Marine and Petroleum Geology 37 (2012) 7e26

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Marine and Petroleum Geology

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Meteoric-water diagenesis in late Cretaceous canyon-ll turbidite reservoirs

from the Esprito Santo Basin, eastern Brazil
H. Mansurbeg a, g, *, L.F. De Ros b, S. Morad a, c, J.M. Ketzer d, M.A.K. El-Ghali e, M.A. Caja f, R. Othman g
a
Department of Earth Sciences, Uppsala University, Villavgen 16, SE 752 36 Uppsala, Sweden
b
Universidade Federal do Rio Grande do Sul, Instituto de Geocincias, Av. Bento Gonalves, 9500, CEP 91501-970 Porto Alegre, Brazil
c
Department of Petroleum Geosciences, The Petroleum Institute, P.O. Box 2533, Abu Dhabi, United Arab Emirates
d
Pontifcia Universidade Catlica do Rio Grande do Sul e PUCRS, Instituto do Meio Ambiente, Prdio 5, Sala 307, Av. Ipiranga 6681, CEP 90619-900 Porto Alegre, Brazil
e
Department of Earth Sciences, College of Science, Sultan Qaboos University, P.O. Box 36, Al-Khodh 123 Sultanate of Oman and Geology Department, Faculty of Science, Tripoli
University, P.O. Box 13696, Tripoli, Libya
f
Departamento de Petrologa y Geoqumica, Facultad de Geologa Universidad Complutense de Madrid, Avda. Jose Antonio Novais, s/n, 28040 Madrid, Spain
g
Department of Petroleum Geosciences, Faculty of Science, Soran University, Soran, Kurdistan Region of Iraq, Iraq

a r t i c l e i n f o a b s t r a c t

Article history: Parameters controlling the diagenetic evolution of passive margin, marine turbidites, which are important
Received 22 March 2012 targets of hydrocarbon exploration, are poorly constrained in the literature. This study aims to unravel
Accepted 26 March 2012 the conditions of diagenesis and its impact on the reservoir quality evolution from late Cretaceous canyon-
Available online 25 April 2012
lling turbiditic sandstones of the onshore portion of Esprito Santo Basin, eastern Brazil. Kaolinization
(d18O 13.3& to 15.2&; d D 96.6& to 79.6&) and dissolution of framework silicate grains is
Keywords:
attributed to meteoric water incursion during eodiagenesis in response to a considerable fall in relative
Turbidites
sea-level. Eogenetic alterations also include cementation by siderite (average d18O 7.2&;
Diagenesis
Reservoir-quality
d13C 9.3&) and pyrite. Progressive sediment burial (present depths 1530e2027 m) resulted in the
Urucutuca formation of poikilotopic calcite, ferroan dolomite-ankerite (average d18O 7.9&; d13C 2.9&), minor
amounts of quartz overgrowths and in partial dickitization of kaolinite. Isotopic values of calcite and
dolomite-ankerite follow two trends of co-variance of d13C with decreasing d18O and increasing temper-
ature. From a composition closer to marine (z0&), one trend goes towards positive d13C values
(up to 22.4& for calcite; 18.6& for dolomite-ankerite), indicating increasing input of carbonate from
methanogenic fermentation. The other trend develops towards negative d13C values (down to 17.2& for
calcite; 15& for dolomiteeankerite), suggesting increasing contribution from thermal decarboxylation
with increasing temperature and depth. Despite the presence of various cement types, mechanical
compaction was more important than cementation in reducing depositional porosity in the onshore
Urucutuca sandstones.
2012 Elsevier Ltd. All rights reserved.

1. Introduction during compaction and mineral-water interaction (Primmer et al.,

Diagenesis and reservoir-quality evolution pathways of sand-
stones are complex, being governed by numerous inter-related
parameters, such as detrital composition, depositional facies,
climatic conditions, tectonic settings and burial history, as well
as the chemical composition and ow patterns of basin uids
(Stonecipher et al., 1984; Wilson and Stanton, 1994; Morad et al.,
2000). The detrital composition of sand controls the mechanical
and chemical properties of sandstones, and hence their behaviour
* Corresponding author. Department of Petroleum Geosciences, Faculty
of Science, Soran University, Soran, Kurdistan Region of Iraq, Iraq.
Tel.: 9647507065558.
E-mail address: howri.mansurbeg@soranu.com (H. Mansurbeg).
1997; Girard et al., 2002). Depositional facies impose profound
impact on primary porosity and permeability, and hence on rates
and patterns of uid ow, mass transfer and on rates of diagenetic
reactions in sandstones (Worden and Burley, 2003). The multiple
parameters controlling the diagenetic alterations usually result in
complex spatial and temporal distribution patterns of reservoir
quality and heterogeneity.
In the past decades, hydrocarbon exploration has been increas-
ingly concentrated in marine, turbiditic sandstone reservoirs
deposited in basins situated along passive continental margins.
The inuence of diagenesis on reservoir quality and heterogeneity
of such sandstones is relatively poorly understood, and is generally
believed to be mediated by marine pore waters (Bjrlykke and
Aagaard, 1992; Dutton, 2008).

0264-8172/$ e see front matter 2012 Elsevier Ltd. All rights reserved.
doi:10.1016/j.marpetgeo.2012.03.009
8 H. Mansurbeg et al. / Marine and Petroleum Geology 37 (2012) 7e26

However, Wilkinson et al. (2006) in order to explain extremely
depleted d18O values of carbonate cements in the North Sea Tertiary
turbiditic sandstones, have suggested a charge of meteoric water
from Shetland platform into these sediments. Diagenesis in the
deep-see sandstones in the San Joaquin Basin, California. has also
been inuenced by meteoric-water circulation (Lee and Boles, 1996).
The amounts and distribution pattern of kaolinite are inuenced
by the amounts of unstable detrital silicates, permeability, annual
precipitation, and the rate of uid ow and hydraulic conductivity
in the sandstone body. Grain dissolution is thus prevalent in
permeable sediments, such as channel sand deposits, which are
subjected to rigorous meteoric water circulation (Morad et al.,
2000). However, it has also been suggested that the blocky kaolin
grew from stagnant meteoric porewater (a relic of the early post
depositional porewater) mixed with some acidic basinal uid
(Haszeldine et al., 1992; McAulay et al., 1994; Osborne et al., 1994).
Recent studies (e.g. Mansurbeg et al., 2006; Prochnow et al.,
2006) have pointed out the role of meteoric water incursion on
diagenetic alterations, and hence on the reservoir quality of
turbiditic sandstones. This study aims to elucidate and discuss the
parameters controlling the distribution of diagenetic alterations
and their impact on reservoir quality evolution of the channel-
complex, canyon-ll Urucutuca turbiditic sandstones, which are
important reservoirs in the Esprito Santo Basin, eastern Brazil.
2. Geological setting
Late Cretaceous-Paleogene turbiditic sandstones of the Urucutuca
Formation are considered as one of the main reservoirs in the Esprito
Santo Basin (Fig. 1), eastern Brazil passive margin, containing close to
60 million barrels of recoverable oil (Carvalho, 1989). In the portion of
the basin currently onshore, these sandstones were deposited within
deeply incised submarine canyons. The incision of the canyons
into Early Cretaceous carbonates, evaporites and sandstones was
controlled by ancient basement faults. In the offshore part of the
basin, extensive turbidite fans were deposited in lows originated by

A
Esprito Santo Basin
MUCURI
Basement PALEOCANYON

BRAZIL
ABROLHOS
COMPLEX

ATLANTIC OCEAN

TERTIARY BASALT COMPLEX FAZENDA CEDRO

PALEOCANYON BOUNDARY
REGNCIA PALEOCANYON
PLATFORM
DOCE RIVER

LAGOA PARDA
OIL FIELD
REGNCIA CANYON 0 10 km

W E

BARRA NO RIO DOCE FM.

VA FM.
CARAVELAS FM.
Urucutuca FM.

MAR
BASEMENT IRIC
U FM.
MUCURI FM.
CRICAR
FM.

5 Km

Figure 1. (A) Location map of the studied oilelds in the Esprito Santo Basin, eastern Brazil, showing the Lagoa Parda and Fazenda Cedro paleocanyons (Modied after Cosmo et al.,
1991). (B) A schematic dip section of the basin showing the thickening of the Urucutuca Formation towards east (modied after Del Rey and Zembruscki, 1991).
 H. Mansurbeg et al. / Marine and Petroleum Geology 37 (2012) 7e26 9

salt tectonics and associated lystric faults. The canyon-ll turbidites
were deposited as channel complexes constituted by coarse-grained,
massive, channel sandstones interbedded with ne-grained,
crevasse-splay levee deposits and bioturbated mudstones, and
covered by thick marine shales (Bruhn and Walker, 1997).
The Esprito Santo Basin covers an area of z 25,000 km2 on the
eastern Brazil passive margin (Fig. 1A) of which only 3220 km2 are
onshore. The basin basement is composed of Precambrian mig-
matites, granulites, gneisses and granites, which occur as homo-
clinal, faulted blocks tilted towards the east (Fig. 1B). The main
source rocks in the basin are Neocomian rift phase lacustrine shales
of the basal Cricar Formation (Fig. 2A and B) (Estrella et al., 1984;
Carvalho, 1989). The Cricar Formation is covered by Aptian alluvial
sandstones and conglomerates of the Mariricu Formation, which in

