Diagenetic evolution of Tortonian temperate carbonates close to evaporites in the Granada Basin (SE Spain)

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Diagenetic evolution of Tortonian temperate carbonates close to
evaporites in the Granada Basin (SE Spain)
A. López-Quirós
a,b,
⁎, M. Barbier
b
, J.M. Martín
c
, Á. Puga-Bernabéu
c
, X. Guichet
b
a
Instituto Andaluz de Ciencias de la Tierra, CSIC-Universidad de Granada, Avda. de las Palmeras 4, 18100 Armilla, Granada, Spain
b
IFP Énergies Nouvelles, 1–4 Avenue de Bois-Préau,92852 Rueil-Malmaison, France
c
Departamento de Estratigrafía y Paleontología, Universidad de Granada, Campus de Fuentenueva s.n., 18002 Granada, Spain
abstractarticle info
Article history:
Received 26 October 2015
Received in revised form 10 February 2016
Accepted 12 February 2016
Available online xxxx
Editor: B. Jones
The Granada Basin(SE Spain) is a small basin located in the central part of the Betic Cordillera, structured as such
in the late Tortonian and initially connected to the Atlantic Ocean and to the Mediterranean Sea.During the late
Tortonian, normal marine conditionsprevailed, leadingto the deposition of skeletalcarbonate sedimentson plat-
forms around structural highs. The marine connections were later interrupted, first to the Atlantic Ocean and
then to the MediterraneanSea, and a thick evaporite sequence, markingthe transition from marine to continental
conditions, was deposited duringthe latest Tortonian. In this work,the diagenetic evolution of theTortonian tem-
perate carbonates (TTC), underlying and close to the evaporite bodies, isrevealed anddiscussed. The diagenetic
study includes petrographic analyses (conventional petrography, cathodoluminescence, and fluorescence), geo-
chemical analyses (major, minor and trace elements, and δ
13
C and δ
18
O stable isotopes), and microthermometry
of fluid inclusions. In the TTC, marine diagenetic processes such as micritization and fibrous calcite-cement pre-
cipitation and mechanical compaction took place during or just after deposition (Eogenesis). An initial burial
event (Mesogenesis 1) is characterized by: 1) stabilization of the temperate-water carbonates by freshwater,
and 2) porosity occlusion via precipitation of low-Mg bladed and syntaxial/mosaic calcite cements. The TTC
were then subaeriallyexposed (or got close tothe surface) duringevaporite deposition and underwent pedogen-
esis, Mg-smectite infiltration, and pyrite formation (Telogenesis 1). Subsequent brine-related diagenetic alter-
ations, such as dolomitization and silica, halite, and sylvite replacements of carbonate grains occurred during a
second burial episode (Mesogenesis2) concomitant with the Messinian lacustrine deposition, this being follow-
ed by chemical compaction (stylolite formation). Finally, the area was uplifted and the TTC exhumed.
Microstalactitic (dripstone) and fibre/whisker calcite cement precipitation and extensive dissolution relate to
this Pliocene–Quaternary late event (Telogenesis 2). In the study case diagenetic history is closely linked to
basin evolution, as diagenetic pathways of carbonate rocks were related to major geodynamic events, including
basin restriction leading to evaporite deposition, and several episodes ofsubsidence and uplift. Up to now, only
very few diagenetic studieshave attempted to demonstrate thiscorrelation betweendiagenetic historyand basin
evolution.
© 2016 Elsevier B.V. All rights reserved.
Keywords:
Granada Basin
Temperate-water carbonates
Diagenesis
Migrating brines
Evaporites
Tortonian
1. Introduction
The study of diagenesis bears significant economic interest, given
that diagenesis accounts for porosity and permeability evolution
(Ehrenberg, 2007). Diagenetic transformations can strongly influence
the ability of the sedimentary rocks to host economic quantities of
water, gas, oil, and minerals (Ehrenberg and Nadeau, 2005; Rossi,
2010). In this respect, it is essential to ascertain thechemicalconditions,
nature, and timing of the diagenetic processes altering sediment and
sedimentary-rock properties.
Focusing on the diagenetic evolution of carbonate rocks underlying
evaporites, the present work examines the impact of brine circulation
and associated diagenetic transformations on potential, carbonate-
rock reservoirs close to evaporites, calibrating their relative importance
with respect to other, non-evaporite-linked diagenetic transformations
that these same rocks could have undergone. The relevance of this study
relates to the considerable interest for the exploration and production of
pre-salt reservoirs, which represent some of the main oil and gas
sources discovered over the last decade. For example, the “Pre-Salt Car-
bonates of the South Atlantic”have emerged as among the most prolific
petroleum systems in the world, providing many billions of barrelsof oil
reserves (Beasley et al., 2010; Verwer and Lukasik, 2014).
The Granada Basin (SE Spain), selected for this study, is located in
the central part of the Betic Cordillera. This basin was initially marine
Sedimentary Geology xxx (2016) xxx–xxx
⁎Corresponding author at: Instituto Andaluz de Ciencias de la Tierra, CSIC-Universidad
de Granada, Avda. de las Palmeras 4, 18100 Armilla, Granada, Spain.
E-mail address: alquiros@iact.ugr-csic.es (A. López-Quirós).
SEDGEO-04998; No of Pages 17
http://dx.doi.org/10.1016/j.sedgeo.2016.02.011
0037-0738/© 2016 Elsevier B.V. All rights reserved.
Contents lists available at ScienceDirect
Sedimentary Geology
journal homepage: www.elsevier.com/locate/sedgeo
Please cite this article as: López-Quirós, A., et al., Diagenetic evolution of Tortonian temperate carbonates close to evaporites inthe Granada Basin
(SE Spain), Sedimentary Geology (2016), http://dx.doi.org/10.1016/j.sedgeo.2016.02.011

and was isolated from the sea during the latest Tortonian. As a result, a
thick (up to 500 m thick) salt (halite) sequence accumulated at its
centre (García-Veigas et al., 2013). In the Granada Basin, post-salt sedi-
ment burial is not deep enough to reach the critical values needed to in-
duce halokinesis salt movements (Hudec and Jackson, 2007). This
young sedimentary basin thus provides the suitable context to check
the effects of early diagenetic processes in carbonates underlying
evaporites before a strong burial event occurs, such as the one under-
gone by the South Atlantic carbonate reservoirs. The structural and
sedimentological framework of the Granada Basin is well constrained
(see below), but no diagenetic studies have been conducted until now
in any of its deposits.
The Tortonian temperate-carbonate (TTC) sediments, deposited
prior to the evaporites in the Granada Basin, constitute the target for
this work. Temperate-water carbonates (Lees and Buller, 1972), also
known as cool-water (Brookfield, 1988) or non-tropical carbonates
(Nelson, 1988), are common shallow-water marine deposits in the
Neogene basins of southern Spain. In the Mediterranean-linked basins
of the Betic Cordillera (sensu Braga et al., 2003), such as the Granada
Basin, they developed at different times during the Neogene and
alternate with tropical carbonates (Martín et al., 2010). In the Atlantic-
linked basins (Guadalquivir and Ronda basins) their presence was
overwhelming in siliciclastic-free, shallow-water platform areas all
along the Neogene (Baceta and Pendón, 1999; Gläser and Betzler,
2002; Martín et al., 2009; Braga et al., 2010; Aguirre et al., 2015).
2. Geological setting
The Granada Basin is a small (50 ×50 km) Neogene intramontane
basin located in the central sector of the Betic Cordillera (Fig. 1), at the
contact between the two major domains, i.e. the Internal Zones
(cropping out at Sierra Tejeda, Sierra de la Pera and Sierra Nevada),
and the External Zones (cropping out at Sierra Gorda and Sierra
Arana; Fig. 2). Its Neogene–Quaternary infilling (Fig. 3) unconformably
overlies an irregular, fault-controlled, basement palaeorelief surface
(Morales et al., 1990). The main fault systems have an EW orientation
(Sanz de Galdeano, 2008). Secondary faults, trending NW–SE, cut and
displace the major EW faults and define the principal subsiding areas
of the central and eastern part of the basin (Rodríguez-Fernández and
Sanz de Galdeano, 2006).
The current Granada Basin depression formed in the late Tortonian
(at around 8.3 Ma: Braga et al., 2003; Rodríguez-Fernández and Sanz
de Galdeano, 2006; Corbí et al., 2012). The sedimentary infilling extends
from the upper Tortonian to the Quaternary. Older continental and ma-
rine, lower–middle Miocene sediments (Braga et al., 1996), cropping
out at the eastern and southern margins of the depression (Figs. 2, 3),
were deposited in a former basin with a completely different structure
(Braga et al., 2003).
During the late Tortonian(8.3 to 7.3 Ma) major tectonic activity took
place in the north-eastern and eastern highland edges of the basin
(Sierra Arana and Sierra Nevada, Figs. 2, 3), leading to the deposition
of significant quantities of terrigenous sediments at the base of the
uplifted areas (Braga et al., 1990, 2003; Martín and Braga, 1997).
Marine conditions prevailed and skeletal carbonate sediments accumu-
lated in siliciclastic-free areas on platforms all around the margins of
the basin. Temperate-water carbonates (Puga-Bernabéu et al., 2008)
formed first, between 8.3 and 7.8 Ma (Corbí et al., 2012), followed by
tropical, coral-reef carbonates (Braga et al., 1990), between 7.8 and
7.3 Ma (Corbí et al., 2012). The Tortonian temperate carbonates (TTC)
have been studied in detail at one locality (Alhama de Granada) by
Puga-Bernabéu et al. (2008). They consist of carbonates (calcarenites
and calcirudites), and mixed siliciclastic–carbonate sediments, contain-
ing abundant fragments of bryozoans, bivalves, and coralline algae, and
smaller amounts of echinoids, benthic foraminifers and brachiopods.
During the late Tortonian the Granada Basin was a marine embay-
ment initially connected to the Atlantic Ocean to the northwest
(Martín et al., 2014) and to the Mediterranean Sea to the south and
west (Braga et al., 1990). In the course of the late Tortonian, these ma-
rine connections were interrupted first to the Atlantic Ocean and then
to the Mediterranean Sea (Martín et al., 1984, 2014; Braga et al., 1990,
2003). As a result the basin desiccated (Martín et al., 1984) in the
latest Tortonian (7.3 to 7.2 Ma, Corbí et al., 2012). An evaporitic basin
developed with stromatolites at the margin (Martín et al., 1984;
García-Veigas et al., 2015), selenite gypsum accumulating in its
shallow-water areas (Dabrio et al., 1982) and halite in its centre
(García-Veigas et al., 2013). The resulting evaporitic unit, the “Lower
Evaporite Unit”sensu Dabrio et al. (1982), marks the marine-to-
continental transition in basin evolution (Martín et al., 1984).
During the Messinian, the uplift of the Granada Basin continued and
it was filled by continental alluvial-fan, and fluviatile and lacustrine de-
posits including carbonates and evaporites (the“Upper Evaporite Unit”
Fig. 1. Neogenesedimentary basins of the Betic Cordillera, Spain(modified from Bragaet al., 2003).1): Fortuna Basin, 2): LorcaBasin, 3): Sorbas Basin,4): Tabernas Basin, 5): Guadix-Baza
Basin, 6): Granada Basin, 7): Ronda Basin, and 8): Guadalquivir Basin.
2A. López-Quirós et al. / Sedimentary Geology xxx (2016) xxx–xxx
Please cite this article as: López-Quirós, A., et al., Diagenetic evolution of Tortonian temperate carbonates close to evaporites inthe Granada Basin
(SE Spain), Sedimentary Geology (2016), http://dx.doi.org/10.1016/j.sedgeo.2016.02.011

