) were
performed using a Hewlett Packard 5890 gas chro-
matograph fitted with an HP-5 fused silica capillary
column (25 m X 0.2 mm i.d.; 0.11 p_m film thick-
ness> and linked to a Hewlett Packard mass selective
detector (electron energy 70 eV; filament current 220
p,A; source temperature 220°C). Helium was used as
carrier gas. The initial oven temperature was 5O”C,
ramped to 300°C at 6”C/min, and held isothermally
at this temperature for 20 min. Compounds were
identified by comparing their mass spectra (or ion
responses) and relative retention times with either
those of reference compounds or with literature data.
For quantification of GC-MS data, a deuterated
sterane standard, (20R)-5o, 14o, 17a(H)-[2,2,4,4-
D,]-cholestane, was added to the aliphatic hydrocar
bon fractions (molecular ion m/z 376 and a base
peak of m/z 221). No correction was made for the
differences in mass spectral response of various hy-
drocarbons relative to the internal standard.
2.5. Carbon isotopes
S13C ratios of organic matter were measured from
carbon dioxide gas generated by the combustion of
decarbqnated samples. An aliquot (1 to 5 g> of bulk
powdered sample, was treated with 1 N hydrochlo-
ric acid solution for 24 to 36 h, filtered with precom-
busted glass fibre filters (Whatman GF/C) and dried.
The carbon dioxide from the organic fraction was
Geology I30 (1996) 271-288
obtained following the original method described by
Craig ( 1957) and modified by Hollander (1989). The
C-isotope composition of the obtained pure carbon
dioxide gas was measured on a triple collector VG
Micromass 903 Mass Spectrometer (ETH, Zurich),
using NBS-22 Hydrocarbon Oil Standard (613C =
-29.63%0), and the 613C values are reported as per
mil (o/00)relative to the PDB isotopic standard. Preci-
sion of the isotopic analyses (+0.20%0) was calcu-
lated using values obtained from duplicate analyses
of samples.
3. Results and discussion
3.1. Organic-carbon isotopic variation
In this study, isotopic-composition measurements
made on inorganic carbon in the samples of the La
Luna Formation, indicate diagenetic alteration, par-
ticularly by secondary carbonate precipitation in the
sulphate reduction zone, giving considerable scatter
and unreliable negative values. Similar results have
been reported by Schlanger et al. (1987) for the
Cenomanian-Turonian Bridge Creek Limestone at
Rock Canyon, Colorado. These authors associated
the scatter in the isotopic results of biogenic carbon-
ate to cyclically varying amounts of organic matter
in the section which caused diagenetic alteration of
the primary signal of the skeletal calcite. Therefore,
only organic carbon isotopic measurements made on
isolated kerogen residues are considered in this study
of the La Luna Formation. These S13Corg values
display a marked positive excursion from between
- 27.6 to - 28.0%0 and - 25.0 to - 25.5%0 in the 55
to 92 m interval of the section (Fig. 2). Visual
kerogen analysis and biomarker composition (see
later) show no significant changes at the boundaries
of this interval, indicating that the isotopic excursion
cannot be directly correlated to a change in organic
matter composition. In sediments of similar age from
Deep Sea Drilling Project sites and in several on-
shore sections in high latitudes, a similar isotopic
shift occurs, often accompanied by a lithological
change, an increase in the amount of TOC (e.g.
Schlanger et al., 1987; Farrimond et al., 1990) and in
the hydrocarbon generating potential of kerogen (HI).
However, in the La Luna Formation the isotopic
 J. Perez-lnfante et al./Chemical Geology 130 (1996) 271-288 275

excursion is not associated with any marked change
in lithology, TOC or HI, and it occurs within a
thicker interval with good hydrocarbon source rock
potential (Fig. 2), suggesting that dysoxic-anoxic
bottom waters were already locally established in the
basin.
Fluctuations in TOC and carbonate contents within
the interval of the isotopic excursion (Fig. 2) indicate
that local palaeoenvironmental conditions changed.
However, isotopic values show no apparent correla-
tion with these changes. Bulk parameters such as
TOC and carbonate contents are directly influenced
by intra-basin processes affecting productivity and
preservation of biogenic carbonate, opal and organic
matter (Hut, 1988; Morse and Mackenzie, 1990;
Ricken and Eder, 1991). Local biogenic productivity
can vary according to the relative proximity of a
specific site to upwelling systems. Modem coastal
upwelling areas have a ‘core region’ of very high
productivity and high nutrient abundance that is
commonly lo-20 km wide (Hilbrecht et al., 1992).
Within these zones, the plankton is strongly domi-
nated by siliceous organisms (Bremner, 1983; Suess
and Thiede, 1983; Molina Cruz, 1984). With increas-
ing distance from this region the carbonate-produc-
ing organisms become more abundant, and their
remains contribute increasingly to the sediment
(Hilbrecht et al., 1992). On the other hand, total
organic matter accumulated in sediments may not
only be controlled by the primary productivity of the
overlying water column but also by local redox
conditions. In an extensive review of the literature
related to the ‘productivity versus preservation de-
bate’, Tyson (1995) pointed out that “in detail there
is rather poor spatial correlation between areas of
high marine productivity and areas of organic-rich
sediment deposition ( . . . ) due to the combined influ-
ence of other key factors including water depth,
bottom water oxygenation, sediment grain size, down
slope redeposition and dilution and auto dilution
effects.” The lateral and stratigraphic heterogeneity
of the La Luna Formation (e.g. Macellari and De
Vries, 1987; Martinez and Hemandez, 1992) sug-
gests the existence of temporal and area1 variations
in nutrient-rich upwelling currents during deposition.
However, primary productivity may have had only a
minor influence on the final TOC signal in the site
considered in this study since this parameter does not
change markedly in those intervals where an increase
in primary productivity can be expected (i.e marl-
chert alternations of Unit 2). We interpret that TOC
in the La Luna Formation was mainly controlled by

