Sedimentary Geology 178 (2005) 197 – 217

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A model of early calcite cementation in alluvial fans:

Evidence from the Burdigalian sandstones and limestones
of the Vallès-Penedès half-graben (NE Spain)
D. Parcerisaa, D. Gómez-Grasb,*, A. Travéc
a
Centre d’Informatique Géologique, École des Mines de Paris, 77305 Fontainebleau CEDEX, France
b
Dpt. de Geologia, Facultat de Ciències, Universitat Autònoma de Barcelona, 08193 Bellaterra, Spain
c
Dpt. de Geoquı́mica, Petrologia i Prospecció Geològica, Facultat de Geologia, Universitat de Barcelona, 08028 Barcelona, Spain
Received 21 June 2004; received in revised form 14 April 2005; accepted 22 April 2005

Abstract

The Vallès-Penedès half-graben developed during a Neogene extensive period as part of the Catalan Coastal Ranges
in the northwestern edge of the Valencia Trough. The Neogene deposits of the Vallès-Penedès half-graben consist of,
from base to top, three lithostratigraphic complexes: i) a lower continental complex of Aquitanian?–early Langhian age;
ii) a continental to marine complex with reefal carbonate platforms of Langhian age and; iii) an upper continental
complex of middle Serravallian–Tortonian age. This study focuses on the calcite cements of the lower continental
complex consisting of red beds (mudstones, sandstones and conglomerates) and lacustrine limestones deposited in alluvial
fan environments.
The studied materials are cemented by calcite precipitated from meteoric waters that circulated through the sediments
during the early diagenesis at shallow burial depths. The calcite cement was studied by means of petrographic,
cathodoluminescence, microprobe and y18O and y13C isotopic analysis. The petrographic and geochemical results show
that these cements vary according to the sedimentary environment: (i) sandstones deposited in proximal alluvial fan
environments cemented by calcite with low contents of Mg, Fe, Mn, Sr and Na, y13C values of 7,4xPDB and y18O values
from 6.5 to 6.2xPDB; (ii) sandstones sedimented in medium to distal alluvial fan environments cemented by Mn-rich
and Mg, Fe, Sr and Na-poor calcite with y13C values from 7.9 to 6.9xPDB and y18O values from 10.5 to 8.6xPDB;
and (iii) lacustrine limestones of distal alluvial fan environments cemented by Fe-rich calcite with variable contents of Mn
and low contents of Mg, Sr and Na. The distribution of these calcite cements allows us to propose a model of fluid
circulation and early calcite cementation within an alluvial fan indicating spatial and temporal variations in chemical
composition of meteoric water during migration from proximal to distal alluvial fan environments. Residence time of

* Corresponding author. Fax: +34 93 581 12 63.

E-mail addresses: parcerisa@cig.ensmp.fr (D. Parcerisa), david.gomez@uab.es (D. Gómez-Gras), atrave@ub.edu (A. Travé).

0037-0738/$ - see front matter D 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.sedgeo.2005.04.004
198 D. Parcerisa et al. / Sedimentary Geology 178 (2005) 197–217
waters, Eh–pH conditions, and the degree of sediment–water interactions, influenced by the mineral composition of the host
sediments, are the most important parameters controlling variations in calcite cement composition.
D 2005 Elsevier B.V. All rights reserved.
Keywords: Early diagenesis; Calcite cement; Alluvial fan; Mn and Fe oxides; Vallès-Penedès half-graben
1. Introduction
Diagenetic alterations of alluvial sediments have
been studied from different points of view: carbonate
cementation (Lattman, 1973; De Ros et al., 1994),
iron oxides remobilisation (Buurman, 1980; Pipujol
and Buurman, 1994, 1997), and clay diagenesis
(Inglès et al., 1998; Calvo et al., 1999; Pimentel,
2002). The occurrence of these alterations depends
on three main factors: the mineralogy of the sedi-
ments, the diagenetic environment and the chemistry
of the fluids (Morad et al., 2000). During early dia-
genesis of alluvial sediments these three factors are
directly constrained by their distance from the source
area (proximal to distal sedimentary environments).
Few studies (Inglès et al., 1998; Pimentel, 2002) deal
with early diagenetic processes in relation to deposi-
tional environments in alluvial fans and lacustrine
deposits. The aim of this paper is to understand the
chemistry of the fluids which circulated through prox-
imal, medium and distal alluvial fan sandstones and
lacustrine limestones based on the geochemistry of
early authigenic calcite cements in order to produce a
qualitative model of fluid circulation and early calcite
cementation within an ideal alluvial fan.
2. Geological setting
The Catalan Coastal Ranges display a well-devel-
oped horst-and-graben structure acquired during the
late Oligocene–early Miocene opening of the North-
western Mediterranean (Roca and Guimerà, 1992;
Roca, 1994; Roca et al., 1999). The main extensional
structures are NE–SW and ENE–WSW trending faults
which split the area into three major blocks: the
Litoral range, the Vallès-Penedès half-graben and the
Prelitoral range (Fig. 1).
The Litoral and Prelitoral ranges are composed
of a Palaeozoic basement, made up of granites and
metamorphic rocks, that is unconformably overlain
by Mesozoic limestones and dolomites and detrital
(conglomerates, sandstones and mudstones with
abundant paleosoils) Cenozoic rocks in the Prelitoral
range (Fig. 1).
The Vallès-Penedès half-graben, approximately
100 km long and 10 to 14 km wide (Bartrina et
al., 1992), is mostly filled by terrigenous sediments
which have been divided into three lithostrati-
graphic complexes (Cabrera et al., 1991; Cabrera
and Calvet, 1996) (Fig. 1) that, from base to top,
are: (i) a lower continental complex of Aquita-
nian?–early Langhian age; (ii) a continental to ma-
rine complex of Langhian age, with reefal carbonate
platforms; and (iii) an upper continental complex of
middle Serravallian–Tortonian age.
The present study deals with the alluvial fan and
lacustrine deposits of the lower continental complex,
which have been divided from base to top (Cabrera,
1979) (Fig. 2) into: (i) Lower Detrital Unit, made up
of sandstones, conglomerates and breccias deposited
in proximal alluvial fan environments; (ii) Detrital-
Carbonatic Unit, consisting of clays and lacustrine
limestones deposited in distal alluvial fan environ-
ments; and (iii) Upper Detrital Unit, mainly consisting
of clays, sandstones and conglomerates deposited in
medium to distal alluvial fan environments.
3. Methods and analytical techniques
Three study areas near the cities of Rubı́, Martorell
and El Papiol (Fig. 1) were selected because of the
good exposure of the lower continental complex.
A total of 114 unweathered samples of sandstones
and limestones were collected from the three lithos-
tratigraphic units (Fig. 2). Modal compositions were
obtained by counting 500 points in 22 selected colour-
epoxy impregnated thin sections. Elemental composi-
tion of calcite cements was determined in 13 polished,
carbon-coated thin sections using a CAMECA model
SX-50 microprobe equipped with four vertically dis-
 D. Parcerisa et al. / Sedimentary Geology 178 (2005) 197–217 199

Fig. 1. Location, geological map and cross-section of the studied zone.