Figure 2. (A) Schematic cross-sectional view of the Lagoa Parda Field. Notice the Urucutuca reservoirs in direct contact with the Lower Cretaceous Mucuri and Cricar sandstones.
(B) Simplied stratigraphic chart for the Esprito Santo Basin (modied after Del Rey and Zembruscki, 1991).
10 H. Mansurbeg et al. / Marine and Petroleum Geology 37 (2012) 7e26

turn are overlain by Aptian evaporites of the Itanas Member.
Shallow marine carbonates (Regncia Member) and fan-deltaic
clastics (So Mateus Member, Barra Nova Formation) were depos-
ited during the Albian-Cenomanian.
During the Late Cretaceous and Lower Tertiary, thermal
subsidence, generalized tilting towards the east, and related salt
tectonics controlled the deposition of a thick sequence of marine
mud and turbiditic sands of the Urucutuca Formation (Fig. 2B).
Intraplate basic alkaline magmatism occurred in the northern
part of the basin during the early Tertiary (37 m.y.; Cordani and
Blazekovic, 1970), building the large Abrolhos volcanic platform.
Sedimentation since the late Tertiary has been characterized by
a regressive sequence of platform carbonates (Caravelas Formation)
and coastal fans (Rio Doce Formation).
The deposition of Urucutuca turbidites in the onshore portion of
the basin occurred dominantly within submarine canyons incised in
the border of the platform during relative sea-level falls that punc-
tuated the overall transgressive setting of the late Cretaceous and
early Tertiary (Bruhn and Walker, 1997). However, the deposition of
only a few of the turbidite successions can be connected with global,
eustatic sea-level curves. Sediment supply to deep water was related
to tectonic reactivation in the source-areas and basin margin, and/or
to high rates of climatically-controlled denudation in the source
area (Bruhn, 1993). Canyon incision was directly controlled by
ancient fault zones in the basement (Carvalho, 1989). Two major
canyons have been recognized in the Esprito Santo Basin, namely
the Regncia Canyon, containing the Lagoa Parda oil eld, and the
Fazenda Cedro Canyon, containing the oileld with the same name,

7-LP-33-ES

Top of occurence
of overflow facies

Amplified
1500 Resistivity

1525

1525

cored intervals

1600 Resistivity

S A MA

1550

7-LP-36-ES

1550

1550 Top of occurence

of overflow facies

Amplified
Resistivity

cored intervals 1575

1600

1575

S A MA
GR Resistivity

Figure 3. Canyon-lling turbidite successions of the Lagoa Parda oileld are composed of channelized complexes of coarse-grained turbiditic sandstones and ne-grained levee
deposits (modied after Bruhn and Walker, 1997).
 H. Mansurbeg et al. / Marine and Petroleum Geology 37 (2012) 7e26
amongst others. Additional canyons lled by Urucutuca turbidites
were incised in the Mucuri, Jequitinhonha and Almada basins, which
are located northwards and are similar, structurally and strati-
graphically, to the Esprito Santo Basin (Bruhn and Moraes, 1989).
The canyon-lling turbidite deposits are composed of channel
complexes of coarse-grained channel deposits interbedded with
bioturbated mudstones and ne-grained levee deposits (Fig. 3).
The levee deposits in the Lagoa Parda turbidites are typically
asymmetrical, being higher and thicker on the left side when
looking down stream (Fig. 4; Bruhn and Walker, 1997). In the Lagoa
Parda eld, the channel lls are w9 to >50 m thick, 210 to w1050 m
wide and >1 km long, and become narrower, thinner, and ner-
grained upwards (Bruhn, 1993). These turbidites do not outcrop in
the Esprito Santo basin, yet the high-resolution subsurface strati-
graphic study of the Lagoa Parda turbidites by Bruhn (1993) showed
geometric characteristics similar to the correlatable outcropping
deposits in the Almada Basin (Bruhn and Moraes, 1989). Fauna
described for the Eocene mudstones drilled in the Lagoa Parda
oileld is very diversied (Bruhn, 1993). A deep neritic to upper
bathyal (200e500 m) association of a large number of genera and
individual benthic foraminifera have been identied (Azevedo,
1985), indicating highly oxygenated sea-bottom environment
(Azevedo, 1985). Oxygenated bottom conditions are further reec-
ted by the low total organic carbon content (z1e2% by weight) and
the low Hydrogen Index of the dominantly terrestrially-derived
kerogen in the mudstones (Estrella et al., 1984).
Abundant plant debris in the cores of the Lagoa Parda eld
suggests a warm and humid climate for the Esprito Santo Basin
area during the Eocene. Important continental runoff and local
salinity decrease in the Regncia Canyon during the early Eocene
is suggested by the small number of individuals in the calcareous
nannofossil assemblage (Antunes, 1990) and also by the large
amount of woody terrestrial plant remains (Bruhn, 1993). These
local observations agree well with global paleoclimatic recon-
structions (Parrish et al., 1982).
3. Samples and methods
A total of sixty samples from four wells cored through the
Urucutuca Formation (two in the Fazenda Cedro and two in the
Lagoa Parda oilelds) were selected for this study. The samples
cover the variations in depositional facies, including coarse-grained
to conglomeratic, channel sandstones and ner-grained crevasse-
splay sandstones. Modal compositions of the sandstones were
i on
vuls
A
5 -50 m
Marginal
Levees
Channels
1 -3 km
Figure 4. Schematic cross-sectional view of the channel-levee complexes of the Urucutuca Formation. The levee successions are asymmetrical, being higher and thicker on the left
side of the channels looking downstream (modied after Bruhn and Moraes, 1989).
11
obtained from 18 representative samples (Table 1) by counting 300
points in each blue epoxy resin-impregnated thin section. Mineral
chemical analyses were performed using a Cameca Camebax SX50
electron microprobe (EMP), equipped with a backscattered electron
detector (BSE). Operating conditions were: 20 kV acceleration
voltage, 8 nA (for carbonates and clay minerals) to 12 nA (for
feldspars) measured beam current, and a 1e10 mm beam diameter
(depending on the extent of homogeneous areas). Standards and
count times were wollastonite (Ca, 10 s), orthoclase (K, 5 s), albite
(Na, Si, 5 and 10 s, respectively), corundum (Al, 20 s), MgO
(Mg, 10 s), MnTiO3 (Mn, 10 s) and hematite (Fe, 10 s). Precision of
analyses was better than ca. 100 ppm for the carbonate cements.
The texture, occurrence habits, and paragenetic relationships
among diagenetic components were examined using a Jeol
JSM-T330 scanning electron microscope (SEM). Stable carbon
and oxygen isotope analyses were performed on 22 carbonate-
cemented sandstone samples. Carbon and oxygen isotope compo-
sitions of the calcite fraction were determined by the method
described by Al-Aasm et al. (1990). The samples were treated in an
O2 plasma to remove volatile organic matter and then reacted with
100% H3PO4 in vacuo at 25  C for one hour (calcite), at 50  C for 24 h
(Fe-dolomite/ankerite) and for three days at 50  C (siderite).
The evolved CO2 gas was analysed for carbon and oxygen isotopes
in a SIRA-12 mass spectrometer. The phosphoric acid fractionation
factors used were 1.01025 for calcite (Friedman and ONeil, 1977),
1.01060 for Fe-dolomite/ankerite, and 1.010454 for siderite
(Rosenbaum and Sheppard, 1986). Data are reported in & relative
to the Vienna Pee Dee Belemnite (V-PDB) standard. The oxygen and
hydrogen isotopes of kaolinites from 11 samples were analysed,
and the results are reported in & relative to the Vienna Standard
Mean Ocean Water (V-SMOW) standard. Samples were subjected to
removal of organics by exposing them to NaOOH solution adjusted
to a pH of 9.5 while placed in boiling water bath for 15 min,
followed by centrifugation at 800 rpm for 5 min. The remaining
mud was centrifuged at 750 rpm for 3.3 min to separate the clay
fraction. Samples containing carbonates were exposed to the same
procedure above after being subjected to carbonate removal by
simmering in a buffer solution of acetic acid for at least eight hours.
87
Sr/86Sr ratios were determined for two calcite-rich samples using
an automated Finnigan 261 mass spectrometer equipped with
nine Faraday collectors. Correction for isotopic fractionation during
the analyses was made by normalization to 86Sr/88Sr 0.1194.
The mean standard error of mass spectrometer performance
was 0.00003 for standard NBS-987.
12 H. Mansurbeg et al. / Marine and Petroleum Geology 37 (2012) 7e26

Table 1
(A) and (B) Point-counting data of Urucutuca sandstones based on 300 points per thin-section for coarse-grained channel complex sandstones and ne-grained crevasse-splay
sandstones respectively.

