Marine and Petroleum Geology 18 (2001) 287306

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Diagenetic and oil migration history of the Kimmeridgian Ascla Formation, Maestrat Basin, Spain
C. Rossi a,*, R.H. Goldstein b, R. Marl a, R. Salas c, M.I. Benito d, A. Permanyer c, a a, M.A. Caja a J.A. de la Pen
a

a y Geoqu mica, Facultad de Ciencias Geolo gicas, Universidad Complutense, 28040 Madrid, Spain Departamento de Petrolog b Department of Geology, University of Kansas, Lawrence, KS 66045-7613, USA c mica, Universidad de Barcelona, 08028 Barcelona, Spain Departamento de Geoqu d a, Universidad Complutense, Madrid, Spain Departamento de Estratigraf Received 17 November 2000; received in revised form 14 January 2001; accepted 19 January 2001

Abstract The marine limestones of the Kimmeridgian Ascla Formation in the Maestrat Basin reached more than 3500 m in burial depth during the Cretaceous era. Despite containing organic-rich intervals, mature in parts of the basin, its potential as oil source-rock has been either overlooked or questioned. A petrographic, geochemical and uid-inclusion (FI) study of the cements of the Ascla was performed in order to unravel its diagenetic and thermal evolution. We particularly sought evidence of oil migration and its timing. Three sequences of cement were distinguished. Sequence 1 lls the primary porosity and began with Fe-poor calcites with geochemistry and FIs consistent with precipitation from marine-derived waters during shallow burial. These calcites were followed by burial cements, including ferroan calcite, dolomite, and minor celestite and barite. Sequence 2 consists of Mg-rich, fracture-lling calcite cement zones. The earlier ones are ferroan and contain primary aqueous and oil FIs with homogenization temperatures suggesting precipitation at temperatures as high as 1178C. Sequence 3 is dominated by fracture-lling calcites with geochemistry and FIs indicating precipitation at low temperatures (less than ,508C) from meteoric waters. Cross-cutting relationships with compressional microstructures indicate that Sequence 3 formed after the Eocene Oligocene tectonic inversion of the basin. Oil FIs in Sequence 2 provide evidence that light oils migrated through the Ascla Formation via fractures and microfractures. These oils were likely generated in the organic-rich marls of the basal part of the Ascla. The paragenetic sequence and burial history are consistent with oil generation when the Ascla was at or close to maximum burial depth, but before the Eocene Alpine tectonism, which likely formed the structural traps in the basin. Oil generation and migration occurred long before this event. Therefore, it is probable that early traps were breached by the Alpine structures and that potential in this basin sector is low. q 2001 Elsevier Science Ltd. All rights reserved.
Keywords: Burial diagenesis; Fluid inclusions; Oil migration

1. Introduction The Kimmeridgian Ascla Formation was deposited in open marine environments in the Salzedella sub-basin, which was the main depocenter of the Maestrat Basin (E Spain) (Fig. 1). This formation contains intervals of laminated marly limestones with enough organic matter to be considered as potential oil source rocks (Permanyer, Marl, a, Dorronsoro, & Rossi, 1999; Salas, 1989). The de la Pen source-rock potential of the Ascla was not recognized when the Maestrat basin and adjacent offshore areas were explored for hydrocarbons during the seventies. Onshore,
* Corresponding author. Fax: 134-91544-2535. E-mail address: crossi@eucmax.sim.ucm.es (C. Rossi).

exploration was unsuccessful. Offshore, in the Tarragona basin, several oil elds were discovered. Although most of the oils discovered in the Tarragona basin undoubtedly s, Algaba, originated from Miocene source rocks (Albaige Clavell, & Grimalt, 1986), the oil from Amposta eld, which is located only 40 km to the west of La Salzedella, has unique geochemical characteristics and is not correlated s et al., op. cit.). with the other oils (Albaige It has been postulated that the oil of the Amposta eld could have been generated from the Ascla Formation s et al. (Seifert, Carlson, & Moldowan, 1983). Albaige (1986) discarded the Ascla as a potential source for the Amposta oil, arguing that the Ascla (1) does not have source-rock potential, and (2) it was overmature for oil generation at the time of trap formation (the Miocene).

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Fig. 1. Simplied map of the Maestrat Basin (from Salas et al., 1995).

mpin, and Casson (1990), found that However, Seemann, Pu the Ascla Formation is still in the oil generation phase and has some residual oil generation potential in a nearby offshore well (Cenia-1). Moreover, they found some geochemical similarities between source-rock extracts and the Amposta crude. The Ascla formation is also still in the oil generation phase in outcrops near la Salzedella (Permanyer, Salas, & Marl, 2000a). Here, the formation may have entered the oil window during the Late Cretaceous, when it was buried at depths from about 3000 to 3700 m (Permanyer et al., op. cit). The purpose of the present study was to investigate the diagenetic history of the Ascla Formation in outcrops of the Salzedella sub-basin, with special emphasis on the possible existence of indications of petroleum generation and migration. A combination of petrographic (transmitted light, cathodoluminescence, and mineral epi-uorescence) and geochemical (stable isotopic and microprobe analyses) techniques was used. This combination has provided detailed constraints on the entire diagenetic sequence, with epi-uorescence uniquely able to show the relative timing of petroleum migration. Fluid inclusions (FIs), petrography, and geochemical composition of diagenetic phases were used to constrain thermal history and the evolution of poreuid composition. Special emphasis was made on the distribution and properties of oil inclusions, as they may provide valuable information about oil migration events and their timing relative

to the diagenetic, burial, tectonic, and thermal evolution of the basin (e.g. Burruss, 1989; Karlsen, Nedkvitne, Larter, & Bjrlykke, 1993; McLimans, 1991; Wilkinson, Lonergan, Fairs, & Herrington, 1998). Oil inclusions may also reveal relict migration pathways (Mann, 1994) and oilwater contacts (Lisk, Eadington, & O'Brien, 1998; Oxtoby, Mitchell, & Gluyas, 1995), and conrm the effectiveness of a potential source-rock as an oil generator. The use of oil inclusions as geothermometers may be difcult, because of the variable and commonly high differences between their homogenization temperatures (Th) and their entrapment temperatures. However, if the oil inclusions were trapped as single homogeneous liquid phases in equilibrium with a gas phase, their Th may reect true temperatures of entrapment and thus represent excellent geothermometers (Goldstein & Reynolds, 1994, p. 40). 2. Geological setting The Maestrat Basin is located in the eastern part of the Iberian rift system, that developed during the Mesozoic opening of the western Tethys in the eastern part of the Iberian Peninsula. The Maestrat Basin (Fig. 1) contains up to 5.8 km of Mesozoic strata dominated by carbonates. It experienced two major rifting stages (Salas & Casas, 1993; , 1996; Salas, Guimera , Gime nezSalas & Guimera n-Closas, & Roca, 1997; Salas, Guimera , Montsant, Mart

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Fig. 2. Restored cross-section of the Maestrat Basin during late Albian time, showing the Salzedella and nearby sub-basins (after Salas et al., 2001). See Fig. 1 for location.

n-Closas, Mele ndez, & Alonso, 2001). The rst Mas, Mart stage occurred during the Triassic and resulted in high-angle normal faults in the Palaeozoic basement. The second stage occurred during the latest JurassicEarly Cretaceous in

association with the opening of the North Atlantic, and created an extensional fault system which divided the basin into several sub-basins. The Salzedella sub-basin, which was the main depocenter of the Maestrat basin,

Fig. 3. Post-Hercynian restored stratigraphy of the Salzedella area, showing the calculated magnitude of the post-Eocene erosion and the location of the sampled outcrop section. The dashed lines represent the restored pre-Tertiary stratigraphy. The Alpine structure is not considered.