Unit
-
.
5
-
.
.
.
4 .
??? ?
a
- ??
. ??

3 8
.
- . 8
.
2 . L=
.
-
.O
.
1
.
- 0 I I q

-28 -25 -24 0 5 10 15

%CaCQ %TOC Carbonate free H.I. %SiOr/O/.Alz~

Fig. 2. S’3C(org) = carbon isotopic composition of organic matter (%o PDB); % carbonates (as CaCO,); % TOC (expressed on a
carbonate-free basis); H.I. = hydrogen index (from pyrolysis Rock-Eval, mg HC/g TOC); silica/alumina data of the La Luna Formation at
Quebrada Maraca. Lithological units are those proposed in this work. (Only values for marls and shales are plotted.)
276 J. Perez-Infante et al./Chemical Geology 130 (1996) 271-288

local environmental factors related to the preserva- increase in radiolarian abundance, the absence of
tion/degradation of organic matter. In contrast, the Rotalipora cushmani and the occurrence of hetero-
similarity of the La Luna Formation organic-carbon helicid/hedbergellid-dominated planktonic
isotopic excursion at Maraca Ravine with other sec- foraminiferal assemblages. The position of this
tions of North America, Africa and Europe suggest boundary between the R. cushmani and W. ar-
that these isotopic records reflect variation in the chaeocretaceu biozones in the La Luna Formation
global carbon cycle which responds to widespread (55 m) is additionally supported by a significant
geochemical changes in the hydrosphere and atmo- change in microfossil assemblage, including the first
sphere around the Cenomanian-Turonian Boundary appearance of Whiteinella balh’ca and Heterohelix
(Arthur et al., 1985; Hayes et al., 1989; Popp et al., reussi. The latter species is considered a morphotype
1989). of H. globulosa that, according to Nederbragt (199 1),
The timing and cause of the Cenomanian/ records the Cenomanian/Turonian boundary fauna1
Turonian isotopic event and its relationship with turnover. However, the placing of the Cenomanian-
microfossil assemblages has been a subject of dis- Turonian boundary depends upon which fossil groups
cussion for many years. Bralower (1988; U.S. West- are applied. The datums considered here are based
em Interior Basin) and Hilbrecht and Hoefs (1986; mostly on appearances and disappearances of spe-
NW Germany) found differences in the dating of the cific foraminifera. The biostratigraphy of Gale et al.
isotopic excursion based on nannofossils, suggesting (1993) largely employs macrofossils, and a compari-
that it was diachronous even on an intra-basin scale. son of our C-isotope curve with theirs indicates that
However, more recently, Gale et al. (1993) have the Cenomanian-Turonian boundary in the La Luna
shown convincing evidence that the timing and struc- Formation may actually be somewhat higher in the
ture of carbon-isotope curves of expanded Cenoma- section, nearer the top of Unit 3 (cf. Fig. 3). Unfortu-
nian-Turonian boundary sections in England (East- nately, our sampling resolution over this part of the
boume, Sussex) and North America (Pueblo, Col- section does not allow us to identify the detailed
orado) are identical with reference to first appear- C-isotope curve characteristics which appear later-
ances and disappearances of macro- and mi- ally correlatable (Gale et al., 1993; Jenkyns et al.,
cropalaeontological markers. 1994). Future macro- and micropalaeontological
Foraminifera and macrofossil assemblages appear studies and more detailed isotope stratigraphy of the
to be strongly influenced by palaeoenvironmental section need to be performed to support or correct
factors, and it seems likely that the fauna1 changes the interpretation proposed here.
observed in the La Luna Formation were to some At the top of the section, 6’“C values again shift
extent controlled by the local development of envi- gradually towards heavier values (Fig. 2), possibly
ronmental conditions that allowed the accumulation corresponding to a third anoxic event of the Creta-
of organic matter before the CTBE. Gale et al. ceous (OAE-3; Coniacian-Santonian period;
(1993) have pointed out that not all taxa of the Jenkyns, 1980; Arthur et al., 1990). This isotopic
Cenomanian-Turonian interval have identical ranges shift at the top of the La Luna Formation is consis-
at Pueblo (Colorado) and in Europe. However, a tent with the C-isotope curves for the Coniacian of
detailed correlation of the C/T isotopic event to the English Chalk and the Coniacian/Santonian of
planktonic foraminiferal zonation has been proposed the Italian Scaglia in the Bottaccione Gorge, Gubbio
by Kuhnt et al. (1990) for sections (e.g. Tarfaya (Jenkyns et al., 1994).
coastal basin, Morocco) deposited in similar palaeo-
latitudes (15”N) and water depths (200-300 m) to 3.2. Lithostratigraphic variation and sea-level
the La Luna Formation. They correlated the onset of changes
the isotopic shift in the Tarfaya to the top of the R.
cushmani biozone by the presence of important In the La Luna Formation, two major scales of
‘events’ that are also clearly recognisable at the base lithological variation can be distinguished both in the
of the isotopic excursion in the La Luna section field and from geochemical data. Marl-limestone
studied here (Fig. 3). These events include a marked and marl-chert alternations are easily recognisable
 J. Perez-Infanie et al./Chemical Geology 130 (1996) 271-288 271