sensu Dabrio et al., 1982)(Dabrio et al., 1982; Martín et al., 1984;
Fernández et al., 1996; García-Alix et al., 2008;Figs. 2, 3). Finally,
during the Pliocene and the Quaternary, deposition was limited to
small, fault-controlled, high-subsidence depocentres (Morales et al.,
1990; Rodríguez-Fernández and Sanz de Galdeano, 2006; García-Alix
et al., 2008), filled by detrital sediments (Fig. 3).
3. Database and analytical methods
3.1. Facies analysis
This study is based on the detailed examination of two outcrop
sections near the village of Cacín, located between Ventas de Huelma
Fig. 2. Simplified geological map of the Granada Basin and location of the studied outcrops (modified from Dabrio et al., 1982; Martín et al., 1984). (P–M: Palaeozoic–Mesozoic; Aq–lT:
Aquitanian–lower Tortonian; uT: upper Tortonian; Me: Messinian; Pl–Q: Pliocene–Quaternary). 1-a: Nevado-Filábride and Alpujárride basement rocks from the Betic Internal Zones;
1-b: Subbetic basement rocks from the Betic External Zones; 2-a: Older Miocene continental and marine deposits; 2-b: Bioclastic calcareous sandstones (conglomerates) and
limestones (coastal and shallow-marine, platform deposits; TTC unit); 2-c: Conglomerates, sands and silts (fan-delta deposits); 2d: Marls (open-marine deposits); 3: Evaporite unit
(marine to continental transitional deposits); 4-a: Silts and clays (distal-lake deposits); 4-b: Sandstone turbidites and silts (proximal-lake deposits); 4-c: Conglomerates, sands and
silts (marginal, fluviatile deposits); 4-d: Lacustrine gypsum (gypsarenites); 4e: Sands, silts and coal (lignites); 4-f: Limestones; 5: Alluvial and fluviatile detrital deposits. Blue dots
mark the position of the sampled TTC sections. (For interpretation of the references to colour in this figurelegend, the reader is referred to the web version of this article.)
Fig. 3. Miocene to Quaternary stratigraphy of the Granada Basin (after Braga et al., 1990).
3A. López-Quirós et al. / Sedimentary Geology xxx (2016) xxx–xxx
Please cite this article as: López-Quirós, A., et al., Diagenetic evolution of Tortonian temperate carbonates close to evaporites inthe Granada Basin
(SE Spain), Sedimentary Geology (2016), http://dx.doi.org/10.1016/j.sedgeo.2016.02.011

and Alhama de Granada (Fig. 4A). The two sections are named Cacín-1
(3630 m south of Cacín) and Cacín-2 (1400 m southward from Cacín-
1) (Fig. 4B). Both outcrops lie within the depositional area of the
evaporites (Fig. 4A). According to the dipping of the TTC in the Cacín
River Canyon (general dip of the strata is about 5° to the north-
northwest), both sections represent the same stratigraphic interval. At
Cacín, TTC are up to 40 m thick. They unconformably overlie and
onlap an irregular basement palaeorelief made up of Triassic dolostones
and are covered by upper Tortonian marls, about 50 m thick (Fig. 5A).
These marls are the basinal, lateral equivalents of coastal fan-delta
detrital deposits and coral-reef limestones (Fig. 3). The whole succes-
sion is capped by uppermost Tortonian evaporites (Fig. 5A), consisting
here of a 40 m-thick selenite-gypsum succession (Dabrio et al., 1982;
García-Veigas et al., 2015).
Outcrop sections were logged in detail (Fig. 5) and 32 carbonate rock
samples were collected (17 from Cacín-1 and 15 from Cacín-2). Facies
analysis was made, based on macroscopic and microscopic observations
on thin sections. Facies types were differentiated and interpreted in
terms of lithology, components, textures, grain sizes, sedimentary-
structures and bioturbation, following Purser (1980) and Tucker and
Wright (1990). Facies classification is after Dunham (1962);Embry
and Klovan (1971), and James and Bourque (1992).
3.2. Petrographic analysis
Thirty-two thin sections (from each rock sample), about 30 μm thick,
were prepared and impregnated by a blue epoxy (EpoBlue®) to
distinguish pores from textural components. The thin sections were
stained with Alizarin red-S and potassium ferricyanide in order to dis-
tinguish calcite from dolomite, as well as ferroan phases in both min-
erals (Dickson, 1966). Thin sections were scanned before and after the
staining using a high-resolution scanner (Epson Perfection V750 Pro).
All thin sections were examined under polarized and cross-polarized
light with a Nikon Eclipse LV 100 POL optical microscope. During
the petrographic study, several sets of images were taken with a
camera (ProgRes C10) connected to the microscope and captured
with the ProgRes 2.1 image-management program. The thin-
section study using the petrographic microscope allowed the recon-
struction of the paragenetic sequences by careful examination of the
relationships among grains, cements, and porosity. Four thick sec-
tions (100 μm) were prepared to calibrate the microthermometry
of fluid inclusions.
Cathodoluminescence (CL) microscopy with an optical polarization
microscope (Nikon Eclipse ME 600) equipped with a Technosym Cold
CL connected to an OPEA system (Cathodyne OPEA, France) was used
to identify different cement types, growth features, and relationships
among the crystals (see Meyers, 1974; Scholle and Ulmer-Scholle,
2003). The gunpotential was 16–20 kV, with a 420–66 μA beam current,
0.05 Torr vacuum and 5 mm beam width.
For further investigation on the origin of depositional and diagenetic
carbonate phases, the thin sections were also examined with a Nikon
Eclipse LV 100 POL microscope equipped with a mercury vapour lamp
(100 W). Applied to carbonates UV-light enables the identification of
organic substances, to distinguish grains and textures, and to highlight
Fig. 4. Studyarea. A) Satelliteview of the southern partof the Granada Basin.B) Location of Cacín-1and Cacín-2 sections(yellow dots).(For interpretation of the references to colourin this
figure legend, the reader is referred to the web version of this article.)
4A. López-Quirós et al. / Sedimentary Geology xxx (2016) xxx–xxx
Please cite this article as: López-Quirós, A., et al., Diagenetic evolution of Tortonian temperate carbonates close to evaporites inthe Granada Basin
(SE Spain), Sedimentary Geology (2016), http://dx.doi.org/10.1016/j.sedgeo.2016.02.011

diagenetic fabrics, specifically different stages of cement-growth gener-
ations, and porosity evolution (Dravis and Yurewicz, 1985).
SEM examinations were performed on two carbon-coated samples
(from the Cacín-2 outcrop) analysed with a Zeiss Evo Ma 10 (10–15 kV
beam current). High-resolution images, surface topographies, and spec-
trographic analyses of the composition of the samples were made
using secondary electron image (SEI), backscattered electron image
(BEI) and energy dispersive X-ray spectroscopy (EDS), respectively.
3.3. Mineralogical and geochemical analysis
X-ray diffraction (XRD) was used to identify minerals as well as to
determine the average bulk composition. For XRD determinations, 19
powders from carbonates were prepared with an agate mortar, and
then analysed with an X'pert Pro PW 3040/60 diffractometer operated
at 50 kV, 30 mA. Samples were scanned in the 2θrange from 2 to 79°,
with a step size of 0.033° (2θ)/s. The counting time was 120 min per
sample.
Major, minor and trace elements were analysed by inductively
coupled plasma mass spectrometry (ICP-MS). Thirty-one powders
from carbonate rocks were sampled with a dental drill (Dremel 225).
Contamination between two subsequently drilled samples was avoided
by using diluted HCl to dissolve the carbonates from the drill before
each sampling. Sample splits of the powders between 0.25 and 0.5 g
were analysed in the ACME Analytical Labs Ltd. (Vancouver, Canada).
Prepared powders were digested for 1 h, in a heating block of a hot
water bath, with a modified aqua regia solution of equal parts concen-
trated HCl, HNO
3
and DI H
2
O. Samples were made up to volume with
Fig. 5. TTC outcrops at Cacín. A) Panoramic view of theCacín River Canyon. B) Cacín-2 section. Close-up picturesare from the three major facies identified: 1) cross-bedded grainstone to
rudstone (blue in C); 2) chaotic packstone to grainstone (yellow in C); 3) bioclastic conglomerates (green in C). C) Sedimentary log of the Cacín-2 outcrop. D) Cacín-1 section (red line
marks the position of the sampled log). Old Roman Bridge can be seen at the background of the picture. (For interpretation of the references to colour in this figure legend, the reader
is referred to the web version of this article.)
5A. López-Quirós et al. / Sedimentary Geology xxx (2016) xxx–xxx
Please cite this article as: López-Quirós, A., et al., Diagenetic evolution of Tortonian temperate carbonates close to evaporites inthe Granada Basin
(SE Spain), Sedimentary Geology (2016), http://dx.doi.org/10.1016/j.sedgeo.2016.02.011

diluted HCl. Analyses were performed for 37 elements, of which Ca, Mg,
Mn, Fe, Sr, Na, K, Ba, S, Zn, and Al were considered the most important in
this study because of their significance in carbonate sedimentology and
diagenesis (Brand and Veizer, 1980; Banner, 1995).
Thirty-two carbonate powders were sampled with a micro-drill
(Olympus SZ61 —MicroMill Sampling System) from six thin sections,
in order to measure carbon and oxygen stable-isotope composition
(δ
13
C
PDB
and δ
18
O
PDB
) of bioclastic components and cement phases
(b200 μm). A micro-drill was used in order to avoid mixing all the ce-
ment phases. The same procedure as for the sampling of major, minor,
and trace elements wasfollowed to avoid contamination between sub-
sequently drilled samples. The isotope analyses were performed at the
GeoZentrum Nordbayern (Friedrich-Alexander-Universität, Erlangen-
Nürnberg, Germany). The carbonate powders resulting from micro-
drilling were reacted with 100% phosphoric acid at 70 °C using a
Gasbench II connected to a Thermo Finnigan Five Plus mass spectrome-
ter. The values were presented inper mil relative to the V-PDB standard.
All measurements were calibrated by assigning a δ
13
C value of +1.95‰
and a δ
18
O of −2.20‰to NBS19. Reproducibility, checked by replicate
analysis of laboratory standards, proved better than ±0.04‰for δ
13
C
and ±0.08‰for δ
18
O (1 std. dev.).
4. Results
4.1. Sedimentology
In the two study sections (Cacín-1 and Cacín-2), three major
sedimentary facies were distinguished. They are most clearly exposed
at the Cacín-2 section (Fig. 5A, B and C). The main textural components
of these facies are shown in Fig. 6D to I.
The first facies consists of metre- to decimetre-thick beds of a mod-
erately sorted, cross-bedded (Fig. 5B-1, C), sandy, bioclastic grainstone
to rudstone (Fig. 6A). Bioclasts come mainly from bryozoans,
echinoderms, coralline algae, bivalves and brachiopods. Siliciclastic
and dolomitic detrital grains, removed from the basement, are common.
This facies is interpreted as a shoal deposit originally close to the shore
line. Comparable shoal deposits are a common feature in temperate-
water carbonates from the Mediterranean-linked Neogene basins of
the Betic Cordillera (Martín et al., 1996; Betzler et al., 1997a; Martín
et al., 2004; Braga et al., 2006; Puga-Bernabéu et al., 2007, 2008).
The second facies consists of decimetre-thick beds of poorly sorted,
sandy packstone to grainstone (Fig. 6B). The field appearance is chaotic
(Fig. 5B-2), showing no sedimentary structures with the exception of
Fig. 6. Major faciesand textural components in the TTC sediments at Cacín. A)plain-polarized light (PPL) photomicrograph showing cross-bedded grainstone-to-rudstone microfacies.
B) PPL photomicrograph showing chaotic packstone-to-grainstone microfacies. C) PPL photomicrograph showing bioclastic conglomerate microfacies. D) PPL photomicrograph
showing broken longitudinal/tangential sections of bryozoans. E) PPL and cross-polarized light (CPL) photomicrographs showing large bivalve shell with homogeneous, calcite wall
structure. F) PPL photomicrograph of an echinoid spine, in cross section. Porosity in blue. G) PPL photomicrograph showing a crustose coralline red algal fragment. H) PPL
photomicrograph showing planktonic foraminifers and detrital, irregularly shaped grains. I) CPL photomicrograph showing metamorphic-rock lithoclasts. Staining in red is for calcite.
(For interpretation of the references to colour inthis figure legend, the reader is referred to the web version of this article.)
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Please cite this article as: López-Quirós, A., et al., Diagenetic evolution of Tortonian temperate carbonates close to evaporites inthe Granada Basin
(SE Spain), Sedimentary Geology (2016), http://dx.doi.org/10.1016/j.sedgeo.2016.02.011