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represents a large, northwards-tilted block bounded by a , 1996). deep-seated fault (Fig. 2) (Salas & Guimera The late Kimmeridgian Ascla Formation was deposited in the depocenter of the Salzedella sub-basin, recording the onset of the second rifting stage (Salas et al., 2001). The Ascla Formation is composed of calcareous mudstones and marlstones, deposited in a relatively deep platform setting (Salas, 1989), and thickens towards the centre of the sub-basin, where it reaches 800 m in thickness (Fig. 2). It is overlain by a thick succession (up to 3500 m in the depocenters) of Tithonian-to-Albian synrift strata (Fig. 3) dominated by platform carbonates and deltaic siliciclastics, and up to 500 m of late Cretaceous, post-rift shallowmarine carbonates (Salas, 1987). During the Eocene Oligocene, the extensional faults were inverted as a result of Alpine compressional tectonics, resulting in the formation of a fold-and-thrust system known as the Iberian chain, which crosses eastern Spain in a NWSE direction lvaro, 1990; Salas et al., 2001). Post-Eocene &A (Guimera erosion removed signicant portions of the Jurassic Cretaceous sedimentary section of the earlier depocenters of the Salzedella sub-basin (Fig. 3). During the Late Oligocene to Early Miocene, extensional tectonics linked to the opening of the offshore Valencia trough led to the development of large grabens in nearby inshore and offshore areas , & Roca, (Vegas, 1992; Bartrina, Cabrera, Jurado, Guimera 1992). 3. Methods The Ascla Formation was sampled in outcrops in its type locality near La Salzedella (Figs. 1 and 3) (Salas, 1989). From an initial set of 320 samples (Permanyer et al., 1999), 31 samples were selected on the basis of the presence of visible cements. Samples were treated using `cold preparation techniques' (Goldstein & Reynolds, 1994) to avoid reequilibration of FIs. Double-polished thin and thick sections were prepared from each sample. In the thick sections, FI analyses were performed before any electron microprobe, cathodoluminescence or staining work to protect the FIs. In addition to transmitted light microscopy, cathodoluminescence (CL) microscopy of calcite cements was accomplished using a Technosyn MK4 system. Incident-light uorescence microscopy employed Olympus BX-60 and Diastare epiuorescence systems. A 490 nm excitation lter and a 520 nm barrier lter were used for most photographic work. Most epiuorescence photomicrographs were performed on very thin (,20 mm), polished sections in order to improve denition of mineral uorescence. The polished thin sections were stained by immersion in an acid solution of alizarin red S and potassium ferricyanide (using the recipe of Lindholm & Finkelman, 1972) for two minutes, which allowed for the optical detection of Fe-enriched growth bands in calcite cements with as little as 0.3 mole% FeCO3. BSE petrography on a JEOL

JXA-8900 electron microprobe was used to further observe chemical variability of cements. Detailed petrography and microthermometry of oil and aqueous FIs were performed on selected unheated thick sections using a Fluid Inc gas-ow heating and freezing stage. Its thermocouple was calibrated using synthetic FI standards. Thick sections were then cut into small chips, and a single eld of view was selected for each chip for performing microthermometry. Low heating rates were used for measuring homogenization temperatures (Th), which were recorded in the order of increasing Th. The chemical composition of the different carbonatecement zones were determined by wavelength dispersive X-ray spectrometry using a JEOL JXA-8900 electron microprobe (15 kV accelerating voltage, 2.047E-08 A beam current, 5 mm beam size, 100 ^ 3.5% totals accepted). Detection limits are approximately 150 ppm for Ca, 100 ppm for Mg, 300 ppm for Fe, 275 ppm for Mn, and 250 ppm for Sr. The results were normalized to 100 mol% CaCO3, MgCO3, FeCO3, MnCO3, and SrCO3. Selected calcite-cement zones were micro-sampled using a microdrill mounted on a microscope, and their oxygen and carbon isotopic compositions were determined at the University of Michigan using a Finnigan MAT 251 mass spectrometer. Isotopic enrichments were corrected for acid fractionation and the values are reported in notation relative to VPDB standard.

4. General texture and composition The analyzed samples are predominantly calcareous mudstones, with rare wackestones and grainstones, more common towards the top of the formation. Bioclasts include serpulids, arenaceous foraminifera, and bivalves, with rare echinoderms, miliolids, and sponge spicules (cf. Salas, 1989). The micritic matrix is cathodoluminescent and uorescent, and is less brightly luminescent in haloes bordering fractures and stylolites. The matrix typically contains small amounts of illite, silt-sized quartz, and disseminated hematitic pseudomorphs after authigenic pyrite. The original intraparticle porosity in bioclasts is lled by: internal sediment, hematitic pseudomorphs after authigenic pyrite, drusy calcite cement, and, in places, cloudy calcite with dolomite and hematite inclusions. Several generations of fractures, in part cut by vertical stylolites, are lled by generations of sparry calcite cements.

5. Cement stratigraphy and geochemistry Three cement sequences were distinguished. The petrographic and geochemical data of the different cement generations are summarized in Table 1.