- -
?trE Planktonic Foraminifera
in Unit foraminifera relative n.y.O.
ctic zonation abundance
increase *
- - ........
..........
...........
............
............
5
.............
............
.............
............
D.ccmcavata .............
5 ............
- ............ - 08
140 .............
............
.............
............
.............
............
............
.............
............
............
............
.............
120 f ............
.............
4 3 D. primtiim
4 ............
.............
............
.............
............
-----_
............
g-z-- .............
............
......................

.............
............
- 89

100
3

I
............
H. helvetica
......................................
............
............. - 91
............
............
- ...........
...........
.........
.........
........
........
...... i
80 3
W. atchaeo-
cretacea 2
- - 92

60
2 - 92.:

40

R. cushmani

20

Fig. 3. Chronostratigraphic framework and biostratigraphic correlation used. ’Time scale of Haq et al. (1987). ’ Defined by first
appearance (F.A.) of Whiteinella baltica along with Heterohelix reussi (Ncderbragt, 1991); strong increase of radiolarian abundance,
positive 613C (organic) excursion, assemblages dominated by heterohelicid/hedbergellid, absence of Rotalipora cushmani (Kuhnt et al.,
1990); and decrease of planktonic foraminifera abundance around the C/T boundary (Kauffman, 1984). 3 Lower boundary defined by F.A.
of Marginotruncana coronata. 4 Lower boundary defined by F.A. of Dicarinella primitiva. ’ Lower boundary defined by F.A. of
Dicarinella concavata.

on a bed to bed scale (commonly < 1 m). Consider-
ing the average sedimentation rates suggested for the
La Luna Formation (Martinez and Hemandez, 1992;
and the present study; Fig. 4), the duration of such
bed-scale couplets in the La Luna Formation corre-
sponds to 10 to 50 Ka, apparently within the Mi-
lankovitch frequency band. The bed-scale variations
are superimposed onto records of longer-term pro-
cesses which affected the basin; it is these longer-term
variations which are addressed in this paper.
The La Luna Formation at Quebrada Maraca has
been subdivided into five informal units in the pre-
sent study, based upon lithological changes (Table 1,
Figs. 4 and 5):
Unit I (the lowermost unit) is the most calcare-
ous, consisting of limestone layers (0.3 to 1 m thick)
interbedded with approximately 30% of thinner lami-
nated marls containing ellipsoidal carbonate concre-
tions. As in the rest of the section studied, the
carbonate fraction is composed mainly of planktonic
foraminifera and calcareous nannoplankton.
Unit 2 consists mainly of alternating layers of
278 J. Perez-lnfante et al./ Chemicd Geology 130 (1996) 271-288

T
etres Sedimentation t3.M. Accumulatiof 1
in Unit
rate (cm/l OOOy)2 rate (g/m2.y)3
dion

5 n.d. n.d
--_-
140

120-
4 1.5 (1.3) 1.1

lOO-

ao- 3 1.7 (1.5) 1.3

60-
2 5.5 (5.2) 5.1

40-

1 n.d n.d
20 -

m Shale pzJ Marlstone

lzz i%z”.a El Chetimarl
alternation

Fig. 4. Sedimentation and organic matter accumulation rates for the units of the La Luna Formation at Quebrada Maraca. Time zonation is
proposed on the basis of planktonic forammifera assemblages, scdimentological features and carbon isotope stratigraphy (see Fig. 3). ’ The
Haq et al. (1987) time scale has been used to calculate sedimentation rates. Differences of average compaction between units were
considered negligible. 3 The following formula has been used: O.M. AC = 0.1 X TOC X SR X D. D = 2.3 g/cm3 (average dry density
estimated for fine-grained, organic-rich rocks; Kuhnt et al., 1990).

well-laminated marls bearing abundant radiolarian
tests and thin bands of chert (up to 15 cm; approxi-
mately 15% of the unit).
Unit 3 lacks chert bands and the Si/Al ratio
drops to a minimum (Fig. 2). This unit also has the
lowest carbonate contents and the highest occurrence
of shale beds in the section (approx. 15% of this
unit).
Unit 4 sees an increase in carbonate content with
an increase in the number of limestone beds. Rare
thin arenaceous layers with abundant bivalve shells
are found in this unit, probably formed by storm
action.
Unit 5 displays a gradual decrease in carbonate
content, and a few thin chert bands ( < 2 cm) are
observed.
These changes in lithology appear to reflect the
local response to eustatic sea-level variations and
changes in the productivity of biogenic silica, proba-
bly controlled by variations in the relative proximity
of an upwelling belt to the site studied. Whilst local
subsidence (in combination with sediment accumula-
 J. Perez-lnfanre et al./ Chemical Geology 130 (1996) 271-288 219

Table 1
Average values (mean f standard deviation) of bulk geochemical parameters for the units of the La Luna Formation differentiated in this
study
Unit Metres n % CaCO, % TOC %TOC * H.I.