Well 7-LP-33-ES 7-LP-33-ES 7-LP-33-ES 7-LP-33-ES 7-LP-36-ES 7-LP-36-ES 7-LP-36-ES 7-LP-36-ES 3-FC-18D-ES

Depth (m) 1518.65 1559.45 1570.65 1576.6 1531.9 1538.25 1544.7 1571.8 1978
Detrital minerals
Total detrital quartz 31.4 30.7 33.7 34 41.7 41.7 38.6 35 27.7
Quartz monocrystalline 28.7 30 31.7 32.3 38.7 38.7 36.3 32.7 26
Quartz polycrystalline 2.7 0.7 2 1.7 3 3 2.3 2.3 1.7
Total detrital Feldspar 12.7 7.3 14.3 12.3 15.7 17.3 11.7 15 19.3
Detrital K-feldspar 11 7 13.3 12 13.7 15.7 10.7 14.7 19.3
Orthoclase 1 0 3 1 2.3 4 2.7 4.7 2.3
Microcline 8.7 4.3 7.7 6.3 9.7 9.7 5.3 7.3 11
Perthite 0.7 0.3 0.7 0.7 0.3 0.7 0.3 0 0.7
Detrital Plagioclase 1.7 0.3 1 0.3 2 1.7 1 0.3 0
Plagioclase monocrystalline 1.3 0.3 0.7 0 1.3 1 0.7 0.3 0
Plutonic lithic fragments 8.7 6.3 8 10 9 5.7 7.7 11.7 12.3
Metamorphic lithic fragment 0 0 0 0.7 0 0 0.3 0.3 0
Volcanic lithic fragments 0 0 0 0 0 0 0 0 0
Muscovite 0 1 0 0.7 0 0.3 0 0 0
Biotite 0 0 0 0 0 0 0 0 0
Garnet 0.3 0 0.7 0 0.7 0.7 0.7 0 0.3
Opaques 0 0.3 0.7 0 0.3 0.3 0 0 0
Other Heavy Minerals 0 0 0 0.3 0.7 0.7 0.3 0.3 0.3
Mud intraclast 0 0 0 0 0 0 0 0 0
Carbonate bioclast/intraclast 0.3 0 0 0 0 0 0 0 0
Pseudomatrix 0.7 0 0.7 2 0 1 0 0 0

Diagenetic minerals
Diagen. total 27.7 50.7 25 37.3 26.7 16.3 28 21 43.7
iron oxides 0 0 0.3 1 0 0 0 0 0.7
Quartz overgrowth 0.7 0.3 0.7 3.3 0 0 0 1.7 0
Quartz fracture healing 0.3 0.3 0 1 0 0 0 0.7 0
K-feldspar overgrowth 0 0 0 0 0 0 0 0 0
Kaolin intergranular 3.3 1.7 7 3.7 0.3 1 4.7 4 0.3
Kaolin in feldspar grain 7.7 4 4.3 4.7 0.7 2.7 4 5 0
Kaolin in grain 0 0 0.3 0 0 0 0.7 0 0
Kaolin in mica 3.3 4.7 3 1.7 2.3 4.3 7 6.7 0
Kaolin replacing pseudo matrix 4.7 1.7 0.3 7.3 0 0.7 0 0 0
Kaolin oversized patch 0 0 0 0.7 0 0.7 1 0.7 0
Calcite poikilotopic intergr. 0 15 0 0 0 0 0 0 0
Calcite mosaic intergr./repl.kaol. 0.3 1.7 3.7 0 8 0.7 3 0 0
Calcite coarse in feldspar 0 5.3 1.3 0 2 0.7 0.3 0 0
Calcite coarse in quartz 0 4 0 0 0 0 0 0 0
Calcite replacing sideritized mica 0 0 0 0 0 0 0 0 0
Calcite in mica 0 2.3 0.7 0 0.7 0.3 0 0 0
Calcite replacing pseudomatrix 0.7 0 0 0 0 1 0 0 0
Calcite mosaic overs. patch 0 2.7 0 0 0 0 0.3 0 0
Dolom./Ankerite coarse intergr. 0.7 0 0 4.3 6.3 0.3 0.7 0 2.7
Dolom./Ankerite microcr. intergr. 0 0 0.3 0 0 0 0 0 0
Dolom./Ankerite in feldspar 0 0 0.7 0.3 1 0.7 1 0 2.7
Dolom./Ankerite in quartz 0 0 0 0.7 0 0 0 0 1
Dolom./Ankerite in mica 0.3 0.7 0.7 0 1.7 0.7 2.7 0 0
Dol./Ank. repl. sideritized mica 2 1 0 1 0 0 0 0 0
Dolom./Ankerite repl. ps. matrix 0 0 0.3 5 0.3 1.3 0 0 30.7
Dolom./Ankerite in bioclast 0 0 0 0 0 0 0 0 2
Siderite microcr. intergranular 0 0 0.7 0 1 0 0 0 0
Siderite in mica 0.7 2.3 0.7 0.7 2 0 0 0 0
Siderite replacing ps. matrix 1.7 2.3 0 1.3 0 0 0 0 0
Illite in feldspar grain 0 0 0 0 0 0 0 0 0
Illite intergranular 0 0 0 0 0 0 0 0 0
Anatase intergranular 0.3 0 0 0.3 0 0 0 0 0
Anatase replacing grain 0 0 0 0 0 0 0 0 0
Pyrite intergranular 0 0 0 0 0 0 0.3 0 2.7
Pyrite in grain 0.7 0.3 0 0.3 0.3 1.3 2.3 0.7 1
Albite repl. plagioclase 0 0 0 0 0 0 0 0 0
Albite repl. K-feldspar 0 0 0 0 0 0 0 0 0
Albite overgrowth 0 0 0 0 0 0 0 0 0
Albite discrete 0 0 0 0 0 0 0 0 0
Baryte 0 0 0 0 0 0 0 0 0
Bitumen 0.3 0.3 0 0 0 0 0 1.7 0

Porosity
Macroporosity 19.3 6 19.3 7 7.3 18 15.3 19.3 1.7
Intergranular 11 1.7 12.3 4 2 6.7 11.7 16.7 0
Intragranular in feldspar 4.7 2.7 4.7 2 1.7 5.7 1.7 2 0.7
Intragranular in plutonic r.f. 0.7 0.3 0.7 0 0.3 0.7 0 0.7 0.3
Intragranular in mica 0.3 0 0 0 0 0 0 0 0
 H. Mansurbeg et al. / Marine and Petroleum Geology 37 (2012) 7e26 13

3-FC-18D-ES 3-FC-18D-ES 7-LP-33-ES 7-LP-33-ES 7-LP-33-ES 7-LP-33-ES 7-LP-36-ES 3-FC-3-ES 3-FC-3-ES

2008.75 2026.45 1517.7 1522.3 1533.35 1577.35 1556.5 1730.4 1731.8 Average Std. Dev.

33.7 36.7 33 31.4 23.7 24 39 25.6 32 33.0 5.4

33 36 30 27.7 21.7 23 36 25.3 31.3 31.1 5.0
0.7 0.7 3 3.7 2 1 3 0.3 0.7 1.9 1.3
13.7 17 16.7 15 18 10.7 9.7 8.3 18.3 14.1 4.2
12.3 17 15 11.3 16 7.7 8.7 7 16 12.7 4.0
2.7 2.3 3.7 0.3 5.7 2.3 1 1 2.7 2.4 1.9
6 9.3 9.7 5.3 8.3 4 6.7 5 11.7 7.6 2.8
0.7 1 1.3 3.7 0.7 0 0.3 0.3 0.7 0.7 1.3
1.3 0 1.7 3.7 2 3 1 1.3 2.3 1.4 1.0
1 0 1.7 2 1.7 2.3 0.7 1.3 2 1.0 0.5
13 14 6 10.3 4.3 7.3 3 1.7 8 8.2 3.0
0 0 0 0.7 0 0 0 0 0 0.1 0.3
0 0 0 0 0 0 0 0 0 0.0 0.0
0 0 0 0.3 0.7 1 0 0.3 0.3 0.3 0.4
0.3 0.3 0 0 0.3 0 0 1.7 1.3 0.2 0.7
1.3 2.3 1 0 0 0 0.3 0 1 0.5 0.5
0 0 0 0.3 1 0 0.3 0.3 0.3 0.2 0.3
1 1.3 0.3 0.3 0 0 0.7 1 0.7 0.4 0.4
0 0 0 0 0 0 0 0.7 0.7 0.1 0.3
0 0 0 0 0 0 0 0 0 0.0 0.0
1 0 0.7 0 2 0 0 0.7 0 0.5 0.7

20.7 15 27.7 22.3 31.7 32.7 42.7 59.3 18.3 30.4 13.8
0 0 0 0 0 0 0 1 0 0.2 0.4
0 0 0 0.3 0.3 2.7 0 0 0 0.6 1.0
0 0 0 0.3 0 0.3 0 0 0 0.2 0.1
0 0 0 0 0 0 0 0.7 0 0.0 0.3
3.7 1.7 1.7 2 2.3 4.3 1.7 0 0 2.4 1.5
5.3 6.3 4.3 2.3 4.3 5.7 2.3 3.3 5.7 4.0 1.4
0 0 0.3 0 0.3 0 0.3 0 0 0.1 0.2
0.3 1 1.7 2.3 6 5 3 5.7 7.3 3.6 2.1
0.3 0 2.7 2.3 0 2 0 0 0 1.2 1.3
0 0.3 0 0 0 0 0 0 0 0.2 0.0
0 1.3 0 0 0 0 20.3 0 0 2.0 7.7
4 0.7 7.7 6.3 0 1 2 0 0 2.2 3.2
1.3 0 0.7 0.7 0 0 3.7 0 0 0.9 1.4
0 0 0 0 0 0 1 0 0 0.3 0.4
0 0 0 0 0 0 0 0 0 0.0 0.0
0 0 0 0 0 0 1.7 0 0 0.3 0.6
0 0 1.7 0 0 0 0 0 0 0.2 0.6
0 0 0 0 0 0 0 0 0 0.2 0.0
1.3 0.7 0.3 0.3 2 4 0.7 25 0 2.7 9.1
0 0 0.3 0 0.3 0 0 0 0 0.1 0.1
0.3 1 0 0 1 1 0 4.7 0.3 0.8 1.7
0.7 0 0 0 0 0 0 5 0 0.4 1.9
0 0 0 3 9.3 1 2 6.3 0.3 1.6 3.5
0 0 0 1.3 0 1.3 0 0 0 0.4 0.6
0 0 1 0 2.7 0.7 0 0.7 0 2.4 1.0
0 0 0 0 0 0 0 0 0 0.1 0.0
0 0 2 0 0.7 0 0 0 0 0.2 0.8
0 0 1.3 0 1 1.3 0.3 0 0 0.6 0.6
0 0 1.3 0 0 0.3 0 0 0 0.4 0.5
0 0 0 0 0 0.3 0 0 0 0.0 0.1
0 0 0 0 0 0 0 0 0 0.0 0.0
0 0 0 0 0 0.3 0 0 0 0.1 0.1
0 0 0 0.3 0 0 0 0.7 0 0.1 0.3
0.7 0 0 0 0 0.3 0 1.3 0.3 0.3 0.5
0.7 1.3 0.3 0 1 0.7 3.7 5 3.7 1.3 2.0
0 0 0 0 0 0 0 0 0 0.0 0.0
0 0 0 0 0 0 0 0 0 0.0 0.0
0 0 0 0 0 0 0 0 0 0.0 0.0
0 0 0 0 0 0 0 0 0.3 0.0 0.1
1.7 0 0 0.3 0 0 0 0 0 0.1 0.1
0.3 0.7 0.3 0.3 0.3 0.3 0 0 0.3 0.3 0.1

