G e o l o g i c a A c t a , Vo l .

5 , N º 1 , 2 0 0 7 , 8 9 - 1 0 7
Av a i l a b l e o n l i n e a t w w w. g e o l o g i c a - a c t a . c o m

The Impact of carbonate cements on the reservoir quality in

the Napo Fm sandstones (Cretaceous Oriente Basin, Ecuador)

1 1 2 3
J. ESTUPIÑAN R. MARFIL A. DELGADO and A. PERMANYER

1 Dpto. de Petrología y Geoquímica, Facultad de Geología, UCM

28040 Madrid, Spain. Estupiñan E-mail: jestupin@geo.ucm.es Marfil E-mail: marfil@geo.ucm.es

2 Estación Experimental del Zaidín (CSIC), Laboratorio de isótopos estables

18008 Granada, Spain

3 Dpt. de Geoquímica, Petrologia i Prospecció Geològica, Facultat de Geologia, Universitat de Barcelona

08028 Barcelona, Spain. E-mail: albert.permanyer@ub.edu

ABSTRACT
The Napo Formation of Lower-Middle Cretaceous age in the Oriente basin, Ecuador, is an important sandstone
reservoir. The formation is buried at a depth of 1,500 m in the eastern part of the basin and down to 3,100 m in
the western part. The sandstones display higher porosity values (av. 20%) than other reservoirs in the region.
These sandstones were deposited in fluvial, transitional and marine environments, and they are fine to medium
grained quartzarenites and subarkoses. The principal cements are carbonates, quartz overgrowth and kaolin,
with scarce amounts of pyrite-pyrrhotite and chlorite. Carbonate cements include: Eogenetic siderite (S1),
mesogenetic and post-compactional calcite, Fe-dolomite, ankerite and siderite (S2). Early siderite and chlorite
helped to retain porosity by supporting the sandstone framework against compaction. Dissolution of feldspars
and carbonate cements are the main mechanism for secondary porosity development during mesodiagenesis.
The high intergranular volume (IGV) of the sandstones indicates that cementation is the predominant contribu-
tor to porosity loss in the reservoir and that the precipitation of the carbonate cement occurred in early and late
diagenetic stages. The stable–isotope composition of the S1 siderite is consistent with precipitation from mete-
oric waters in fluvial sandstones, and from mixed meteoric and marine waters in transitional sandstones. The
low
18O‰ values of some of these carbonate phases reflect the replacement and recristalization from S1 to S2
siderite at deep burial and high temperature. Textural evidence, together with a low Sr content, also suggests
that siderite (S1) in fluvial environment is an early cement that precipitated from meteoric waters, near the sedi-
ment/water interphase, followed by the generation of calcite with a higher Fe and Mg content. However, due to
this higher Mg content, siderite S2 could have precipitated as a result of the thermal descarboxilation of the Mg
rich organic matter. The progressive decrease in
18O values in all carbonate cements could be related to the
continued precipitation at different temperatures and burial depth.

KEYWORDS Carbonate cement. Geochemistry. Sandstone reservoirs. Oriente Basin. Ecuador.

© UB-ICTJA 89
J. ESTUPIÑAN et al. The impact of carbonate cement on the Napo Cretaceous sandstones

INTRODUCTION secondary porosity. A combination of optical microscopy,

CL and SEM, as well as geochemical (microprobe and
The most important oil reservoirs in Ecuador are stable isotopic) analyses were used in order to provide
found in the Oriente Basin (Fig. 1). The sandstones of the detailed constraints on the diagenetic sequence, the evolu-
Hollín and Napo Fms (Fig. 2) of Cretaceous age contain tion of pore fluid composition, and the relative timing of
the largest hydrocarbon reserves. Analyses related to the carbonate cement precipitation.
diagenesis effect on these reservoir sandstones are scat-
tered. A complete petrological and geochemical study GEOLOGICAL SETTING
including diagenetic processes, isotopic analyses of the
carbonate cements, as well as a general diagenetic The Oriente Basin is part of a major morfo-structural
sequence of the principal events, would improve and unit called the Upper Amazon Basin which comprises
optimise hydrocarbon recovery production. parts of Colombia, Ecuador, Peru, Bolivia, and Brazil.
The structure of the basin is the result of transpressive
The spatial distribution of diagenetic alterations in flu- stress from the Upper Cretaceous deposits which pro-
vial, transitional and marine sediments is strongly influ- duced the uplift of the Cordillera Real and the formation
enced by sea-level changes, depositional facies and the of the back-arc basin. Nevertheless, a previous stage of
extent of mixing between marine and meteoric waters oil-bearing process existed which was of fundamental
(Morad et al., 2000). Likewise, the burial depths at which importance. It began in the Turonian age with compres-
the mesogenetic reactions occurred may vary consider- sive stress that marked the tectonic inversion developed in
ably depending on the burial-thermal history of the the Permo-Triassic and Jurassic periods. During this tec-
sequence. tonic inversion, the whole oil structure of the basin devel-
oped (Baldock, 1982; Dashwood and Abbotts, 1990).
The purpose of this study is to investigate the diage-
netic history of the reservoir sandstones of the Napo Fm, The Hollín, Napo and Basal Tena formations, located at
as well as to discuss the distribution of the carbonate the east of the Andes Cordillera, belong to the Cretaceous
cements and their possible relation to the depositional period in the Oriente Basin. The oil reservoirs studied cor-
environment or with the fluids that circulate at burial respond to the Napo “U” and “T” sandstones (Upper
depth. The study also includes the relationship between Albian – Upper Cenomanian; Fig. 2). They are charac-
the preservation of primary porosity and the generation of terised by cyclic sequences of limestone, shale, and sand-

FIGURE 1 Location, distribution and paleogeographical map of the Napo Formation showing the shoreline at the maximum sea level fall and the ini-
tial sea level fall. The black dots show the sampled wells (adapted from White et al., 1995).

G e o l o g i c a A c t a , Vo l . 5 , N º 1 , 2 0 0 7 , 8 9 - 1 0 7 90
J. ESTUPIÑAN et al. The impact of carbonate cement on the Napo Cretaceous sandstones

FIGURE 2 General stra-

tigraphical column of
the Oriente Basin with
lithostratigraphic
nomenclature (modified
from Almeida, 1986).
Detailed chart showing
the reservoirs “U” and
“T” sandstones from the
Napo Formation [after
Christophoul and Riva-
deneira (1986)] modi-
fied from Jaillard, 1997).

stone, whose deposition and distribution were controlled by rise again, facies from the estuary and nearshore were
relative changes in the sea level (White et al., 1995; Fig. 2). deposited in the incised valleys (Fig. 1).

The Napo Fm age is between Aptian and Campanian SAMPLING AND METHODS
and was deposited over a stable sea platform in a passive
margin with low subsidence. Seismic interpretation and The well samples studied from the Napo “U” and “T”
data from the wells show the complex structural history sandstones were taken from a depth of 1459 m to 3123 m
of the Oriente Basin, where extensional and compression- where the formation temperature ranges from 80 to 110ºC.
al events occurred. The recent structures were influenced Fifty four samples of the cored intervals from 22 wells were
by previous tectonic events that took place during Pre- selected. After eliminating oil from the porosity, the samples
cambrian and Lower Palaeozoic. In the Lower Cretaceous were impregnated with blue-stained resin and then ground
a regional compression affected the entire basin. In the deeply enough to avoid artifact porosity. Thin sections were
Eastern part some faults were inverted and erosion pro- stained for feldspar and carbonates. Quantification of mine-
duced an unconformity during the Aptian. ralogy and porosity was performed by counting 300 points
per thin section. A standard petrographic microscopic Zeiss
The interval of the studied sandstones represent two (Axioskop) with x2.5, x10, x20, x40 lenses was used.
cycles of regression and transgression. The boundaries of Cathodoluminescence (CL) observations were performed
the sequences at the base of the reservoir are erosional using “cold” Technosyn 8200 Mk 4 models connected to an
events associated with the fall of the sea level during the Olympus BHA-P microscope with 4x and 10x magnifying
Upper Albian and Cenomanian. As the sea level began to lens. The conditions for the observation were 11-16 Kv volt-