some burrows at the top of the beds. Brachiopod, bivalve, coralline-algal
and bryozoanfragments are common. Sub-angular, up to 750 μm in size,
quartz and feldspar grains also appear, mixed with the skeletal grains
and the micritic matrix. This facies occurs as an intershoal deposit,
interbedded with the bioclastic bars of the shoals (Fig. 5B, C).
The third facies, occurring on top of the section (Fig. 5B, C), consists
of planar-parallel, finely bedded bioclastic conglomerates (Figs. 5B-3,
6C). Clasts in the conglomerate are mainly cm-sized, angular to well-
rounded siliciclastic and dolomitic basement pebbles. Bioclastic grains
are the same as those found in the previous facies. This facies was the
result of the mixing on the platform of bioclastic carbonate with
terrigenous sediment, the latter supplied by continental (fluvial) flows
entering the sea.
Temperate-carbonate facies similar to the ones described here
are well exemplified in most of the Neogene basins in the western
Mediterranean. They characterize inner-ramp deposits within the
temperate-carbonate realm (Martín et al., 1996; Betzler et al., 1997a;
Martín et al., 2004; Braga et al., 2006; Puga-Bernabéu et al., 2007, 2008).
4.2. Diagenesis
The petrographic study of TTC samples from the Cacín sections
shows that the carbonate sediments underwent the effects of seven
major diagenetic processes (micritization, cementation, compaction,
neomorphism, clay infiltration, dolomitization and dissolution), and
four, less intense, minor ones (pyrite formation, silica precipitation,
and halite and sylvite replacement). These processes are described
below.
4.2.1. Micritization
This process was found at the border of bioclasts (Fig. 7A, B), such as
bryozoan, foraminifer, and brachiopod shells, as well as of some carbon-
ate lithoclasts (Fig. 7A). It appears as a thin, μm-sized micrite envelope,
and when affecting crinoid fragments, it prevents the development of
syntaxial overgrowths. In general, micritization helps to preserve grains
from subsequent leaching/dissolution processes.
4.2.2. Cementation
In the study samples, cements, although sharing the same mineralo-
gy, exhibit a great variety of types and fabrics (Fig. 8). Observed fabrics
are:
4.2.2.1. Fibrous calcite cement. This is a non-ferroan, up to ~ 10 μm in
width and ~ 50 μm in length, isopachous (radiaxial) fibrous calcite
cement (Fig. 8A, B). It consists of inclusion-rich dirty crystals, which dis-
play a dull-green colour under UV light and a dull-orange luminescence
under CL.
4.2.2.2. Bladed calcite cement. This cement consists of a non-ferroan, up
to 50 μm in width and 100 μm in length, bladed (to dogtooth) calcite ce-
ment (Fig. 8C to F). It occurs as a circumgranular, pore-lining cement
rim around skeletal and non-skeletal grains. This cement displays a
dull- to bright-orange luminescence under CL and it is black under UV
light.
4.2.2.3. Syntaxial and mosaic calcite cements. Both cements consist of
non-ferroan, inclusion-rich sparite crystals. Syntaxial cements occur as
overgrowths around echinoid fragments (Fig. 8G). Mosaic cements,
exhibiting the typical polycrystalline, xenomorphic pattern (Fig. 8H),
fill in inter- and intra-granular voids, and also crystallize within grain
micro-fractures created by mechanical compaction. Both cements dis-
play a concentric zoning under CL, with alternating non-luminescent
and dull-orange zones (Fig. 8I) and contribute to significantly reduce
the inter-particle, primary-pore network.
4.2.2.4. Dripstone (pendant or microstalactitic) calcite cement. This occurs
as thin (up to 70 μm) crusts beneath grains or under the roofs of
intergranular and solution voids, and is often observed together with
“whisker crystals”(Supko, 1971; also termed “needle-fibre cement”,
Ward, 1970; James, 1972) precipitated after the microstalactitic calcite
cement. The latter consists of elongated, fine-fibre crystals, up to 2 μm
in diameter and 50 μm in length (Fig. 8J to L).
4.2.3. Compaction
The study samples show the effect ofboth mechanical and chemical
compaction.
4.2.3.1. Mechanical compaction. This process implies the reorganization,
deformation, and fracturing of bioclastic grains such as coralline-algal
fragments and brachiopod/bivalve shells (Fig. 9A, B). Bladed and mosaic
calcite-cements fill in micro-fractures created by mechanical compac-
tion (Fig. 9A).
4.2.3.2. Chemical compaction. In TTC samples, this is exemplified by
microstylolites (grain-to-grain sutured contacts; Fig. 9C), and, locally,
by more persistent stylolites, cross-cutting grains and all the above-
described cements, except for thedripstone/whisker cements. Insoluble
material (e.g. clay; Fig. 9D) usually concentrates at the stylolite.
4.2.4. Neomorphism
Bivalve and gastropod shells, originally in aragonite are now re-
placed by low-Mg calcite. This transformation took place in most cases
by inversion and the initial structure/fabric of the previous mineral is
normally preserved. The mineralogical change of echinoid plates and
spines from high-Mg calcite into low-Mg calcite was via incongruent
dissolution (Land, 1967), andno dolomite was formed. Recrystallization
Fig. 7. Micritization at Cacín samples. A) PPL photomicrograph showing micritization of a brachiopod shell (yellow arrow) and of a carbonate lithoclast (white arrow). B) PPL
photomicrograph showing micritization on a benthic foraminifer shell (yellow arrow). (For interpretation of the references to colour in this figure legend, the reader is referred to the
web version of this article.)
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Please cite this article as: López-Quirós, A., et al., Diagenetic evolution of Tortonian temperate carbonates close to evaporites inthe Granada Basin
(SE Spain), Sedimentary Geology (2016), http://dx.doi.org/10.1016/j.sedgeo.2016.02.011

also took place in TTC samples, as attested to by the transformation of
micrite (b4μm) into microsparite (4–10 μm), and sparite (N10 μm;
Fig. 10A, B).
4.2.5. Clay minerals
Clay minerals such as Mg-smectite and illite were identified by X-ray
diffraction and EDS (energy dispersive X-ray spectroscopy) as a later,
pore-filling material in intra- and inter-particle voids, introduced after
precipitation of the fibrous, bladed and syntaxial/mosaic calcite cements
(Fig. 11A). They are also found in stylolites (Fig. 9D). SEM observations
show silt-size terrigenous grains and pyrite crystals within the clay
(Fig. 11B).
4.2.6. Dolomitization
In the study samples, dolomitization is characterized either by the
crystallization of ~ 50 μm in size, planar-e (sensu Sibley and Gregg,
Fig. 8. A) and B) PPL photomicrographs showing fibrous calcite cement (yellow arrows) formed around skeletal grains (isopachous calcite cement crusts). C) PPL photomicrograph
showing bladed (to dogtooth) calcite cement (yellow arrow) (stained sample). D) and E) PPL and corresponding fluorescence photomicrographs showing bladed (to dogtooth) calcite
cement (yellow arrows). F) Cathodoluminescence (CL) photomicrograph showing bladed (to dogtooth) calcite cement (yellow arrow) inside a bivalve shell. This cement displays a
dull to bright orange luminescence. G) PPL photomicrograph showing syntaxial-overgrowth calcite cement (yellow arrow) developed around an echinoderm grain. H) and I) PPL and
corresponding CL photomicrograph showing syntaxial (yellow arrow) and mosaic (blue arrow) calcite cements displaying the same concentric zoning under cathodoluminescence.
The typical pattern consists of alternating non-luminescent and dull orange zones. J) PPL photomicrograph showing dripstone (pendant or microstalactitic) calcite cement (yellow
arrow). Calcite fibres/whisker crystals (red arrow) are also present together with the microstalactitic calcite cement. Stained sample. K) SEM photomicrograph (BSD) showing the
same cements as in J. L) PPL (right) and corresponding fluorescence (left) photomicrographs showing in detail calcite fibres/whisker crystals (red arrow). Stained sample. Porosity in
blue. (For interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article.)
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Please cite this article as: López-Quirós, A., et al., Diagenetic evolution of Tortonian temperate carbonates close to evaporites inthe Granada Basin
(SE Spain), Sedimentary Geology (2016), http://dx.doi.org/10.1016/j.sedgeo.2016.02.011

1987), euhedral dolomite rhombohedrons, or by the development of up
to ~40 μm thick overgrowth around terrigenous dolomitic grains
(Fig. 12). The euhedral dolomite crystals exhibit dark cores with limpid
rims (Fig. 12A, B). They replace the initial micrite or the Mg smectite-
rich matrix (Fig. 11C). Detrital dolomite and overgrowths (Fig. 12C)
display different green intensities in the EDS mapping (Fig. 12D).
4.2.7. Dissolution
This process took place at two different times, named dissolution
stages 1 and 2.
1. Dissolution stage 1 equally affected the micrite matrix and some
bioclasts (such as bryozoan skeletons and brachiopod/bivalve
shells). This dissolution phase was responsible for the creation/
enhancement of moldic and vuggy porosity (Fig. 13A), which, in
some cases, was later partially to totally occluded by bladed and
syntaxial/mosaic calcite cements. It clearly preceded mechanical
compaction as dissolved shells are preferentially compacted.
2. Dissolution stage 2. A second phase of dissolution affected grains and
fibrous, bladed and syntaxial/mosaic calcite cements (Fig. 13B to D).
In addition, this late dissolution also affected dolomite and itwas also
active along stylolites. A more significant, intra-particle porosity was
generated during this latter dissolution process (Fig. 13D).
4.2.8. Silicification, and halite and sylvite crystallizations
These processes were not very significant in extent. Silica cement
followed by halite and sylvite crystallizations (Fig. 14A, B) are observed
either within the pore network, or as replacements. Both, halite and
Fig. 9. Compaction processes (mechanical and chemical) at Cacín.A) PPL photomicrograph showing the effects of mechanical compaction in a red algalfragment (red arrow: fibrouscalcite
cement; yellow arrow: bladed calcite cement; bluearrow: mosaic calcite cement). The precipitation of the fibrous calcite cementwas prior to the formation of the fracture. Bladed and
mosaic calcite cements fill in the space created by mechanical fracturing as well as the inter-granular voids between bioclasts. B) CL photomicrograph showing mechanical compaction
(yellow arrow) affecting a bivalve fragment. C) PPL photomicrographs showing micro-stylolites(grain-to-grain sutured contacts) (yellow arrows). The stylolites clearly cut and thus
postdate prior mechanical compaction features (microfracture) (red arrow). D) Fluorescence photomicrograph showing residual silty clay concentrated along an irregular stylolite
surface (yellow arrow). (For interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article.)
Fig. 10. Recrystallization at Cacín TTC samples. A) and B) PPL photomicrographs showing recrystallization in bryozoanskeletons from micrite into sparite (sample A;yellow arrow), and
from micrite into microsparite(sample B; yellowarrow). Sample A is stained with Alizarin. Porosity in blue.(For interpretation of thereferences to colourin this figure legend,the reader is
referred to the web version of this article.)
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Please cite this article as: López-Quirós, A., et al., Diagenetic evolution of Tortonian temperate carbonates close to evaporites inthe Granada Basin
(SE Spain), Sedimentary Geology (2016), http://dx.doi.org/10.1016/j.sedgeo.2016.02.011