200 D. Parcerisa et al. / Sedimentary Geology 178 (2005) 197–217

Fig. 2. Regional stratigraphic section of the Burdigalian materials showing location of the studied samples.
 D. Parcerisa et al. / Sedimentary Geology 178 (2005) 197–217
played WD X-ray spectrometers. Operating condi-
tions were an accelerating voltage of 20 kV, a beam
current of 15 nA and a spot size of 10 Am. The
detection limits were 115 ppm for Mg, 380 ppm for
Mn, 200 ppm for Fe, 130 ppm for Na, and 165 ppm
for Sr. Analytical totals (97% to 103%) were normal-
ized to 100% for the purpose of comparison. Polished
thin sections containing calcite cements were exam-
ined with a Technosyn Cold Cathodoluminescence
Model 8200 MkII operating at 16–19 kV and 350
AA gun-current.
Finally, samples chosen for stable isotope analyses
were first examined with optical cathodoluminescence
microscope selecting those with one single generation
of calcite cement and b 1% of detrital carbonate. Only
eight samples accomplish these conditions. The small
size of the intergranular pores prevented microsam-
pling. Thus, the analyses presented here represent
bulk samples, where CO2 was extracted from the
amount of powdered bulk sample necessary to obtain
10 mg of calcite cement (established by point-count-
ing). Powdered samples were reacted with 103%
phosphoric acid for 10 min in vacuum at 90 8C. The
CO2 was analysed using a VG-Isotech SIRA IITM
mass spectrometer. Results were precise to F 0.02x
for y13C and F 0.12x for y18O. Results were cor-
rected using standard procedures (Craig and Gordon,
1965) and are expressed in per mil with respect to the
PDB standard.
4. Detrital composition and provenance of
sandstones
Sandstones are litharenites and sublitharenites in
all units (cf. Dott’s classification, 1964) with high
quartz and rock fragment contents (Table 1). Rock
fragments are mainly metamorphic, carbonatic and
plutonic. Feldspars, micas and other accessory frag-
ments occur in low percentages (Table 1).
4.1. Lower Detrital Unit
Sandstones of this unit are characterized by poor to
moderate sorting, with high matrix contents and sub-
angular grains (Table 1). Matrix is essentially ferrugi-
nous conferring to the sediment a characteristic red
colour.
201
The El Papiol area sandstones have a framework
consisting essentially of quartz and minor amounts
of metamorphic rock fragments (sublitharenites; Fig.
3). Siltite fragments, chert, feldspars and other ac-
cessory fragments (tourmaline and zircon) occur in
low percentages. In the Rubı́ area, sandstones present
large amounts of metamorphic or carbonatic rock
fragments (litharenites; Fig. 3) depending on the
stratigraphic layer (Table 1 and Fig. 2); quartz also
occurs in significant amounts. Mud intraclasts, feld-
spars and other accessory fragments (biotite and
muscovite) appear occasionally. In the Martorell
area, this unit is made up exclusively of breccia
deposits with high amounts of metamorphic rock
fragments.
The observed compositional variability in the sand-
stone framework reflects the original distribution of
the lithologies which cropped out in the Litoral range
during Burdigalian times (Parcerisa, 2002) and acted
as a source area during deposition of this Unit.
4.2. Detrital-Carbonatic Unit
Sandstone layers are very scarce in this unit due to
its distal depositional position. Consequently, the cal-
cite cements in limestones deposited in lacustrine
environments were analysed. These limestones are
mudstones and wackestones with ostracoda and
algae (characea) as their principal components. Moul-
dic and vug porosity, originated by gypsum dissolu-
tion (Cabrera, 1979; Anadón and Cabrera, 1986), and
fracture porosity are present.
4.3. Upper Detrital Unit
Sandstones located in this unit are moderate to well
sorted, with moderate matrix contents and subrounded
grains (Table 1). The decrease in ferruginous matrix
compared with the Lower Detrital Unit produces a
change from red to brick-orange colourations. Detrital
composition of the Upper Detrital Unit is similar in
Martorell and Rubı́ areas. Two compositional groups
can be distinguished:
- Lower part: sandstones of the lower part are made
up of metamorphic rock fragments and minor
amounts of quartz (litharenites plotted in the Q-
FR edge; Fig. 3). Feldspars, carbonatic rock frag-
 202
Table 1
Point count percentages of the Burdigalian Vallès sandstones calculated using the Gazzi–Dickinson’s method (Ingersoll et al., 1984)
Unit Lower Detrital Unit Upper Detrital Unit (lower part) Upper Detrital Unit (upper part)

El Papiol Rubı́ Martorell Rubı́ Martorell Rubı́

Sample CP 1 CP 2 MC-1 MC-4 TS-2 TS-3 MC-11 MC-15 MC-21 CB-8 CB-9 CB-20 AT-12 AT-15 AT-28 LC-7 MC-25 MC-28 MC-30 MC-33 MP-3 MP-6

Detrital components 85.4 66.0 92.0 89.8 91.1 92.2 95.4 96.9 86.9 85.0 87.5 88.0 75.2 72.8 87.4 79.9 73.7 74.6 83.6 81.4 77.6 70.7
Quartz 40.7 31.4 16.6 13.0 30.2 21.8 16.4 18.6 19.8 30.7 35.2 24.0 37.1 37.0 31.8 30.0 28.3 29.7 22.4 37.3 33.7 36.4
K feldspar – – – – – – – – 1.0 8.9 6.9 3.9 8.9 7.5 8.9 10.5 8.0 10.7 6.0 9.6 9.1 10.7
Plagioclase – 0.2 0.2 – – 0.2 – 0.2 0.6 3.3 2.6 1.2 1.8 1.8 3.6 2.6 1.0 1.5 0.5 1.3 3.6 1.8