G e o l o g i c a A c t a , Vo l . 5 , N º 1 , 2 0 0 7 , 8 9 - 1 0 7 91
J. ESTUPIÑAN et al. The impact of carbonate cement on the Napo Cretaceous sandstones

age, with an intensity of 300-500 µA and 0.2-0.1 Torr of SANDSTONE PETROGRAPHY

vacuum. Mineralogy was confirmed by X- ray diffraction,
using a Philips PW 1720 diffractometer equipped with Napo “U” sandstones have a rather uniform composi-
Cu(Kα) radiation. The data were processed with the Philips tion in terms of quartz, feldspar and rock-fragments,
APD program. To determine the textural relationship being quartzarenites with a few subarkoses. The average
between the cements and clay minerals, we used a scanning composition is Qt 96.5 F 3.1 Lt 0.4. Napo “T” sandstones,
electron microscope (SEM) model JEOL JSM 6400 on the other hand, are subarkoses, with an average com-
equipped with an energy–dispersive X-ray microanalyzer in position of Qt 89.8 F 6.8 RF 3.1 (Fig. 3). In general all the
secondary electron and backscattered electron modes (BSE). sandstones are fine to coarse grained, with moderate to
good sorting, and round to subround grains, including
Thirteen representative samples were selected for the some angular and subangular subordinated grains. The
carbonate cements analyses. Their chemical compositions argillaceous matrix is scarce (< 1 %).
were determined by microprobe analyses. Ninety eight
analyses corresponding to the Napo “U”, and 192 to Napo Modal analyses reveal that the most common detrital
“T” sandstone, were performed. A JEOL JXA–8900 model component is quartz, dominantly monocrystalline in rela-
(15 Kv accelerating voltage, 2.147E-08 A beam current, 5 tion to the polycrystalline quartz grains (Tables 1 and 2).
m beam size, 100 % ± 3.5% total accepted) was used. Zircons and minor tourmaline amounts are frequently
Detection limits are approximately 100 ppm for Mg, 250 included in the monocrystalline quartz. Chert occurs in
ppm for Mn and 300 ppm for Fe. The BSE system of the trace amounts. Rock fragments are igneous (volcanic),
microprobe was used for detection of zonation. For all metamorphic (quartzite), and scarce sedimentary rocks
cements, results were normalized to 100 mol% FeCO3, (< 2%). The detrital quartzs are corroded by the carbonate
MnCO3, MgCO3, CaCO3 and SrCO3 . cements. K-feldspar dominates over plagioclase in all
depositional facies and they vary between 0-7%. These
Oxygen and carbon isotopic compositions of the car- feldspars are occasionally replaced by carbonates and in
bonate cements were determined at the Experimental Sta- some cases, albitized. Most of the feldspar grains show
tion of Zaidín (CSIC) Granada, using a Finnigan MAT 251 evidence of dissolution. Micas (biotite and muscovite),
mass spectrometer. The samples containing more than one zircons and tourmaline are only minor constituents in the
phase of cement were separated after the treatment for the sandstones (av. 0-2%). The intrabasinal components are
chemical sequential (Al-Aasm et al., 1990). The isotope glauconite and phosphatized micritic grains.
values were obtained in ‰ and the isotopic relation from
the oxygen and carbon referent to the standard (V-PDB). Besides the carbonate cements, there are other fairly
abundant cements such as quartz overgrowths (av. 16%)
and pyrites-pyrrhotite (av. 2%). Kaolin occur as pore-filling
and epimatrix, (av. 0–7.3%). Dickite is distinguished from
kaolinite by SEM and XRD analyses. Dickite crystals show
no etching and are much thicker (5-10 m) than the kaoli-
nite which postdates the quartz overgrowth and the carbon-
ate cements. Chlorite appears as rims (av. 3%) composed of
platelets oriented perpendicularly to the grain surface.

PETROGRAPHY AND CHEMISTRY OF CARBONATE

CEMENTS

Postdepositional processes resulted in a quite significant

modification of depositional porosity. In addition to com-
paction, quartz, carbonate and clay mineral cementation are
the major porosity reducing factors. Carbonate cements occur
in the hydrocarbon reservoir of the Napo Fm. They include:
siderite, calcite, dolomite-Fe and ankerite phases (Tables 1 and 2).

Siderite
FIGURE 3 Detrital composition of representative sandstones from
the Napo Formation, plotted on Qt-F-RF (Dott, 1964 and modified by
Pettijohn, 1972). Abbrevations: Qt: Quartz; F: Feldspar; RF: Rock frag- Two siderite cement generations were distinguished.
ments. Siderite (S1) occurs as small lenticular crystals (10–50 m)

G e o l o g i c a A c t a , Vo l . 5 , N º 1 , 2 0 0 7 , 8 9 - 1 0 7 92
J. ESTUPIÑAN et al. The impact of carbonate cement on the Napo Cretaceous sandstones

FIGURE 4 Petrographic aspects of siderite cements. Left: optical photomicrograph. Right: BSE images. A and B) Thin lens crystals of siderite (S1)
replacing feldspar. C and D) Fe-dolomite engulfing siderite lens and small rhombs (S1). E) Optical photomigraph. Petrography aspects of siderite (S1)
corroding quartz grains and replacing clay intraclast. F) BSE image of siderite (S2) showing zonation with higher Mg content in the core and outer
zone.

G e o l o g i c a A c t a , Vo l . 5 , N º 1 , 2 0 0 7 , 8 9 - 1 0 7 93
 TABLE 1 Representative modal analysis of the “U” sandstones from the Napo Formation.

U MARINE TRANSITIONAL FLUVIAL

depth (ft) PC-2 AA-10 AT-2 CN-4 IY- B6 p JV-1 JV-3 LM-9 SC-126 TT-1 YC-2 Average ED-10 MR-1 TM-1 Average Average
J. ESTUPIÑAN et al.

9374' 9192,5' 9402' 9988' Av. Av. Av. 9435' 9431' 9026' 9549' TRANSITIONAL 7365' 8958,2' 4787' "FLUVIAL" "TOTAL U"
n= 7 n= 2 n=4
% % % % % % % % % % % % % %

Qmr 32.6 31.8 44.30 34.6 39.6 38.0 38.2 38.6 36.0 40.0 34.3 37.5 35.3 36.7 40.7 37.6 35.9
Qmo 6.7 5.3 6.67 10.0 8.0 14.0 10.2 9.3 7.0 7.5 12.4 9.0 11.0 10.0 4.7 8.6 8.1
Qp2-3 6.0 11.3 6.67 8.3 5.0 3.8 7.4 7.0 4.4 10.7 9.7 7.4 5.0 4.7 3.3 4.3 5.9
Qp >3 1.7 3.0 2 2.7 1.0 1.8 2.6 0.3 1.0 1.3 3.7 1.9 2.0 0.9 1.0 1.3 1.6
Q fr.met. 0.0 0.0 0.3 0.2 0.25 0.3 0.3 0.1 0.3 0.0 0.3 0.2 0.1
K-F 0.7 0.7 1.3 1.0 2.0 2.0 0.5 0.7 2.3 0.3 1.1 6.7 0.0 2.3 3.0 1.6