sylvite replaced Mg-smectite, former calcite cements and carbonate
grains. Sylvite also replaced halite crystals.
4.3. Geochemistry analysis
4.3.1. Major, minor, and trace elements
The results of the element geochemistry analyses are given in
Table 1 and are represented in cross-plots in Fig. 15.
Mg/Ca: The Mg/Ca mo lar ratio rang ed from 0.01 to 0.07, with bu lk
composition from 23.32 to 37.93 wt.% for Ca and from 0.25 to
1.04 wt.% for Mg. The concentration of these elements was nega-
tively correlated, as the Mg content decreased with increasing
amounts of Ca (Fig. 15A). The calcite samples analysed were
low-Mg calcite (b4%).
Sr/Ca: The Sr/Ca molar ratio ranged from 0.00063 to 0.00093, with Sr
ranging from 692.2 to 447.1 ppm.The concentration of Ca and Sr was
positively correlated (Sr increased parallel to Ca; Fig. 15B).
Fe/Al and Fe/K: These ratios were positively correlated as the Fe
increased with the Al and K contents (Fig. 15C, D). The amounts of
Fe and Al ranged from 0.09 to 0.82 wt.% and from 0.06 to
0.36 wt.%, respectively. The amount of K was from 0.02 wt.% to
0.13 wt.%.
K/Al: The K/Al molar ratios were positively correlated as the K
increased parallel to Al (Fig. 15E).
Fe/Mn: The Fe and Mn contents reflected good covariance between
these two elements. Theamount of Mn ranged from 94 to 810 ppm.
The concentration of Fe and Mn was positively correlated as the Fe
increased parallel to Mn (Fig. 15F).
Fig. 11. Clay minerals in TTC samples at Cacín. A) PPL photomicrograph showing pore-filling, silty clay (ochre colour and turbid “muddy”appearance) (yellow arrow). Porosity in blue.
B) SEM (EDS mapping) showing silty clay (red colour) with small pyrite crystals (blue arrow) and dolomite (white arrow). Porosityshown in black. C) SEM (EDS mapping) showing
pore-filling Mg-smectite (Mg-s; grey colour), after crystallization of calcite cement (brownish-grey colour). Dolomite (red arrow) in turn is replacing Mg-smectite. (For interpretation
of the references to colour in this figure legend, the reader is referred to the web version of this article.)
Fig. 12. Dolomitization in TTC samples at Cacín. A) andB) SEM (BSD) and CL photomicrographsof rhombohedral dolomite replacing the carbonate matrix. The euhedral dolomitecrystals
exhibitdark cores and limpidrims. C) and D) PPL photomicrographand corresponding SEM (EDS mapping) of a detritaldolomite grain(red arrow) and its diagenetic dolomite overgrowth
(blue arrow). In the EDS mapping, thedetrital dolomite nucleus exhibits a greenercolour intensity,reflecting a higher Mg
2+
content.(For interpretation of the referencesto colour in this
figure legend, the reader is referred to the web version of this article.)
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Please cite this article as: López-Quirós, A., et al., Diagenetic evolution of Tortonian temperate carbonates close to evaporites inthe Granada Basin
(SE Spain), Sedimentary Geology (2016), http://dx.doi.org/10.1016/j.sedgeo.2016.02.011

Sr/Mn: Sr and Mn concentrations were negatively correlated, since
the Mn decreased as Sr increased (Fig. 15G).
Fe/Zn: The concentration of Fe and Zn was positively correlated, as
Fe increased parallel to Zn (Fig. 15H). Zn amount ranged from 3 to
17.5 wt.%.
Fe/Ca: Fe and Ca were negatively correlated, as Fe concentration
decreased with increasing Ca amount (Fig. 15I).
4.3.2. Stable isotopes: carbon and oxygen isotopes (δ
13
C
V-PDB
vs. δ
18
O
V-PDB
)
The stable-isotope study was made on selected samples from calcitic
bioclasts (7 from brachiopod/bivalve shells and 3 from echinoderm
skeletons) and diagenetic calcite cements (3 from fibrous calcite, 4
from bladed calcite, 7 from luminescence, mosaic sparry-calcite and 5
from non-luminescence, mosaic sparry-calcite). Isotopic analyses were
also performed on euhedral dolomite (3 samples) but no values were
reliable due to the presence of micrite inclusions inside the tiny
dolomite crystals. The results of O and C isotope analysis are listed in
Table 2 and are represented as δ
18
O
V-PDB
vs. δ
13
C
V-PDB
cross-plots in
Fig. 16. In addition, the ranges of δ
18
O and δ
13
C isotope values for calcitic
skeletal components and for the main diagenetic cement generations
are also displayed in Table 2. Isotope data of the studied samples fall
into two groups.
Group 1 is represented by a significant part of the calcitic brachio-
pod/bivalve shells, which exhibits positive values of δ
13
C
V-PDB
(+1.18
to +3.03‰) and negative to slightly positive δ
18
O
V-PDB
(−1.77 to
0.32‰). These values fall in the marine-seawater, O/C calcite field
(Veizer et al., 1999).
Group 2 shows a wide range of isotopic values, with δ
13
C
V-PDB
vary-
ing between +0.9‰and −0.88‰and δ
18
O
V-PDB
between −9.03‰and
−3.32‰. This second group includes echinoderm skeletons and fibrous,
bladed, and mosaic calcite cements.
Fig. 13. Dissolution processes observed at Cacín TTC samples. A) PPL photomicrograph showing dissolution 1 stage affecting micrite matrix (red arrow), and bioclasts (bryozoans,
brachiopods and bivalves) (white arrows). Vuggy porosity resulted (yellow arrow). B) and C) PPL and fluorescence photomicrographs showing dissolution 2 stage affecting bladed (to
dogtooth) calcite cement (yellow and white arrows). D) PPL photomicrograph (stained sample) showing late intra-particle porosity created by dissolution in stage 2 (white arrow).
Porosity shown in blue in A, B and D pictures. (For interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article.)
Fig. 14. Silicification, halite, and sylvite crystallizations. A) SEM (EDS mapping) showing silica cement (blue in colour) and Mg-smectite (Mg-s), dolomite (D), halite (H) and sylvite
(S) (white arrows). B) SEM (EDS mapping) showing the replacement of Mg-smectite (green) (white arrow) by dolomite (purple) (yellow arrow), halite (dark orange) (red arrow)
and sylvite(orange) (blue arrow). (For interpretation of the references to colour in this figure legend, the reader is referred to the webversion of this article.)
11A. López-Quirós et al. / Sedimentary Geology xxx (2016) xxx–xxx
Please cite this article as: López-Quirós, A., et al., Diagenetic evolution of Tortonian temperate carbonates close to evaporites inthe Granada Basin
(SE Spain), Sedimentary Geology (2016), http://dx.doi.org/10.1016/j.sedgeo.2016.02.011

5. Interpretations and discussion
The sequence of diagenetic events in a carbonate system depends on
factors such as the sediment itself, grain size, texture, mineralogy, na-
ture of pore fluid and climate (Tucker and Wright, 1990; Tucker,
1993; Flügel, 2004). The classification scheme proposed by Choquette
and Pray (1970) for carbonate diagenetic regimes was followed in this
study. These authors distinguish between Eogenesis, in which rocks
are affected by surficial syn- to post-depositional diagenetic processes;
Mesogenesis, in which buried rocks are no longer affected by surficial
diagenetic processes; and Telogenesis, in which diagenetic processes
are associated with uplift and related subaerial exposure.
5.1. Sequence of diagenetic events
Syn-depositional diagenesis is shown by micritization of skeletal
grains, fibrous calcite-cement precipitation and mechanical compaction.
Micritization of skeletal grains is a diagenetic process that occurs at the
sediment–water interface in the marine realm under low-energy condi-
tions (Tucker and Wright, 1990; Adams and Mackenzie, 1998; Flügel,
2004). Thisprocess is dueto microorganism (bacteria, algaand fungi) ac-
tivity on carbonate-grain surfaces (Carols, 2002). Alternative explana-
tions for micritization have been given by Neugebauer (1978) and
Martín-García et al. (2009).
Fibrous calcite was the first cement to be formed. This cement
commonly crystallizes in well-oxygenated and moderate- to high-
hydrodynamic marine phreatic conditions (Moore, 2001). According
to Ehrenberg et al. (2002), isopachous, syn-depositional marine ce-
ments reflect a high saturation state of CaCO
3
and a low sedimentation
rate during their crystallization. Some of the grain fragments in the
sediment include broken fibrous calcite coats, which indicate that they
underwent remobilization after fibrous calcite-cement precipitation.
However,the oxygen and carbon isotope compositions of the fibrous
calcite cement (Fig. 16) do not match the values reported by Veizer et al.
(1999) for Miocene seawater calcite cements. Consequently, if the
fibrous calcite cement crystallized from a marine phreatic realm, then
the initial chemical composition of the cement may have been changed
later during the diagenesis, most likely by recrystallization.
Mechanical compaction postdates the precipitation of the fibrous
calcite cement (Fig. 9A). In between the two events, some dissolution
occurred, clearly preceding mechanical compaction, since dissolved
shells are preferentially compacted.
The next diagenetic episode encompasses the two major cementa-
tion phases observed, which resulted in the precipitation of the bladed
and the syntaxial/mosaic sparry calcite cements. As pointed out above,
both syntaxial and mosaic calcite cements consist of non-ferroan,
inclusion-rich sparite crystals and display the same concentric zoning
under CL (Fig. 8I), and so it is inferred that they grew at the same
time. Thin sections indicate that the bladed calcite cement clearly pre-
dates the syntaxial/mosaic sparry calcite cements. All these cements
also crystallized within microfractures created by mechanical compac-
tion (Fig. 9A). Crystal fabrics and cathodoluminescence patterns (from
concentric to sector zoning in the syntaxial/mosaic sparry cements;
Fig. 8I) point to a reducing, shallow-burial realm dominated by fresh
waters or by mixed, marine-fresh waters (Moore, 2001; Flügel, 2004).
The fact that a dissolution phase occurred before the formation of the
bladed and the syntaxial/mosaic sparry calcite cements is in line with
fresh-waters. Calcite cements crystallizing from fresh-waters are com-
monly depleted in Sr
2+
, Mg
2+
, and enriched in Fe
2+
,Mn
2+
,Zn
2+
com-
pared to their marine precursors (Brand and Veizer, 1980; Scholle and
Ulmer-Scholle, 2003). The Mg/Ca molar ratio ranges from 0.01 to 0.07
(Fig. 15A) indicating a low-Mg calcite, which is the stable form of
CaCO
3
in fresh water. The Sr andMn contents are negatively correlated
(Fig. 15G), pointing to diagenetic stabilization of the carbonates by fresh
water (Brand and Veizer, 1980). Furthermore, thepositive correlation of
the Fe/Zn ratio and low Fe/Ca ratio (Fig. 15H, I) is consistent with the
stabilization of the TTC rocks by fresh water during shallow burial dia-
genesis (Brand and Veizer, 1980).
The δ
18
O
V-PDB
and δ
13
C
V-PDB
values determined from the bladed and
the syntaxial/mosaic sparry calcite cements are lighter than the isotopic
composition of the Miocene seawater calcites (Veizer et al., 1999). They
exhibit a wide range ofnegative, oxygen isotopic composition (−9.03‰
to −3.32‰in δ
18
O
V-PDB
), and a small, positive to negative range of car-
bon isotopic composition (+0.9‰to −0.88‰;Fig. 16;Table 2). Such
fractionation in oxygen composition may be related to higher tempera-
tures from the burial of the carbonates. Based on the presence of
monophasic, aqueous fluid inclusions, it can be inferred that these cal-
cite cements crystallized at temperatures below 55 to 60 °C (Goldstein
and Reynolds, 1994; Goldstein, 2001). With this information, and the
oxygen-isotope compositions taken into account, these calcite cements
can be assumed to have crystallized from fluids evolving from marine to
meteoric (0‰to −8‰in δ
18
O
SMOW
). The fact that the echinoderm
plates display the same fluorescence and luminescence colour as these
cements points to a stabilization process (Brand and Veizer, 1980),
from high-Mg calcite to low-Mg calcite. In the case of bivalve and
gastropod shells originally in aragonite and now replaced by low-Mg
calcite the mineralogical stabilization took place by inversion. Further-
more, the echinoderm plates display the same oxygen/carbon isotopic
composition as these calcite cements, reflecting the geochemical
resetting of the bioclasts during stabilization.
Mg-smectite and illite occur as a pore-filling, internal sediment in
the TTC sediments post-dating all the above-mentioned (fibrous, blad-
ed, and syntaxial/mosaic) cements. The type of smectite (Mg-rich)
is commonly found in evaporitic, continental playa environments
(Hillier et al., 1995). Such clay presumably formed within a surficial,
mud-flat, marginal evaporitic environment and percolated inside the
TTC sediments. The presence of coarser terrigenous grains (silt) within
the clay points to a near-surface process as well. All this suggests that
Table 1
Geochemistry-analysis results of Cacín TTC samples. Major, and minorand trace element
contents are given in wt.% and ppm, respectively.
Samples Mn
(ppm)
Fe
(%)
Sr
(ppm)
Ca
(%)
Mg
(%)
K
(%)
Zn
(ppm)
Al
(%)
CA01 349 0.54 483.0 29.60 0.76 0.09 15.9 0.36
CA02 305 0.21 692.2 34.98 0.33 0.02 3.0 0.08
CA03 273 0.30 460.9 33.36 0.32 0.04 5.4 0.15
CA04b 257 0.21 582.8 37.93 0.26 0.02 3.2 0.06
CA05 314 0.25 566.3 35.98 0.27 0.03 4.6 0.10
CA06 313 0.25 619.5 33.84 0.29 0.02 4.2 0.08
CA07 810 0.68 453.9 31.30 0.26 0.03 9.1 0.13
CA08 559 0.35 447.1 32.71 0.28 0.04 7.5 0.14
CA09 272 0.28 531.5 32.29 0.37 0.04 7.7 0.18
CA10 238 0.27 511.1 33.02 0.30 0.03 7.7 0.12
CA11 432 0.40 529.4 31.86 0.31 0.03 5.4 0.10
CA12 201 0.35 565.1 31.27 0.30 0.04 6.1 0.15
CA13 295 0.30 575.3 32.21 0.25 0.02 3.4 0.07
CA14 173 0.21 542.1 33.35 0.29 0.03 9.9 0.12
CA15 371 0.35 618.7 33.00 0.29 0.04 7.1 0.13
CA16 307 0.19 527.8 34.75 0.26 0.03 3.1 0.09
C01 218 0.14 616.5 35.59 0.35 0.03 8.2 0.09
C02 249 0.27 640.7 32.85 0.45 0.03 7.5 0.10
C03a 150 0.23 644.3 32.33 0.49 0.04 10.7 0.12
C04 586 0.82 467.8 23.32 1.04 0.13 13.6 0.36
C05 297 0.54 644.5 31.9 0.67 0.09 13.4 0.27
C06a 181 0.40 575.3 29.84 0.48 0.07 17.5 0.19
C07 406 0.49 450.7 26.46 0.75 0.08 13.7 0.23
C08 258 0.30 548.2 30.57 0.46 0.06 10.6 0.17
C09b 94 0.13 519.6 32.61 0.32 0.03 5.2 0.07
C10a 154 0.22 562.3 31.73 0.52 0.06 8.7 0.16
C11 113 0.10 593.0 35.03 0.33 0.03 4.7 0.07
C12a 98 0.09 514.6 34.25 0.34 0.03 4.2 0.08
C13a 374 0.32 643.8 31.58 0.38 0.05 5.5 0.13
C15 347 0.29 546.2 33.66 0.38 0.07 7.4 0.16
C16 298 0.29 502.5 33.05 0.27 0.05 9.3 0.15
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Please cite this article as: López-Quirós, A., et al., Diagenetic evolution of Tortonian temperate carbonates close to evaporites inthe Granada Basin
(SE Spain), Sedimentary Geology (2016), http://dx.doi.org/10.1016/j.sedgeo.2016.02.011