D. Parcerisa et al. / Sedimentary Geology 178 (2005) 197–217

Chert 0.6 0.2 – – – – – 0.7 – 0.6 – 0.6 – 0.4 1.2 0.6 0.6 – 0.5 0.7 0.6 0.6
Metamorphic fragment 2.6 3.4 49.6 8.2 38.5 41.5 51.1 44.4 36.0 17.5 20.4 18.7 14.9 15.4 12.8 16.4 22.2 15.8 9.4 19.3 14.9 11.7
Plutonic fragment – – 0.8 – – – – – – 0.2 0.2 0.4 0.6 0.6 1.6 0.2 – – 0.5 0.4 – –
Siltite fragment – 1.6 – – – – – – – – – – – – – – – – – – – -
Carbonatic fragment – – 1.4 48.7 0.2 1.0 – 1.3 1.6 2.0 0.8 1.6 2.6 2.2 1.8 4.7 1.2 0.9 5.0 0.2 7.9 5.7
Bioclast – – – – – – – – – – – – – – – – – – – – – –
Mud intraclast – – – 2.4 – 2.0 – – 1.4 – – 4.7 – – – 0.2 – – – 0.2 – –
Accessory 0.6 1.1 3.7 1.6 1.6 2.0 2.2 0.2 4.9 2.4 0.8 4.1 2.6 1.6 2.8 3.2 3.8 4.3 2.2 3.9 5.6 2.2
Siliciclastic matrix 8.9 4.1 1.0 1.6 – 3.6 5.0 7.6 5.9 19.3 1.0 7.1 6.7 0.6 4.2 4.5 3.6 3.0 37.1 1.1 1.8 1.2
Ferruginous matrix 32.0 23.9 18.8 14.2 20.6 20.2 20.6 23.8 15.5 – 19.8 21.7 – 5.7 18.8 7.1 5.0 8.6 – 7.3 0.4 0.2
Total diagenetics 13.8 33.5 7.8 9.4 8.9 6.6 3.9 2.9 12.9 15.0 11.5 12.0 24.6 24.4 12.6 15.4 25.5 18.6 16.2 13.6 22.0 28.9
Pseudomatrix – – 1.8 1.0 0.6 1.0 0.9 0.2 1.0 0.6 1.0 2.0 2.6 0.4 – 1.4 3.4 0.8 5.5 2.7 1.2 0.6
Clay in K feldspar – – 0.4 – – – – – – 0.6 0.4 0.2 0.6 0.8 1.6 1.2 0.4 – – 0.9 0.2 0.4
Kaolinite in K feldspar – – 0.4 0.8 – – – – – – – – – – – – 0.2 0.4 – 0.2 – –
Spar calcite cement 8.9 10.3 4.9 7.6 8.3 5.4 0.2 2.6 11.0 13.6 10.1 9.6 21.4 22.8 – 12.8 20.4 17.5 10.4 9.6 20.6 26.9
Micrite calcite cement 4.9 23.2 – – – – 2.9 – – – – – – – 11.1 – – – – – – –
Intrag. calcite cement – – 0.4 – – 0.2 – – 0.4 0.2 – – – – – – 0.8 – 0.2 – – 1.0
Barite cement – – – – – – – – 0.4 – – 0.2 – 0.4 – – 0.2 – – – – –
Porosity 0.8 0.5 0.2 0.8 – 1.2 0.7 0.2 0.2 – 1.0 – 0.2 2.8 – 4.7 0.8 6.8 0.2 5.0 0.4 0.4
Intergranular 0.4 0.2 – 0.8 – 1.2 0.2 0.2 0.2 – 1.0 – – 2.8 – 4.7 0.6 6.6 – 5.0 0.4 0.4
Intragranular – 0.2 – – – – 0.4 – – – – – – – – – 0.2 0.2 – – – –
Fracture 0.4 – 0.2 – – – – – – – – – 0.2 – – – – – 0.2 – – –
Granular volume 44.5 38.3 73.4 74.7 70.6 68.7 70.2 65.5 65.8 66.5 67.2 59.4 69.0 67.3 66.0 69.4 66.7 63.5 46.8 74.3 75.6 70.6
Matrix 40.9 28.0 21.5 16.8 21.2 24.8 26.5 31.6 22.5 19.9 21.7 30.7 9.3 6.7 22.9 13.0 12.0 12.4 42.5 11.0 3.4 2.0
Primary porosity 0.4 0.2 – 0.8 – 1.2 0.2 0.2 0.2 – 1.0 – – 2.8 – 4.7 0.6 6.6 – 5.0 0.4 0.4
Secondary porosity 0.4 0.2 0.2 – – – – – – – – – 0.2 – – – – 0.2 0.2 – – –
Cemented 13.8 33.5 4.9 7.6 8.3 5.4 3.1 0.4 11.5 13.6 10.1 9.8 21.4 23.2 11.1 12.8 20.6 17.5 10.4 9.6 20.6 26.9
Intergranular volume 55.5 61.7 26.6 25.3 29.4 31.3 29.8 34.5 34.2 33.5 32.8 40.6 31.0 32.7 34.0 30.6 33.3 36.5 53.2 25.7 24.4 29.4
Granulometrya M-C M-C M-C M M-C M M M - C M M - Vc M-C M-C M M M - Vc M M M - C M M M F - M
Sortingb M P M M M P W M M P M P - M M M-W P M P - M M P M M M-W
Ternary plot Dott (1964)
Q 90.3 82.7 21.4 60.4 37.0 30.8 19.8 26.0 30.5 44.2 48.5 47.0 53.0 52.7 44.1 47.5 43.0 46.1 51.3 50.2 50.2 52.1
F – – – – – 0.3 – 0.4 1.8 13.3 10.9 9.2 13.2 13.2 14.1 18.7 12.3 17.9 12.5 11.4 16.7 17.0
Fr 9.7 17.3 78.6 39.6 63.0 68.9 80.2 73.7 67.7 42.5 40.6 43.8 33.9 34.1 41.8 33.8 44.7 36.0 36.3 38.4 33.1 30.8
a
Granulometry- F.: Fine, M.: Medium, C.: Coarse, Vc.: Very coarse.
b
Sorting- P.: Poor, M.: Moderate, W.: Well.
 D. Parcerisa et al. / Sedimentary Geology 178 (2005) 197–217
Fig. 3. Triangular plot showing modal composition of Burdigalian sandstones (Dott, 1964). L.D.U. (Lower Detrital Unit); D.C.U. (Detrital-
Carbonatic Unit); U.D.U. (Upper Detrital Unit).
ments, mud intraclasts and other accessory frag-
ments (biotite, chlorite, tourmaline and zircon) ap-
pear sporadically.
- Upper part: sandstones of the upper part undergo a
significant increase in their feldspar and quartz
contents, although their content in metamorphic
rock fragments is yet significant (litharenites; Fig.
3). Carbonatic rock fragments increase upwards, up
to 4% at the top of the section (Fig. 2). Chert,
plutonic rock fragments, mud intraclasts and other
accessory fragments (muscovite, biotite, chlorite,
tourmaline and zircon) occur in minor amounts.
This compositional change in the Upper Detrital
Unit is interpreted as a change in the location of
source areas (Parcerisa, 2002) from the Litoral range
in the lower part to the Prelitoral range in the upper
part. This change is very well marked in lutitic
layers by the appearance of smectite deriving from
the erosion of the Eocene paleosoils of the Ebro
basin and is probably related to a migration of the
tectonic activity towards the NW margin of the basin
(Parcerisa et al., 2002).
203
5. Calcite cement
Calcite occurs in primary pores (intergranular and
intragranular), locally in secondary pores resulting
from fracturing or evaporitic gypsum dissolution
(mouldic porosity), but cementation is rarely complete
and usually forms small, scattered aggregates as a
consequence of the high matrix contents that partially
occlude the intergranular volume (Table 1). Each one
of the three lithostratigraphic units of the lower con-
tinental complex is characterised by a distinctive cal-
cite cement (LD1, DC1 and UD1, respectively; Table
2). Locally, a second generation of calcite cement
occurs in the Lower Detrital Unit and in the Detri-
tal-Carbonatic Unit (LD2 and DC2, respectively;
Table 2).
5.1. Lower Detrital Unit
The first generation of calcite cement (LD1) fills
intergranular and mouldic porosity in sandstones of
this unit. This cement generally consists of 100 Am
thick subhedral non-luminescent or poorly-zoned
204 D. Parcerisa et al. / Sedimentary Geology 178 (2005) 197–217

Table 2
Petrological and geochemical features of the first generation of calcite cements (LD1, DC1 and UD1)
Petrology and cathodoluminiscence* Elemental composition Isotopic data
LD1 LD1 LD1
Sparitic and micritic Low Mg. Mean/Sample δ13C
cement filling intergranular, between 2128 and 800 ppm −7.4 ‰PDB
Low Mn. Mean/Sample 18O
mouldic and vug porosity
(sparite 100 µm aprox.). <482 ppm between −6.5 and
Non luminescent, Low Fe. Mean/Sample −6.2 ‰PDB
occasionally, zoned. <566 ppm
Rarely in coexistence Undetectable Sr.
predating a bright–orange Mean/Sample <d.l.
luminescent calcite Low Na. Mean/Sample <d.l.
cement (LD2).