G e o l o g i c a A c t a , Vo l . 5 , N º 1 , 2 0 0 7 , 8 9 - 1 0 7
CO3-KF 0.7 1.30 0 1.3 0.2 0.0 0.0 0.3 0.7 3.7 1.4 0.8
Plg + Alb 0.0 0.3 0.7 0.8 0.3 0.1 1.4 0.7 0.4 0.7 1.4 0.7 0.4
Chert 0.0 0.3 0.1 0.3 0.1 0.0 0.0 0.0
Opaques 0.3 0.7 0.8 1.6 0.7 4.3 0.0 0.8 0.0 0.0 0.0 0.4
Muscovite 1.0 0.3 0.3 0.2 1.0 0.3 1.0 0.0 0.3 0.2
Biotite 0.0 0.3 0.3 0.1 0.0 0.0 0.0
Heavy minerals 0.2 0.1 0.1 0.1 0.1 0.6 0.3 0.3 0.1
Total 48.6 54.7 61.9 58.9 57.8 61.3 60.9 57.5 56.7 59.9 61.9 59.2 61.9 53.9 57.4 57.8 55.2
Quartz 12.0 15.0 18.10 10.0 15.0 14.0 16.0 17.0 7.0 14.0 9.0 13.5 11.0 10.0 12.0 11.0 12.2
Calcite 2.00 1.0 0.2 0.3 0.2 21.0 1.0 7.3 3.2
Fe-dolomite/ankerite 10.66 2.00 14.70 1.7 1.67 0.6 4.3
Siderite 2.4 0.00 0.0 0.4 0.0 0.7 0.1 0.0 3.0 1.0 1.2
Kaolin 0.0 3.3 3.70 2.0 2.8 3.0 5.0 6.7 1.3 4.0 3.0 3.5 2.1 0.0 0.3 0.8 1.4
Pyrite 0.7 0.7 0.7 0.3 0.8 0.0 0.0 0.0 0.2 2.3 0.8 0.6
Chlorite 0.0 2.7 0.00 1.0 0.0 1.0 0.0 0.0 0.7 0.5 1.0 0.0 0.0 0.3 0.3
Total cement 27.7 23.7 21.8 14.7 18.3 18.8 21.3 24.1 23.0 18.7 12.7 19.7 14.1 33.3 18.0 21.8 23.1
Epimatrix 3.3 7.0 2.3 6.3 2.8 0.2 0.4 2.0 2.0 4.0 6.0 3.3 1.7 0.3 1.3 1.1 2.6
Pseudomatrix 1.0 1.0 1.0 0.3 0.3 0.3 1.6 0.5 0.7 0.2 0.3
Total 3.3 8.0 2.3 7.3 2.8 1.2 0.7 2.3 2.3 4.0 7.6 3.8 2.4 0.3 1.3 1.3 2.8
Glauconite 5.7 1.0 0.6 0.1 0.2 0.3 0.1 0.2 0.3 5.7 2.0 2.6
P1 porosity 9.0 5.7 8.3 11.7 13.1 10.6 14.3 14.4 16.0 13.4 7.0 11.5 13.3 4.7 13.3 10.4 10.3
P2 porosity 5.7 7.0 5.1 7.3 7.9 7.9 2.8 1.7 1.7 4.0 10.7 5.6 8.0 2.0 10.0 6.7 6.0
(P1+P2) 14.7 12.7 13.4 19.0 21.0 18.5 17.2 16.1 17.7 17.4 17.7 17.1 21.3 6.7 23.3 17.1 16.3
Total 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0
Grain size Fu - Fl Fu-mu fl-ml fu-ml fu-ml fu-ml Fu-ml fu-fu Fl-fl fl-ml fu-ml mu-Crsl Fu-ml Fl-fu
Sorting good Mod. good mod good good good good good mod good good mod.
IGV 36.80 38.00 35.80 32.33 35.52 34.80 37.16 38.40 37.70 33.70 28.00 35.1 31.33 39.67 36.33 35.8 35.9
COPL 5.00 3.30 6.6 11.33 6.95 7.90 3.90 2.60 3.60 9.50 15.90 7.2 6.70 1.60 5.80 4.7 5.6
CEPL 23.60 24.50 20.9 15.40 20.85 16.60 19.70 21.70 21.20 16.90 10.70 18.8 16.40 33.40 19.10 23.0 21.8
ICOMPACT 0.12 0.10 0.2 0.38 0.25 0.23 0.20 0.10 0.07 0.31 0.63 0.2 0.45 0.02 0.26 0.2 0,2

94
The impact of carbonate cement on the Napo Cretaceous sandstones
 TABLE 2 Representative modal analysis of the “T” sandstones from the Napo Formation.

MARINE TRANSITIONAL FLUVIAL

Arenisca "T" PC-2 AA.-10 AC-16 CN-4 CN-4 IT- B-6 JV-1 JV-3 LM-9 SC-99 SC-105 SC-126 YC-2 YB-1 Average AZ-1 CR-1 ED-10 HT-1 S RQ-1 Average Average
Prof. (ft) 9623 9412,0 9976,0 10248' 10249,0 Av. 9500,0 9492,0 9699,0 9649,0 9757,0 9670,0 9791,0 9829' Transitional 9663,0 8863,0 Av. 9488,0 Prom. fluvial Total
J. ESTUPIÑAN et al.

% % % % % nº = 5 % % % % % % % % % % nº = 4 % nº = 2
Qmr 36.0 27.7 32.3 31.9 22.0 38.1 32.0 26.7 35.0 33.6 32.4 32.3 31.4 37.0 31.7 27.2 23.0 30.0 29.0 34.6 28.8 32.2
Qmo 3.0 10.3 10.0 5.0 6.3 6.6 11.0 3.0 5.0 7.4 6.7 4.0 6.1 8.2 6.9 4.7 10.0 6.0 6.0 4.3 6.2 5.4
Qp2-3 6.0 10.0 6.3 5.7 2.3 8.0 7.0 5.3 4.3 5.3 5.0 8.3 3.0 2.4 5.6 3.7 5.7 5.0 3.3 6.7 4.9 5.5
Qp>3 0.7 1.7 1.3 0.7 0.7 1.6 1.0 3.0 2.0 1.7 1.7 0.3 1.4 1.7 1.4 1.3 3.0 3.0 2.0 1.0 2.1 1.4
Q fr.met 1.0 1.0 0.0 0.7 0.7 0.0 0.0 1.0 0.7 0.3 0.0 0.3 0.0 0.0 0.4 0.3 0.3 0.3 0.7 0.2 0.4 0.6
K-F 1.0 0.0 0.0 0.0 1.0 0.3 5.0 1.0 0.3 1.0 1.0 1.2 1.4 3.0 1.7 0.0 1.5 1.1
CO3-KF 2.6 0.0 0.0 0.0 0.0 0.0 0.0 1.0 0.0 0.0 0.0 0.3 0.0 0.1 0.0 0.0 0.0 2.3 0.0 0.5 1.1
Plg +Alb. 2.0 2.0 3.0 4.0 4.6 0.7 3.0 0.0 1.7 1.7 0.6 2.6 1.0 1.0 2.0 4.0 4.9 0.1 4.5 1.8 3.1 2.4