the TTC sediments were subaerially exposed, or got close to the surface,
during the incorporation of the clay minerals. Positive correlation of
Fe/K and K/Al ratios in the carbonates (Fig. 15D, E) testifies to this
terrigenous (aluminosilicate and clay) influence.
Pyrite is also found associated with the Mg-smectite (Fig. 11B). Py-
rite (FeS
2
) is a common early-diagenetic mineral formed within
organic-rich sediments in reducing surficial/shallow-depth environ-
ments (Raiswell, 1982; Passier et al., 1997). According to Berner
(1970), pyrite results from the reaction of sulphide (produced via bacte-
rial sulphate reduction) with either Fe
3+
(in sediments) or Fe
2+
produced by bacterial Fe
3+
reduction (Lovley, 1991).
Dolomitization occurred afterwards as “partial dolomitization”in
TTC sediments. Dolomite rhombs replaced Mg-smectite in the carbon-
ates and, to a lesser extent, micritic (microsparite) carbonate matrix
(Figs. 11C, 12A, B). Cloudy cores in dolomite crystals resulted from the
incorporation of inclusions and impurities within the crystalline net-
work. Sucha dirty dolomite is generally the result of a quick crystalliza-
tion near or at surface conditions (Tucker and Wright, 1990). The fact
that the dolomite replaces Mg-rich smectite associated with pyrite
points to a reducing environment. Such conditions are thought to
have occurred during the deposition of the Tortonian Evaporites
(García-Veigas et al., 2013). The shallow burial conditions and the
high Mg-content in the smectite could have been additional factors
that prompted dolomitization. The role of Mg-clays acting as templates
for the precipitation of dolomite has been pointed out by Martín-Pérez
et al. (2015) in some present-day caves in western Spain. Dolomite
formation could be linked to reflux brines formed during deposition of
the overlying evaporites.
Silicification, halite, and sylvite crystallization occurred after do-
lomitization (some dolomite crystals are now replaced by these min-
erals; Fig. 14). They resulted probably from the percolation of highly-
saline, silica-rich brines migrating through the TTC sediments. The
diagenetic transformations introduced were not, however, signifi-
cant in extent.
The occurrence of stylolithes affecting all the previous, above-
mentioned diagenetic features points to the role played by chemical com-
paction as a major, late-stage diagenetic process. Chemical compaction
resulted from pressure-dissolution and re-precipitation of carbonates at
burial depths of several hundred metres.
The latest diagenetic stage to be recognized is exemplified by the
crystallization of non-luminescent, microstalactitic calcite cement and
calcite fibres/whisker crystals. Such fabric and CL pattern suggest that
this dripstone (pendant or microstalactitic) calcite cement probably
formed within the meteoric vadose-zone (Moore, 2001; Flügel, 2004).
Calcite fibres/whisker crystals are also found in vadose environments
(Jones and Kahle, 1993). The structural inversion and final uplift of the
study area involved the interaction with meteoric waters as the carbon-
ate rocks were being exposed, implying extensive dissolution as well.
5.2. Diagenetic evolution in relation to the regional geodynamic
In the late Miocene, the Granada Basin was subjected to two
main burial episodes, separated by a minor subaerial exposure event
(Martín et al., 1984). The first burial episode occurred during the late
Tortonian, followed by the subsequent exposure during the latest
Tortonian, at the time of evaporite deposition (Fig. 17). The second buri-
al episode coincided with the accumulation of the Messinian lacustrine
strata (up to 300 m thick). The study area within the Granada Basin
(Cacín) was uplifted in the early Pliocene (García-Alix et al., 2008) and
subaerially exposed since then (Fig. 17).
The diagenetic processes observed agree with the regional history:
syn-depositional processes (Eogenesis), comprising micritization,
fibrous-calcite cementation, dissolution (dissolution stage 1) and
mechanical compaction, occurred during the late Tortonian.
The first diagenetic burial episode (Mesogenesis 1), concomitant to
Tortonian marl deposition, is characterized by the precipitation of the
bladed and syntaxial/mosaic cements and the stabilization of the
temperate-water carbonates by fluids evolving from marine to fresh
waters.
Clay (Mg-rich smectite) was incorporated into TTC sediments
when they were subaerially exposed or got close to the surface
(Telogenesis 1) in the latest Tortonian, at the time of the lower-
evaporite deposition. Pyrite formed as well within the Mg-smectite
contemporaneously or shortly afterwards (Fig. 17).
0.0
0.5
1.0
1.5
0 20
Mg (%)
Ca (%)
0
200
400
600
800
40 40
Sr (ppm)
Ca (%)
0.0
0.5
1.0
0.00 20 0.2 0.4
Fe (%)
Al (%)
0.0
0.5
1.0
0.00 0.10 0.20
Fe (%)
K (%)
0.00
0.05
0.10
0.15
0.0 0.4
K (%)
Al (%)
0.0
0.5
1.0
0.2 05001000
Fe (%)
Mn (ppm)
0
200
400
600
800
0 500 1000
Sr (ppm)
Mn (ppm)
0.0
0.5
1.0
Fe (%)
Zn (ppm)
0.0
0.5
1.0
01020 02040
Fe (%)
Ca (%)
ABC
DE F
GHI
Fig. 15. Cross-plots ofmajor, minor, and traceelements fromCacín TTC samples (revealed by ICP-MSanalysis). A)Mg/Ca; B) Sr/Ca; C) Fe/Al;D) Fe/K; E) K/Al; F)Fe/Mn; G) Sr/Mn; H) Fe/Zn;
I) Fe/Ca.
13A. López-Quirós et al. / Sedimentary Geology xxx (2016) xxx–xxx
Please cite this article as: López-Quirós, A., et al., Diagenetic evolution of Tortonian temperate carbonates close to evaporites inthe Granada Basin
(SE Spain), Sedimentary Geology (2016), http://dx.doi.org/10.1016/j.sedgeo.2016.02.011