1 O-42 18 78.4 + 12.3 2.84 + 1.31 13.96 f 4.17 438 F 6 191 + 61

2 42-70 25 50.3 + 24.5 3.98 f 1.84 9.59 * 4.40 44Ok-3 214 rf: 62
3 70-91 14 31.3 5 23.0 3.29 + 1.29 5.94 + 3.99 439,l 210 + 33
4 91-140 19 70.1 + 17.2 3.02 f 1.53 10.89 + 4.32 439 f 2 274 + 83
5 140- 157 14 49.2 * 19.0 3.75 f 1.86 8.07 f 3.81 438 * 2 338 * 93

n = number of samples in each unit. Organic carbon content is additionally expressed on a carbonate-free basis (% TOC ’ ). HI. = hydrogen
index.

tion rate) could be an additional influence, Macellari America at this time. The middle Cenomanian-early
(1988) and Erikson and Pindell (1993) argue for Turonian comprises a transgressive period (Haq et
little regional tectonic activity in northern South al., 1987), followed by high-stand deposits corre-
sponding to the peak of maximum eustatic rise
(91.5-90.75 m.y. ago). Late Turonian to Santonian
Unit 5 times are characterised by a succession of transgres-
100
. sive and low-stand wedge systems tracts within a
80
long-term regressive period (Haq et al., 1987). The
following discussion examines geochemical and mi-
cropalaeontological records of sea-level changes in
the Maracaibo Basin, affecting the lithofacies pattern
of the La Luna Formation.
All the facies changes described above are consis-
tent with a pelagic belt in a distal pericratonic basin
as suggested for northwestern South America during
the Late Cretaceous by several authors (Zambrano et
80
Unit 3 al., 1971; Macellari, 1988; Martinez and Hemandez,
.
60 1992). Except for Unit 3, the La Luna Formation is
low in siliciclastic components (screening tests of
XRD analyses indicate clay content lower than 5%
in marl samples), supporting the hypothesis of very
Unit 2 distant sources of elastic sediment. Therefore, we
100
consider a low and fairly steady supply of detrital
80 II . .
input, with local changes in production and preserva-
tion of carbonate and opal, as being the most impor-
tant factors controlling sedimentation of the La Luna
Formation.
Unit 1
Carbonate sedimentation is strongly affected by
water depth, reaching its highest rates in clear, warm
and shallow waters. Consequently, the mass of bio-
genie carbonate grows most rapidly along preferred
positions on the upper part of any seaward slope,
% TOC within the zone of maximum biological productivity
Fig. 5. Plots of % TOC against % carbonates (as CaCO,) for the (see for example Wilson, 1975, and Morse and
units of the La Luna Formation at Quebrada Maraca. Mackenzie, 1990). At the site studied, the La Luna
280 J. Perez-infante et al./ Chemical Geology 130 (1996) 271-288
Fm. overlies platform deposits predominantly com-
posed of shallow-marine carbonates (Cogollo Group).
The uppermost part of these shallow deposits (Maraca
Formation) consists of coarse bioclastic grainstones
with large, partly leached bivalves and echinoderm
debris that were deposited during rapid deepening of
a shallow platform environment (Vahrenkamp et al.,
1993). Considering that elastic dilution by runoff
was locally minimal (since positive areas were dis-
tant) during the Late Cretaceous, we interpret the
units of La Luna with higher carbonate content
(Units 1 and 4) to have been deposited on shallow
outer-shelf/slope areas, while the carbonate-poor
Units (2 and 3) represent deeper environments and
maximum sea-level periods. Although changes in
nutrient supply can bring about profound changes in
sedimentation rates independently of sea level
(Gawthorpe et al., 1994), foraminifera and radiolar-
ian assemblages (see later), and the correlation of the
units with global eustatic curves (Haq et al., 1987)
further support this interpretation.
In the deeper-water units (2 and 3), foraminiferal
shells are commonly well preserved, suggesting that
the water depth never became sufficiently great to
cause extensive dissolution of these organisms.
(Berger (19701, based on suspended tests of
foraminifera from the East Pacific Rise, found slight
dissolution of the foraminifera from 300 m.) In
general, the lithofacies of the La Luna Formation
remarkably resemble coeval pelagic sequences of the
North African Margin (e.g. Tarfaya coastal basin,
Morocco; Einsele and Wiedmann, 1982) where max-
imum palaeowater-depths of 300 m have been re-
ported by Kuhnt et al. (1990).
As carbonate dissolution is unlikely in the studied
section, the lower carbonate contents of Units 2 and
5 suggest a relative decrease in primary carbonate
productivity and/or dilution by a relative increase in
biogenic silica production. Opal bioproductivity
strongly controlled by the availability of nutrients,
and obviously, of dissolved silica in marine waters.
In Unit 2, radiolarian tests and chert bands along
with small-sized foraminifera (Het&ohelix,
Globotruncana), high fauna1 density of Hedbergella
SP* and Globigerinoides and scarcity of Prae-
globotruncana, strongly suggest the presence of nu-
trient-rich upwelling currents (Einsele and Wied-
mann, 1982). Although the occurrence of a vigorous
upwelling system in the area could have increased
both carbonate and biogenic silica productivity, the
palaeolocation of the maximum carbonate and opal
productivity belts need not have coincided since
radio&a and calcareous planktonic organisms ap-
pear to be highly tuned to specific oceanographic
environments (see Welling et al., 1992). Spumellar-
ian and Nassellarian radiolarians, present in Unit 2,
suggest open-water conditions with a peak in abun-
dance in middle-outer shelf or deeper upper-slope
environments (Koutsoukos and Hart, 1990).
In Unit 3, the absence of chert bands, preserved
radiolarian tests and the lowest Si/Al ratios of the
section (< 5; Fig. 2) shown for some beds of this
unit, suggest that the inferred belt of high opal
bioproductivity had shifted away before its deposi-
tion. A striking decrease in the density of planktonic
foraminifera and the occurrence of dwarfed speci-
mens of unkeeled foraminifera (Herdbergella and
Heterohelix) in Unit 3 (cf. Ford and Houbolt, 19631,