G e o l o g i c a A c t a , Vo l . 5 , N º 1 , 2 0 0 7 , 8 9 - 1 0 7
Opaques 1.3 3.2 3.0 1.0 2.0 1.8 1.0 1.0 1.3 3.7 0.0 4.0 1.0 1.0 1.8 1.0 0.3 1.0 2.0 1.1 1.4
Muscovite 0.0 0.3 0.3 0.5 1.7 0.0 0.3 1.0 0.0 1.0 1.0 1.0 2.0 2.4 0.9 0.3 0.3 1.0 1.0 0.7 0.5
Biotite 0.0 0.3 0.4 1.3 0.0 1.0 0.0 0.0 0.3 0.3 0.4 0.3 1.0 0.1 0.0 0.0 0.3 0.2
Heavy minerals 0.0 0.7 0.3 0.3 1.0 1.4 1.6 0.0 0.7 0.7 2.0 0.1 1.0 1.0 0.6
Total 53.6 56.6 57.0 50.1 41.9 57.8 56.7 46.0 53.0 56.4 48.9 52.9 46.6 55.8 52.3 46.1 50.0 49.7 49.5 52.6 49.5 51.8
Quartz 19.0 17.3 17.0 16.3 17.0 17.4 15.7 14.0 23.0 16.0 19.0 16.3 12.2 16.1 16.7 16.4 16.0 23.0 24.2 16.0 19.1 18.3
Calcite 2.0 0.8 0.7 4.7 3.3 2.0 2.0 1.0 3.0 2.4 2.2 2.0 1.7 2.0 0.5 1.5 1.9
Fe-dolomite/ankerite 3.0 1.0 0.0 0.7 1.0 2.0 1.0 4.1 1.4 5.0 4.0 1.0 1.0 2.8 2.4
Siderite 2.0 3.0 1.0 2.7 3.3 3.7 3.9 1.3 5.0 2.0 2.0 1.7 2.7 3.0 1.0 1.0 1.0 1.0 1.4 2.0
Kaolin 2.3 6.7 1.7 2.3 6.7 3.0 5.0 0.0 1.7 2.7 4.3 5.7 8.0 3.4 3.9 1.5 3.3 3.3 1.0 5.0 2.8 3.0
Pyrite 0.0 0.0 0.3 1.0 1.0 0.0 1.3 0.0 0.3 0.3 0.0 3.0 0.0 0.6 0.3 0.1 0.2 0.2 0.3
Chlorite 0.0 1.0 0.0 0.7 2.7 0.1 1.0 0.0 0.0 0.0 0.0 1.1 4.1 1.0 0.9 0.0 2.3 0.2 0.3 0.6 0.7 0.5
Total cement 28.3 29.8 20.3 27.0 34.0 21.5 26.0 19.2 29.0 26.0 26.7 25.1 33.3 28.8 26.7 27.9 28.7 30.7 26.5 24.2 27.6 27.5
Epimatrix 1.7 1.0 2.0 3.2 5.7 1.1 1.3 0.7 1.3 3.1 4.3 1.6 0.0 2.1 3.0 6.3 0.2 0.3 3.7 2.7 2.2
Pseudomatrix 0.0 0.0 0.0 0.7 0.0 1.0 0.6 0.3 0.0 0.0 0.3 1.0 0.0 0.1 0.7 0.5 0.5 0.2
Total 1.7 1.0 2.0 3.2 6.4 1.1 1.3 0.7 0.0 2.3 3.7 4.6 1.6 0.0 2.1 4.0 6.3 0.3 1.0 4.2 3.2 2.3
Glauconite 0.0 0.0 0.7 0.0 0.7 0.1 0.3 16.7 0.0 0.3 0.7 0.0 0.0 3.4 1.8 7.3 0.0 0.0 12.0 0.3 3.9 1.9
P1 porosity 13.7 10.0 15.7 14.3 9.7 16.0 9.0 12.3 16.7 11.0 15.0 16.7 16.9 9.9 13.3 11.7 9.0 12.4 10.0 15.9 11.8 12.9
P2 porosity 2.7 2.7 4.3 5.3 7.3 3.5 6.7 5.0 1.3 4.0 5.0 0.7 1.7 2.1 3.8 3.0 6.0 6.9 1.0 2.9 3.9 3.5
P1 + P2 16.4 12.7 20.0 19.7 17.0 19.5 15.7 17.3 18.0 15.0 20.0 17.4 18.6 12.0 17.1 14.7 15.0 19.3 11.0 18.7 15.7 16.4
Total 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0
Grain size Fl - Fu Fu-mu Fl - Fu Fl -Fl Fl -Fl Fu-mu Fl -Fu Fl -Fu Fl - Ml Fu - Fl Fu -Ml Fl - Fu Fl Fu - Fl Fu- Crsl Fu-crsl Fu- Crsl Fu -Mu Fu-mu
Sorting good good good good good good good good good good good good poor good mod. mod. good good mod
IGV 36.30 29.00 36.60 36.70 36.70 37.50 31.7 32.0 35.3 31.70 39.00 35.30 35.70 31.00 34.5 30.30 31.00 34.60 36.30 32.10 32.9 34.5
COPL 5.8 15.50 5.30 5.26 5.30 4.60 12.2 11.8 7.2 12.2 1.60 7.20 6.7 13.0 8.3 13.90 13.90 8.20 5.80 11.70 10.7 8.3
CEPL 18.80 13.80 15.80 16.10 18.80 16.90 14.20 12.90 17.00 14.00 18.70 16.70 16.20 16.80 16.0 13.50 13.50 16.60 23.20 14.20 16.2 17.0
ICOMPACT 0.20 0.50 0.20 0.20 0.20 0.22 0.40 0.50 0.30 0.50 0.10 0.30 0.30 0.40 0.3 0.50 0.40 0.30 0.20 0.50 0.38 0.3

95
The impact of carbonate cement on the Napo Cretaceous sandstones
J. ESTUPIÑAN et al. The impact of carbonate cement on the Napo Cretaceous sandstones

FIGURE 5 A and B) Fe-dolomite replacing glauconite and preceding the overgrowth development of S2 siderite. Fe-dolomite and S2 siderite are post
quartz overgrowth (see arrows).

and as euhedral rhombs that fill intergranular pores and in est samples in S1 or S2, in order to separate both phases
some case, replaces feldspars and clay intraclasts (Figs. in the isotopic plot.
4A to 4E). Siderite (S2) occurs as large rhombic crystals
(Fig. 4F), which partially replace dolomitized glauconite Calcite
(Figs. 5A and 5B). Under CL, siderite S1 is not lumines-
cent but S2 shows orange luminescence. S1 cement is par- Calcite cement is scarce in the fluvial sandstones and the
tially replaced by Fe-dolomite (Figs. 4C and 4D), calcite or average content is 5% of the total volume (Tables 1 and 2).
ankerite. Siderite cement forms 5% of the total volume of Calcite appears as sporadic patches (up to 80 µm), poiki-
all the analysed samples. Siderite (S1) pre-dates quartz lotopic texture of 50–100 µm (Figs. 8A and 8B) with no
cement, as is shown under optical microscope and SEM luminescence or red orange luminescence. Calcite replaces
observations. However, the quartz overgrowth shows corro- feldspars (Figs. 8C and 8D). Calcite cement appears as
sion or embayment by S2 siderite. S1 siderite cement
appears in all sandstones and S2 only in transitional and
marine sandstones from Pucuna, Yuca and Jivino (Fig. 1)

The average composition of siderite (S1) is (Fe 81.8

Mg 10.2 Mn 0.9 Ca 7.1)CO3, (Table 3). Some samples have
values up to 99% of FeCO3, and a high content in Mn
(>3.9). The average composition of S2 siderite is (Fe 67.8
Mg 20.5 Mn 0.8 Ca 11.1) CO3 (Table 3). These cements are
zoned in terms of Mg which is higher in the core than in
the outer zone (Fig. 4F). The average compositions of
siderites S1 and S2 are similar except for low Mn content
(< 1%) and the high Mg of the S2 (Table 3, and Figs. 6 and
7). Another characteristic of the marine sandstones is the
presence of glauconite partially replaced by S2 siderite and
later replaced by Fe-dolomite (Figs. 5A and 5B).

The
13C ‰ PDB values in Napo “U” sandstones vary

between -3.2 and -10‰, and
18O between -3.2 and
–11.4‰ PDB (Table 3). The
13C ‰ PDB in “T” sand-
stones vary from -2.4 to -9.6 ‰, and
18O from -3.0 to -
13.8 ‰ PDB (Table 3). These data correspond to FIGURE 6 Chemical composition of representative carbonate cements
(S1+S2). Likewise, we have selected under BSE the rich- (Ca, Fe+Mn, Mg)CO3, from the Napo Formation.