The diagenetic evolution continued with a second burial phase
(Mesogenesis 2) in Messinian times. Dolomite formation occurred
sometimein the early Messinianas well as silica precipitation and halite
and sylvite replacements. The Tortonian evaporites may have provided
the reducing brines which percolated through the TTC sediments and
promoted such diagenetic transformations at shallow burial depths.
Maximum burial diagenesis at Mesogenesis 2 is characterized by
chemical compaction with stylolite formation (Fig. 17).
Finally, the uplift of the study area from the early Pliocene to the
present day favoured microstalactitic and fibre/whisker calcite-cement
precipitation and extensive dissolution (dissolution stage 2) (Fig. 17).
5.3. Comparable examples
In temperate and tropical-carbonates diagenetic features are con-
trolled mainly by a) the depositional setting and the relative sea-level
fluctuations, b) the pore-fluid chemistry and their residence time, and
c) the basin tectonic evolution (James and Bone, 1989; Nelson et al.,
1994; Hood and Nelson, 1996; Caron et al., 2005; Caron and Nelson,
2009). The main differences between the two types of carbonates are
highlighted by the facts that in the temperate-water carbonates early
diagenesis is strongly conditioned by theoriginal composition and pres-
ervation potential of the bioclasts, as extensive leaching of aragonite
skeletons usually takes place directly on the sea floor (Alexandersson,
1978; Betzler et al., 1997b; James et al., 2005, 2011), while in tropical
carbonates widespread synsedimentary cement-precipitation is nor-
mally ubiquitous (Bathurst, 1975; James and Choquette, 1990). In
temperate-water carbonates diagenetic studies have been carried
out mainly on Cenozoic examples from New Zealand and southern
Australia (Nelson et al., 1988; Reeckmann, 1988; James and Bone,
1989; Dix and Nelson, 2006; Caron and Nelson, 2009). All these studies,
however, have failed in connecting diagenesis to basin evolution, as
shown for TTC of the Granada Basin where the diagenetic history is con-
sistently integrated within the geodynamic framework.
Most diagenetic studies on carbonates are overall carried out asindi-
vidual study cases given the diversity of depositional and diagenetic
processes that affect the shallow-water carbonates, and the variety of
regional tectonic settings. Therefore, comparisons between different
basins are not always straightforward.
In this respect, Jurassic carbonates in the Paris Basin are one of the
few well-studied examples (Vincent et al., 2007; Brigaud et al., 2009;
Carpentier et al., 2014) that can be directly compared with the TTC in
the Granada Basin. In both cases, the diagenetic pathways of carbonate
rocks were linked to major geodynamic events, which include several
episodes of subsidence and uplift, and the development of telogenetic
features during the final exhumation of the basins. A significant
difference during the telogenetic evolution of both basins lies in the
fact that the final exhumation of the TTC (Telogenesis 2) was not
accompanied by extensive fracturing as in the Paris Basin, which gener-
ated a more complex diagenetic evolution of the limestones. TCC
underwent dissolution by meteoric fluids and subsequent precipi-
tation of microstalactitic and fibre/whisker calcite-cements during
the progressive basin inversion (uplifting). In the case of the
Paris Basin, open fractures, which likely formed in a transitional,
compressional- to-extensional tectonic regime (Carpentier et al.,
2014), were used as pathways for fluorine and sulphur fluids con-
temporaneously to the dissolution of the limestones by meteoric
waters, yielding to the subsequent fluorite and pyrite precipitation in
the resulting cavities.
The comparison of the diagenetic evolution of the TTC with other
shelf carbonates from different ages and tectonic settings such as the
Persian Gulf, Indonesia, Louisiana, the Mediterranean-Sea and Paris
Basin, yields the following results:
(1) Micritization and formation of bioclast rims was a common
process during the earliest diagenesis in most shallow-water
limestones (Wilson and Evans, 2002; Wilson et al., 2013;
Daraei et al., 2014), as well as in the TCC.
(2) Dissolution during the early burial and extensive leaching of
aragonite (Crevello et al., 1985; Wilson et al., 2013) was not a
widespread phenomenon as might be expected in the TTC,
probably due to the existence of a prior neomorphic, aragonite-
to-calcite inversion (mineralogical stabilization) that prevented
dissolution.
Table 2
Oxygen and carbon stable-isotope values for calcitic skeletal components and diagenetic
cements at Cacín TTC samples. Outcrops codes: Cacín-1 (CA); Cacín-2 (C).
Sample δ
13
C
V-PDB
‰δ
18
O
V-PDB
‰
CA 02c Brachiopod/bivalve shells 0.74 −3.37
CA 02d …2.58 −0.05
CA 03b …1.93 −0.85
CA 03d …3.03 0.32
CA 14c …1.48 −1.77
CA 14d …1.18 −1.54
C 02c …0.74 −4.30
CA 02a Echinoderms skeletons 0.90 −7.09
CA 03f …0.89 −7.44
C 08b …−0.13 −5.28
C 15d Radiaxial fibrous calcite cement 0.24 −5.84
CA 02g …0.32 −6.90
CA 14a …0.55 −6.31
CA 02e Dull orange bladed cement 0.66 −6.41
CA 03a …−0.19 −8.82
CA 03c …−0.88 −8.26
CA 03e …0.59 −8.85
C 12a Orange mosaic cement −0.28 −4.46
C 12b …−0.25 −4.74
C 13c …0.24 −3.32
C 15b …−0.44 −6.41
C 15c …0.33 −6.30
CA 02b …0.67 −9.03
CA 02f …0.23 −8.65
C 13a Non-luminescence mosaic cement −1.58 −4.57
C 13b …−0.74 −3.61
C 15a …0.20 −7.59
C 02a …0.08 −4.18
C 08c …0.02 −5.60
-10 -8 -6 -4 -2 0 2
Group 1
Group 2
δ
δ18O ‰ (V -PDB)
δ13C ‰ (V -PDB)
Radiaxial fibrous calcite
Dull orange bladed
Orange mosaic
Non-luminescence mosaic
Miocene seawater calcite
(Veizer et a l., 1999)
4
3
2
1
0
-1
-2
Fig. 16. A scatter plot of δ
13
C and δ
18
O values of Cacín TTC samples. Isotope data fall into
two groups. Group 1, represented by a significant part of the calcitic brachiopod/bivalve
shells, yields positive values of δ
13
C
V-PDB
and negative to slightly positive δ
18
O
V-PDB
.
These values fall in the marine-seawater, O/C calcite field (Veizer et al., 1999). Group 2
exhibits a wide range of δ
18
O
V-PDB
and relatively small range of δ
13
C
V-PDB
isotopic values.
This second group includes echinoderm skeletons and fibrous, bladed, and mosaic
calcite cements. These latter isotope values reflect the effects of fluids evolving from
marine to meteoric.
14 A. López-Quirós et al. / Sedimentary Geology xxx (2016) xxx–xxx
Please cite this article as: López-Quirós, A., et al., Diagenetic evolution of Tortonian temperate carbonates close to evaporites inthe Granada Basin
(SE Spain), Sedimentary Geology (2016), http://dx.doi.org/10.1016/j.sedgeo.2016.02.011

3) The development of the syntaxial overgrowthswas very minor in
the TTC and was presumably conditioned by the facies type
(Wilson and Evans, 2002; Wilson et al., 2013) and subsequent
abundance of suitable skeletal (crinoid and echinoid) particles.
4) Dolomitization formed mainly by replacement of Mg-rich
smectite in the TTC. Direct replacement of the limestones was a
very minor process. Mg-rich fluids were not released during
chemical-compaction as exemplified by Vincent et al. (2007).
5) Pyrite in the TCC is scarce and its precipitation is linked to the
degradation of organic matter, favouring sulphate reduction,
during the first telogenetic stage contemporaneously to evapo-
rite formation. Sulphate-rich waters may have reached the
carbonates through the existing fracture network, as shown in
the example described by Carpentier et al. (2014).
Carbonates and evaporites are intimately associated in a variety of
sedimentary environments (e.g. semi-restricted carbonate platforms,
evaporitic basins, lacustrine basins) and thus diagenetic studies dealing
with these two types of rocks together have focused on carbonate
to evaporite transitions (Rouchy et al., 2001; Schoenherr et al., 2009;
Daraei et al., 2014; Amel et al., 2015). In these environments, the dia-
genesis is influenced by the different solubility of the carbonates and
evaporites under the influence of meteoric waters. However, in sedi-
mentary sequences where carbonates and evaporites are not genetically
linked, as in the case of the TTC, the influence of the evaporites on the
diagenetic evolution is conditioned by the ability of the highly saline
fluids to percolate into the limestone units. In the Granada Basin, the in-
fluence that evaporites close to the TTC exerted on the carbonates was
only slight and restricted to the replacement by dolomite, halite and
sylvite. This weak influence suggests the absence of a well-developed
fracture network throughout the Upper Tortonian marls between the
evaporites and the TTC, whichis consistent with the more ductile nature
of those soft sediments.
6. Conclusions
The paragenetic sequence in the TTC sediments from the Granada
Basin shows a diagenetic evolution that encompasses five episodes:
Eogenesis (syn-depositional), late Tortonian in age; Mesogenesis 1
(first burial event), late Tortonian in age; Telogenesis 1 (first uplift
event, contemporaneous to evaporite deposition), latest Tortonian in
age; Mesogenesis 2 (shallow- to deep-burial event), Messinian in age,
and Telogenesis 2 (second uplift event), Pliocene to Recent in age.
During the syn-depositional stage (Eogenesis) marine diagenetic
processes such as micritization, fibrous calcite-cement precipitation
and mechanical compaction occurred. The first burial diagenetic event
(Mesogenesis 1) is characterized by the stabilization of the temperate-
water carbonates by fluids evolving from marine to fresh water, and
by porosity occlusion by bladed and syntaxial/mosaic calcite cements.
The first uplifting episode (Telogenesis 1) involved clay (Mg-smectite)
incorporation in TTCsediments, during evaporite deposition, and pyrite
formation. During the second burial episode (Mesogenesis 2) dolomite,
silica, and halite/sylvite formed first, at shallow-burial conditions, in
connection with reducing brines percolating from the evaporite
deposits. Later on, in deeper burial conditions, pressure-dissolution
features (stylolites) developed in a closed diagenetic system. The last
diagenetic episode (Telogenesis 2) comprises microstalactitic and
fibre/whisker calcite-cement precipitation and extensive dissolution.
The study case clearly exemplifies the close link between diagenetic
history and basin evolution. Diagenetic processes were related to major
geodynamic events, includingbasin restriction leading to evaporite de-
position,and several episodes of subsidence and uplift.Up to now, only
very few diagenetic studies have succeeded in showing a tight correla-
tion between diagenetic history and basin evolution.
Acknowledgements
This work is part of the “Study MFT08.003”(IFP Energies Nouvelles,
France). A significant part of this work was carried out at IFP Energies
Nouvelles laboratories in Rueil-Malmaison (France), during an intern-
ship stay of the senior author (ALQ) sponsored by IFP. JMM and APB
work was funded by the project “Productores de carbonato en
plataformas carbonatadas neógenas de la Cordillera Bética. Factores
que controlan la composición y la resedimentación”(CGL2013-47236-
P) (2014-18) (Ministerio de Economía y Competitividad, Spain and
Fondo Europeo de Desarrollo Regional FEDER). Thanks are given to
Prof. Michael Joachimsky (University of Erlangen) for the isotopic anal-
ysis, ACME Lab for the measurement of the element concentrations, and
Dr. Julio Aguirre and Dr. Isabel Sánchez-Almazo (University of Granada),
and Dr. Javier García-Veigas (University of Barcelona) for their helpful
Non surficial-linked
Syntaxial/mosaic
Stylolite
(Depth)
cement
Messinian
e forma on
te precipita on
Lower Pliocene
to Recent
Tortonian
Shallow-burial Burial Subaerial expo.
MESOGENESIS 1 TELOGENESIS 1 MESOGENESIS 2 TELOGENESIS 2
Halite and sylvite
Meteoric fluids
diagenetic processes
sparry calcite
cement
replacements
calcite cement
EOGENESIS
Surficial-linked
Subaerial expo.
Brines
Meteoric fluidsMarine fluids
Fig. 17. TTC diagenetic evolution. The paragenetic sequence in the TTC show a diagenetic evolution that encompasses five diagenetic episodes: Eogenesis (syn-depositional to shallow
burial) and Mesogenesis 1 (shallow burial to burial), both late Tortonian in age; Telogenesis 1 (subsequential uplift) during the latest Tortonian at the time of evaporite deposition;
Mesogenesis 2, Messinian in age; and Telogenesis 2, Pliocene to Recent in age.
15A. López-Quirós et al. / Sedimentary Geology xxx (2016) xxx–xxx
Please cite this article as: López-Quirós, A., et al., Diagenetic evolution of Tortonian temperate carbonates close to evaporites inthe Granada Basin
(SE Spain), Sedimentary Geology (2016), http://dx.doi.org/10.1016/j.sedgeo.2016.02.011