18.7 17.7 15 23 20 26.3 5.3 1 20.3 14.5 9.4

7.7 11 5.7 8.7 12.3 12.7 3 0 12.7 7.8 5.1
8.7 5.3 3 7.3 4.7 7 0.7 0 4.7 3.7 2.8
0.3 0.3 0.7 2 0.7 0.3 0.3 0 1 0.5 0.7
0 0 0 1 0 0.3 0 0 1.3 0.2 0.5
14 H. Mansurbeg et al. / Marine and Petroleum Geology 37 (2012) 7e26

Table 1 (continued)

Well 7-LP-33-ES 7-LP-33-ES 7-LP-33-ES 7-LP-33-ES 7-LP-36-ES 7-LP-36-ES 7-LP-36-ES 7-LP-36-ES 3-FC-18D-ES
Depth (m) 1518.65 1559.45 1570.65 1576.6 1531.9 1538.25 1544.7 1571.8 1978
Intragr. in heavy mineral 0 0 0 0 0 0 0 0 0
Intra/intercrystal. in carbonate 0 0.7 0 0 2.7 3 1 0 0.7
Dissolution of pseudomatrix 1.3 0.7 0.3 0 0 0.7 0 0 0
Moldic 0.3 0 0.3 1 0.3 1 0.3 0 0
Fracture 0.7 0 1 0 0.3 0.3 0.7 0 0
Oversized 0.3 0 0 0 0 0 0 0 0
Microporosity Abundant Common Abundant Abundant Abundant Abundant Abundant Common Rare
Intergranular volume 12.7 23 13.3 26.3 16 5 8.7 7.3 37
Grain volume 87.3 77 86.7 73.7 84 95 91.3 92.7 63
Carbonate total 6.3 37.3 9 13.3 23 5.7 8 0 39
Calcite total 1 31 5.7 0 10.7 2.7 3.7 0 0
Siderite total 2.3 4.7 1.3 2 3 0 0 0 0
Dolomite/Ankerite total 3 1.7 2 11.3 9.3 3 4.3 0 39
Kaolin total 19 12 15 18 3.3 9.3 17.3 16.3 0.3
Albite total 0 0 0 0 0 0 0 0 0
Grain replacement total 15 27.7 11.7 11 10.7 11.3 19.3 13.7 6.7

Nominal grain size Coarse Coarse Coarse Very coarse Very coarse Medium Coarse Coarse Granule
Modal grain size (mm) 0.77 0.85 0.9 1.3 1.25 0.4 0.6 0.65 2
Nominal Sorting Poor Poor Poor Poor Very poor Poor Poor Poor Very poor
Sorting 1.4 1.7 1.6 1.8 2.5 1.9 1.8 1.4 2.2
Packing index (Pp) 36 33 31 48 11 24 28 30 1
G/NG 64 67 69 52 89 76 72 70 99
TC 100 100 100 100 100 100 100 100 100

4. Detrital composition of sandstones and B), whereas coarse-grained, channel sandstones contain higher
amounts of detrital quartz and feldspar grains (Fig. 6C and D).
The sandstones generally are poorly to moderately-sorted and
medium-to coarse grained. Rarely, very poorly sorted, very coarse-
5. Petrography and chemistry of diagenetic minerals
grained and conglomeratic sandstones occur. The sandstones are
arkoses sensu Folk (1968; Fig. 5; average QFL). Quartz is the domi-
5.1. Kaolinite
nant detrital constituent and occurs as mono-and, less commonly,
polycrystalline grains (averages 31 vol% and 2 vol%, respectively;
Kaolinite is the dominant clay mineral (Up to 7.3%; average 2%;
Table 1A and B). Among feldspars, microcline (average 8 vol%)
Table 1A and B) in the Urucutuca sandstones. Kaolinite occurs
dominates over orthoclase (average w 2 vol%), perthite (average 1
as grain-replacive (Fig. 7A) and, less commonly, as intergranular
vol%), and plagioclase (average 1 vol%). Lithic fragments are plutonic
pore-lling, vermicular aggregates composed of irregular or pseudo-
(average 16 vol%) and, rarely, metamorphic (trace amounts) in
hexagonal platelets. Kaolinite replaces feldspars, micas, mud intra-
origin. Other detrital grains include muscovite, biotite, heavy
clasts and pseudomatrix. Mica grains, which are replaced by
minerals (garnet, zircon, apatite, opaques), carbonate bioclasts and
kaolinite, have expanded into adjacent pores (Fig. 7B). Kaolinite that
mud intraclasts. Fine-grained, crevasse-splay sandstones are char-
has replaced feldspars occurs as aggregates of vermicular and
acterized by abundant mica akes and coal fragments (Fig. 6A
booklet-like crystals that are rich in intercrystalline micro-porosity,
whereas patches that have resulted from the kaolinitization of
Quartz
mica and, particularly, mud intraclasts contain smaller amounts of
Quartzarenite intercrystalline micro-porosity (Fig. 7A and B). Kaolinized mud
intraclasts occur as large patches (up to 900 mm across), which
Subarkose Sublitharenite contain remnants of detrital mud and silt-sized quartz grains. In
some cases, kaolinized mud intraclasts show variable but overall
smaller crystal size (ca 3 mm; Fig. 7C) than kaolinite that has replaced
micas and feldspars. Kaolinite is engulfed by, thus predates, calcite,
dolomite and quartz cements (Fig. 7D). Kaolinite is more abundant in
nite

the coarse-grained to conglomeratic, channel sandstones than in

ic lithare
ose

the ner-grained crevasse splay. Kaolinite in the more deeply buried

ite
e

Lithic Ark
kos

aren

sandstones has frequently been transformed into euhedral dickite

Ar

Lith

(Fig. 7E and F).

th
Feldspa

The oxygen and hydrogen isotopic values of kaolinite vary

between d 18OV-SMOW 13.3& and 15.2& and d2HV-SMOW 96.6&
and 79.6&, respectively (Fig. 8). A plot of d18OV-SMOW versus d2HV-
SMOW values reveals that the isotopic values of the studied kaolinite
Feldspar Rock Fragment
are situated close to the meteoric kaolinite line (Fig. 8).
Fine-grained crevasse-splay sandstones
Coarser-grained, channel complexes 5.2. Siderite

Figure 5. Detrital composition of 18 samples of Urucutuca sandstones plotted in Folk Siderite (av. Fe0.69Mg0.19Mn0.01Ca0.11CO3) is common but occurs in
(1968) diagram. Urucutuca sandstones are classied as arkose. small amounts in the Urucutuca sandstones (up to 3%; av. w 1%).
 H. Mansurbeg et al. / Marine and Petroleum Geology 37 (2012) 7e26 15

Table 1 (continued)

3-FC-18D-ES 3-FC-18D-ES 7-LP-33-ES 7-LP-33-ES 7-LP-33-ES 7-LP-33-ES 7-LP-36-ES 3-FC-3-ES 3-FC-3-ES

2008.75 2026.45 1517.7 1522.3 1533.35 1577.35 1556.5 1730.4 1731.8 Average Std. Dev.
0 0 0 0 0 0 0 0 0 0.0 0.0
1.3 0.7 3.7 1.3 0 0 1 0 0 0.9 1.4
0 0 1.7 0.7 1 0.7 0 0 0 0.4 0.6
0.7 0.3 0.3 1 1.3 0.3 0.3 0 0.7 0.5 0.5
0 0 0 0 0 0 0 1 0 0.2 0.4
0 0 0 1 0 5 0 0 0 0.4 1.9
Abundant Common Abundant Abundant Common Abundant Abundant Trace Common
12 5 19 12 8.7 16 24.7 28.7 1 15.4 9.5
88 95 81 88 91.3 84 75.3 71.3 99 84.6 9.5
7.7 3.7 16.3 11.7 17 10.7 31.7 41.7 0.7 15.7 13.8
5.3 2 10 7 0 1 28.7 0 0 6.0 10.5
0 0 4.7 0 1.7 1.7 0.3 0 0 1.2 1.7
2.3 1.7 1.7 4.7 15.3 8 2.7 41.7 0.7 8.5 14.6
9.7 9.3 10.7 9 13 17 7.3 9 13 11.6 3.3
0 0 0 0 0 0 0 0 0.3 0.0 0.1
8.7 10 8.7 10.3 23 16.7 18 30.7 17.3 15.0 7.5