DC1 DC1 DC1

Sparitic cement filling
intergranular, mouldic,
vug and fracture
porosity (50 to 200 µm
aprox.).
Dull orange luminescent.
Usually predating a
non-luminiscent/zoned
calcite cement (DC2).
Low Mg. Mean/Sample Not analysed
between 3725 and 1273 ppm
Variable Mn. Mean/Sample
between 3369 and 751 ppm
High Fe. Mean/Sample
between 4578 and 2354 ppm
Low Sr. Mean/Sample <355
ppm
Na not detectable.
Mean/Sample <d.l.

UD1 UD1 UD1

Sparitic cement filling
intergranular porosity
(100 µm aprox.).
Brigth–orange
luminescent.
Low Mg. Mean/Sample δ13C
between 2087 and 913 ppm between −7.9 and
High Mn. Mean/Sample −6.4 ‰PDB
between 7395 and 2685 ppm 18
O
Low Fe. Mean/Sample <d.l. between −10.5 and
Low Sr. Mean/Sample −8.6 ‰PDB
<278 ppm
Undetectable Na.
Mean/Sample <d.l.

*XPL image (left) and cathodoluminescence image (right). Bar scale = 200 Am.

crystals, although it can be micritic in samples with 5.2. Detrital-Carbonatic Unit

high matrix contents (Table 2). Geochemically, LD1
cement is characterised by low trace element con-
tents: Mg content from below the detection limit
(bd.l.) to 5188 ppm, very low Mn, Fe, Sr and Na
content (Table 3). Two analysed samples show
y18O values ranging between 6.5 and
xPDB and y13C values of 7.4xPDB (Table 3
and Fig. 4). Occasionally, LD1 cement is post-
dated by a bright-orange luminescent calcite ce-
ment (LD2 in Table 2) that fills mouldic residual
porosity.
Calcite cement in limestones of this unit (DC1) fills
secondary porosity (mouldic and fracture porosity)
and consists of 50 Am thick subhedral dull-orange
luminescent crystals (Table 2). DC1 cement has a
6.2 high Fe content (between 1233 and 7772 ppm) and
a variable but usually high Mn content (between 303
and 7252 ppm) causing its dull-orange luminescence
(Hemming et al., 1989). Mg content varies between
698 and 13,085 ppm and Sr and Na contents are very
low. Isotope data were not analysed in DC1 cement
 D. Parcerisa et al. / Sedimentary Geology 178 (2005) 197–217
due to technical difficulties in separating the authi-
genic calcite from the host limestone. Locally, this
cement is post-dated by a non-luminescent or zoned
calcite cement that fills residual mouldic porosity
(DC2 in Table 2).
5.3. Upper Detrital Unit
Calcite cement in sandstones of this unit (UD1)
occurs in intergranular porosity and is made up of 100
Am thick subhedral to euhedral bright-orange lumi-
nescent crystals (Table 2). UD1 cement shows a high
Mn content (from below the detection limit to 17437
ppm) and low contents in Fe, Sr and Na (Table 3). Mg
content ranges from below the detection limit to 6240
ppm. The high Mn content of UD1 calcite cement is
responsible for its bright-orange luminescence (Hem-
ming et al., 1989). Six samples were analysed for
isotope data (Table 3 and Fig. 4) showing y18O values
between 10.5 and 8.7xPDB and y13C values be-
tween 7.9 and 6.4xPDB.
6. Chemical composition of calcite cementing fluids
Using McIntire’s (1963) distribution coefficient
equation, the elemental composition of fluids from
which calcite precipitated can be inferred from the
chemical composition of the carbonate (i.e. Banner
and Hanson, 1990; Travé et al., 1997, 1998).
The Mn / Ca ratio of the precipitating fluid was
calculated using a distribution coefficient K Mn = 8
(Dromgoole and Walter, 1990). Results are shown in
Table 4 and Fig. 5. Each type of calcite cement has a
distinctive Mn content, hence calculations on Mn / Ca
ratios permitted us to distinguish three different fluids
that hereafter will be called: A, B and C. Fluid A had
low Mn / Ca ratios (most of them below the detection
limit); fluid B had high Mn / Ca ratios (mean values
between 0.0006 and 0.0017); and fluid C had inter-
mediate Mn / Ca ratios (mean values between 0.0002
and 0.0008).
The Ca / Fe ratio of the precipitating fluid was
calculated using a distribution coefficient K Fe = 5
(Dromgoole and Walter, 1990). Results are shown in
Table 4 and Fig. 5. As in the Mn / Ca ratio, every type
of calcite cement has a distinctive Fe content. Fluid A
had high Ca / Fe ratios (mean values above 2935 if
205
they are not below the detection limit) indicating low
Fe contents; fluid B had mostly Fe contents below the
detection limit, hence mean values in Ca / Fe were not
assessable; and fluid C showed low Ca / Fe values
(below 2223) indicating higher Fe contents than fluids
A and B.
The Mg / Ca distribution coefficient strongly
depends on the temperature of the precipitating
fluid. Experimentally, different distribution coeffi-
cients have been calculated at different temperatures,
for example, Mucci and Morse (1983) and Mucci
(1987) obtained K Mg = 0.012 and 0.028 for 25 8C
and 40 8C, respectively, and Katz (1973) calculated
a K Mg = 0.1163 for 90 8C. In accordance with the low
temperatures expected for the studied calcite cements,
the Mg / Ca ratio was calculated using a distribution
coefficient K Mg = 0.012. Calculated Mg / Ca ratios
(Fig. 5 and Table 4) show that fluids which circulated
through the Detrital-Carbonatic Unit (fluids A and C)
had higher Mg / Ca ratios (mean values between 0.446
and 1.318) than the others (mean values always below
0.863).
The Sr / Ca ratio of the precipitating fluid was
calculated using a distribution coefficient K Sr = 0.06
(Kinsman, 1969; Katz et al., 1972; Pingitore and
Eastman, 1986; Stoessel et al., 1987). Results are
shown in Table 4 and Fig. 5 and are very similar to
those of the Mg / Ca ratio with high Sr / Ca ratios for
samples related to the Detrital-Carbonatic Unit (mean
values usually above 0.004).
Summarising, three different fluids were identified
from elemental analysis of early calcite cements: fluid
A with a low Mn / Ca ratio and a high Ca / Fe ratio;
fluid B with both high Mn / Ca and Ca / Fe ratios; and
fluid C with both low Mn / Ca and Ca / Fe ratios. All
three fluids had low Mg / Ca and Sr / Ca ratios, al-
though these ratios are slightly higher in those fluids
that precipitated the calcite cements of the Detrital-
Carbonatic Unit.
7. Other authigenic minerals
Gypsum occurs as coarse-crystalline nodules fill-
ing fractures in mudstones and limestones of the
Detrital-Carbonatic Unit. Frequently, nodules are dis-
solved and form secondary mouldic porosity which
may be filled by calcite cement.
Table 3