comments. We would also like to thank Editor Dr. Brian Jones and two
anonymous referees for their suggestions to improve the paper. We
thank David Nesbit for the correction of the English text.
References
Adams, A.E., Mackenzie, W.S., 1998. A Colour Atlas of Carbonate Sediments and Rocks
Under the Microscope. Manson Publishing, Londres, p. 180.
Aguirre,J., Braga, J.C., Martín, J.M.,Puga-Bernabéu, Á.,Pérez-Asensio,J.N., Sánchez-Almazo,
I.M., Génio, L., 2015. An enigmatic kilometre-scale concentration of small mytilids
(Late Miocene, Guadalquivir Basin, S Spain). Palaeogeography Palaeoclimatology Pa-
laeoecology 436, 199–213.
Alexandersson, E.T., 1978. Destructive diagenesis of carbonate sediments in the eastern
Skagerrak, North Sea. Geology 6, 324–327.
Amel, H., Jafarian, A., Husinec, A., Koeshidayatullah, A., Swennen, R., 2015. Microfacies,
depositional environment and diagenetic evolution controls on the reservoir quality
of the Permian Upper Dalan Formation, Kish Gas Field, Zagros Basin. Marine and
Petroleum Geology 67, 57–71.
Baceta, J.I., Pendón, J.G.,1999. Estratigrafíay arquitectura de facies de la Formación Niebla,
Neógeno superior, sector occidental de la Cuenca del Guadalquivir. Revista de la
Sociedad Geológica de España 12 (3–4), 419–438 (in Spanish).
Banner, J.L., 1995. Application of the trace element and isotope geochemistry ofstrontium
to studies of carbonate diagenesis. Sedimentology 42, 805–824.
Bathurst, R.G.C., 1975. Carbonate Sediments and Their Diagenesis. second ed. Elsevier,
Amsterdam, p. 658.
Beasley, C.J., Fiduk, J.C., Bize, E.,Boyd, A., Frydman, M.,Zerilli, A., Dribus,J.R., Moreira, J.L.P.,
Capeleiro Pinto, A.C., 2010. Brazil's presalt play: oilfield review. Schlumberger 22,
28–37.
Berner, R.A., 1970. Sedimentary pyrite formation. American Journal of Science 268, 1–23.
Betzler, C., Brachert, T., Braga, J.C., Martín, J.M., 1997a. Nearshore, temperate, carbonate
depositional systems (lower Tortonian, Agua Amarga Basin, southern Spain): impli-
cations for carbonate sequence stratigraphy. Sedimentary Geology 113, 27–53.
Betzler, C., Brachert, T.C., Nebelsick, J., 1997b. The warm-temperate carbonate province.
A review of facies, zonations, and delimitations. Courier Forschungsinstitut
Senckenberg 201, 83–99.
Braga, J.C., Martín, J.M., Alcalá,B., 1990. Coral reefs in coarse-terrigenous sedimentary en-
vironments (Upper Tortonian, Granada Basin, southern Spain). Sedimentary Geology
66, 135–150.
Braga, J.C., Jimenez, A.P., Martín, J.M., Rivas, P., 1996. Middle Miocene, coral-oyster reefs
(Murchas, Granada, southern Spain). In: Franseen, E., Esteban, M., Ward, B., Rouchy,
J.M. (Eds.), Models for Carbonate Stratigraphy From Miocene Reef Complexes of the
Mediterranean Regions. SEPM, Concepts in Sedimentology and Paleontology Series
5, pp. 131–139 (Tulsa, Oklahoma).
Braga, J.C. , Martín, J.M., Quesa da, C., 2003. Pattern s and average rates of l ate Neogene–
Recent uplift of the Betic Cordillera, SE Spain. Geomorphology 50, 3–26.
Braga, J.C., Martín, J.M., Betzler, C., Aguirre, J., 2006. Models of temperate carbonate depo-
sition in Neogene basins in SE Spain: a synthesis. In: Pedley, M., Carannante, G. (Eds.),
Cool-water Carbonates: Depositional Systems and Palaeoenvironmental Control.
Geological Society, London, Special Publications 255, pp. 121–135.
Braga, J.C., Martín, J.M., Aguirre, J., Baird, C.D., Grunnaleite, I., Jensen, N.B., Puga-Bernabéu,
A., Sælen,G., Talbot, M.R., 2010. Middle-Miocene (Serravallian) temperate carbonates
in a seaway connecting the Atlantic Ocean and the Mediterranean Sea (North Betic
Strait, S Spain). Sedimentary Geology 225, 19–33.
Brand, U., Veizer, J., 1980. Chemical diagenesis of multicomponent carbonate system, I:
trace elements. Journal of Sedimentary Petrology 50, 1219–1236.
Brigaud, B., Durlet, C., Deconinck, J.-F., Vincent, B., Thierry, J., Trouiller, A., 2009. Theorigin
and timing of multiphase cementation in carbonates: impact of regional scale
geodynamic events on the Middle Jurassic limestones diagenesis (Paris Basin,
France). Sedimentary Geology 222, 161–180.
Brookfield,M.E., 1988. A mid-Ordovician temperate carbonate shelf —theBlack River and
Trenton Limestone Groups of southern Ontario, Canada. Sedimentary Geology 60,
137–153.
Carols, L.J., 2002. Diagenetic historyof the Upper JurassicSmackover Formation and its ef-
fects on reservoir properties: Vocation Field, Manila Sub-Basin, Eastern Gulf Coastal
Plain. Gulf Coast Association of Geological Societies Transactions 52, 631–644.
Caron, V., Nelson, C.S., 2009. Diversity of neomorphic fabric in New Zealand Plio-
Pleistocene cool-water limestones: insights into aragonite alteration pathways and
controls. Journal of Sedimentary Research 79, 226–246.
Caron, V., Nelson, C.S., Kamp, P.J.J., 2005. Sequence stratigraphic context orf
syndepositional diagenesis in cool-water shelf carbonates: Pliocene limestones,
New Zealand. Journal of Sedimentary Research 75, 231–250.
Carpentier, C., Brigaud, B., Blaise, T., Vincent, B., Durlet, C., Boulvais, P., Pagel, M., Hibsch, C.,
Yven, B., Lach, P., Cathelineau, M., Boiron, M.-C., Landrein, P., Buschaert, S., 2014. Im-
pact of basin burial and exhumation on Jurassic carbonates diagenesis on both sides
of a thick clay barrier (Paris Basin, NE France). Marine and Petroleum Geology 53,
44–70.
Choquette, P.W., Pray, L.C.,1970. Geological nomenclature andclassification of porosity in
sedimentary carbonates. American Association of Petroleum Geologists Bulletin 54,
207–250.
Corbí, H., Lancis, C., García-García, F., Pina, J.A., Soria, J.M., Tent-Manclús, J.E., Viseras, C.,
2012. Updating the marine biostratigraphy of the Granada Basin (central Betic
Cordillera). Insight for the Late Miocene palaeogeographic evolution of the
Atlantic–Mediterranean seaway. Geobios 45, 249–263.
Crevello, P.D., Harris, P.M., Stoudt, D., Baria, L.R., 1985. Porosity evolution and burial
diagenesis in a Jurassic reef-debris reservoir, Smackover Formation, Hico Knowles
Field, Louisiana. In: Roehl, P.O., Choquette, P.C. (Eds.), Carbonate Petroleum Reser-
voirs. Springer-Verlag (622 pp).
Dabrio, C.J., Martín, J.M., Megias, A., 1982. Signification sédimentaire des évaporites de la
depression de Granade (Espagne). Bulletin de la Societe Geologique de France 24,
705–710 (in French).
Daraei, M., Rahimpout-Bonab, R., Fathi, N., 2014.Factors shaping reservoirarchitecture in
the Jurassic Arab carbonates: a case from the Persian Gulf. Journal of Petroleum Sci-
ence and Engineering 122, 187–207.
Dickson, J.A.D., 1966. Carbonate identification and genesis revealed by staining. Journal of
Sedimentary Petrology 34, 491–495.
Dix, G.R., Nelson, C.S., 2006. Diagenetic potential for lithification of cool-water carbonate
shelf mud. Sedimentary Geology 185, 41–58.
Dravis, J.J., Yurewicz, D.A., 1985. Enhanced carbonate petrography using fluorescence mi-
croscopy. Journal of Sedimentary Petrology 55, 795–804.
Dunham, R.J.,1962. Classification of carbonate rocks according to depositional texture. In:
Ham, W.E. (Ed.), Classification of Carbonate Rocks. A Symposium. Am. Assoc. Petrol.
Geol. Memoir 1, pp. 108–121.
Ehrenberg, S.N., 2007. Porosity destruction in carbonate platforms. Journal of Petroleum
Geology 29, 41–52.
Ehrenberg, S.N., Nadeau,P.H., 2005. Sandstonevs. carbonate petroleumreservoirs: a glob-
al perspective on porosity–depth and porosity–permeability relationships. American
Association of Petroleum Geologists Bulletin 89, 435–445.
Ehrenberg, S.N., Pickard, N.A.H., Svana, T.A., Oxtoby, N.H., 2002. Cement geochemistry of
photozoan carbonate strata (Upper Carboniferous–Lower Permian), Finnmark
Carbonate Platform, Brents Sea. Journal of Sedimentary Research 72, 95–115.
Embry, A.F., Klovan, J.E., 1971. A Late Devonian reef tract on northeastern Bank Island,
Northwest Territories. Canadian Society of Petroleum Geologists Bulletin 19,
730–781.
Fernández, J., Soria, J., Viseras, C., 1996. Stratigraphic architecture of the Neogene basins
in the central sector of the Betic Cordillera (Spain); tectonic control and base
level changes. In: Friend, P.F., Dabrio, C.J. (Eds.), Tertiary Basins of Spain: The Strati-
graphic Record of Crustal Kinematics. Cambridge University Press, Cambridge, UK,
pp. 353–365.
Flügel, E., 2004. Microfacies of Carbonate Rocks: Analysis, Interpretation and Application.
Springer, New York, p. 976.
García-Alix, A., Minwer-Barakat, R., Martín, J.M., Martín-Suarez, E., Freudenthal, M., 2008.
Biostratigraphy and sedimentary evolution of Late Miocene and Pliocene continental
deposits of the Granada Basin (southern Spain). Lethaia 41, 431–446.
García-Veigas, J., Cendón, D.I., Rosell, L., Ortí, F., Torres Ruiz, J., Martín, J.M., Sanz, E., 2013.
Salt deposition and brine evolution in the Granada Basin (Late Tortonian, SE Spain).
Palaeogeography Palaeoclimatology Palaeoecology 369, 452–465.
García-Veigas, J., Rosell, L., Cendón, D.I., Gibert, L., Martín, J.M., TorresRuiz, J., Ortí, F., 2015.
Large celestine orebodies formed by early-diagenetic replacement of gypsified
stromatolites (upper Miocene, Montevive-Escúzar deposits, Granada basin, Spain).
Ore Geology Reviews 64, 187–199.
Gläser, I., Betzler, C., 2002. Facies partitioning and sequence stratigraphy of cool-water,
mixed carbonate–siliciclastic sediments (Upper Miocene Guadalquivir Domain,
southern Spain). International Journal of Earth Sciences (Geologische Rundschau)
91, 1041–1053.
Goldstein, R.H., 2001. Fluid inclusions in sedimentary and diagenetic systems. Lithos 55,
159–193.
Goldstein, R.H., Reynolds, T.J., 1994. Systematics of fluid inclusions in diagenetic minerals.
Soc. Econ. Paleont. Mineral. Tulsa, Oklahoma, Short Course 31, p. 199.
Hillier,S., Matyas, J., Matter, A., Vasseur,G., 1995. Illite/smectite diagenesis and its variable
correlation with vitrinite reflectance in the Pannonian Basin. Clays and Clay Minerals
43, 177–183.
Hood, S.D., Nelson, C.S., 1996. Cementation scenarios for New Zealand Cenozoic nontrop-
ical limestones. New Zealand Journal of Geology and Geophysics 39, 109–122.
Hudec, M.R., Jackson, M.P.A., 2007. Terra infirma: understanding salt tectonics. Earth
Science Reviews 82, 1–28.
James, N.P.,1972. Holocene and Pleistocene calcareous crust (caliche) profiles: criteria for
subaerial exposure. Journal of Sedimentary Petrology 42, 817–836.
James, N.P., Bone, Y., 1989. Petrogenesis of Cenozoic, temperate water calcarenites, South
Australia: a model for meteoric/shallow burial diagenesis of shallow water calcite
cements. Journal of Sedimentary Petrology 59, 191–203.
James, N.P.,Bourque, P.A., 1992.Reefs and mounds. In:Walker, R.G., James,N.P. (Eds.), Fa-
cies Models. Response to Sea Level Change. Geol. Ass., Canada, Ottawa, pp. 323–348.
James, N.P., Choquette, P.W., 1990. Limestone diagenesis, the meteoric environment. In:
McIlreath, I., Morrow, D. (Eds.), Sediment Diagenesis. St. John's, Geological Associa-
tion Canada, Reprint Series, pp. 36–74.
James, N.P., Bone, Y., Kyser, T., 2005. Where has all the aragonite gone? Mineralogy of
Holocene neritic cool-water carbonates, southern Australia. Journal of Sedimentary
Research 75, 454–463.
James, N.P., Jones, B., Nelson, C.S., Campbell, H.J., Titjen, J., 2011. Cenozoic temperate and
sub-tropical carbonate sedimentation on an oceanic volcano —Chatham Islands,
New Zealand. Sedimentology 58, 1007–1029.
Jones, B., Kahle, C.F., 1993. Morphology, relationship, and origin of fiber and dendrite
calcite crystals. Journal of Sedimentary Petrology 63, 1018–1031.
Land, L.S., 1967. Diagenesis of skeletal carbonates. Journal of Sedimentary Petrology 37,
914–930.
Lees, A., Buller, A.T., 1972. Modern temperate-water and warm-water shelf carbonate
sediments contrasted. Marine Geology 13, 1767–1773.
Lovley, D.R., 1991. Dissimilatory Fe (III) and Mn (IV) reduction. Microbiological Reviews
55, 259–287.
16 A. López-Quirós et al. / Sedimentary Geology xxx (2016) xxx–xxx
Please cite this article as: López-Quirós, A., et al., Diagenetic evolution of Tortonian temperate carbonates close to evaporites inthe Granada Basin
(SE Spain), Sedimentary Geology (2016), http://dx.doi.org/10.1016/j.sedgeo.2016.02.011