Coarse Coarse Medium Medium Very thin Medium Medium Very thin Thin
0.7 0.9 0.5 0.45 0.11 0.4 0.45 0.1 0.2
Poor Poor Moderate Poor Good Poor Moderate Very well sort. Very well sort.
1.5 1.9 0.7 1.5 0.4 1.5 0.6 0.1 0.2
37 31 17 19 23 34 18 33 38
63 69 83 81 77 66 82 67 62
100 100 100 100 100 100 100 100 100

Siderite has a microcrystalline habit (5e50 mm across) and occurs as
scattered patches that have replaced pervasively to nearly completely
mud intraclasts, biotite, and feldspars (Fig. 9A and B). In some cases,
siderite occurs as pore-lling cement adjacent to the replaced grains
(Fig. 9B). Siderite is closely associated with kaolinite, particularly in
kaolinitized mica and mud intraclasts (Fig. 9A). Siderite crystals are,
in rare cases, arranged perpendicular to the framework grains and
may partly ll adjacent moldic porosity formed by dissolution and/or
kaolinitization of framework grains (Fig. 9B). Siderite is engulfed
by, and hence pre-dates, Fe dolomite/ankerite (Fig. 9C). Siderite is
moderately to enriched strongly in magnesium (14.8e26.4 mole%
MgCO3; av. 18.8%; Fig. 10) and displays no chemical zoning. Siderite

Figure 6. Optical photomicrographs (plane-polarized light): (A) and (B) of typical ne-grained, crevasse splay sandstones, which are rich in mica akes (A) and in coal fragments
(B). Brown masses in (B) are expanded biotite akes that are replaced by siderite. (C) and (D): Coarse-grained, poorly-sorted, channel complex sandstones showing dissolved and
kaolinitized feldspar grains.
16 H. Mansurbeg et al. / Marine and Petroleum Geology 37 (2012) 7e26

Figure 7. (A) Optical photomicrograph (plane polarized light) showing feldspar grains extensively dissolved and replaced by kaolinite. (B) Optical photomicrograph (crossed
polarized light) showing expanded kaolinized mica. (C) Optical photomicrograph (plane polarized light) showing mud intraclasts that have been replaced by kaolinite. (D) SEM
image showing dolomite cement engulng kaolinite. (E) SEM image showing kaolinite as booklets and vermicular aggregates composed of several platelets. (F) Enlarged view of
(E) showing that part of the kaolinite has been partly transformed into euhedral dickite (arrows).

d18OV-PDB values range from 8.8 to 5.6&, and d13CV-PDB values
range from 4.9& to 13.8& (Table 2). Siderite occurs in both ner-
grained crevasse splay sandstones and in the coarse-grained to
conglomeratic, channel sandstones (average 1.2%b.v.).
5.3. Calcite
Calcite occurs as intergranular pore-lling cement, displaying
poikilotopic habit (Fig. 11A) (up to 20%; average 3 vol%) or anhedral,
ne to coarse mosaic habit (up to 8%; average 2.6 vol%). Calcite also
lls intragranular pores in feldspars and micas and replaces quartz,
feldspars, micas, and pseudomatrix (Fig. 11B). Pore-lling calcite
covers and engulfs, thus post-dates, quartz and K-feldspar over-
growths, framboidal pyrite, siderite and kaolinite. Calcite engulfs
and lls, partly to completely, secondary pores in zoned dolomite
and ankerite. Calcite cement is commonly etched owing to partial
dissolution (Fig. 11C), which may contribute locally to porosity
enhancement.
Calcite is slightly ferroan, with average contents of FeCO3 1.5
mole% and MgCO3 0.4 mole% (Fig. 10). The SrCO3 and MnCO3
contents are below detection limits in most samples. Carbon,
oxygen and strontium isotopic analyses of calcite revealed a range of
d13CV-PDB between 17.2& and 22.4&, d18OV-PDB between 8.7&
and 7.1& (Table 2) and 87Sr/86Sr ratios measured for two samples
are 0.710508 and 0.711714. Calcite is slightly more abundant in
ne-grained, crevasse splay than coarser-grained, channel sand-
stones (average 6.5 and 5.8, respectively).
5.4. Fe-dolomite/ankerite
Fe-dolomite/ankerite, which has an average composition of
Fe0.11Mg0.29Mn0.01Ca0.59CO3 (Fe varies from ca 1 mole% FeCO3
 H. Mansurbeg et al. / Marine and Petroleum Geology 37 (2012) 7e26 17

-20

-40
DSMOW

-60

-80

-100

-120

-140
+5 +10 +15 +20 +25 +30 +35
18O
SMOW

Kaolin from Urucutuca

Meteoric kaolinites line
Weathering kaolinite (Savin and Epstein, 1970)
Cretaceous of Canada (Longstaffe, 1989)
Kaolin from Brent (Glassman et al., 1989)
Kaolinite from Brent (McAulay et al., 1994)
Dickite from Brent (McAulay et al., 1994)

Figure 8. Plot of dDV-SMOW versus d18OV-SMOW values of diagenetic kaolin from

different sandstones and weathering kaolinites. Kaolinites from the studied Urucutuca
sandstones are situated close to the line of meteoric kaolinites.

to <20%; Fig. 10), occurs mainly as rhombohedral crystals within

intergranular pores (Fig. 9C) and as cement engulng kaolinitized
pseudomatrix, micas and feldspars (Fig. 12A).
Dolomite cement commonly displays evidence of partial disso-
lution. Fe-dolomite/ankerite occurs locally as saddle-like crystals
(Fig. 12B) and show irregular chemical zonation. However, some
dolomite crystals have Fe-rich core and thin Fe-poorer rims
(Fig. 12C), or a thin outer, Fe-rich rim (Fig. 12D). Dolomite that
replaces mica displays complex zoning patterns in terms of
variations in Fe content. In some cases, dolomite displays evidence
of partial replacement by and, thus, predates, calcite cement
(Fig. 12E). The d13CV-PDB for dolomite/ankerite varies from 15&
to 18.6&. The d18OV-PDB varies from 9.0& to 5.9& (Table 2).
Fe-dolomite/ankerite cement is more common in the ne-grained,
crevasse-splay than coarser-grained, channel sandstones
(10.6% and 7% respectively).

5.5. Other diagenetic minerals

Other diagenetic minerals include K-feldspar overgrowths and

pyrite. K-feldspar overgrowths display euhedral faces and envelop
detrital K-feldspars. Pyrite occurs as framboids and euhedral
crystals that are engulfed by intergranular carbonate cements and
occur within partly dissolved and kaolinized biotite grains.
Some of the quartz grains in sandstones that are poor in extensive
carbonate cement and pseudomatrix show thin quartz over-
growths (Fig. 12F).
6. Compaction, porosity and permeability
Features indicative of mechanical compaction, such as forma-
tion of pseudomatrix by deformation of mud intraclasts, bending
of mica plates and fracturing of quartz grains are common in the
Urucutuca sandstones. Most fractured quartz grains are healed
by quartz cement. Porosity of the Urucutuca sandstones includes
Figure 9. (A) BSE image of microcrystalline siderite (bright), which has replaced partly
kaolinized and expanded micas. (B) Optical photomicrograph (plane polarized)
showing a biotite ake, which has been partly replaced and expanded by siderite. (C)
BSE image of zoned dolomite crystals engulng and replacing microcrystalline siderite.
intergranular, intragranular and moldic pores, which vary from
micro (<10 mm) to macro sizes. The intergranular porosity (up to
8%) is more abundant than intragranular and moldic pores together
(up to 6%). Moldic pores have been formed by complete dissolution
of detrital feldspar, heavy minerals, mud intraclasts and mica.
Feldspar dissolution has altered slightly to profoundly the frame-
work composition of the sandstones. Plagioclase feldspar was
preferentially dissolved, resulting in moldic secondary macropores
(Fig. 13A and B). Dissolution of chemically unstable grains has
18 H. Mansurbeg et al. / Marine and Petroleum Geology 37 (2012) 7e26

Fe

Siderite

0.50

Ankerite

Dolomite
Calcite

Ca 0.50 Mg
Figure 10. Ternary diagram of the relative Ca, Mg and Fe contents of diagenetic calcite,
dolomite/ankerite and siderite in the Urucutuca sandstones.

created secondary macropores, which are in some cases poorly

connected to the intergranular pore network owing to the presence
of feldspar remnants and clay coatings (Fig. 13C).
Secondary porosity has also resulted from the dissolution of
carbonate cement, particularly of calcite cement (Fig. 11B). Signi-
cant microporosity is contained within the kaolinite aggregates
that have replaced feldspar grains (Fig. 13C and D). The extent of
framework grain and cement dissolution was more signicant in
permeable, coarser-grained, channel sandstones than the ner-
grained, less permeable crevasse splay sandstones. Intragranular
and moldic porosity have also resulted from the dissolution of
heavy minerals (garnet, staurolite, sphene, opaques). Grain disso-
lution macroporosity has contributed to permeability enhance-
ment of some samples because signicant portions of these

Table 2
Carbon and oxygen isotope data from bulk carbonate in the Urucutuca sandstones.