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TABLE 3 Chemical composition from microprobe analyses and isotopic ratios of representative carbonate cements in the Napo Formation.

MARINE TRANSITIONAL FLUVIAL

sandstone CO3 CO3 CO3
13C
18O Remarks
Samples Mg Ca Mn Fe Sr Mg Ca Mn Fe Sr Mg Ca Mn Fe Sr (‰ V-PDB) (‰ V-PDB)
"U" Sandstone
SIDERITE S1

average 18.6 11.6 0.9 69.1 0.0 12.4 9.2 0.9 77.5 0.0 -3.4 -3.7 Siderite lens
maximum 19.3 12.2 0.7 70.5 0.0 13.9 10.9 1.0 80.0 0.0 -3.6 -4.3
minimum 17.8 11.0 0.6 67.8 0.0 11.2 7.0 0.7 75.4 0.0 -3.2 -3.2
SIDERITE S2
average 23.8 13.9 0.4 61.8 0.0 -8.5 -10.8 Rhombic siderite
maximum 27.6 27.0 0.8 66.5 0.0 -10.0 -11.4 Occasionally zoned
minimum 20.7 8.0 0.2 45.8 0.0 -7.1 -10.3
CALCITE
average 3.8 96.5 0.1 0.5 0.1 1.3 95.4 1.0 2.3 0.0 -3.5 -11.4 poikilotopic calcite
maximum 4.0 97.0 1.3 0.9 0.1 1.9 97.6 1.3 3.1 0.0 -3.5 -10.5
minimum 3.7 96.0 0.1 0.2 0.1 0.3 94.2 0.3 1.4 0.0 -9.3 -13.8
Fe-DOLOMITE
average 26.6 57.3 0.4 15.6 0.0 26.6 56.6 0.6 16.1 0.0 -4.0 -9.2 Patches Fe-dolomite
maximum 31.6 59.7 0.9 18.8 0.1 30.3 59.2 1.4 19.0 0.1 -3.3 -4.6 Occasionally zoned
minimum 23.1 51.8 0.2 12.7 0.0 22.9 54.2 0.3 12.4 0.0 -6.2 -14.2
ANKERITE
average 23.2 52.7 0.8 23.2 0.0 22.9 52.1 0.9 21.1 0.0 - - Patches ankerite
maximum 27.5 57.2 1.4 48.7 0.1 25.9 57.1 1.0 0.0 - - Occasionally zoned
minimum 20.0 21.9 0.2 19.3 0.0 20.0 51.9 0.7 19.3 0.0
"T" Sandstone
SIDERITE S1
average 0.1 2.7 0.1 97.2 0.0 9.5 5.0 1.0 83.4 0.0 -2.7 -4.7 Siderite lens
maximum 0.1 5.2 0.1 99.8 0.0 16.4 8.6 3.9 99.9 0.2 -2.8 -6.3
minimum 0.0 0.1 0.1 94.5 0.0 0.0 0.0 0.0 71.5 0.0 -2.6 -3.0
SIDERITE S2
average 17.2 7.2 0.4 73.7 0.0 -6.5 -12.4 Rhombic siderite
maximum 33.7 13.0 2.0 94.5 0.1 -9.6 -13.1 Occasionally zoned
minimum 0.1 1.2 0.0 52.5 0.0 -3.4 -11.6
CALCITE
average 0.6 97.2 0.3 1.9 0.0 0.7 96.5 0.6 2.2 0.0 0.8 96.2 0.6 2.4 0.0 -7.7 -10.5 Patches calcite
maximum 0.7 97.5 0.3 2.0 0.1 2.5 98.5 1.6 7.9 0.1 2.5 98.5 1.6 7.9 0.1 -1.3 -6.7
minimum 0.5 97.0 0.3 1.7 0.0 0.2 89.0 0.1 1.0 0.0 0.2 89.0 0.4 1.0 0.0 -12.7 -11.6
Fe-DOLOMITE
average 26.7 56.0 0.3 17.0 0.0 24.9 57.6 0.4 17.2 0.0 -4.7 -9.4 Fe-dolomite zoned rhombs
maximum 27.7 57.4 0.4 19.0 0.1 27.3 59.0 0.5 19.4 0.0 -3.4 -4.8 reemplacing feldspar
minimum 25.4 54.8 0.2 16.0 0.0 22.5 53.9 0.2 15.5 0.0 -7.1 -13.7
ANKERITE
average 19.6 56.9 0.7 22.8 0.0 18.4 57.6 0.8 23.2 0.0 16.1 57.3 2.1 24.6 0.0 - - Patches ankerite
maximum 25.5 59.7 1.0 26.9 0.0 21.2 59.6 1.9 25.8 0.0 17.6 59.2 3.2 25.5 0.0 - - Occasionally zoned
minimum 16.7 54.3 0.5 19.7 0.0 15.5 56.2 0.5 19.7 0.0 14.7 55.0 1.3 22.3 0.0 - -

MARINE + TRANSITIONAL FLUVIAL

“U” SANDSTONE CO3 CO3
Mg Ca Mn Fe Sr Mg Ca Mn Fe Sr
SIDERITE S1 (av) 18.6 11.6 0.9 69.1 0.0 1.4 9.2 0.9 77.5 0.0
SIDERITE S2 (av) 23.8 13.9 0.4 61.8 0.0
CALCITE (av) 3.8 96.5 0.1 0.5 0.1 1.3 95.4 1.0 2.3 0.0
DOLOMITE (av) 26.6 57.0 0.5 15.9 0.0
ANKERITE (av) 23.1 52.4 0.9 22.2 0.0

MARINE + TRANSITIONAL FLUVIAL

“T” SANDSTONE CO3 CO3
Mg Ca Mn Fe Sr Mg Ca Mn Fe Sr
SIDERITE S1 (av) 0.1 2.7 0.1 97.2 0.0 9.5 5.0 1.0 83.4 0.0
SIDERITE S2 (av) 17.2 7.2 0.4 73.7 0.0
CALCITE (av) 0.7 96.9 0.5 2.1 0.0 0.8 96.2 0.6 2.4 0.0
DOLOMITE (av) 25.8 56.8 0.4 17.1 0.0
ANKERITE (av) 19.0 57.3 0.8 23.0 0.0 16.1 57.3 2.1 24.6 0.0

MARINE + TRANSITIONAL FLUVIAL

“U” + “T” CO3 CO3
Sansdstones
Mg Ca Mn Fe Sr Mg Ca Mn Fe Sr
MARINE + TRANSITIONAL + FLUVIAL
SIDERITE S1 9.4 7.2 0.5 83.2 0.0 11.0 7.1 1.0 80.5 0.0 “U” + “T” CO3
SIDERITE S2 20.5 10.6 0.4 67.8 0.0 Sansdstones
SIDERITE S1+S2 14.9 8.9 0.5 75.5 0.0 Mg Ca Mn Fe Sr
CALCITE (av) 2.2 96.7 0.3 1.3 0.1 1.1 95.8 0.8 2.4 0.0
DOLOMITE (av) 26.2 56.9 0.4 16.5 0.0 S1 (FLUVIAL, MARINE AND TRANSIT.) 10.2 7.1 0.7 81.8 0.0
ANKERITE (av) 21.0 54.8 0.8 22.6 0.0 16.1 57.3 2.1 24.6 0.0 TOTAL SIDERITE (S1 + S2) 13.6 8.3 0.6 77.1 0.0

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J. ESTUPIÑAN et al. The impact of carbonate cement on the Napo Cretaceous sandstones

Ca 54.8) CO3 (Table 3). The average composition of

ankerite in the fluvial sandstones is (Mg 16.1 Fe 24.6 Mn 2.1
Ca 57.3) CO3 ; Fig. 1). The Fe-dolomite/ankerite displays a
patchy zonation in BSE images (Figs. 9C to 9F), which is
due to the variations in the FeCO3 content ranging from
12-28 mol % (Figs. 6 and 7). The following isotopic data
were obtained for Fe-dolomite and ankerite:
13C values
in Napo “U” sandstones range from -3.3 to -6.2‰, and