Table 1 Summary of the petrographic, geochemical, and FI data of the different cement generations. CL, cathodoluminescence; FL, uorescence; NL, non luminescent; DL, dull luminescent; BL, bright luminescent; NF, non uorescent Sequence Sequence 1 Cement Pyrite C1.1 C1.2 C.12 C1.3a C1.3a C1.3b C1.4 Dolomite Celestite Barite Sequence 2 C2.1 Fluorite C2.2 C2.2 Sequence 3 C3.1 C3.2 C3.3 C3.4 C3.5 Mineralogy Replaced by hematite Non-ferroan calcite Non-ferroan calcite Non-ferroan calcite Non-ferroan calcite Non-ferroan calcite Non-ferroan calcite Ferroan calcite Replaced by calcite Replaced by calcite Replaced by calcite Ferroan calcite Fluorite Non-ferroan calcite Non-ferroan calcite Fer./non-fer. calcite Non-ferroan calcite Ferroan calcite Slightly ferroan calcite Non-ferroan calcite CL NL BL orange NL sectors DL dark orange NL sectors DL dark orange DL dark orange NL to DL orange BL blue BL orange NL sectors DL/BL yellow NL to BL yellow DL orange DL orange-BL BL(yellow)-NL FL NF to yellow Yellow-green NF Weak NF Weak NF NF NF NF NF NF to green Bright green NF NF to green Weak, green CO3Mg 1.76 1.96 0.07 0.82 0.85 1.49 1.37 1.83 1.82 0.40 0.80 0.84 0.59 0.49 0.59 CO3Fe 0.00 0.04 0.01 0.04 0.05 0.13 0.37 0.36 0.02 0.02 0.22 0.05 0.52 0.20 0.04 CO3Mn 0.02 0.01 0.01 0.02 0.01 0.02 0.02 0.02 0.02 0.00 0.02 0.01 0.02 0.03 0.05 CO3Sr 0.00 0.04 0.41 0.03 0.14 0.00 0.01 0.01 0.02 0.19 0.01 0.00 0.07 0.00 0.00 10.8 to 11.4 26.3 28.0 to 28.6 26.4

d 13C (VPDB)
1109 to 12.2 11.9 11.2 to 11.3 20.7 to 20.2

d 18O (VPDB)
20.2 to 10.2% 20.3 25.9 to 25.3 211 to 211.4

FIs Aqueous: all liquid primary. Oil: pseudosec. Aqueous: second. and pseudosec. Oil: pseudosec. Aqueous: second. and pseudosec. Oil: pseudosec. Aqueous: second. and pseudosec. Oil: pseudosec. Aqueous: primary, sec. and pseudosec. Oil: primary. Aqueous: secondary, and pseudosecondary Aqueous: secondary, and pseudosecondary Aqueous: all liquid primary, second. and pseudosec. Aqueous: secondary, and pseudosecondary Aqueous: secondary, and pseudosecondary

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Fig. 4. Transmitted-light, uorescence and CL petrography of sequence-1 calcite cements lling intraparticle porosity in serpulids. A: epiuorescence photomicrograph showing an initial predominantly non-uorescent generation of brous calcite (C1.1), which predated some internal sediment, followed by brightly uorescent C1.2 with non-uorescent sectors and nally, weakly uorescent C1.3. B: CL photomicrograph showing the predominantly bright orange luminescent C1.2 with prominent non luminescent sectors, followed by subordinate darker orange luminescent C1.3. Notice that compaction breakage of grains predates precipitation of C1.2 (arrow). C: transmitted-light photomicrograph of C1.1C1.3, which appear as a drusy mosaic of spar crystals with abundant twin lamellae. D: CL photomicrograph showing C1.1C1.3 lling primary porosity. Note (arrow) the presence of a thin fracture lled by luminescent, oil-FI-bearing C2.1 calcite. E: same eld of view as D in blue-light epi-illumination. Both C1.2 and C1.3 show non-uorescent sectors. Note the presence of small brightly uorescent oil FI enclosed in the non-uorescent C2.1 fracture (arrow). F: uorescence photomicrograph showing relict brousfan textures (center-left) in C1.2. Pore is nally lled by non-uorescent ferroan calcite of C1.4 (center right). Note the presence of abundant oil FIs (bright spots) trapped along microfractures in both C1.2 and C1.4.

5.1. Cement sequence 1 The rst cement sequence lled the primary porosity and some vertical fractures. Pyrite, which is now replaced by

hematite, was the rst cement to precipitate, followed by three generations of non-ferroan calcite (C1.1 to C1.3), one generation of ferroan calcite (C1.4) and one generation of dolomite, which is currently replaced by cloudy calcite.

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Fig. 5. A: transmitted light photomicrograph of primary pore in the upper part of the Ascla Formation rimmed by brous calcite (C1.1 1 C1.2) and lled by cloudy calcite. This calcite contains dolomite (arrows) and hematite inclusions, which dene ghosts of rhombs. B: CL photomicrograph showing the brous and non luminescent nature of pore-rimming C1.1 and the bright, patchy luminescence of the cloudy calcite, due to the high inclusion density. Note the presence of a less cloudy, darker luminescent band postdating the inclusion-rich patchy core.

C1.1 is typically very thin and has a brous texture, which commonly is only visible under blue-light epi-illumination (Fig. 4A). It is non-cathodoluminescent and non- to yellowish uorescent. It is best developed towards the top of the formation, where it rims the primary porosity. C1.1 has a mean composition of (Ca0.982Mg0.0176Fe0Mn0.0002Sr0)CO3. C1.2 is predated by `grain-breakage' compaction of bioclasts (Fig. 4B). It is predominantly yellow- to green uorescent and bright orange in CL with sector zoning. Non luminescent sectors show prominent triangular cross sections (Fig. 4BE) and are highly enriched in Sr and depleted in Mg, with a mean composition of (Ca0.995Mg0.0007Fe0.0001Mn0.0001Sr0.0041)CO3. Luminescent sectors have mean composition of (Ca0.979Mg0.0196Fe0.0004Mn0.0001Sr0.0004)CO3. In places, C1.2 shows a relict brous-fan texture which can be seen under blue-light epi-illumination (Fig. 4F) or after slight etching. C1.2 has moderately positive d 13C values (11.9 to 12.2) and d 18O close to 0 (20.2 to 10.2). C1.3 is also sector zoned, but less bright orange under CL (Fig. 4B and D), weakly uorescent (Fig. 4E), and terminated by a distinctive greenish band in blue-light epi-