Well Depth d18O (SMOW) d18O (PDB) d13C (PDB) Carbonate

7-LP-33-ES 1559.45 21.99 8.66 20.14 Calcite
7-LP-33-ES 1576.60 23.5 7.15 9.77 Calcite
7-LP-36-ES 1531.90 23.62 7.07 9.55 Calcite
7-LP-36-ES 1538.25 23.63 7.06 14.58 Calcite Figure 11. (A) Optical photomicrograph (plane polarized light) of poikilotopic calcite
7-LP-36-ES 1556.50 22.41 8.25 22.43 Calcite cement (arrows) occluding intergranular porosity. (B) Optical photomicrograph
3-FC-18D-ES 1993.90 23.31 7.37 13.34 Calcite (crossed polarized light) showing vermicular and booklet-like aggregates of kaolinite
3-FC-18D-ES 2008.75 22.41 8.25 14.47 Calcite and remnants of micas (brown) replaced by calcite. (C) Photomicrograph (plane polar-
3-FC-18D-ES 2026.45 22.71 7.96 17.21 Calcite ized light) showing partly dissolved intergranular calcite cement (stained red) and
detrital feldspar.
7-LP-33-ES 1533.35 23.16 7.52 5.52 Ankerite
7-LP-33-ES 1559.45 21.82 8.82 17.78 Ankerite
7-LP-33-ES 1576.60 22.7 7.97 11.66 Dolomite
7-LP-33-ES 1577.35 22.55 8.11 11.34 Dolomite secondary pores are well linked to the intergranular pore system.
7-LP-36-ES 1531.90 24.88 5.85 6.22 Ankerite
7-LP-36-ES 1538.25 21.82 8.82 6.38 Ankerite
Signicant reduction in the porosity of some samples has resulted
7-LP-36-ES 1556.50 22.12 8.53 18.57 Dolomite from the compaction of mud intraclasts to pseudomatrix.
3-FC-3-ES 1730.40 21.62 9.01 4.92 Dolomite
3-FC-18D-ES 1978.00 24.17 6.54 5.99 Dolomite 7. Discussion
3-FC-18D-ES 1993.90 22.99 7.68 12.53 Dolomite
3-FC-18D-ES 2008.75 22.89 7.78 13.82 Dolomite
3-FC-18D-ES 2026.45 22.49 8.17 15.02 Dolomite The petrographic observations suggest that diagenesis of the
Urucutuca sandstones has been accomplished during eodiagenesis
7-LP-33-ES 1559.45 21.85 8.79 13.8 Siderite
7-LP-36-ES 1531.90 25.12 5.62 4.92 Siderite
and mesodiagenesis (sensu Morad et al., 2000). However, because
of the lack of detailed burial history curves for all the wells
 H. Mansurbeg et al. / Marine and Petroleum Geology 37 (2012) 7e26 19

Figure 12. (A) SEM image showing dolomite rhombs engulng kaolinite. (B) Optical photomicrograph (crossed polarized) showing coarse rhombic dolomite crystals with wavy
extinction and curved or stepped faces typical of saddle dolomite that has partially replaced vermicular kaolinite. (C) BSE image of dolomite crystals with Fe-rich cores covered by
Fe-poor outer zones and these by Fe-rich zones. (D) SEM image showing dolomite crystals with Fe-poor core and Fe-rich rims (FeCO3 1 mole% and 20 mole%, respectively). (E)
Optical photomicrograph (crossed polarized light) showing calcite cement that has replaced rhombs of dolomite. (F) Optical photomicrographs (plane polarized light)) showing
thin, discontinuous quartz overgrowths.

studied, the fairly complex diagenetic pattern, and the lack of
uid-inclusion and other geo-thermometric data, it is not possible
to achieve exact timing and burial depths or temperatures for the
diagenetic phases observed. Based on the distribution pattern
of diagenetic minerals and their textural relationships and inte-
gration of optical microscopy, SEM and BSE observations, a para-
genetic sequence has been constructed (Fig. 14). The paragenetic
sequence of diagenetic events as well as the mineralogy and
isotopic composition of the eogenetic minerals suggest that the
turbiditic succession has been inuenced by meteoric, brackish
and marine uids at shallow and moderate depths. Mesodia-
genesis was presumably accomplished by formation waters, which
were evolved geochemically owing to watererock interactions.
7.1. Eodiagenesis
The main eogenetic processes include the dissolution and
kaolinization of framework silicates as well as cementation by
pyrite and CaeMg rich siderite.
7.2. Kaolinization of framework silicates
The presence of high concentrations of dissolved cations, like K,
Na , Ca2 and Mg2 in marine pore waters preclude the possibility
of kaolinitization by such waters (Berner, 1978). The shallow burial
diagenetic origin of kaolinite, which is evidenced by e.g. the
expansion of kaolinitized into open pores (Ketzer et al., 2005),
precludes the involvement of organic acids (Surdam et al., 1984).
Therefore, as for sandstones successions elsewhere, extensive
kaolinization of micas, feldspars and mud intraclasts in the turb-
ditic reservoir sandstones is attributed to meteoric water circula-
tion (cf. Meisler et al., 1984; Hancock and Taylor, 1978; Sommer,
1978; Morad et al., 2000; Ketzer et al., 2003). However, the
circulation of considerable volumes of meteoric water into marine
turbiditic deposits is not anticipated and the mechanism of mete-
oric water ow into turbidite reservoir sandstones is still enigmatic
(Morad et al., 2000).
Nevertheless, there are several possible explanations for the
meteoric water ux into such sandstones, including: (i) creation of
20 H. Mansurbeg et al. / Marine and Petroleum Geology 37 (2012) 7e26

Figure 13. Optical photomicrographs (plane polarized light) showing: (A) and (B) nearly complete feldspar dissolution that resulted in the formation of moldic pores. (C) Secondary
porosity formed by the dissolution of chemically unstable grains. The secondary porosity is poorly connected to the effective pore network owing to the presence of clay coatings,
which have not been dissolved. (D) Photomicrograph (uncrossed polarizer) showing abundant microporosity among vermicular, grain-replacive kaolinite aggregates.

hydraulic head along basin margins during shallow burial (Deming
and Nunn, 1991), (ii) meteoric water ux during hyperpycnal
ow (Plink-Bjorklund and Steel, 2004), and (ii) uplift and inux of
meteoric water into the basin during telodiagenesis (Choquette and
Pray, 1970). The probable conduits for the meteoric waters to reach
the Urucutuca sandstones include: (i) basal or lateral contact of
turbidites with Early Cretaceous alluvial sandstones exposed
onshore, or cut by major, basin-margin faults; and (ii) large fault
systems along the canyon margins (Bruhn and Walker, 1997). The
interconnectivity of Urucutuca sandstones with the Lower Creta-
ceous sandstones of the Mariricu Formation along the margins of
the canyons (Fig. 2A) would allow the circulation of meteoric water.
Differences in the amounts of kaolinite in the sandstones
reect facies-controlled variations in depositional permeability.
The channel sandstones had higher depositional permeability
and thus have experienced more efcient meteoric-water
percolation, and consequently a greater extent of eogenetic
grain dissolution and kaolinitization than the ne-grained,
et al., 1993; McAulay et al., 1994; Morad et al., 1994), and (iv) the
engulfment of kaolinite by mesogenetic carbonate cements.
Furthermore, stable oxygen and hydrogen isotopes of the kaolin
(d18OV-SMOW 13.3& to 15.2&; dDV-SMOW 96.6& to 79.6&)
fall close to the kaolinite meteoric water line, and hence support the
suggested meteoric origin (Fig. 8; Morad et al., 2003). Deviation of
the stable isotopic values from this line is attributed to partial
conversion of kaolinite into dickite during mesodiagenesis (Morad
et al., 2003). The stable O and H isotopic composition of the
kaolinite, when combined with their early diagenetic features
indicate that kaolin is of eogenetic origin (Fig. 8).
Eodiagensis Mesodiagensis
Pyrite
Siderite
Kaolinite (ordered), dickite
Kaolinite (disordered)

crevasse splay sandstones. However, the occurrence of large Mechanical compaction