18O from -4.6 to -14.2‰ PDB. The
13 C values in Napo
“T” sandstones vary between -3.4 and -7.1‰ and
18O
between -4.8 and -13.7‰ PDB.
FIGURE 7 Plot of magnesium (Mg) and iron contents (Fe) in carbon-
ate cements.
POROSITY
patches of individual crystals and frequently replaces early
siderite (S1) in the transitional and marine sandstones. The assumed average original porosity is 40% (i.e.
moderately to well-sorted sandstones) but varies depen-
Calcite cement postdates quartz overgrowths and ding on sorting and cementation. The present porosity of
chemical compaction. Under SEM, and in BSE mode, the sandstones is both primary, intergranular porosity,
quartz and their overgrowths are corroded by this calcite (P1; Fig. 10A) and secondary (P2), with moldic, inter-
(Fig. 8E), and no chemical zonation was observed. Glau- granular and intragranular textural types in minor percen-
conite is partially or totally replaced by calcite (Figs. 8D tages (Schmidt and McDonald, 1979). Moldic porosity
and 8F), and pyrite is occluded in this cement (Fig. 8C). occurs as partial or complete dissolution of feldspars, par-
ticularly plagioclase (Fig. 10B). The average porosity
The average composition of the calcite cement in the (P1+P2) attains a value of approximately 17%, and ranges
fluvial environment is (Ca 95.8 Fe 2.4 Mg 1.1 Mn 0.8) CO3 between 7 and 23%. In most of the samples, there is
(Table 3) and the intergranular volume (IGV) in the sand- minor chemical compaction, as grains display long and
stones showing calcite cement are 27.7% (Table 1). The minor concavo-convex contact.
average composition of calcite from transitional to marine
environment is (Ca 96.7 Fe 1.3 Mg 2.2 Mn 0.3) CO3, and the The maximum reduction of the porosity is 33%. How-
IGV for these sandstones is 13% (Tables 1 and 2). The con- ever, in others areas of the basin these values decrease to
tents of Mg are < 2 mol % (Figs. 6 and 7) and Sr content 14% with respect to the initial porosity. An appreciable
varies from below detection limit up to 0.2 mol% (Table 3). primary porosity is preserved by early formation of clay
rims (chlorite) that retarded further cementation (Pittman
The
13 C values in Napo “U” sandstones vary between et al., 1992; Ehrenberg, 1993).
-3.5 and -9.3‰, and
18O from -10.5 to -13.8‰ PDB (Table
3). The
13 C values in “T” sandstones vary between -1.3 The diagram proposed by Houseknecht (1987; Fig.
and -12.7‰, and
18O from -6.7 to -11.6‰ PDB (Table 3). 11A) revealed insignificant impact of compaction com-
pared to cementation in porosity loss. 99% of the data
Ferroan dolomite /Ankerite points cluster in the upper right portion of the diagram,
indicating that these samples have undergone significant
The Fe-dolomite/ankerite cements are more abundant reduction of intergranular volume by cementation processes.
in the central and the western part of the basin than in The average values for all data are 35% of intergranular
eastern part (Fig. 1). These phases replace siderites S1 volume and 25% cement (Tables 1 and 2). Assuming that
and enclose S2 (Figs. 9A and 9B). The cements form the average original porosity of the sandstone was 40%,
intergranular mosaics of subeuhedral no luminescent then 12.5% of the original porosity has been destroyed by
crystals (up to 100 µm), but occasionally they show dis- compactional processes, whereas 63% has been destroyed
persed patches that corrode quartz and replace feldspars. by cementation leaving intergranular porosity for all sam-
The percentage of these cements is from 0 to 4% and they ples at 10%. However, by plotting parameters that take into
post-date quartz overgrowths (Figs. 9C to 9F) and me- consideration the reduction in bulk volume due to com-
chanical compaction. paction (Lundergard, 1992), a more realistic evaluation of
the relative roles of cementation and compaction is
The chemical composition of Fe dolomite in the tran- obtained (Fig. 11B). In this diagram some of the samples
sitional and marine sandstones (Fig. 1) is (Mg 26.2 Fe 16.5 are plotted in the field of the compactional porosity loss, and
Mn 0.4 Ca 56.9) CO3, and ankerite is (Mg 21. Fe 22.6 Mn 0.8 the values of intergranular porosity is around 25%.

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J. ESTUPIÑAN et al. The impact of carbonate cement on the Napo Cretaceous sandstones

FIGURE 8 A) Petrographic aspects of poikilotopic calcite cement, postdating quartz overgrowth in the “U” sandstones. B) Patch of calcite cement
postdating quartz overgrowth, corroded by kaolin pore-filling. C) Optical photomicrograph of calcite cement corroding feldspar, glauconite and
quartz overgrowth. Pyrite crystals are engulfed in the quartz and carbonate cements. D) BSE image of calcite patches replacing k-feldspar. Note that
the calcite and feldspar are partly dissolved. E) Optical photomicrograph of patchy calcite cement corroding quartz overgrowth. F) BSE image of cal-
cite cement post quartz overgrowth. Note glauconite is partially replaced by calcite.

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J. ESTUPIÑAN et al. The impact of carbonate cement on the Napo Cretaceous sandstones

FIGURE 9 A and B) Petrographic aspects of Fe-dolomite cements, optical photomicrograph (left), BSE image (right) Rhombohedral Fe-dolomite par-
tially replaced by Mg-siderite (S2). C and D) Mottle aspect of zoned Fe-dolomite cement post quartz overgrowth. The dark core is poor in Fe. E and F)
Aspect of patches of zoned ankerite cement post and replacing quart overgrowth (see arrows). Note that in picture F the core is richest in Fe.

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J. ESTUPIÑAN et al. The impact of carbonate cement on the Napo Cretaceous sandstones

FIGURE 10 A) SEM image showing intergranular primary porosity. The amorphous material in the centre of the photo is tight oil (grains up to 200
µm). B) Optical photomicrograph. Petrographic aspect of secondary porosity (intragranular) related to partially dissolved feldspar surrounded by
quartz overgrowths (see arrows).

DISCUSSION zones of organic matter in both environments. Fram-

boidal pyrite occurred in this stage, appearing in all
Diagenetic sequence and overall diagenetic depositional facies.
evolution of the sandstones
The mesogenetic alterations were largely controlled
Diagenetic processes in the Cretaceous Napo Fm by increases in temperature and by the composition of the
show that the reservoir sandstones have undergone several diagenetic fluids. In the immature stage, mechanical com-
changes during burial history. Postdepositional processes paction affected the argillaceous intraclasts, mica, and
caused a significant modification of depositional porosity. glauconite grains. In the semimature stage, quartz precipi-
The major porosity reducing factors are cementation by tation started and moderate processes of chemical com-
quartz, carbonate and clay mineral, as well as the paction took place. Quartz cement was postdated by cal-
mechanical compaction. Despite the complexity involved cite cement in the marine sediments and Fe-dolomite and
in the interpretation of carbonate cementation, owing to ankerite cement-replacement in all sandstones. The Fe-
the presence of multiple generations and subsequent dis- dolomite/ankerite phases were replaced by Mg-siderite
solutions, diagenetic carbonates can provide valuable (S2), which is the last carbonate phase. During the mature
information regarding the geochemical evolution of the stage, at maximum burial depth and related to the organic
pore waters involved (Morad, 1998). The terms eodiage- matter descarboxilation (Smith and McDonald, 1979),
nesis, mesodiagenesis immature, semi mature and mature siderite (S1, S2), calcite and Fe-dolomite cements were
stages are used sensu Schmidt and McDonald (1979), partially dissolved producing secondary porosity (P2).
modified by Morad et al., (2000). This dissolution event coincided with the beginning of the
entries of the hydrocarbon in the Oriente Basin in the
Petrographic and SEM observations, as well as the Miocene at 8 Ma (Debra, 2001; Dashowood and Abbotts,
different intergranular volumes (IGV, in Tables 1 and 2) 1990). Dickite and pyrite-pyrrhotite were the last phase
of the carbonate cemented sandstones, indicated that the cements after oil entrance in the reservoirs. This diage-
cementation is pre-compactional as well as post-com- netic sequence is similar to the one described in the
pactional. The relative sequence of the main diagenetic Lower Cretaceous fluvial and transitional reservoir
processes is presented schematically in Fig. 12. Due to sandstones in the Salam Field (Egypt´s Western Desert),
the complex diagenetic pattern and the implicated fluids, where well formation temperatures are slightly higher
the exact timing and origin for certain carbonate phases than in the Napo Fm (112ºC to 3,000 m depth; Marfil et
can not be established. During eodiagenesis, in shallow- al., 2003).
water marine facies, a chlorite clay rim from a possible
early berthierine, was formed beginning at temperature of Siderite cement
≈ 70º (Morad et al., 2000). During this stage thin lens of
siderite (S1), and replacements of argillaceous grains Siderite cement (S1) was among the first carbonate to
and feldspar by this siderite, precipitated in the richest precipitate in all the sedimentary environments. In the flu-