206
Trace element content and isotopic values of calcite cements in Burdigalian materials
Sample Mg Ca Mn Fe Sr Na y13CxPDB and
(ppm) (ppm) (ppm) (ppm) (ppm) (ppm) y18OxPDB
L.D.U. El Papiol FR-4 (n = 71) LD1 Mean F Std. Dev. 800 F 501 397401 F 3783 bd.l. bd.l. bd.l. b d.l. Sample CP-1 7.4
Maximum 1850 404816 4069 1865 313 233 and 6.5 Sample
Minimum b d.l. 388853 bd.l. bd.l. bd.l. b d.l. CP-2 7.4 and 6.2
Rubı́ L.D.U. MC-3 (n = 49) LD1 Mean F Std. Dev. 1148 F 651 397406 F 3261 bd.l. 234 F 349 bd.l. b d.l. Not analysed
Maximum 2862 409274 2880 1714 195 179
Minimum 131 392022 bd.l. bd.l. bd.l. b d.l.
MC-4 (n = 15) LD1 Mean F Std. Dev. 2128 F 1391 396158 F 3686 482 F 2224 566 F 547 bd.l. b d.l.
Maximum 5188 403707 8728 1543 bd.l. 218
Minimum 365 391812 bd.l. bd.l. bd.l. b d.l.
D.C.U. MC-6 (n = 53) DC1 Mean F Std. Dev. 3725 F 1523 393341 F 4858 3369 F 1755 4578 F 1512 355 F 391 b d.l. Not analysed

D. Parcerisa et al. / Sedimentary Geology 178 (2005) 197–217

Maximum 6510 404456 7252 7772 1663 125
Minimum 698 379085 1312 2222 bd.l. b d.l.
MC-6 (n = 4) Mean F Std. Dev. 3589 F 1539 395617 F 4626 394 F 301 471 F1032 2620 F 1513 794 F 389
Ostracode shell Maximum 5250 400346 957 2469 3373 986
Minimum 1737 389507 302 294 bd.l. b d.l.
U.D.U. MC-24 (n = 33) UD1 Mean F Std. Dev. 1321 F 642 404363 F 3865 7396 F 3072 bd.l. 207 F 158 b d.l. Lower part Sample
(U. part) Maximum 2757 409786 13791 686 460 243 MC-18 7.9 and
Minimum b d.l. 397579 bd.l. bd.l. bd.l. b d.l. 9.4 Sample MC-21
MC-32 (n = 49) UD1 Mean F Std. Dev. 1582 F 717 400007 F 3314 6373 F 3785 bd.l. bd.l. b d.l. 7.7 and 10.5
Maximum 2765 405218 17437 530 437 207 Upper part Sample
Minimum b d.l. 391376 bd.l. bd.l. bd.l. b d.l. MC-26 7.0 and
MP-2 (n = 74) UD1 Mean F Std. Dev. 1197 F 717 400418 F 2660 4130 F 1530 bd.l. 176 F 190 b d.l. 8.7 Sample MC-32
Maximum 4859 408498 8340 820 1187 193 6.9 and 9.9
Minimum b d.l. 394777 bd.l. bd.l. bd.l. b d.l.
Martorell L.D.U. TT-1 (n = 72) LD2 Mean F Std. Dev. 2474 F 1387 391575 F 6291 8244 F 2775 319 F 187 bd.l. b d.l. Not analysed
Maximum 5861 403599 14280 1131 554 270
Minimum 337 374400 3772 bd.l. bd.l. b d.l.
D.C.U. CB-15a (n = 28) DC1 Mean F Std. Dev. 1273 F 2260 393775 F 5568 751 F 225 2354 F 528 215 F 223 b d.l. Not analysed
Maximum 13085 405458 1243 3264 929 200
Minimum 732 374339 303 1233 bd.l. b d.l.
CB-15b (n = 22) DC2 Mean F Std. Dev. 2591 F1069 394059 F 4390 bd.l. bd.l. 471 F 300 b d.l.
Maximum 6166 403527 3538 773 1102 284
Minimum 1018 386672 bd.l. bd.l. bd.l. b d.l.
CB-6 (n = 63) DC2 Mean F Std. Dev. 2691 F 904 395087 F 4148 355 F 207 582 F 182 bd.l. b d.l.
Maximum 5305 407266 708 999 503 252
Minimum 994 379046 bd.l. bd.l. bd.l. b d.l.
U.D.U. CB-9 (n = 80) UD1 Mean F Std. Dev. 1007 F 782 390024 F 4026 4589 F 2023 bd.l. 156 F 158 b d.l. Lower part Sample
(U. part) Maximum 6240 407039 11183 478 636 226 TS-2 7.2 and
Minimum b d.l. 380326 bd.l. bd.l. bd.l. b d.l. 9.9 Upper part
AT-4 (n = 54) UD1 Mean F Std. Dev. 2087 F 674 392736 F 4621 6887 F 1609 bd.l. 248 F 186 b d.l. Sample CB-7 6.4
Maximum 3177 402763 10065 6837 644 222 and 9.0
Minimum 477 384899 2963 bd.l. bd.l. b d.l.
LC-2 (n = 60) UD1 Mean F Std. Dev. 913 F 410 398769 F 2794 2685 F 1040 bd.l. 278 F 177 b d.l.
Maximum 1747 405983 5467 311 621 188
Minimum b d.l. 392379 bd.l. bd.l. bd.l. b d.l.
L.D.U. (Lower Detrital Unit); D.C.U. (Detrital-Carbonatic Unit); U.D.U. (Upper Detrital Unit).
 D. Parcerisa et al. / Sedimentary Geology 178 (2005) 197–217
Fig. 4. Diagram showing y18O and y13C data (xPDB) for first generation of calcite cements in Lower Detrital Unit and in Upper Detrital Unit.
Barite occurs as small, disseminated crystals filling
primary intergranular porosity of the Upper Detrital
Unit. Barite crystals are subhedral and 100 to 150 Am
thick. Although it is difficult to assess its contempor-
arity, this cement is always associated with calcite
cement.
Clay minerals appear as partial or total replacement
of detrital feldspars. Sometimes, these clay minerals
comprise numerous stacked pseudohexagonal crystals
that often develop into vermicular aggregates and are
interpreted to be kaolinite.
8. Discussion
8.1. Timing of calcite precipitation
The relationships between the studied calcite
cements and the different structural elements affecting
the Burdigalian sandstones (folds and fractures) allow
us to reconstruct the chronology of calcite cement
precipitation.
The alluvial fan deposits of the Lower Detrital Unit
are affected by N–S trending, nearly vertical, exten-
sional fractures filled by two generations of calcite
cements (Travé and Calvet, 2001). These calcite
207
cements filling fractures are affected by horizontal
slikensides formed during the Langhian–Serravallian
NNW–SSE compression (Travé and Calvet, 2001).
The non luminescent character of the first calcite
cement filling these fractures, as well as its geochem-
istry, with y18O values ranging from 9.0 to
5.2xPDB, y13C values varying from 9.3 to
6.7xPDB, relatively high values of Mg and variable
values of Mn, Sr and Fe (Travé and Calvet, 2001), are
similar to the geochemical characters of the LD1
cement. These similarities can indicate that LD1 ce-
ment within the host sandstone may have precipitated
synchronously with the first calcite cement within
fractures from the same fluid and, therefore, LD1
cement precipitated at shallow burial depth, during
the early diagenesis prior to Langhian–Serravallian
times.
On the other hand, the alluvial fan deposits of the
Upper Detrital Unit are affected by predominantly
NE–SW and NW–SE oriented normal faults filled
by calcite and barite cements, by a crack-seal mech-
anism and tilted during the Messinian compressive
deformation that uplifted and folded the basin sedi-
ments (Travé et al., in press). The crack-seal mecha-
nism observed in calcite veins filling these fractures
indicates that cement precipitation occurred synchro-
208 D. Parcerisa et al. / Sedimentary Geology 178 (2005) 197–217