amounts of kaolinite in some of the crevasse splay sandstones is Silicate grain dissolution
related to the kaolinitization of the micas concentrated in these ? ?
K-feldspar overgrowth Chemical compation
ne-grained deposits. (pressure dissolution)
The eogenetic rather than telogenetic origin of kaolinite in the Quartz
studied sandstones is evidenced by: (i) the expanded texture of the
Calcite
kaolinitized micas, which typically implies poorly-compacted sand
(Ketzer et al., 2003), (ii) the coarse size of vermicular crystals of Dolomite/saddle dolomite
kaolinite (McAulay et al., 1994; Osborne et al., 1994; Wilkinson
Ankerite
et al., 2006), (iii) the close association of kaolinite with eogenetic
Carbonate grain/cement dissolution
siderite, a mineral that is preferably formed in low SO42-waters
(i.e. not fully marine in composition), (iv) partial transformation of
kaolinite into dickite, which occurs during progressive burial of the Figure 14. Paragenetic sequence of diagenetic events in the studied Urucutuca
sandstones to depths greater than 2 km (T > ca 70  C; Ehrenberg sandstones.
 H. Mansurbeg et al. / Marine and Petroleum Geology 37 (2012) 7e26
7.3. Origin of siderite cement
The occurrence of siderite in large pores between loosely packed
grains and expanding replaced biotite akes suggest that precipi-
tation commenced near the seaoor. However, the stable isotope
values of the siderite cements (d18OV-PDB 5.6 to 8.8&) are not
compatible with precipitation from Cretaceous seawater (1.2&;
Shackleton and Kennett, 1975; Huber et al., 2002) at near-sea
bottom temperatures of 15e25  C. Assuming such low tempera-
tures, and using the fractionation equation of Carothers et al. (1988),
it is suggested that cementation occurred from pore waters with
extremely low d18OV-SMOW values between 12 and 6&. Even
considering that the formation of siderite may have occurred in
connection with the incursion of meteoric water into the Urucutuca
sandstones during periods of signicant fall in the relative sea level
(Bethke, 1989; Carvalho et al., 1995; Mansurbeg et al., 2006), some
degree of recrystallization during burial must be invoked to explain
the lowest d18OV-PDB values of the analysed siderites. Furthermore.
the commonly too low d18O values of texturally early diagenetic
siderite has raised doubts about the level of understanding of
fundamental isotopic fractionation processes (e.g. Raiswell and
Fisher, 2000). Experimental work has shown that microbial
involvement in iron reduction may result in the formation of more
18
O-depleted siderite compared to values obtained using fraction-
ation factors from the literature (Mortimer and Coleman, 1997).
The incursion of meteoric water is the mechanism frequently
considered to explain low d18O values in early carbonate cements in
marine successions (Machemer and Hutcheon, 1988; Morad et al.,
1996). Siderite is closely associated delete with kaolinite, which
further supports the postulated common meteoric-water origin. It is
likely, however, that meteoric waters would be mixed with, rather
than totally displace, the marine pore-waters in the turbiditic
channels (Ketzer et al., 2003). The mixed meteoric-marine water can
account for the elevated amounts of Mg and Ca in the studied
siderites (Morad et al., 1996). However, Mozley and Carothers (1992)
and McAulay et al. (1993) reported the presence of Mg-rich siderite
in Cretaceous and Jurassic reservoir sandstones form at 77e86  C
and 90  C. Thus the role of temperature in depleted d18O signatures
of the siderite cannot be totally excluded (Morad et al., 1994). Part of
the Fe and Mg needed for the precipitation of siderite has presum-
ably been derived from the kaolinization of the micas.
The carbon isotopic composition of siderite (d13CV-PDB 4.9
to 13.8&; Table 2) does provide unequivocal evidence of precip-
itation under methanogenic conditions (e.g. Irwin et al., 1977).
Barro Nova Form
1000
2000
Depth (m)
3000
4000
5000
6000
135 120 105
Figure 15. Burial-history curve of the Urucutuca sandstones at Lagoa Parda oileld, showing the absence of uplift phases (modied after Chang et al., 1991). Hence, meteoric water
incursion did not occur during telodiagenesis.
21
The formation of siderite in the studied sandstones is favoured by
low concentrations of SO4 in the inltrated meteoric pore waters
(Postma, 1982). High concentrations of dissolved sulphate ions in
pure marine pore waters would have resulted in the formation of
pyrite, owing to the greater afnity of Fe2 to dissolved sulde than
to dissolved carbonate ions (Curtis et al., 1986).
7.4. Burial diagenetic processes
The burial history diagram for the canyon-ll turbidites (Fig. 15)
indicates that the Urucutuca Formation may have never been
buried to depths signicantly more than 2 km in the area. The
onshore area where the canyons are located (Fig. 1A and B) was
not affected by the progressive and intense thermal subsidence
experienced by the offshore area of the basin (Carvalho, 1989).
Therefore, truly mesogenetic conditions (sensu Morad et al., 2000)
were probably only incipient in the Lagoa Parda and Fazenda Cedro
reservoirs. However, although not recorded in the burial history
diagrams of the area (Fig. 15), it is possible that the turbidites have
been buried to greater depths (<2 km) than today, i.e. prior to uplift
and erosion during the Tertiary. Burial to greater depth than is
indicated by the burial history curve (Fig. 15) is suggested by the
occurrence of diagenetic processes and products in the studied
sandstones that are typical of mesogenetic conditions, including
quartz cementation (Walderhaug et al., 2001), cementation by
saddle dolomite at inferred precipitation temperatures up to 114  C
(discussed below), and partial conversion of kaolinites into dickite
(Parnell et al., 2001).
7.5. Origin of calcite cement
Sandstones cemented by blocky and poikilotopic calcite show
tight packing indicative of syn-compactional cementation. Using the
d18OV-PDB values of calcite cement (8.7& and 7.1&), assuming that
precipitation occurred from evolved to moderately evolved forma-
tion waters with a d18OV-SMOW value of 1& (Egeberg and Aagaard,
1989), and using the fractionation equation of Friedman and ONeil
(1977), the precipitation temperatures of these calcites would be
57e68  C. Somewhat higher temperatures (64e76  C) are obtained
assuming isotopically more evolved formation waters with d18OV-
SMOW of 2% (Fig. 16A). Precipitation temperatures from unmodied
marine porewaters (d18OV-SMOW 1.2&; Shackleton and Kennett,
1975) would indicate precipitation temperatures of 42e51  C. The
Sr-isotopic ratios of these calcites (87Sr/86Sr 0.710508e0.711714)
Rio Doce Formation
ation
Mariricu Formation Urucutuca Formation
Basement
TTI = 15
Oil Window
90 75 60 45 30 15 0
Age (Ma) before present
22 H. Mansurbeg et al. / Marine and Petroleum Geology 37 (2012) 7e26

A 100
Calcite

-8
75

Temperature C
-10 -6

50

25
-10 0 10
18
OSMOW

B 140 C
Ankerite -10 120
-8 Dolomite -6
-6
-4
-10
Temperature C

Temperature C

70 80

-5 -8

40
0 -10 0 +10
-10 0 +10 18
18 OSMOW
OSMOW

Figure 16. Oxygen isotope fractionation curves for calcite (A), ankerite (B) and dolomite (C) as a function of temperature. The shaded eld represents possible range of precipitation
temperatures assuming moderately evolved brines (d18OV-SMOW between 0& and 2&).

indicate input of radiogenic strontium, most likely from partial

-5
albitization of detrital K-feldspars (Egeberg and Aagaard, 1989).
Calcite
The calcite cement has a wide range of carbon isotopic values Dolomite
(d13CV-PDB 17.2& to 22.4&; Table 2), indicating derivation of Siderite
-6
M

dissolved carbonate from several sources. The low carbon and oxygen n
Ankerite io
eth

ylat
an

isotopic signatures preclude signicant input from marine pore ox

og

b
waters. Plot of d18O versus d13C values (Fig. 17), suggests the existence ar
en

c
de
ic

-7 al
of two trends of d13C variation with decreasing d18O (i.e. increasing
fer

m
er
me

temperature). From slightly modied marine values with d13C values Th

nta
tio

close to 0&, one trend goes towards positive d13C values (up
n

-8
to 22.4&) with decreasing d18O, suggesting increasing input of
carbonate from bacterial methanogenesis with progressive burial
(Fig. 17). The other trend develops towards negative d13C values (down
-9
to 17.2&), suggesting increasing input of dissolved carbonate ions
from oxidation of oil (cf. Prochnow et al., 2006) and thermal decar-
boxylation of organic matter with progressive burial (Fig. 17).
-10
-20 -10 0 10 20 30
7.6. Origin of dolomite and ankerite