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J. ESTUPIÑAN et al. The impact of carbonate cement on the Napo Cretaceous sandstones

vial sandstones, some (S1) siderites have up to 99% water (-0.1 to -2.3‰ vs V-SMOW) are just in the present
FeCO3 and high values in Mn (3.9%; Table 3), suggesting range of temperatures, indicating equilibrium conditions
that the siderite cement had precipitated from meteoric (Fig. 14). This impoverishment in
18O of the carbonate
fluids, possibly near to the surface water-sediment inter- cements have been attributes to meteoric incursion
phase or in the phreatic zone (Morad et al., 2000; Morad (Hudson, 1978; Prosser et al., 1993), to the recrystaliza-
et al., 1998; Mozley, 1989). These authors suggested that tion of the cements at higher temperatures (Morad and
siderite richer than 90% FeCO3 and higher than 2.0% Eshete, 1990), to Rayleigh fractioning related to the pre-
MnCO3 indicates an eogenetic process in fluvial environ- cipitation of early diagenetic minerals (Irwin et al.,
ment. However, a Mn-rich siderite was described by 1977; Mozley and Carothers, 1992), and to the oxidation
Rossi et al. (2001) in the Jurassic reservoir sandstone of of the organic matter in the sulphate reduction zone
Egypt’s Western Desert and the high Mg and Ca content (Morad and Eshete, 1990). All of these processes could
was interpreted as precipitated from mixed meteoric and contribute to the lighter oxygen isotopic composition.
marine water. The thin rhomboidal crystals of (S1 and
S2) siderites show chemical zonation, supporting the Optical microscope and SEM observations show
hypothesis that these cements were formed by precipita- that the S1 siderite maintains the original texture but
tions related to the successive changes in the sea level effectively the major part of the S1 crystals have been
(White et al., 1995), possibly from mixed fluids (Mat-
sumoto and Iijima, 1981; Mozley, 1989; Pye et al.,
1990; Moore et al., 1992).

The average composition of the siderite cement (S2)

has little differences with respect to the siderite (S1).
Siderite (S2) has a higher content of Mg and lower con-
tent of Fe and Mn. The chemical values from this meso-
genetic siderite cements with high Mg indicates sidero-
plesite composition (5–30% m MgC03) (Table 3) (Deer
et al., 1962). The Mg could be related to the water
enrichment in organic acids (Smith and Ehrenberg,
1989; Morad et al., 2000). Likewise, the increase in the
Mg/Fe relation in diagenetic waters formed S2 siderite
which could have been caused by the siderite precipita-
tion combined with the increase of the reduction of Fe
with depth (Berner, 1980; Canfield, 1989; Fisher and
Knipe, 1998). The low values of intergranular volume
(19%) indicate that this siderite is post-compactional in
origin.

Siderite (S1) precipitated in the early diagenetic

phase, possibly due to mica alteration and other argilla-
ceous intraclasts rich in organic matter, as we have
observed under optical and fluorescence microscope.
The
13C ‰ and
18O ‰ values for siderite are relatively
negatives (Table 3). However, there are two different
groups of data that possibly reflect the meteoric origin
of S1 with moderate negative values, and S2 with more
negative
18O, indicating mixed meteoric and marine
origin or waters modified by diagenetic processes (Fig.
13). The most negative
13C values, together with the
low
18O values, which are interpreted (Irwin et al.,
1977; Irwin, 1980; Mozley and Carothers, 1992) as a
gradual evolution in the composition of the isotopes
during burial, can also be interpreted as related to differ-
ent origins. Likewise, the most negative δ18O curves of
FIGURE 11 A) Plot of intergranular volume (%) versus cement (see
siderite (-13.1‰ vs V-PDB) and calcite (-13.8‰ vs V- Houseknecht, 1987). B) Plot of compactional porosity loss (COPL)
PDB) to cross the shadow area of current formation versus cementation porosity loss (CEPL) (see Lundergard, 1992).

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cement was derived from very different sources and pre-

cipitated at different diagenetic temperatures and from
different compositional waters. The most negative δ18O
curves of calcite cement (-13.8‰ vs V-PDB) to cross the
shadow area of current formation water (-0.1 to -2.3‰
vs V-SMOW) are just in the present range of tempera-
tures, indicating equilibrium conditions (Fig. 14). The
most negative values could indicate burial trend in the
presence of organic-derived CO2 (Heydary, 1997) while
the less negative values could suggest an evolution from
marine waters to modified mesogenetic waters (Hudson,
1978).

Ferroan Dolomite/Ankerite cements

The ferroan dolomite/ankerite cement-replacement

precipitated after quartz overgrowth and mechanical and
chemical compaction. Optical microscope and BSE show
FIGURE 12 Paragenetic sequences of the diagenetic processes in that these carbonates replaced eogenetic siderite (S1) and
the Napo Formation.
quartz cement, and in many cases they replaced the
feldspars too. The chemical composition of the dolomite
replaced by S2. This argument could justify the low and ankerite in the different depositional facies shows no

18O of the S2 siderite cement. Moreover, siderite S2 major differences, which suggests that the evolution of
could have precipitated as a result of the thermal the fluid in a thermobaric regime in the basin was mainly
descarboxilation of the Mg rich organic matter at tem- ferroan-carbonates precipitated (Galloway, 1984). The
peratures between 80-100ºC. They are slightly lower high content in Mg and Fe in both cements suggests that
than the formation temperatures measured in the sam- the principal sources of solutes for Fe-dolomite-/ankerite
pled wells and similar to the temperatures in the North precipitation were the sea water, clay minerals, ferromag-
Sea Cretaceous reservoirs (McAulay et al., 1993; nesian minerals and the oxidation of sulphides (Curtis and
Morad, 1998).