illumination (Fig. 4F). In the lower part of the studied interval, C1.3a has a mean geochemical composition of (Ca0.991Mg0.0082Fe0.0004Mn0.0002Sr0.0003)CO3 in the brighter sectors, with the darker luminescent sectors slightly enriched in Sr ((Ca0.989Mg0.0085Fe0.0005Mn0.0001Sr0.0014)CO3). In the upper part of the formation, C1.3 (C1.3b) is signicantly richer in Mg and Fe, having a mean composition of (Ca0.984Mg0.0149Fe0.0013Mn0.0002Sr0)CO3. C1.3a has an isotopic composition d13 C 11:9; d18 O 20:3 practically identical to C1.2. C1.4 consists of ferroan, non-uorescent (Fig. 4F), dull orange cathodoluminescent calcite with a mean composition of (Ca0.982Mg0.0137Fe0.0037Mn0.0002Sr0.0001)CO3. Cements of C1.1 to C1.4 are cross-cut by subvertical fractures. Cement sequence 1 is terminated by a distinctive generation of cloudy calcite, which reduces the fracture and the remaining primary porosity. Its cloudiness results from abundant uid, dolomite and hematite inclusions (Fig. 5A). These inclusions typically dene ghosts of rhombs, which in places, show the curved cleavages typical of saddle dolomite. The cloudy calcite is thus interpreted as dedolomite, i.e. a replacement product after original dolomite. The cloudy calcite typically has a bright, patchy luminescence in CL (Fig. 5B), but in places it shows a less cloudy, dull cathodoluminescent band which may represent a later calcite cement which overgrew the dedolomitized material. The mean composition of the cloudy calcite is (Ca0.988Mg0.0108Fe0.0008Mn0.0001Sr0)CO3. Although the more inclusion-rich areas were avoided for analysis, the Mg and Fe concentrations obtained probably do not reect true concentrations in the calcite, because they must be inuenced by the abundance of small dolomite and hematite inclusions. Calcitic pseudomorphs after dolomite rhombs are also found enclosed in the micritic matrix, isolated or more commonly in the vicinity of fractures (Fig. 6A). These pseudomorphs are of dark-cathodoluminescent, non-ferroan calcite with a microspar texture. They typically have small inclusions of dolomite and Fe-oxides. Thus, they are interpreted as calcitized matrixreplacive dolomite, with timing of calcitization probably different from that of the dolomite cements. In some fractures, celestite and minor Sr-rich barite cement postdated the original dolomite precipitation. In these fractures, both celestite and barite are preserved only as inclusions, and the original crystals have been replaced by ferroan calcite (Fig. 6BC) with a geochemical composition identical to that of generation C3.3 (see below). The Mg and Fe contents of sequence-1 calcites are summarized in Fig. 7. 5.2. Cement sequence 2 Cement sequence 2 is virtually only found in fractures, which usually cut across cement sequence 1.C2.1 appears to include several subgenerations, all consisting of relatively Mg-rich ferroan calcite usually containing oil FIs. In places C2.1 contains a prominent corrosion surface which is postdated by later C2.1 cements containing primary oil FIs

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Fig. 6. A: calcite pseudomorphs after dolomite rhombs (arrows) are present on the borders of this fracture. The pseudomorphs are of microspar, have small inclusions of dolomite and Fe-oxides, and are interpreted as a replacement after matrix-replacive, inclusion-rich dolomite rhombs. The reactivation of this fracture allowed for the precipitation of oil-FI-bearing ferroan calcite (C2.1) and later non-ferroan calcite (C2.2). B: purple-coloured, K-ferricyanide-stained prismatic pseudomorphs after celestite. The pseudomorphs consist of ferroan C2.2 calcite, and are enclosed in brighter-coloured (unstained by K-4ferricyanide) non-ferroan C3.3 calcite. Note that the celestite-replacive C3.3 calcite contains corroded celestite inclusions (arrows), shows a mottled texture, and overgrowths, and hence postdates, C2.2. The interpreted paragenetic sequence in this fracture is thus celestite-C2.2 calcite-C3.3 calcite. C: BSE image of another view of the same fracture shown in A. Note the patchy aspect of the celestite-replacive ferroan calcite. The bright spots represent the sites of microprobe analyses.

(Fig. 8A and B). In some fractures, C2.1 is altered and partially replaced by subsequent generations (Fig. 8C). C2.1 is slightly more magnesian than C1.4, having a mean composition of (Ca0.977Mg0.0183Fe0.0036Mn0.0002Sr0.0001)CO3. C2.1 has d 13C from 11.2 to 11.3 and d 18O from 25.3 to 25.9. Minor amounts of uorite have been observed postdating C2.1. Where present, it is predated and postdated by corrosion surfaces. C2.2 is predated by fractures which cut across at low angles C2.1-bearing fractures. C2.2 reduces signicant amounts of porosity and is composed of non-ferroan prismatic calcite. C2.2 is bright orange cathodoluminescent and shows prominent, darker-luminescent, irregularly shaped sectors (Fig. 8C and B). In the bright sectors, the mean

composition is (Ca0.981Mg0.0182Fe0.0002Mn0.0002Sr0.0002)CO3. As in C1.2 and C1.3, the dark sectors in C2.2 are depleted in Mg and enriched in Sr, having a mean composition of (Ca0.994Mg0.004Fe0.0002Mn0Sr0.0019)CO3. 5.3. Cement sequence 3 Sequence 3 postdates a phase of compressive tectonics that produced vertical stylolites and extensive deformation structures, which cut across sequence 2 cements. Deformation includes twin lamellae, abundant planes of secondary aqueous FIs (Fig. 8C and D), and fractures which are in places parallel to the stratication. Sequence 3 cements ll those fractures. Deformation appears to have continued

Fig. 7. Plot of Mg versus Fe for sequence-1 calcites. Earlier cements (C1.1, C1.2) are Mg- and Sr-rich and Fe-poor. Late sequence-1 generations (C1.3b, 1.4) have higher Fe and lower Mg contents (NL, non luminescent).

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Fig. 8. Petrography of sequence-2 calcites. A: In this CL photomicrograph, the earlier calcites are ferroan, dull luminescent, oil-FI bearing, and affected by a prominent corrosion surface. This surface is covered by a layer of dark luminescent calcite (late C2.1, arrows) bearing primary oil inclusions, which is postdated by non-ferroan and lighter luminescent C2.2 calcite and nally by C3.3 ferroan calcite. B: Transmitted light photomicrograph after staining. Note the differences between the two darker-coloured, ferroan generations: the rst ferroan calcite (2.1) is more rich in inclusions and forms the central parts of the crystals, whereas the last ferroan calcite (C3.3) has a cleaner aspect, forms the outer parts of the crystals, and replaces celestite. C: CL photomicrograph showing dark luminescent, prismatic C2.1 ferroan calcite postdated by thicker and non-ferroan C2.2 calcite with, relatively bright and dull orange luminescence and sector zoning. Note that C2.1 is altered and partially replaced. Note also that C2.2 has abundant aqueous FIs which appear as trails of bright spots that terminate against a growth zone boundary (arrow). The formation of these pseudosecondary inclusions was postdated by the precipitation of sequence-3 calcites, which lled the residual porosity of this fracture (lower right). D: CL photomicrograph showing sector and diffuse concentric zoning in C2.2 calcite. Note the presence of trails of bright spots (upper right) representing aqueous FIs trapped along microcracks.