Dolomite cement in the studied sandstones has two different Figure 17. Cross plot of carbon and oxygen isotopes of the carbonate cements in the
chemical compositions. One group is Fe-poor and the other includes studied sandstones, showing two separate trends of evolution from close to marine
ferroan dolomite and ankerite (Fig. 10). The d18OVPDB values of towards methanogenic fermentation and thermal decarboxylation input.
 H. Mansurbeg et al. / Marine and Petroleum Geology 37 (2012) 7e26
Fe-dolomite/ankerite (6.5& to 9.0&) can be used to constrain
the composition and/or temperature precipitating pore-waters.
Using the fractionation equation of Land (1983), and assuming
d18OV-SMOW values of 0& to 2& (Lundegard and Land, 1986) for the
pore waters, which is equivalent to moderately to highly evolved
formation waters relative to the inferred contemporary Cretaceous
d18OV-SMOW value of marine water (1.2&; Shackleton and Kennett,
1975; Huber et al., 2002), precipitation of Fe-dolomite/ankerite
would have occurred at temperatures of 70  C to 114  C (Fig. 16B
and C), which are compatible with the petrographic observation.
The d13CV-PDB values of Fe-dolomite/ankerite (15.0&
to 18.6&; Table 2), which fall within the range of carbon isotopic
signature of calcite, suggest that carbon was derived from diverse
sources during progressive burial (Irwin et al., 1977; Morad, 1998).
Dolomite-ankerite follows the two trends of co-variance of d13C with
decreasing d18O and increasing temperature observed for calcite
(Fig. 17), i.e., from a composition closer to marine, one trend towards
increasing input of carbonate from methanogenic fermentation,
other towards increasing contribution from thermal decarboxyl-
ation with increasing precipitation temperature and depth.
In some samples, Fe-poor dolomite with curved and stepped
faces (saddle-dolomite) engulfs, and thus post-dates, Fe-dolomite/
ankerite cement. The formation of saddle dolomite has been linked
to relatively high temperatures (Radke and Mathis, 1980; Lee
and Friedman, 1987; Zenger and Dunham, 1980; Sptl et al., 1993;
Sptl and Pitman, 1998) and even considered as a semiquantitative
geothermometer (Radke and Mathis, 1980). Sptl and Pitman (1998)
concluded that the precipitation of saddle dolomite may start from
highly saline uids at relatively low temperatures (60e80  C), but
occurs mostly between 90 and 160  C.
7.7. Conversion of kaolinite into dickite
The poorly developed, meteoric kaolinite crystals, which
are commonly suggested to reect disordered lattices (Lanson et al.,
2002), in the Urucutuca sandstones were transformed with
progressive increase in burial depth and temperature (depth
2e3 km; T 70e90  C) into dickite (Ehrenberg et al., 1993; Morad
et al., 1994). In most cases, kaolinite and dickite occur in the same
sample, indicating that the progressive burial transformation of
kaolin was incomplete, presumably owing to the relatively shallow
burial diagenetic conditions encountered in the studied Urucutuca
sandstones. The transformation of kaolinite into dickite was more
intense in the more permeable, channel sandstones than in the
ne-grained crevasse-splay sandstones. Higher permeability allows
a more efcient uid ow and mass ux, and hence enhances
the dissolution-precipitation processes, which are involved in the
conversion of kaolinite into dickite (cf. Cassagnabere, 1998).
The transformation of kaolinite into dickite was suggested to
require low K/H activity ratio (Morad et al., 1994). The low K/H
activity ratio in pore waters of the Urucutuca succession is
presumably related to the combination of low K/H activity ratio
related to organic solvents from thermal decarboxylation, and
moderate temperatures (McAulay et al., 1993; Morad et al., 1994).
Kaolin transformation reactions and progressive ordering have
been suggested to occur at temperatures ranging from z 80 to
130  C (Ehrenberg et al., 1993; McAulay et al., 1993; Morad et al.,
1994). The temperatures calculated from the oxygen isotopic
compositions of carbonate cements in the Urucutuca sandstones
are fairly within this range (Fig. 16AeC).
7.8. The impact of diagenesis on the quality of the reservoirs
Despite the formation of secondary porosity by grain dissolu-
tion, diagenesis has resulted in overall considerable destruction of
23
Figure 18. Plot of intergranular cement volume versus total intergranular volume
(cf. Houseknecht, 1987, modied by Ehrenberg, 1993) of the studied Urucutuca sand-
stones showing that the intergranular porosity has been reduced more by compaction
rather than by cementation.
porosity and permeability. A plot of the total volume of intergran-
ular volume (IGV) versus volume of cement % (Fig. 18) reveals that
compaction has been far more important in porosity destruction
than cementation in the ne-grained crevasse-splay sandstones
than the coarse-grained channel sandstones.
The inuence of compaction on porosity and permeability
reduction was more important in the ne-grained crevasse-splay
sandstones (Fig. 18) owing to their ner grain size and relatively
more abundant contents of micas and mud intraclasts compared
to the coarse-grained channel sandstones. Additionally, the abun-
dance of micas has enhanced the pressure dissolution of quartz
grains (i.e. chemical compaction) in these sandstones, due to the
increased solubility along the mica surfaces (cf. Bjrkum, 1996).
7.9. Summary model for the diagenetic and reservoir-quality
evolution pathways of the turbiditic sandstones
The temporal distribution of diagenetic alterations and related
reservoir evolution pathways of the studied turbiditic sandstones
are strongly controlled by the depositional facies, paleo-climatic
conditions and burial history experienced by the sandstones.
Warm, humid climatic conditions during late Cretaceous and early
Tertiary times, combined with high depositional permeability
in the channel sandstones and good connectivity with Early
Cretaceous successions along the walls of the canyons resulted in
extensive dissolution and kaolinization of feldspars, micas and mud
intraclasts. These processes were less intense in the ner-grained,
thinner and poorly-connected crevasse-splay sandstones. Major
relative sea-level falls during early Tertiary most likely facilitated
the circulation of meteoric water into the turbiditic Urucutuca
sandstones. As a result of shallow burial and limited compaction,
kaolinized micas have expanded into adjacent pore spaces,
hence deteriorating sandstone permeability. Variations in detrital
composition and/or in the distribution of eogenetic alterations in
the channel and ner-grained crevasse-splay sandstones resulted
in variations in the evolution pathways of reservoir-quality,
and hence in considerable reservoir heterogeneity (Fig. 19AeC).
The intensity of kaolinization was controlled by depositional
permeability, as well as by the amounts of mica and chemically
most unstable feldspars, such as Ca-rich plagioclase and orthoclase.
24 H. Mansurbeg et al. / Marine and Petroleum Geology 37 (2012) 7e26

As we had no access to vitrinite reectance or uid inclusion
data for the onshore Urucutuca turbiditic reservoirs, we were
unable to determine the precise maximum temperature reached
by the succession. However, the limited formation of dickite,
quartz overgrowths, saddle dolomite and ankerite suggest burial
temperatures of about 70e90  C (Morad et al., 2000).
Considering the present burial depth of about 2 km, and
assuming a geothermal gradient of 30  C/km and a surface tem-
perat ure of 20  C, the temperature reached by sandstones would
be close to 80  C. Minor, if any, conversion of kaolinite into dickite
was enhanced by low aK/aH in the formation waters, which can
be attributed to the decrease in the amounts of micas and feldspars
owing to eogenetic kaolinization and/or inux of uids charged
with organic acids from the thermal maturation of source-rocks in
the offshore area. In addition to the dissolution and kaolinitization,
of framework silicate grains, diagenetic alterations that also
contributed to quality and heterogeneity of reservoirs include
mainly chemical and mechanical compaction through grain

Coarse-grained
channel complex Fine-grained
sandstones crevasse splay
sandstone
Deposition
Eodiagenesis

2 km
70 CC
Mesodiagenesis

Quartz Kaolinite/ Dickite Feldspar overgrowth

Feldspar Pyrite Quartz overgrowth

Microquartz
Mud intraclast Siderite
coating

Mica Calcite cement Coal fragment

Porosity Ankerite/ Dolomite

Figure 19. Schematic diagenetic model displaying the evolution pathways and spatial and temporal distribution of diagenetic minerals in the turbiditic channel complex and
ne-grained crevasse splay Urucutuca sandstones of Lagoa Parda and Fazenda Cedro oilelds.
 H. Mansurbeg et al. / Marine and Petroleum Geology 37 (2012) 7e26
re-arrangement and pseudo-plastic deformation of mud intra-
clasts. Some samples, however, display limited mechanical
compaction, probably owing to early carbonate cementation.
Chemical compaction occurred more intensely in ner-grained
crevasse-splay sandstones rich in micas, which are known to
enhance the pressure dissolution of quartz grains (Bjrkum, 1996).
Diagenetic alterations that had little impact on reservoir
quality of the sandstones include the formation of small
amounts of predominantly grain-replacive siderite and pyrite.
Reservoir quality and heterogeneity was strongly inuenced by
the precipitation of poikilotopic calcite and blocky ankerite/
dolomite, which occurs in both the channel and crevasse-splay
sandstones.
8. Conclusions
The petrological and geochemical study of Upper Cretaceous/
Paleogene turbiditic canyon-ll reservoirs of Esprito Santo Basin,
eastern Brazil has revealed that:
1) Diagenetic alterations in the turbidite sandstones were
strongly mediated by meteoric rather than marine pore waters.
Meteoric water inux induced pervasive dissolution and
kaolinization of feldspars, micas and mud intraclasts in the
Urucutuca turbiditic sandstones. Meteoric waters inux is
suggested to have occurred during relative sea-level falls, and
was facilitated by the contact with early Cretaceous sandstones
along the walls of the canyons.
2) The diagenetic alterations and related reservoir-quality evolu-
tion pathways are closely linked to depositional facies, hydraulic
connectivity and burial depth reached by the sandstones
(present-day depth is ca. 2 km).
3) Dissolution and kaolinization of silicate grains was more
extensive in channel sandstones owing to their coarser grain
size, higher permeability, and the better connectivity provided
by the amalgamation of successive channel cycles. Meteoric
water ux was therefore more efcient than in the ner-
grained crevasse-splay sandstones.
4) Mechanical compaction was far more important than cemen-
tation in porosity reduction.
5) Lack of correlation between porosity and permeability and the
larger degree of reduction of permeability than porosity in the
reservoir sandstones are attributed to the presence of abundant
micro-porosity and intragranular and moldic pores that are
poorly connected to the overall pore system.
6) The conversion of kaolinite into dickite was more extensive in
the more permeable channel sandstones than in the crevasse-
splay sandstones denoting the conversion reaction occurs via
dissolution and reprecipitation.
7) Diagenetic alterations that had little impact on the reservoir
quality of the sandstones include the formation of small
amounts of predominantly grainreplacive siderite, and
pyrite.
8) In turbidite systems, channel sandstones are characterized by
better reservoir quality than the crevasse-splay sandstones.
9) Identication of meteoric water entry points, deep-marine
channels geometry, and the overall connectivity of distal turb-
ditic sandstone bodies with proximal facies can be used as
an exploration tool and help in pinpointing the location of
good-quality marine turbidite reservoirs.
Acknowledgements
The authors thank PETROBRAS for access to samples, data, and
for permission to publish this work. LFDR wish to acknowledge the
25
support granted by Brazil National Research Council, CNPq.
S. Morad and H. Mansurbeg thank the European Science Founda-
tion and funding by the research councils of Spain, France, Italy,
Norway and Sweden.
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