Calcite cement

Sandstones cemented by calcite have an average inter-

granular volume of 24%. This cement postdates quartz
cement, suggesting precipitation in a mesogenetic stage
(Figs. 8A, 8C, 8E, and 8F). Calcite cement could precipitate
from meteoric and marine waters (Fig. 15A). Calcite cement
from meteoric and marine waters are relatively pure (96.1%
mol de CaCO3) and the Mg + Mn + Fe CO3 does not exceed
5% mol which is within the range suggested by Boles and
Ramseyer, 1987; Ficher and Surdam, 1988; Hayes and Boles
1993; Lee and Boles, 1996. However, the plot of (Fe-Mn-
Mg)CO3 diagram (Fig. 15B) indicates that the majority of
the calcite could have precipitated from marine waters
according to Lee and Boles diagrams (1996). The high va-
lues in Fe could be related to glauconite and mica alterations
and the water expelled in the compaction of the intercalated
shales in the reservoir sandstones. The source of Ca is not
well established, but it can be attributed to the plagioclase FIGURE 13 Isotopic composition of the siderite, calcite and Fe-
dolomite cements. Vertical arrows at the left indicate carbonates in
alteration (García et al., 1998) or clay minerals in the interca- equilibrium with present formation water (-1‰ vs V-SMOW) at 110ºC.
late shales or limestones (Fig. 2). Present DIC (the dissolved inorganic carbon) of formation water has

13C around -4‰ (V-PDB), consequently, present diagenetic process-
es trend toward
18O values are more negatives than -10‰ (V-PDB).
The variable low
13C and
18O values of the calcite The present formation temperature of the bottom hole (110ºC) is re-
cement (Figs.13, 14, and Table 3) suggests that this presented in the upper part of the diagram.

G e o l o g i c a A c t a , Vo l . 5 , N º 1 , 2 0 0 7 , 8 9 - 1 0 7 103
J. ESTUPIÑAN et al. The impact of carbonate cement on the Napo Cretaceous sandstones

Present
diagenetic
water

150
140
130
120
110
Temperature (ºC)

Present diagenetic
100 conditions
90
80 7‰
.2‰ 6‰ -6.
70 14 ‰ -4.
-
ite .1
60 om -13
dol e
50 erit -3‰
sid
40
.8‰
30 ite -13
calc Surficial
20
conditions
10
0
-12 -10 -8 -6 -4 -2 0 2 4
Siderite & calcite

Meteoric water
į18O ‰ (V-SMOW) fluids
FIGURE 14 Diagram showing range of temperature and isotopic composition of the pore fluids constrained for the precipitation of the analyzed cal-
cites, dolomites and siderites. The curves represent the theoretical temperature of carbonates in equilibrium with different waters. Maximum and
minimums
18O values of siderite, dolomite and calcite have been plotted. The O’Neil et al. (1969), Sheppar and Schwarcz (1970) and Carothers et
al. (1988) equations were used to calculate the isotopic fractionation in the systems calcite-water, dolomite-water and siderite-water, respectively.

Coleman, 1986). These could be justified by the abun- some of the most depleted in
18O, could have precipitated
dance of pyrite and glauconite in the both Napo “T” and as consequence of recrystalization of previous carbonates.
“U” sandstones. Although chemical control on the distri-
bution of the siderite and the dolomite-Fe/ankerite has The variation in the isotopic composition of the
been reported by Matsumoto and Iijima (1981) and Curtis dolomite precipitated in organic matter rich sediments is
and Coleman (1986), in our case these cements precipita- relatively well documented (Irwin et al., 1977; Mozley
ted both in the continental and in the marine sandstones. and Burns, 1993). The most negative isotopic values of the
oxygen in dolomite cements could be related to the conti-
The zonation observed in the Fe-dolomite with no nued precipitation at higher temperatures and burial depth,
corrosion bordering implies that the chemical composi- as is supposed by the siderite S2, could have precipitated as
tion of the fluids was continuously changing and they are a result of the thermal descarboxilation of the Mg rich
attributed to episodic fluctuations in the amounts of dilu- organic matter and formation temperatures up to 50ºC. The
tion of the pore waters. Furthermore, this cement is low in variations in the carbon isotopic composition of the diffe-
Mn and high in iron content. rent carbonate cements suggest that rates of organic-carbon
oxidation may control the mineralogy of these cements.
The
18O values of the Fe-dolomite are negative and
show a wide range of values. However, the
13C has a
narrower range (Table 3 and Fig. 14). Dolomite curve CONCLUSIONS
ranging from -14.2 to -4.6‰ vs V-SMOW (Fig. 15) indi-
cates higher temperatures. Likewise, the high content in The reservoir sandstones from the Cretaceous Napo
Fe can explain this apparent increase in temperature and Formation in the Oriente Basin were deposited in fluvial,

G e o l o g i c a A c t a , Vo l . 5 , N º 1 , 2 0 0 7 , 8 9 - 1 0 7 104
J. ESTUPIÑAN et al. The impact of carbonate cement on the Napo Cretaceous sandstones

FIGURE 15 Calcite composition (mole %) from Napo Formation plotted on the Lee and Boles (1996) diagrams. Compositional fields are distin-
guished by their inferred diagenetic origin. In (A) calcite precipitated principally from meteoric pore fluids and less samples from mixed marine and
meteoric fluids. However, in (B) calcite cement precipitated from marine pore fluids. Beside, many samples are enriched in Fe suggesting that the
pore fluids are not related to the depositional fluids and they were enriched in Fe during mesodiagenesis.

transitional and marine environments. The compositions values and elevated primary porosity permitted the preserva-
of these sandstones vary from fine-medium grained tion of the isotopic signal of the fluids even during the first
quartzarenites (av. Qt 96.5 F 3.1 RF 0.4) to medium-coarse stages of burial. However, the high content in Fe and some
subarkoses (av. Qt 89.8 F 6.8 RF 3.1). The principal cements of the isotopic data point out an unclear origin for some of
occluding porosity include carbonates, quartz overgrowth, the calcite and Fe-dolomite cements.
kaolin and subordinated chlorite and pyrite-pyrrhotite.
Carbonate cements occur in four mineral phases: eogenetic Intergranular volume vs cement show that the cemen-
siderite (S1), mesogenetic and post compaction, calcite, tation process was the diagenetic event that mainly influ-
Fe-dolomite as well as ankerite and siderite (S2). enced porosity reduction. These reservoir sandstones
experienced the loss of some primary porosity at an early
S1 siderite shows high Fe-Ca and low Mn, and occa- stage of diagenesis due to the precipitation of chlorite and
sionally zonation. S2 siderite has high Mg and low Fe and siderite S1 cements. However, this early cements helped
Mn content. The increase in Mg/Fe relation in the diage- to retain the porosity delaying the compaction of the
netic waters resulted in the precipitation of S2 siderite sandstone. The high intergranular volume (av. 35%) in the
(sideroplesite). This cement is related to the thermal sandstones cemented by S2 siderite and Fe-dolomite-
descarboxilation of the organic matter and the increase of ankerite confirms that these phases precipitated during
the reduction of Fe with depth. Likewise, the less negative mesodiagénesis but at shallow burial depth. During the
isotopic ratios reflect the meteoric origin of S1. The thermal descarboxilation of the organic matter in a later
replacement and recristalization of S1 to S2 siderite could stage of mesodiagenesis, the dissolution of carbonate
be justified by the low
18O ‰ values of some of these cements and feldspars was the main mechanisms for se-
carbonate phases. condary porosity development.

Fe-dolomite and calcite cements are mesogenetic and Thus, linking diagenesis to the different depositional
post compaction. However, the high Mg and Fe content in environments such as fluvial, transitional and shallow marine
the cements and the most negative values of the isotopic data of siliciclastic sediments has important implications for
could indicate high temperature and deep burial in the pres- unravelling and predicting the spatial and temporal distribu-
ence of organic derived CO2, while the less negative values tion of diagenetic alterations and their influence on reservoir
suggest a transition from mixed meteoric and marine waters quality. The impact of the carbonate cement in the studied
to modified mesogenetic waters. The moderate to high IGV reservoirs has positive influence when these cements are

G e o l o g i c a A c t a , Vo l . 5 , N º 1 , 2 0 0 7 , 8 9 - 1 0 7 105
J. ESTUPIÑAN et al. The impact of carbonate cement on the Napo Cretaceous sandstones
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Foundation, REN2002-11404-E from the Spanish Ministry Association of Petroleum Geologists, 77, 1260-1286.
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Manuscript received January 2005;
revision accepted July 2006.

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