during precipitation of sequence 3 calcite cements. The earliest growth zones of sequence 3 contain extensive deformation twins and aqueous FI-bearing microcracks, whereas the younger growth zones are relatively clean of such features. In one sample, sequence-3 cements ll a re-opened vertical stylolite, indicating precipitation after a local compressionextension cycle. These cements are in turn affected by pressure solution along the borders of the reopened stylolite, indicating its later-stage compressional reactivation. Cements are alternating ferroan and non-ferroan calcite. The non-ferroan cement zones typically luminesce greenish with concentric zones in blue-light epi-illumination, and non luminescent or brightly subzoned in CL. The ferroan zones typically do not luminesce in blue-light and luminesce dully in CL. Growth zones of sequence 3 are

difcult to correlate between different samples, but ferroan zones typically give way to non-ferroan zones (Fig. 9F). The early part of this sequence consists of three zones, C3.1 to C3.3. C3.1 is commonly formed by a ne-scale alternation of ferroan and non-ferroan bands (Fig. 9AC). The transition between late C3.1 (ferroan), and the next generation (C3.2; non-ferroan), is commonly marked by an ironhydroxide-rich surface, which appears bright yellow under transmitted light (Figs. 9DE). C3.3 is predominantly ferroan and dully cathodoluminescent. The later part of sequence 3 is formed by two generations (C3.4 and C3.5). C3.4 is slightly ferroan, dull to bright yellow under CL, and dark green and zoned under blue-light epi-illumination. C3.5 is non-ferroan, predominantly non cathodoluminescent but showing several bright hairlines, green to dark and zoned under blue-light

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Fig. 9. Thin-section petrography of sequence-3 calcites. AB: transmitted light photomicrograph of ne-scale alternations of ferroan and non-ferroan zones in early C3.1. The ferroan zones appear darker as a result of selective staining by K-ferricyanide. As detailed in B, the non-ferroan zones host primary all-liquid aqueous FIs (arrow). C: CL photomicrograph of early C3.1 showing the bright luminescence of the non-ferroan subzones, and the dull luminescence of the ferroan ones. D: transmitted light photomicrograph of iron hydroxide-stained surface (arrow) separating the predominantly ferroan C3.1 (lower part) from the non-ferroan C3.2 (upper part). Plane polarized light. E: CL photomicrograph of approximately the same view as D, showing the predominantly dullluminescent C3.1 and C3.3, and C3.2, which is non- to bright yellow luminescent. F: CL photomicrograph showing a C3.3-lled vertical fracture crosscut by a horizontal fracture lled by C3.4 (bright yellow luminescent and zoned) and C3.5 (predominantly non-luminescent with orange hair-lines and internal sediment).

epi-illumination, and typically includes one or two intervals of uorescent microsparitic internal sediment. In places, these cements ll fractures that postdate C3.3. There is a clear tendency for the sequence-3 cements to be less magnesian than sequence 2 (Fig. 10), but with a wide variation in Fe content, reecting the alternation of ferroan

and non-ferroan subzones. Sr contents are invariably below the detection limits, and the MnCO3 is typically below 0.3 mole% except in some bright luminescent bands, where the mole percent MnCO3 can be as high as 1.4. The earliest cements of sequence 3 (3.1) have d 18O from 28 to 28.6 and d 13C from 10.8 to 11.4. The latest cements

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Fig. 10. Plot of Mg versus Fe content in sequence-2 and sequence-3 calcites. In this diagram, the calcites of both sequences are distinguished by their different Mg contents.

of sequence 3 d 13C 26.4.

(3.5)

have

d 18O 26.3

and

6. FI petrography 6.1. Oil inclusions Oil inclusions have been observed in seven samples, whose stratigraphic position is shown in Fig. 11. Oil inclusions are particularly abundant in samples from the basal part of the formation, which is the interval showing the best source-rock characteristics (Fig. 11). Here, abundant calcite-cemented fractures (less than 0.5 mm in thickness) and groups of closely spaced microfractures are crowded with small oil inclusions (Figs. 12 and 4F). In these fractures and groups microfractures, hundreds of oil FIs per mm are observed even in very thin sections (Fig. 12). In samples located upsection, oil inclusions are signicantly more scarce and, when present, they are only found in one or two fracture llings per sample. These oil-bearing fractures are typically thicker that 0.5 mm (e.g. Fig. 13A), and their oil-inclusion density is usually very low (tens of inclusions per mm in thick sections). Abundant oil inclusions are present in microfractures that cut across the cements of sequence 1 (Figs. 4F and 12), but not in later cements, so they are interpreted as pseudosecondary in origin (sensu Roedder, 1984). Some oil inclusions, however, are primary in the ferroan calcites of sequence 2 (C2.1) (Figs. 4E, 12 and 13A). In this cement generation, oil FIs are restricted to the last growth zone and elongate in the direction of growth (Fig. 13A). The corrosion surface that predates late-stage C2.1 cement is, in

places, marked by abundant oil inclusions, further indicating a primary origin (Fig. 8A). Most oil inclusions uorescence blue in U.V. epi-illumination, which is commonly characteristic of light oils (McLimans, 1991). In samples from the basal part of the formation, inclusions with a yellow uorescence, more typical of lower gravity oils (McLimans, op. cit.), are present in small amounts. The yellow-uorescent inclusions are the only oil inclusion type in some microfractures, while in others, they coexist with the blue ones. The relative timing of the entrapment of these two oils is unclear. The yellowuorescent oil inclusions are typically very small and all liquid, or contain very small vapour bubbles. The blue-uorescent ones, however, are typically larger, most have the appearance of two-phase oil-gas inclusions, and ratios of gas to liquid appear relatively consistent within a given FI assemblage (i.e. a single microfracture: Fig. 13B), but vary widely from one assemblage to another. In one sample from the middle part of the formation, C2.1 contains primary blue-uorescent oil inclusions which show extremely variable gas-to-oil ratios, ranging from all liquid to small amounts of liquid with large bubbles. Some of these inclusions also contain a visible aqueous phase (Fig. 13C). The oil-bearing zones in this sample are crowded with possible fungal or bacterial lament moulds (Fig. 13B and C) that cut across the cement zones. These laments have not been observed in other cement zones or in other samples. In places, the laments are seen to penetrate oil inclusions, apparently causing leakage of the oil inclusion and partial lling of the bacterial or fungal lament mould by oil (Fig. 13D). We interpret the variability in phase ratios of the oil inclusions as a consequence of endolithic biologic

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Fig. 12. Epiuorescence photomicrograph showing abundant uorescent oil inclusions (bright spots) in a very thin (,20 mm) section of a sample from the basal part of the Ascla Formation. Most uorescent oil inclusions are in microfractures that cut across C1.2 and C1.3. These microfractures are aligned with fractures (arrows) lled by C2.1 and also contain uorescent oil inclusions. The oil inclusions are therefore interpreted as primary in C2.1 and pseudosecondary in C1.21.3.