Table 4
a. Mn / Ca and Ca / Fe ratios of fluids that precipitated calcite cements in the Burdigalian materials
Unit Sample Fluid Mn / Ca Ca / Fe
Mean F Std. Dev. Maximum Minimum Mean F Std. Dev. Maximum Minimum
L.D.U. Papiol FR-4 A – 0.0009 – – 17763 –
Rubı́ L.D.U. MC-3 A – 0.0007 – 9630 F 6094 27774 –
MC-4 A 0.0001 F 0.0005 0.0020 – 2935 F 4465 16262 –
D.C.C. MC-6 C 0.0008 F 0.0004 0.0017 0.0003 592 F 230 1255 348
U.D.U. MC-24 B 0.0017 F 0.0007 0.0032 – – 14333 –
MC-32 B 0.0015 F 0.0009 0.0041 – – 15706 –
MP-2 B 0.0009 F 0.0003 0.0019 – – 17157 –
Martorell L.D.U. TT-1 B 0.0019 F 0.0007 0.0034 0.0009 7741 F 3999 16496 –
D.C.C. CB-15a C 0.0002 F 0.0001 0.0003 0.0001 1163 F 321 2223 833
CB-15b A – 0.0008 – – 13548 –
CB-6 A 0.0001 F 0.0000 0.0002 – 4701 F1576 10095 –
U.D.U. CB-9 B 0.0011 F 0.0005 0.0027 – – 16923 –
AT-4 B 0.0015 F 0.0004 0.0023 0.0007 – 17133 –
LC-2 B 0.0006 F 0.0002 0.0013 – – 16623 –

b. Mg / Ca and Sr / Ca ratios of fluids that precipitated calcite cements in the Burdigalian materials
Unit Sample Fluid Mg / Ca Sr / Ca
Mean F Std. Dev. Maximum Minimum Mean F Std. Dev. Maximum Minimum
L.D.U. Papiol FR-4 A 0.281 F 0.174 0.649 – – 0.006 –
Rubı́ L.D.U. MC-3 A 0.397 F 0.223 0.989 0.048 – 0.004 –
MC-4 A 0.737 F 0.485 1.802 0.129 – bl.d. –
D.C.C. MC-6 C 1.318 F 0.542 2.297 0.232 0.007 F 0.007 0.032 –
U.D.U. MC-24 B 0.456 F 0.223 0.950 – 0.004 F 0.003 0.009 –
MC-32 B 0.533 F 0.252 0.959 – – 0.008 –
MP-2 B 0.407 F 0.252 1.667 – 0.003 F 0.004 0.023 –
Martorell L.D.U. TT-1 B 0.863 F 0.504 2.093 0.116 – 0.011 –
D.C.C. CB-15a C 0.446 F 0.824 4.797 0.252 0.004 F 0.004 0.018 –
CB-15b A 0.901 F 0.378 2.181 0.349 0.009 F 0.006 0.021 –
CB-6 A 0.930 F 0.320 1.870 0.349 – 0.010 –
U.D.U. CB-9 B 0.349 F 0.271 2.190 – 0.003 F 0.003 0.012 –
AT-4 B 0.727 F 0.2 32 1.105 0.165 0.005 F 0.004 0.012 –
LC-2 B 0.310 F 0.145 0.611 – 0.005 F 0.003 0.012 –
L.D.U. (Lower Detrital Unit); D.C.U. (Detrital-Carbonatic Unit); U.D.U. (Upper Detrital Unit). Elemental ratio not measurable if trace element
content bd.l.

nously to fracture development and, therefore, prior to
the Messinian compressive deformation.
Calcite cements filling these fractures show a
bright-orange luminescence and are characterised by
y18O values ranging from 14.9 to 11.7xPDB,
y13C values ranging from 7.2 to 6.6xPDB and
up to 29325 ppm of Mn content (Travé et al., in
press). The bright-orange luminescence, the lowest
range of y18O values and the highest values of Mn
are also common features in the UD1 calcite cement
within the host sandstone indicating that they could
have precipitated synchronously from the same fluid
and, therefore, during the early diagenesis, prior to the
Messinian compression.
According to all these data, the first calcite
cement precipitation within the host Burdigalian
sandstones (LD1, UD1 and, probably, DC1) oc-
curred at shallow burial depth during the early
diagenesis. Variations on the cement composition
between the Lower Detrital Unit, the Detrital-Car-
bonatic Unit and the Upper Detrital Unit are thus
attributed to spatial variations in the geochemical
composition of the meteoric water. LD2 and DC2
cements post-date LD1 and DC1 cements, respec-
 D. Parcerisa et al. / Sedimentary Geology 178 (2005) 197–217 209