together with the fact that this unit shows the lowest
average carbonate content of the section (31.3%;
Table l>, indicates that calcareous productivity also
decreased. The linear sedimentation rates for the La
Luna Formation units suggested in this study (Fig. 4)
must be considered as rough estimates since no
correction has been made for compaction of the
sediments. However, assuming similar average com-
paction factors for the different units, the linear
sedimentation rate appears to decrease by a factor of
3 between Units 2 and 3.
Whilst a migrating upwelling system (moving in
response to sea-level changes) could explain the
changes in productivity, an alternative explanation
could be the possible influence of an expanded oxy-
gen-minimum zone upon shallower parts of the wa-
ter column, affecting the development of intermedi-
ate planktic foraminifera (Martinez and Hernandez,
is 1992) and radiolaria. Whatever its origin, the ob-
served decrease in planktonic productivity during the
accumulation of Unit 3 would decrease the sedimen-
tation rate, resulting in the deposition of sediments
passively enriched with clays (Fig. 2); such sedi-
ments are recognised as characteristics of
maximum-flooding black shales (Wignall and May-
nard, 1993).
In Units 4 and 5, the facies patterns of Units 1
and 2 return, and may be associated with a rapid
 J. Perez-lnfante et al./Chemical
regressive pulse during the middle Turonian (Haq et
al., 19871, and the restoration of pelagic sedimenta-
tion on the outer platform. Normal-sized foraminifera
are again observed, along with fragments of small
bivalves, particularly Znocerumus. The upper part of
Unit 5 may also then represent the onset of a new
transgressive phase. The presence of an upwelling
system (less vigourous than that of Unit 2) is sug-
gested by a similar foraminiferal assemblage and the
occurrence of a few chert bands.
3.3. Organic matter enrichment in the La Luna
Formation
Although the La Luna Fm. displays area1 and
stratigraphic changes in lithology throughout the
Maracaibo Basin, its organic matter content remains
relatively high both in exposed sections at the edges
of the basin (Perija Foothills and northern flank of
the Venezuelan Andes) and in cores from wells
drilled all over the basin (Gonzalez de Juana et al.,
1980; Talukdar et al., 1985). Contemporary organic-
rich facies are also found in eastern Colombia (La
Luna and Villeta Formations; Zumberge, 1984) and
eastern Venezuela (Guayuta Group; Talukdar et al.,
1985) suggesting regionally widespread anoxic bot-
tom waters during the Late Cretaceous in northwest-
em South America.
At Quebrada Maraca, the conformable contact
between the La Luna Formation and the underlying,
shelly organic-lean limestones of the Maraca Forma-
tion, displays a striking increase in organic-matter
content, suggesting a rapid decrease in oxicity. Total
organic carbon (TOC) contents of the marl samples
vary from 1.50% to 6.85%, but the hydrocarbon-gen-
erating potential (HI) shows less variation (Fig. 2).
Although maturation of organic matter greatly con-
tributes to diminish original fluctuations in HI, the
data are consistent with relatively constant dysaero-
bit to anoxic conditions throughout most of La
Luna’s sedimentation. This interpretation is further
supported by the near absence of benthic
foraminifera, with only a few occurrences towards
the top of the formation.
Fluctuations in TOC can be produced by the
combined effect of the flux of organic matter from
the water column, its degree of preservation in sedi-
ments, and dilution by changes in the accumulation
Geology 130 (1996) 271-288 281
of inorganic material (biogenic and elastic). Al-
though average TOC values are similar for all units
of the La Luna Fm. (Table 11, plots of carbonate
content versus organic matter distinguish between
the units (Fig. 5). Unit 1 and (to a lesser extent) Unit
4 show inverse carbonate-organic carbon relation-
ships typical of deposition mainly dominated by
changes in the influx of carbonate components
(Ricken, 1994). Units 2 and 5 show more complex
patterns due to greater dilution by biogenic silica in
relatively deeper environments. Unit 3 shows a pat-
tern largely independent of the carbonate concentra-
tion, suggesting (as discussed earlier) that contribu-
tion of biogenic siliceous and calcareous components
remained low during the deposition of this unit. It is
interesting to note that this apparent change in bulk
geochemistry, probably related to palaeoproductivity,
occurs within the positive carbon-isotope excursion.
Despite variations in lithology, microscopic anal-
ysis of kerogens from the studied section show little
variation in the proportion of structured and amor-
phous organic matter. All the samples examined are
,dominated by amorphous kerogen (95% or more>
which has been widely ascribed to marine planktic
and/or bacterial material (Tissot and Welte, 1984).
There is no palynological evidence for fluctuations
in the relative proportions of marine and terrestrial
organic input during the sedimentation of the La
Luna Formation.
3.4. Biomarker composition
Signals preserved in the distributions of biomarker
compounds in a heterogeneous section such as the
La Luna Formation are often sensitive to both envi-
ronmental (source of organic matter, ecological as-
semblages, redox conditions, salinity) and diagenetic
factors (maturation, mineral matrix catalysis). In or-
der to minimise the influence of lithological varia-
tion on the organic matter in the section studied, only
marl samples will be considered here. Furthermore,
organic matter maturity differences are negligible
between the top and the bottom of the section;
neither T,,, values (440-445°C) nor vitrinite (very
scarce particles; reflectance 0.7-0.8% R,) display
any gradient. Therefore, variations in the biomarker
data are considered to be largely dependent upon
282 J. Perez-Infante et al./ Chemical Geology 130 (1996) 271-288