Fig. 11. Stratigraphic distribution of the studied samples, showing the location of the oil-FI-bearing samples and their estimated relative abundance of oil inclusions (RAOI). The total organic content (TOC) values are from Permanyer, Salas, and Bitzer (2000b). Note that the samples with higher RAOIs are from the basal part of the formation, which also has higher TOCs and the best source-rock characteristics according to Permanyer et al. (2000b).

penetration of the FIs, probably at outcrop, leading to their alteration. 6.2. Aqueous inclusions Cement C1.2 typically contains very small primary aqueous inclusions, which are predominantly all liquid, although locally, they contain small bubbles, suggesting an originally low-temperature origin and later thermal reequilibration of variable magnitude or metastability of the all-liquid inclusions (cf. Goldstein & Reynolds, 1994). These inclusions are too small to use for microthermometry. Most of the aqueous inclusions are trapped in microfractures. Some of the microfractures are clearly lled with a cement, so inclusions trapped within them, but

not within the surrounding calcite, are best interpreted as primary. In C2.1, these `primary' aqueous inclusions are extremely rare, but locally, they are associated with primary oil inclusions in the same cement. These aqueous inclusions are generally very small, and in places, they have small bubbles. Aqueous inclusions are abundant in healed microfractures in C2.2. Commonly, the microcracks terminate against the base of sequence 3 cements (Fig. 8C). Therefore, the inclusions formed during the end of C2.2 precipitation or after, but before C3.1, and are thus interpreted as pseudosecondary in origin (sensu Roedder, 1984). These inclusions are predominantly all liquid, but in places, they have bubbles and highly variable vapour-to-liquid ratios, suggesting heterogeneous entrapment of a liquid and gas phase at a low temperature. Overall ratios of vapour to liquid are too high for the variable phase ratios to originate from necking down of homogeneously entrapped liquid inclusions after appearance of the vapour bubble. In sequence 3, some of the earliest growth zones contain very small primary all-liquid inclusions, concentrated along cloudy growth zones and typically elongated in the direction of growth (Fig. 9A and B). In addition, the early sequence 3 cements contain either secondary or pseudosecondary FIs similar to those in C2.2. They are predominantly all liquid,

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Fig. 13. Photomicrographs illustrating oil FIs in thick (,100 mm) sections using a combination of epiuorescence and transmitted light. A: assemblage of primary oil FIs dening a growth zone in a late growth zone of C2.1. B: uorescent FIs in C1.3. They are aligned along what would normally be interpreted as a healed microcrack, containing secondary FIs. In CL and blue-light epi-illumination, however, these oil inclusions occur within a narrow fracture, lled with C2.1, indicating the inclusions are actually primary in origin and were trapped after precipitation of sequence 1 and during precipitation of C2.1. Note that all FIs are two phase and contain similar ratios of vapour to liquid. C: Three-phase inclusion mostly containing uorescent oil, with a gas bubble and a small rim of aqueous liquid visible in the uppermost tip. Note the presence of possible endolithic fungal or bacterial lament moulds (arrows). D: all-liquid oil inclusion, surrounded by possible endolithic fungal or bacterial lament moulds partially lled by uorescent oil (arrows).

but in places, they have bubbles and highly variable vapourto-liquid ratios. 7. FI microthermometry We obtained 61 homogenization temperatures, most of them from oil inclusions, and 6 ice nal melting temperatures on aqueous inclusions (Tm ice). Because the aqueous inclusions of some generations were so small, it was extremely difcult to get microthermometric measurements from them. We avoided microthermometry on oil inclusions suspected to have been altered by biologic processes, or FIAs with inclusions of highly variable vapour-toliquid ratio. The measured Th in oil inclusions are from primary and pseudosecondary, blue-uorescent

inclusions trapped in microfractures lled with C2.1. In these inclusions, the overall range of Th is very wide, from 45 to 115.98C (Fig. 14). Within individual FIAs, the range of Th is narrower but also variable: ,118C (4 FIAs), between 18 and 248C (4 FIAs), and more rarely higher (2 FIAs) (Fig. 14). The aqueous inclusions with measured Th are primary inclusions trapped in the C2.1 fracture-lls along with oil FIs. Data could be obtained only from two FIAs, one with only one measurable inclusion (Th 1148C), and the other showing a wide range of Th variation, from 84.5 to 117.28C (Fig. 14). Tm ice values measured in these inclusions are 22.7 and 23.78C. In the pseudosecondary aqueous inclusions present in generation C2.2, measured Tm ice values are high and relatively consistent from 0.0 to 20.28C. For those in secondary or pseudosecondary inclusions in Sequence 3, Tm ice values ranged from 0.0 to 20.28C.

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Fig. 14. Homogenization temperatures of blue-uorescent oil and aqueous FIs in unaltered C2.1-lled microfractures.

8. Discussion 8.1. Interpretation of FI data The primary aqueous inclusions in C1.2 are dominated by all-liquid FIs. This suggests that C1.2 precipitated at low temperature (less than ,508C; Goldstein & Reynolds, 1994). The oil inclusions are primary in C2.1 and pseudosecondary in cement sequence 1. Thus, we conclude that the oil inclusions must have been trapped broadly during the time of precipitation of C2.1. The variability in Th of the oil inclusions needs to be explained. Some FIAs are narrowly distributed and thus a reliable indicators of minimum entrapment temperatures of 45498C, 55618C, 50 598C, and 63748C. Other FIAs are more wide-ranging and could have been altered by thermal reequilibration. However, if oil inclusions are buried after entrapment and overheated above their entrapment temperatures, the internal pressures are less likely to rise signicantly above the external pressure than aqueous inclusions, and thus oil inclusions are less prone to thermal re-equilibration (Burruss, 1987, 1989; Goldstein & Reynolds, 1994). Another explanation could be that the range in Th reects true variation in entrapment temperature. This is possible, but seems unlikely, given the apparent restriction of oil entrapment to a single position in the paragenesis. Another possibility is that the variation in Th reects entrapment at similar temperatures but under variable pressures, which seems likely given the basinal lithology and complex fracturing history in the system. The Ascla Formation is composed of low-permeability marly limestones that could have developed overpressure during C2.1 time. Episodic fracturing may have

allowed overpressure release. And nally, it remains possible that the variation in Th is merely the result of secular compositional variation of the oils entrapped. This would be consistent with the lightness of the trapped oils (as deduced from their blue uorescence), because the liquid-vapour phase envelopes for light oils often show major variation for only small variations in composition (cf. Goldstein & Reynolds, 1994, p. 39). The meager data on Th in the aqueous inclusions trapped along with the oil in C2.1 also are variable. These Th tend to coincide with the uppermost Th data measured from the oil inclusions measured in the same FIAs. The variability in Th could easily be explained by variable amounts of thermal reequilibration; however, pseudosecondary FIs in C2.2 are dominated by all-liquid inclusions. This shows that between the end of C2.2 and the beginning of C3.1 precipitation, temperatures had dropped to very low values. Although a transient thermal event cannot be disproved for C2.2 precipitation, the simplest hypothesis would be that temperatures decreased after C2.1, and that thermal reequilibration of the aqueous inclusions was unlikely. Thus, as argued above, the variability in Th is most easily explained by pressure or compositional variations. If it is true that neither the aqueous nor petroleum inclusions have reequilibrated, then the coincidence of the petroleum and aqueous, higher temperature Th at 1178C, indicates a period of FI entrapment in which both phases were saturated with respect to the gas phase. This would indicate that at least some of C2.1 precipitated at 1178C in the presence of gas-saturated oil. Primary aqueous FIs in cements of sequence 3 are allliquid, which suggests that these cements precipitated at relatively low temperatures.