Fig. 5. Elemental ratios (MMe / MCa) calculated for fluids which precipitated calcite cements. Symbols not plotted in the diagram correspond to
values below the detection limit (d.l.). L.D.U. (Lower Detrital Unit); D.C.U. (Detrital-Carbonatic Unit); U.D.U. (Upper Detrital Unit).
210 D. Parcerisa et al. / Sedimentary Geology 178 (2005) 197–217
tively, but the time of precipitation cannot be further
constrained.
8.2. Geochemical evolution of the precipitating fluids
As has been discussed in the previous chapter,
precipitation of the calcite cement mainly took place
during an early diagenetic stage at shallow depths
and related with the sedimentary environments. In
this context, fluids related with sedimentary environ-
ments would have acquired an important role in
diagenesis. Detrital components in the Burdigalian
sandstones of the Vallès-Penedès half-graben may
vary between different units and areas (Table 1),
but mineralogically these sandstones are quite homo-
geneous and are essentially made up of silicate
minerals. In contrast, the high carbonate contents
of the Detrital-Carbonatic Unit could have promoted
variations in the geochemistry of fluids precipitating
calcite cements in this unit.
The petrology and geochemistry of calcite cements
in the studied units allow us to discuss their formation.
Petrology and cathodoluminescence have permitted us
to distinguish three different types of early calcite
cements (LD1, DC1 and UD1 in Table 2), every one
of them with a characteristic geochemistry. The Mn,
Fe, Ca, Sr and Mg content and the isotopic data are
used to characterize these cements and the fluids from
which they precipitated (fluids A, B and C) (Figs. 5, 6
and 7 and Tables 3 and 4).
A first approach to diagenetic fluid evolution can
be carried out using Mn–Fe ratios (i.e. Barnaby and
Rimstidt, 1989; Travé et al., 2000). These two ele-
ments either remain diluted in fluids or form minerals
depending on pH, Eh, aO2 and aH2S variations (Ber-
ner, 1981). Assuming that precipitation occurs in
equilibrium, these variations will be reflected in Mn
and Fe calcite contents (Curtis and Coleman, 1986).
In the studied Burdigalian sandstones the three types
of calcite cements have distinctive Mn–Fe ratios (Fig.
6), deriving from fluids with different Mn and Fe
contents, thus:
– Fluid A: Mn and Fe not diluted in very oxidizing
fluids precipitating in form of oxides (A in Fig. 7).
Calcite with low Mn and Fe contents (LD1) prob-
ably precipitated from a very oxidizing fluid with
low Mn and Fe contents.
– Fluid B: fluids in transitional oxidizing-reducing
conditions precipitate Fe oxides but dilute Mn oxi-
des and are enriched in this element (B in Fig. 7).
Calcite with high Mn contents and low Fe contents
(UD1) probably precipitated from a transitional
oxidizing-reducing fluid with high Mn contents.
– Fluid C: more reducing fluids dilute Mn and Fe
oxides and have high Mn and Fe contents (C in
Fig. 7). Calcite with high Fe and Mn contents
(DC1) probably precipitated from a more reducing
fluid than fluids A and B.
On the other hand, Mg and Sr enrichment in fluids
circulating through Detrital Carbonatic Complex is
probably related to exchange reactions between fluids
and the host limestones of this unit. Na content of
calcite cements is always below the detection limit
(Table 3). Chemical data calculated for fluids that pre-
cipitated calcite cements in the Burdigalian sandstones
are in agreement with chemical features of meteoric
waters (cf. Véizer, 1983; Tucker and Wright, 1990).
y13C and y18O values give complementary data
regarding the fluids that precipitated the calcite
cements. All analysed samples have negative and
very similar y13C values (between 7.9 and
6.4xPDB) which agree with calcites precipitated
from meteoric waters (Fig. 4 and Table 3). In shallow
meteoric environments these y13C values probably
indicate the influence of organic carbon deriving
from soils (Cerling, 1984; Morad et al., 1998; Garcia
et al., 1998; Travé and Calvet, 2001).
y18O values between 6.5 and 6.2xPDB char-
acterise the first generation of calcite cement (LD1) in
the Lower Detrital Unit whereas values between
10.5 and 8.7xPDB characterise the first genera-
tion of calcite cement (UD1) in the Upper Detrital
Unit (Fig. 4). Depletion in y18O values of UD1 ce-
ment in the Upper Detrital Unit is possibly due to two
main factors:
– An increase in the residence time of meteoric waters
in sediment which favours exchange reactions bet-
ween fluids and host rocks (Banner and Hanson,
1990; Andrews et al., 1993, 1994; Parente et al.,
1998). This option also agrees with the Mn enrich-
ment of calcite cements of the Upper Detrital Unit.
– A migration of the catchment areas from the Litoral
to the Prelitoral range. In the studied zone, the
 D. Parcerisa et al. / Sedimentary Geology 178 (2005) 197–217
Fig. 6. Mn / Fe ratios calculated for different calcite cements in samples of (A) Lower Detrital Unit, (B) Detrital-Carbonatic Unit and (C) Upper
Detrital Unit.
Prelitoral range would rise 1000 m with respect to
the Litoral range causing a depletion of 3x in y18O
values (cf. Cruz-San Julián et al., 1992; Zamarreño
et al., 1997). However, this hypothesis is only
suitable for calcite cements occurring in the upper
part of the Upper Detrital Unit, since a migration of
the source areas from Litoral to Prelitoral range has
been identified in this unit (see Detrital composi-
tion and provenance of sandstones).
A change to a hotter and wetter climate (Gasse et
al., 1998) and/or fractionation processes due to tem-
perature (Craig and Gordon, 1965; Friedman and
OTNeil, 1977) are not discarded as features also play-
ing a minor role.
There exists no data regarding the relationships
between the fluids that precipitated the first generation
(LD1, DC1 and UD1) and the second generation of
calcite cements (LD2 and DC2). LD2 calcite cement
is rich in Mn (Table 3 and Fig. 6) coming from a
transitional oxidizing–reducing fluid with high Mn
contents; DC2 calcite cement has low Fe and Mn
contents (Table 3 and Fig. 6) deriving from a very
oxidizing fluid with low Mn and Fe contents. Isotopic
analysis was not applied due to the local occurrence of
LD2 and DC2 calcite cements.
8.3. Precipitation of other cements
Other authigenic mineralogies occurring in the
Burdigalian materials are gypsum, kaolinite and
211
barite, but they are very scarce in sandstones
(Table 1).
Gypsum occurs in the Detrital-Carbonatic Unit
related to the evaporitic lacustrine environment
established during its sedimentation (Anadón and
Cabrera, 1986). Primary gypsum dissolution promo-
ted precipitation of secondary fibrous gypsum in
fractures.
Hydrolysis reactions cause transformation of detri-
tal feldspars to clay mineral aggregates. These trans-
formations are usually interpreted as a result of early
diagenetic processes due to meteoric fluids (Morad et
al., 1994, 1998).
Discrete barite cementations are also interpreted as
early diagenetic processes (Morad et al., 1995;
Mátyás, 1998), although the geochemical processes
which controlled the precipitation are unclear.
8.4. Source of authigenic ions
The main sources for Ca, Mg and CO2 are (i)
extrabasinal, with Ca and Mg deriving from reactions
between meteoric waters and rocks in the catchment
areas and CO2 deriving from the biomass and the
atmosphere (Cerling, 1984), and (ii) intrabasinal,
with Ca and Mg deriving from reactions between
meteoric waters and lacustrine limestones of the De-
trital-Carbonatic Unit and CO2 also deriving from the
biomass and the atmosphere (Cerling, 1984). The
influence of an intrabasinal source of Mg is supported
by the enrichment in Mg of calcite cements in Detri-
212 D. Parcerisa et al. / Sedimentary Geology 178 (2005) 197–217
Fig. 7. Stability diagram for Mn and Fe depending on the pH and Eh of waters (cf. Quinby-Hunt and Wilde, 1996).
tal-Carbonatic Unit coinciding with the presence of
ostracode shells enriched in this element (Table 3).
Other significant elements involved in calcite
precipitation are Fe and Mn. Alteration of phyllites
and granitoids can be an extrabasinal source for Fe
and Mn, whereas dissolution of the ferruginous
matrix of the red bed deposits can be an intrabasinal
source for Fe and Mn. FRX data show that Burdi-
galian red bed deposits have higher amounts of Fe
and Mn (Parcerisa, 2002) than phyllites and grani-
toids of the source area. Moreover, the distribution
of blue decolourations of the red beds along the
stratigraphic section points also to an intrabasinal
origin of Fe and Mn. Buurman (1980) relates the
abundance of these structures in sediments with the
geochemistry of circulating fluids (more blue deco-
louration structures in more reducing environments).
In the studied Burdigalian materials the geochemis-
try of fluids which precipitated calcite cements is in
agreement with Buurman’s (1980) hypothesis. Thus,
blue decolourations are absent in sandstones cemen-
ted by calcite with low Fe and Mn contents (very
oxidizing environments). Sandstones cemented by
Mn-rich calcite (transitional oxidizing to reducing
conditions) are characterized by a small number of
blue decolouration structures while sandstones and
limestones cemented by Fe and Mn-rich calcite
(more reducing environments) contain abundant
blue decolouration structures, sometimes arranged
in hydromorphic soils (Fig. 2).
Na and Sr are very scarce throughout the calcite
cements. The small amounts of Sr probably derived
from ostracode shells within lacustrine limestones of
the Detrital Carbonatic Unit (Table 3).
Sulphate ions involved in primary gypsum precip-
itation in the Detrital-Carbonatic Unit are related to
 D. Parcerisa et al. / Sedimentary Geology 178 (2005) 197–217
the evaporation process reached in the lacustrine en-
vironment. These sulphate ions were remobilized
from the primary gypsum to precipitate secondary
gypsum in the Detrital-Carbonatic Unit and barite in
the Upper Detrital Unit. Ba ions needed for barite
precipitation may derive from replacement of detrital
feldspars by clays and/or from dissolution of Mn
oxides of the ferruginous matrix, since Mn oxides
are often enriched in Ba (Vaniman et al., 2002; Nea-
man et al., 2004).
8.5. Cementation model
Two different calcite cementation stages occurred
in the Burdigalian Vallès-Penedès materials. During
the first stage, intergranular primary porosity of sand-
stones and mouldic secondary porosity of limestones
was thoroughly filled; in the second stage, residual
porosity was occasionally filled.
The first stage of calcite cementation was con-
trolled by the sedimentary environments where mete-
oric waters circulated (Fig. 8A and B). Thus, during
deposition of the Lower Detrital Unit (proximal allu-
vial environments), very oxidizing solute-poor waters
(fluid A) arrived from the adjacent highs and precip-
itated a solute-poor calcite (LD1). During Detrital-
Carbonatic Unit sedimentation (distal alluvial and
lacustrine environments), more reducing and evolved
waters (fluid C), enriched in Mn and Fe, precipitated a
Mn and Fe-rich calcite (DC1). Finally, during depo-
sition of the Upper Detrital Unit (medium to distal
alluvial environments), a migration of the catchment
areas to higher altitudes and an increase in the resi-
dence time of the waters resulted in a decrease in their
y18O values and their oxidizing conditions (fluid B).
As a result, these waters precipitated a Mn-rich and
y18O depleted calcite (UD1).
These geochemical changes of the early calcite
cement composition and related meteoric waters can
be used to construct a qualitative model of fluid flow
in an ideal alluvial fan (Fig. 8C). In proximal alluvial
fan environments, very oxidizing waters precipitated a
trace element-poor calcite without Fe and Mn oxides
remobilisation. In medium to distal alluvial fan envir-
onments the increase in the residence time of the
meteoric waters resulted in a depletion of their y18O
values and in a simultaneous decrease in their oxidiz-
ing state causing a discrete remobilisation of Mn
213
oxides and precipitating a Mn-rich calcite. Finally,
distal alluvial fan lacustrine environments were dom-
inated by more reducing waters causing a massive
remobilisation of Fe and Mn oxides and precipitating
a Mn and Fe-rich calcite.
A second stage of calcite cementation is locally
observed in sandstones of the Lower Detrital Unit and
in limestones of the Detrital-Carbonatic Unit. In the
Lower Detrital Unit this second stage is characterized
by a Mn-rich calcite (LD2) interpreted as the result of
an increase in the residence time of meteoric waters in
this unit. This increase in the residence time of pore
waters could be related to a decrease of permeability
as a consequence of first calcite cement precipitation
together with some compaction on this higher buried
setting. Conversely, in the Detrital-Carbonatic Unit
the second stage is characterised by a trace element-
poor calcite (DC2) interpreted as a tardive cementa-
tion due to circulation of oxidizing fluids.
9. Conclusions
Sandstone porosity of the Burdigalian alluvial fan
deposits was mainly occluded during early diagene-
sis. Geochemistry of early calcite cements in these
alluvial fan deposits is essentially governed by a
gradual change in the chemistry of meteoric waters
which circulated from proximal to distal alluvial fan
environments.
Residence time, Eh–pH conditions and host sedi-
ment–water interactions are quite different in proxi-
mal, medium-distal and distal-lacustrine alluvial fan
environments and control the chemistry of meteoric
waters. These chemical differences in waters are well
recorded in elemental and isotopic composition of
early calcite cements precipitating in these environ-
ments. Thus:
1. Interactions between waters and the host lime-
stones of distal-lacustrine environments account
for Mg and Sr input in calcite cements precipitating
in the Detrital-Carbonatic Unit (DC1 and DC2).
2. Eh–pH conditions control leaching of Mn and Fe
from the ferruginous matrix of sandstones and thus
account for Mn and Fe presence/absence in calcite
cements of Burdigalian sediments. The amount of
Fe and Mn in calcite cements can be correlated
214 D. Parcerisa et al. / Sedimentary Geology 178 (2005) 197–217