changes in the primary input of organic matter and Table 2

other palaeoenvironmental factors. Range of concentration (ppm of EOM) for selected compound
groups in the La Luna Formation
As noted earlier, and reported for other sections
UP Hopanes (C,,-C,,) 240-730
of the La Luna Formation in the northwest of the
aI3 Hopanes CC,, -C,J 145-725
Maracaibo Basin (Talukdar et al., 1985), molecular Total hopanes 385-1450
geochemistry and microscopic analyses indicate that Tricyclics (C ,9 -C,,) 180-315
the bulk of the organic matter is algal and bacterial Tricyclics (C,,-C,,) 330-1340
in origin. Saturated hydrocarbons (between 20% and Total tricyclics 50.5-1880
cxp@ Steranes CC,, -C,,) 120-360
30% of EOM) display little apparent molecular vari-
ation through the section. Normal and branched alka-
nes show a dominance of medium molecular weight
components (with a maximum around n-C,,) and
the pristane/phytane ratio is always lower than 0.8. throughout the section are tricyclic terpanes and
(Fig. 6). The most abundant cyclic compounds hopanes, whilst steranes are relatively low (Table 2).
The sterane distributions (C2,-C2s) display very lit-
tle variation, being always dominated by C,, ster-
anes, consistent with a marine source of organic
matter (Volkman, 1988), and suggesting a relatively
constant biotic input.
Principal component analysis (PCA) of biomarker
25 data from GC-MS analyses was used to aid interpre-

Ill
tation of molecular differences between samples.
This type of statistical analysis allows a complex
multivariate data set to be simplified by identifying
the covariance of individual variables (biomarkers)
and discriminating or grouping samples on the basis
of the direction and amplitude to which the distribu-
tions of the variables deviate from that of the aver-
age (see Davis, 1986). This method allows a large
data set to be expressed in terms of a limited number
of components (PCl, PC2, PC3, etc.) which are
19
linear combinations of the individual variables. In
this study, GC-MS peak areas of tricyclic terpanes,
hopanes and steranes (Table 3) were used for the
analysis, making a total of 42 variables for each of
the 27 samples selected. Biomarkers were only se-
lected if they could be accurately integrated for each
sample and suffered no co-elution problems. The
original raw data were normalised (to make each
sample the same ‘size’), autoscaled (i.e. dividing
each variable by its standard deviation, in order to
give them all comparable weight in the analysis) and
centred prior to PCA.
A ‘loadings plot’ can be used to show the rela-
~ Retention time -* tionships between variables (biomarkers) and the
degree to which each variable contributes to the PC’s
Fig. 6. Typical gas chromatograms of the La Luna Formation at
Quebrada Maraca. Pr = pristane; Ph = phytane; selected n-al- (Fig. 7). The first and second principal components
kanes are labelled with their carbon numbers. account for 70% of the total variance within the
 J. Perez-lnfante et al./Chemical Geology 130 (1996) 271-288 283