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301

Fig. 15. Summary of Mg and Fe contents of the different calcite generations. Rectangular elds represent mean values ^ one standard deviation for each zone.

8.2. Interpretation of cement sequence 1: precipitation during the rst burial stage (Kimmeridgian-Valanginian) The rst calcite cements probably precipitated near the surface or at shallow depths, as suggested by their paragenetic position before and just after initial compaction, and low-temperature FIs. Composition is consistent with precipitation from marine water, especially the relatively high overall Mg and Sr content, low Fe content (Fig. 15), and isotopic composition (Fig. 16). Moreover, relict brous texture of both C1.1 and C1.2 is common in modern and ancient marine calcite cements. The presumably marine, Mg- and Sr-rich, Fe-poor cements (C1.1, C1.2) were followed by non-uorescent generations with higher Fe

and lower Mg contents (C1.3b, 1.4; Fig. 15), indicating more reducing waters consistent with progressive burial and a different uid composition (cf. Meyers, 1991). Sequence 1 ended with the precipitation of dolomite, which lled the remnant primary porosity and some new fracture porosity. The dolomite must have precipitated relatively early in the diagenetic history, because it lled remaining primary porosity. The abundance of dolomite increases up section, where the original primary porosities were higher due to the predominance of shallower-water facies (Salas, 1989). This suggests that the original abundance of dolomite was controlled by depositional facies. The dolomite not only lled porosity but also partially replaced the host limestone, especially towards the top of

Fig. 16. Oxygen and carbon isotopic compositions of individual calcite cement zones. Data for meteoric calcites in the Catalan Coastal ranges are from Trave et al. (1998).

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Fig. 17. Generalized paragenetic sequence of the Ascla Formation.

the formation. The dolomitization of Sr-rich marine carbonates might have released the Sr necessary for the precipitation of the celestite that postdated dolomite. In the Salzedella area, the Ascla Formation grades upwards into an extensive unit of dolomitized carbonate (the Talaies Dolomite, sensu Salas, 1987) that replaces the Tithonian to Berriasian Bovalar Formation and the top of the Ascla Formation (Nadal, 2000). The location of dolomitization in the Talaies is related to normal faults. Timing has been interpreted as predating deposition of the upper part of the Valanginian, because the dolomites were partly eroded during development of a late Berriasian-to-late Valanginian unconformity (Fig. 3; Aurell, Mas, Melendez, & Salas, n-Closas, Querol, Guimera , 1994; Nadal, 2000; Salas, Mart & Roca, 1995). If the dolomites in the Ascla and Talaies Formations are equivalent, then the dolomites in the Ascla would have precipitated at burial depths of less than about 10001500 m (Fig. 3), which is consistent with its observed paragenetic position (Fig. 17). Nadal (2000) has reported in the Talaies dolomites the presence of FIs with variable densities, from all liquid to two-phase with inconsistent Th (801258C). If the reported FIs are primary and have not suffered necking down after a phase change, then their relatively high variability in density could be the result of: (1) original entrapment at lower temperatures followed by later incomplete re-equilibration during further burial; or (2) multiple events of dolomite precipitation at variable temperatures. The rst explanation is consistent with the relatively small depth of burial for dolomite precipitation inferred by Nadal (2000). However, the second explanation (multistage dolomitization) is consistent with the association with faults, which could

have acted as conduits for hot uids, and with the evidences of zoning described by Nadal (op. cit). Unfortunately, the relationship between the Ascla and Talaies dolomites could not be evaluated further because the Ascla dolomites have been almost completely calcitized. 8.3. Interpretation of cement sequence 2: main burial stage and oil migration Sequence 2 begins with the precipitation of syntectonic (C2.1) ferroan calcite, which records oil generation and migration through the Ascla Formation via fractures at temperatures of at least 1178C as deduced from the FI data (see above). The Tm ice data indicate that C2.1 precipitated from waters slightly more saline than sea water (4.56 wt% NaCl eq.). Assuming a precipitation temperature of 1178C, the oxygen isotopic data (d 18O 25.6VPDB) indicates that C2.1 precipitated from a water with d 18O 19.8SMOW (Friedman & O'Neil, 1977), which is consistent with a basinal brine enriched in 18O from evaporation or uidrock interaction. The relatively positive d 13C values (Fig. 16) are also consistent with such a uid. C2.1 hosts primary oil inclusions. It postdates the dolomite, which may predate the late part of the Valanginian, so oil migration must have taken place during or after the late Valanginian. The high-temperature FIs in C2.1 and abundant fracturing during this stage is consistent with timing beginning during rapid BarremianAlbian rift subsidence or Late Cretaceous post-rift subsidence and ending with maximum burial during the latest Cretaceous or earliest Tertiary (Fig. 17). Burial-thermal modelling shows that the Ascla

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Formation in the study area probably entered the oil window during the Cenomanian (Permanyer et al., 2000a). Our data are consistent with this, but the least equivocal FI data suggest oil generation and migration continued during the latest Cretaceous or earliest Tertiary, when the Ascla reached its maximum burial depth and presumably maximum temperature. The FI data indicate that C2.1 records the maximum temperatures reached by the Ascla, which are about 1178C. Similar maximum temperatures (1118C) have been obtained by Permanyer et al. (2000a) from vitrinite reectance values using empirical calibrations. In the agolosa sub-basin (Fig. 1), hydrothermal circulanearby Pen tion resulting in ZnPb mineralization (with local presence of uorite), at temperatures as high as 1508C, occurred during the early Paleocene (Grandia, Asmerom, Getty, Cardellach, & Canals, 2000). In the Salzedella sub-basin, ZnPb deposits are not known and there is no evidence that such high temperatures had been reached. Widespread vertical fracturing predated and postdated oil migration. The resulting fractures were partly cemented by ferroan calcites of C2.1 and lled with non-ferroan calcite of C2.2, suggesting increasingly less reducing conditions or limited Fe availability. C2.2 and the rst cements of sequence 1 (C1.1C1.2) are geochemically similar. Both are Mg-rich, Fe-poor and have Sr-enriched sectors (Fig. 15). As in C1.1C1.2, this trace-element composition could be consistent with precipitation from marine-derived waters. The FI data suggest that C2.2 might have been preceded by the maximum temperatures and clearly were postdated by low temperatures. Thus, it makes sense to interpret that C2.2 represents part of the cooling path of this unit. If one were to assume a temperature of 80 1008C for precipitation of C2.2, then the its d 18O of 211.2VPDB would indicate precipitation from a water with d 18O from about 0 to 12 SMOW (Friedman & O'Neil, 1977), i.e. consistent with precipitation from marine-derived water. The carbon isotopic composition of 20.2 to 20.7VPDB is also compatible with marinederived waters. C2.2 is deformed by compressional structures. The onset of compressive tectonics and basin inversion has been interpreted as Eocene in age (Salas et al., 2001). Therefore, C2.2 precipitation, and the events of oil migration that predate it must have taken place before the Eocene. If C2.2 does represent cooling of the unit, and if it predates compressional tectonism and its related unroong, one must question why the cooling has occurred. One possibility would be that some compression and uplift coincided with C2.2, but there are no deformation features that would indicate this change in stress eld until after C2.2 precipitation. Another explanation could be that the unit was cooled by deeply circulating pore uids. Given the fractured nature of the unit and the evidence for a change in pore uid composition, this remains a possibility. Finally, the cooling could easily be related to decreasing heat ow in the basin.