Fig. 8. Sketch representing meteoric water circulation during early calcite cement precipitation in Burdigalian sediments: (A) during
sedimentation of Lower Detrital Unit and Detrital-Carbonatic Unit; (B) during Upper Detrital Unit deposition; and (C) model for an ideal
alluvial fan.

with the abundance of blue decolourations in the
host rock. As a result, blue decolourations were
also formed during the early diagenesis.
3. y18O values of calcite cements are controlled by the
residence time of waters and, probably, by the
palaeotopography of the catchment areas from
where the meteoric waters comes. y13C values
depend on the interactions between meteoric
waters and organic matter from soils of the alluvial
fans and the catchment areas.
The observed spatial change in the chemical com-
position of the meteoric waters from proximal to distal
environments is proposed as a qualitative model of
fluid circulation and calcite precipitation in alluvial
fans.
 D. Parcerisa et al. / Sedimentary Geology 178 (2005) 197–217
Acknowledgments
This research was performed within the framework
of projects BTE2002-04453-C02-01 and CGL2004-
05816-C02-02 supported by Dirección General de
Enseñanza Superior e Investigación Cientı́fica of
Spain and Grup Consolidat de Recerca "Geologia
Sedimentària" 2001/SGR/75. M. Thiry and L. Cabrera
contributed to the discussion on the sandstone diagen-
esis and Burdigalian sedimentology of the Vallès area,
respectively. Helena Turner-Keizer, Bruce Sellwood,
Niaz Khalid and an anonymous reviewer contributed
to improve this paper with their helpful and construc-
tive remarks. We also thank Frances Luttikhuizen for
the revision of the English version. This paper is
dedicated to Francesc Calvet who passed away during
the process of this work leaving on us a deep personal
and professional imprint.
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