scaled data set so they are the only ones discussed
here. Long-chain tricyclic terpanes (> C,,) display
high positive loadings on PCl, identifying a strong
importance of these compounds which vary largely
independently from the other biomarkers considered
(< C,, tricyclics, hopanes and steranes). In confir-
mation, concentrations of long-chain tricyclic ter-
panes (Fig. 8) closely follow the trend of PC1 varia-
tion through the section, with an important increase
in absolute abundance between 35 and 110 m of the
section. Tricyclic terpanes containing up to at least
35 carbon atoms are clearly observed within Units 2,
3 and 4 (Fig. 9). Peters and Moldowan (1993) have
proposed that tricyclic terpanes may be source indi-
cators relating to a group of bacterial or algal lipids,
but their specific origin is still poorly understood.
Several authors (Volkman et al., 1989; Simoneit et
al., 1990; Aquino Neto et al., 1992; McCaffrey et al.,
1994) have pointed out that at least one source of
tricyclic terpane@Fs may be Tasmanites, a genus of
extinct unicellular green algae, frequently associated
with anoxic black shales (Tyson, 1995). Specifically,
extended tricyclic terpane hydrocarbons have been
identified as the major biomarkers in the bitumen of
the Tasmanian tasmanite (Simoneit et al., 1990).
However, remains of Tasmanites were not observed
in the samples studied of the La Luna Formation.
Furthermore, in the La Luna Formation the increase
in abundance of tricyclic terpanes ( > Cz6) is not
correlated to marked changes in any potentially re-
dox-sensitive parameters (i.e. HI, pristane/phytane).
Hopanes and steranes are important variables in
PC2 (Fig. 7). The observed depth trend of PC2
essentially records fluctuations in steranes vs.
hopanes, a parameter commonly associated with
changes in organic matter supply (e.g. Farrimond et
al., 1994). With the exception of the sample at the
bottom of the section which displays a relatively

0.25
T PC2

C2s-C2s Tricyclics

023
24.26,27
b
8262936
e&t

035
C&II& Tricyclics 025
I

($1 -C23 Tricyclics

05

C&-C= Hopanes
013 /

Hopanes

Fig. 7. Loadings plot from the principal components analysis, showing the relationship between the biomarker variables in terms of the first
two principal components.
284 J. Perez-Infante et al./Chemicd Geology 130 (1996) 271-288

greater content of steranes, the sterane/hopane ratio not genetically associated with, the isotopic shift
displays a smooth trend throughout the section. This recorded in the organic matter.
is consistent with other geochemical results of this In general, none of the biomarker trends correlate
study (Rock-Eva1 pyrolysis, GC analyses and optical with the interval of the isotopic shift in the section.
microscopy) that show no evidence of changes in the Since the variation in biomarker composition is
proportion of terrestrial/marine organic matter sup- known to be largely controlled by local environmen-
ply during La Luna’s sedimentation. tal factors (e.g. palaeowater depth, productivity, local
The abundance of 28,30-bisnorhopane (BNH) also anoxia and salinity), the lack of parity with the
shows a clear trend through the section, similar to organic-C isotopic event is consistent with the latter
that shown by the long-chain tricyclic terpanes (Fig. being mainly independent of local conditions but
8). After a marked increase, the absolute concentra- rather a result of global depletion in ‘*C in the
tion of BNH falls from a maximum of 70 ppm oceans in response to widespread organic matter
(EOM) at the top of Unit 1 and the lower part of sequestration into sediments around the Cenoma-
Unit 2 to 10 ppm of the EOM in the upper part of nian/Turonian and Coniacian/Santonian bound-
Unit 4. The origin and significance of this compound aries.
remain unclear, although kerogen pyrolysis studies
indicate that it occurs in sediments as the free hydro-
carbon and is not present within the kerogen (Noble 4. Conclusions
et al., 1984). High abundances of BNH have been
associated with severely oxygen-deficient conditions Oxygen-depleted sedimentation of the La Luna
(Mello et al., 1989, and references within). In the La Formation in the western Maracaibo Basin started
Luna Formation maximum concentrations of BNH well before the CTBE, during the middle-late Ceno-
occur in Unit 2, where we interpret the highest manian in an open-marine environment, with a
productivity within the studied section, perhaps con- palaeowater depth of a few hundred metres and very
sistent with productivity-induced anoxia. Whatever low elastic input. We consider this early deposition
its origin, the presence of BNH in the La Luna of black shales to be the local response to a combina-
Formation clearly records changing local environ- tion of rapid sea-level rise and the presence of
mental conditions which precede, but are apparently upwelling currents. Geochemical evidence suggests

Tdcyclii retpanes’ PC1 Sleranesil-fopanes” 28.30 bisnorhopane

160

140

120

100

eo

so

40

20

i
n
“0 loo0 -10 0 10 0.15 0.35 0.55 10 0 10 0 50 100

pprn of EOM pprn of EOM

Fig. 8. Depth plots of the scores of the first two principal components identified from the biomarker data compared to selected molecular
profiles. The PC1 plot essentially records fluctuations in relative concentrations of long-chain tricyclic terpanes, while PC2 records
fluctuations in steranes vs. hopanes. The distinctive trend of absolute concentration of 28,30-bisnorhopane is also shown. ’ Css-Css.
* * Steranes/hopanes ratio = Speak areas aPP steranes (C,,-C,,)/Xpeak areas oP hopanes (C,,-C,,).
 J. Perez-Infante et d/Chemical Geology 130 (1996) 271-288 285

that high carbonate and silica bioproductivity contin- at the site studied probably due to migration of
ued until the early Turonian. upwelling currents as is inferred from geochemical
The CTBE is, nevertheless, recorded in the mid- and micropalaeontological changes. However,
dle part of the La Luna Formation as a marked preservation of organic matter remained relatively
613C isotopic excursion. This isotopic shift is high due to the expansion of the oxygen-minimum
appg&tly unrelated to locally controlled changes in zone during the peak of the sea-level rise, as indi-
bioproductivity and intensity of oxygen depletion. cated from foraminiferal assemblages.
In the early Turonian, before the end of the Sedimentological and micropalaeontological evi-
isotopic excursion, biogenic productivity decreased dence suggest that the upper part of the La Luna