Martín, J.M., Braga, J.C., 1997. Sierra Nevada: Historia del levantamiento de un relieve
deducida de las unidades conglomeráticas de su borde. In: Calvo, J.P., Morales, J.
(Eds.), Avances en el conocimiento del Terciario Ibérico. Grupo Español del Terciario,
pp. 117–120 (in Spanish).
Martín, J.M., Ortega-Huertas, M., Torres-Ruiz, J., 1984. Genesis and evolution of strontium
deposits of the Granada Basin (southeastern Spain): evidence of diagenetic replace-
ment of a stromatolite belt. Sedimentary Geology 39, 281–298.
Martín, J.M., Braga, J.C., Betzler, C., Brachert, T., 1996. Sedimentary model and high-freque ncy
cyclicity in a Mediterranean, shallow-shelf, temperate-carbonate environment (upper-
most Miocene, Agua Amarga Basin, Southern Spain). Sedimentology 43, 263–277.
Martín, J.M., Braga, J.C., Aguirre, J., Betzler, C., 2004. Contrasting models of temperate-
carbonate sedimentation in a small Mediterranean embayment: the Pliocene
Carboneras Basin, SE Spain. Journal of the Geological Society 161, 387–399.
Martín, J.M., Braga, J.C., Aguirre, J., Puga-Bernabéu, Á., 2009. History and evolution of the
North-Betic Strait (Prebetic Zone, Betic Cordillera): a narrow, early Tortonian, tidal-
dominated, Atlantic–Mediterranean marine passage. Sedimentary Geology 216,
80–90.
Martín, J.M., Braga, J.C., Sánchez-Almazo, I.M., Aguirre, J., 2010. Temperate and tropical
carbonate-sedimentation episodes in the Neogene Betic basin (southern Spain)
linked to climatic oscillations and changes in Atlantic–Mediterranean connections:
constraints from isotopic data. International Association of Sedimentologists. Special
Publication 42, 49–70.
Martín, J.M., Puga-Bernabéu, A., Aguirre, J., Braga, J.C., 2014. Miocene Atlantic–Mediterra-
nean seaways in the Betic Cordillera (southern Spain). Revista de la Sociedad
Geológica de España 27 (1), 175–186.
Martín-García, R., Alonso-Zarza,A.M., Martín-Pérez, A., 2009. Loss of primary texture and
geochemical signatures in speleothems due to diagenesis: evidences from Castañar
Cave, Spain. Sedimentary Geology 221 (1–4), 141–149.
Martín-Pérez, A., Alonso-Zarza, A.M., La Iglesia, A., Martín-García, R., 2015. Do magnesian
clays play a role in dolomite formation in alkaline environments? An example from
Castañar Cave, Cáceres (Spain). Geogaceta 57, 15–18 (in Spanish).
Meyers, W.J., 1974. Carbonate cement stratigraphy of the Lake Valley Formation
(Mississippian) Sacramento Mountains, New Mexico. Journal of Sedimentary Petrol-
ogy 44, 837–861.
Moore, C.H., 2001. Carbonate reservoirs. Porosity Evolution and Diagenesis in a Sequence
Stratigraphic FrameworkDevelopments in Sedimentology 55. Elsevier, Amsterdam,
p. 444.
Morales, J., Vidal, F., de Miguel, D., Aguacil, G., Posadas, A.M., Ibáñez, J.M., Guzmán, A.,
Guirao, J.M., 1990. Basement structure of the Granada Basin, Betic Cordilleras,
southern Spain. Tectonophysics 177, 337–348.
Nelson, C.S., 1988. An introductory perspective on non-tropical shelf carbonates. Sedi-
mentary Geology 60, 3–12.
Nelson, C.S., Harris, G.J., Young, H.R., 1988. Burial-dominated cementation in non-tropical
carbonates of the Oligocene Te Kuiti Group, New Zealand. Sedimentary Geology 60,
233–250.
Nelson, C.S., Kamp, P.J.J., Young, H.R., 1994. Sedimentology and petrography of mass-
emplaced limestone (Orahiri Limestone) on a late Oligocene shelf, western North
Island, and tectonic implications for eastern margin development of Taranaki Basin.
New Zealand Journal of Geology and Geophysics 37, 269–285.
Neugebauer, J., 1978. Micritization of crinoids by diagenetic dissolution. Sedimentology
25, 267–283.
Passier, H.F., Middelburg, J.J., de Lange, G.J., Bottcher, M.E., 1997. Pyrite contents,
microtextures, and sulfur isotopes in relation to formation of the youngest eastern
Mediterranean sapropel. Geology 25, 519–522.
Puga-Bernabéu, A., Martín, J.M., Braga, J.C., 2007. Tsunami-related deposits in tem-
perate carbonate ramps, Sorbas basin, southern Spain. Sedimentary Geology
199, 107–127.
Puga-Bernabéu, Á., Martín, J.M., Braga, J.C., 2008. Sedimentary processes in a submarine
canyon excavated into a temperate-carbonate ramp (Granada basin, S. Spain). Sedi-
mentology 55, 1449–1466.
Purser, B.H., 1980. Sedimentation et diagènese des carbonates néritiques récents. Éditions
Technip, Paris, p. 366.
Raiswell, R., 1982. Pyrite texture, isotopic composition and the availability of iron.
American Journal of Science 82, 1244–1263.
Reeckmann, S.A., 1988. Diagenetic alterations in temperate shelf carbonates from south-
eastern Australia. Sedimentary Geology 60, 209–219.
Rodríguez-Fernández, J., Sanz de Galdeano, C., 2006. Late orogenic intramontane
basin development: the Granada basin, Betics (southern Spain). Basin Research
18, 85–102.
Rossi, C., 2010. Introducción a la diagénesis de las rocas carbonáticas. In: Arche, A. (Ed.),
Sedimentología. Del proceso físico a la cuenca sedimentaria. Consejo Superior de
Investigaciones Científicas, España, pp. 1105–1182 (in Spanish).
Rouchy, J.M., Taberner, C., Peryt, T.M., 2001. Sedimentary and diagenetic transitions be-
tween carbonates and evaporites. Sedimentary Geology 140, 1–8.
Sanz de Galdeano, C., 2008. The Cádiz-Alicante fault: an important discontinuity in the
Betic Cordillera. Revista de la Sociedad Geológica de España 21, 49–58.
Schoenherr, J., Reuning, L., Kukla, P.A., Littke, R., Urai, J.L., Siemann, M., Rawahi, Z., 2009.
Halite cementation and carbonate diagenesis of intra-salt reservoirs from the Late
Neoproterozoic to Early Cambrian Ara Group (South Oman Salt Basin). Sedimentolo-
gy 56, 567–589.
Scholle, P.A., Ulmer-Scholle, D., 2003. A Color Guide to the Petrography of Carbonate
Rocks: Grains, Textures, Porosity, Diagenesis. Am. Assoc. Petrol. Geol. Memoir 77,
p. 474 (Tulsa, Oklahoma).
Sibley, D.F., Gregg, J.M., 1987. Classification of dolomite textures. Journal of Sedimentary
Research 57, 967–975.
Supko, P.R., 1971. ‘Whisker’crystal cement in a Bahamian rock. In: Bricker, O.P. (Ed.),
Carbonate Cements. Studies in Geology 19, pp. 143–146.
Tucker, M.E., 1993. Carbonate diagenesis and sequencestratigraphy. In: Wright, V.P. (Ed.),
Sedimentology Review. Blackwell, Oxford, pp. 51–72.
Tucker, M.E., Wright,P., 1990. CarbonateSedimentology. Blackwell Scientific Publications,
Oxford, p. 482.
Veizer, J., Ala, D., Azmy, K., Bruckschen, P., Buhl, D., Bruhn, F., Garden, G.A.F., Diener, A.,
Ebneth, S., Godderis, Y., Jasper, T., Korte, Ch., Pawellek, F., Podlaha, O.G., Strauss, H.,
1999.
87
Sr/
86
Sr, δ
13
C and δ
18
O evolution of Phanerozoic seawater. Chemical Geology
30, 59–88.
Verwer, K., Lukasik, J., 2014. Pre-salt carbonates of the South Atlantic. AAPG 2014 Annual
Conference and Exhibition, Houston, Texas, USA, Abstract 90189.
Vincent, B., Emmanuel,L., Houel, P., Loreau, J.-P., 2007. Geodynamic control on carbonate
diagenesis: petrographic and isotopic investigation of the Upper Jurassic formations
of the Paris Basin (France). Sedimentary Geology 197, 267–289.
Ward, W.C., 1970. Diagenesis of Quaternary Eolianites of N.E. Quintana Roo, Mexico. Rice
Univ., Houston, p. 206 (Ph.D. dissert.).
Wilson, M.E.J., Evans, M.J., 2002. Sedimentology and diagenesis of Tertiary carbonates on
the Mangkalihat Peninsula, Borneo: implications for subsurface reservoir quality.
Marine and Petroleum Geology 19, 873–900.
Wilson, M.E.J., Ee Wah, E.C., Dorobek, S., Lunt, P., 2013. Onshore to offshore trends in
carbonate sequence development, diagenesis and reservoir quality across a land-
attached shelf in SE Asia. Marine and Petroleum Geology 45, 349–376.
17A. López-Quirós et al. / Sedimentary Geology xxx (2016) xxx–xxx
Please cite this article as: López-Quirós, A., et al., Diagenetic evolution of Tortonian temperate carbonates close to evaporites inthe Granada Basin
(SE Spain), Sedimentary Geology (2016), http://dx.doi.org/10.1016/j.sedgeo.2016.02.011