7
a

15

16

Fig. 9. Hopanes
Table 3.
JLL
and tricyclic terpanes (m/z 191) in typical samples from Units 2-3 (b) and Units 4-5 (a). Peak identities are given in
286 J. Perez-Infante et al./Chemical Geology 130 (1996) 271-288

Table 3 Formation (middle-Turonian to Santonian) experi-

Biological marker compounds used in the principal components
enced a rapid regressive pulse followed by a second
analysis (the numbers are used as peak labels in Figs. 7 and 9)
period of milder upwelling influence. Isotopic
Hopunes:
stratigraphy at the top of the La Luna Fm. indicates
I. 18a(H)-nisnomeohopane (Ts) the onset of a positive carbon isotopic excursion
2. 17o(H)-trisnorhopane (Tm) related to OAE-3 (Coniacian-Santonian).
3. 28,30-bisnorhopane
Biological marker data appear generally similar
4. C,, 17o (H), 21E (H) hopane
5. C,, 17o (H), 21B (H) hopane
for all samples upon initial inspection, although ap-
6. C,, 17~ (HI, 21p (H) hopane (22s) plication of principal components analysis identified
7. C,, 17o. (H), 21f3 (H) hopane (22R) some significant variability, particularly in the
8. C,, 17~ (H), 21p (HI hopane (22s) amount of extended tricyclic terpanes, 28,30-bi-
9. C,, 17a (H), 2lB (HI hopane (22R)
snorhopane and the sterane/hopane ratio. However,
IO. C,, 17a (H), 2lp (H) hopane (22s)
11. C,, 17a (H), 2lB (H) hopane (22R)
these biomarker variations do not occur in associa-
12. C,, 171~(H), 2lp (H) hopane (22s) tion with the isotopic excursion and are probably
13. C 34 I7a (H), 2 1p (HI hopane (22R) controlled by local fluctuations in organic matter
input and preservation. PCA identifies the abundance
Tricyclic terpanes:
of extended ( > C 27) tricyclic terpanes as the major
14. C ,9 13P(H),l4cx(H) tricyclic terpane source of biomarker variability. The significance of
15. C,, 13P(H), I4a(H) tricyclic terpane these compounds remains unclear, but they are ap-
16. C,, 13B(H),14a(H) tricyclic terpane
parently unrelated to the shorter-chain tricyclics, and
17. C,, 13P(H),14o(H) tricyclic terpane
18. Cz4 13@(H), 14a(H) tricyclic terpane
appear to have a different biological source.
19. C,, 13P(H),l4u(H) tricyclic terpane
20. C,, 13f3(H),l4cx(H) tricyclic terpane (22s)
21. C,, 13B(H),14a(H) tricyclic terpane (22R) Acknowledgements
22. C,, 13P(H),l4o(H) tricyclic terpane (22s)
23. C,, 13E(H),14u(H) tricyclic terpane (22R)
24. C,, 13E(H),14cx(H) tricyclic terpane (22% The authors are grateful to INTEVEP for financial
25. C,, 13B(H),l4a(H) tricyclic terpane (22R) support and a Ph.D. studentship (J.P.1). We also
26. C,, 13P(H), 141x(H) tricyclic terpane (22s) thank W. Scherer, M. Alberdi and A. Pilloud (IN-
27. C,, 13P(H),14a(H) tricyclic terpane (22R)
TEVEP) for their assistance during collection of
28. C,, 13P(H),14u(H) tricyclic terpane (22s)
29. C,, 13P(H),l4o(H) tricyclic terpane (22R)
outcrop samples. GC and GC-MS technical assis-
30. C,, 13E(H),14a(H) tricyclic terpane (22s) tance was provided by I. Harrison and P. Donahoe,
3 1. C,, 13@(H), 14o(H) tricyclic terpane (22R) and the artwork produced by Ms. C. Jeans (NRG).
32. C,, 13B(H),14a(H) tricyclic terpane (22s) D. Ariztegui, S. Bernasconi and J. McKenzie (ETH,
33. C,, 13B(H),14o(H) tricyclic terpane (22R) Zurich) are thanked for their help in obtaining the
34. C,, 13B(H),14u(H) tricyclic terpane (22s)
35. C,, 13B(H), 141x(H) tricyclic terpane (22R)
stable isotopic data. We are also grateful to R. Tyson
(NRG) for invaluable discussions regarding this
Tetracyclic terpane: work, and to the reviewers of the manuscript for
36. C,, tetracyclic terpane
their constructive comments. (RA)

Sterunes:

37. C,, k(H), 14E(H), 17P(H) sterane (20R) References

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