8.4. Interpretation of cement sequence 3: Tertiary uplift Sequence 3 typically lls fractures that cut the sequence-2 fractures at high angles, suggesting a radical change in the stress eld. The cements of sequence 3 are syntectonic. Because they ll re-opened vertical stylolites, they must postdate at least one compressional and one extensional tectonic event, at least at a local scale. These cements are cut across by further vertical stylolitization, indicating further compression. These relationships suggest that sequence 3 precipitated during and after the EoceneOligocene (Fig. 17), when the area suffered its rst major stage of compressional tectonics. Some sequence-3 zones may have precipitated during the Late Oligocene to Early Miocene, a period which was characterized by extensional tectonics leading to the development of large grabens in nearby inshore areas and to the opening of the offshore Valencia trough (Bartrina et al., 1992; Vegas, 1992). Later sequence3 compressive structures could be Middle Miocene, when the area suffered a subordinate compressional tectonic pulse , Roca, Soler, & (the Betic compression of Calvet, Trave , Calvet, Soler, & Labaume, 1998). Labaume, 1996; Trave Sequence-3 cements are characterized by low Mg and Sr contents relative to sequences 12 (Fig. 15). This suggests a change from predominantly marine-derived waters in sequences 1 and 2, to meteoric waters in sequence 3. Pseudosecondary FIs that formed between the end of sequence 2 and the beginning of sequence 3 contain fresh waters that were trapped at low temperature. Sequence 3 is typically formed by alternating ferroan and non-ferroan calcites, which suggests nely alternating reducing and oxidizing conditions compatible with a meteoric origin. Thus, we interpret that sequence 3 precipitated from low-temperature meteoric water, after the inversion of the Maestrat basin and its transformation into an emergent fold and thrust belt. The earliest sequence-3 calcites precipitated at lowtemperature (less than about 508C), as indicated by the presence of abundant all-liquid primary FIs (Goldstein & Reynolds, 1994) (Fig. 9B). Assuming a precipitation temperature of 30408C, then the d 18O of C3.1 (28.3VPDB) indicates precipitation from a water with d 18O from about 25.2 to 23.3 SMOW (Friedman & O'Neil, 1977), i.e. consistent with meteoric-derived water. However, the relatively positive carbon isotopic composition (10.8 to 11.4VPDB) is not consistent with the incorporation of soil-derived carbon, and must then reect uidrock interaction in a setting distal from the soil zone. The low trace element content and moderately light d 18O (26.3) and d 13C (26.4) of the last sequence-3 zone (C3.5) are typical of meteoric calcites precipitated at lowtemperature in open systems. The low d 13C is consistent with the incorporation of soil-derived CO2. The overall trend of the carbon and oxygen isotopic compositions of sequence 3, from C3.1 to C3.5 (Fig. 16) is also compatible with precipitation during a phase of erosional unroong, in which cooler and more soil-inuenced waters progressively

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predominated. Overall, the isotopic compositions of sequence-3 calcites are similar to the values reported by et al. (1998) for Tertiary fracture-lling calcites of Trave meteoric-water origin in the nearby Catalan Coastal Ranges (Fig. 16). Some of the latest sequence-3 zones may even have formed in the vadose zone, as suggested by the crystal silt internal sediments coinciding with precipitation. The earliest cements in sequence 3 contain the most abundant fresh-water inclusions along healed fractures, which could point to entrapment during late sequence 3. These inclusions are essentially fresh water with extremely inconsistent gas to liquid ratios, compatible with trapping in the vadose zone. Precipitation of sequence 3 in some solution-enlarged fractures and presence of some solutional discontinuities within sequence 3 may also point to a late-stage, near-surface origin. 8.5. Implications for oil potential The oils observed as inclusions in the Ascla Formation were likely generated in the organic-rich intervals of the formation. This is suggested by (1) the absence of other feasible source rocks in this part of the basin, and (2) the higher abundance of oil inclusions in the basal part of the Ascla, which contains the richer potential source rocks (Fig. 11). In samples from this part of the formation, oil inclusions are abundant in fractures and especially in clusters of microfractures (Fig. 12), and have variable compositions as indicated by their uorescence (blue and yellow). These features are typical in source rocks which have generated oil (Norman Oxtoby, pers. comm.). However, the overall abundance of oil FIs is perhaps lower than one should expect for a very rich source-rock. Possible causes are: (1) The studied samples are from limestones, and the richer source beds are the interbedded marls. Therefore, the oil inclusions likely represent trapping along a migration route in close association with the source-rock. (2) the source-rock potential, even in the richer intervals, is not particularly high (Permanyer et al., 1999). In the middle and upper parts of the Ascla, samples bearing oil inclusions are scarce, the trapped oils are restricted in composition, and the oil inclusions are only found in fractures showing low oil-FI densities. These characteristics suggest trapping along a migration route through fractures. The possible contribution of oils generated in the Ascla Formation to the Amposta oil eld has been a matter of s et al., 1986; Seemann et al., 1990; Seifert debate (Albaige et al., 1983). This eld is located offshore, 40 km to the west of Salzedella (Fig. 1), and reservoirs oil in Paleogene-aged karst developed in Lower Cretaceous carbonates (Seemann et al., 1990). The age of the trap and seal is Miocene, when the area experienced an important rifting phase. The Amposta oil has unique geochemical characteristics and is not correlated with the other oils in the Tarragona offshore basin, which have their source in Miocene rocks deposited s et al., 1986). in the Tarragona Trough (Fig. 1) (Albaige

It has been argued that the Ascla Formation cannot be the source for the Amposta oil, because (1) lacks source-rock potential and (2) it was already overmature for oil genera s et tion in the Amposta area during the Miocene (Albaige al., 1986). However, the Ascla formation is still in the oilgeneration phase and have some oil-generation potential at least in two locations: an offshore well near Amposta Field (Seemann et al., 1990) and in outcrops near la Salzedella (Permanyer et al., 1999). Moreover, Seemann et al. (1990) found geochemical similarities between Ascla-source-rock extracts and the Amposta crude. The results of the present study indicate that oil indeed migrated from the Ascla Formation, at least in the sampled location. This migration, however, took place when the formation was at or near maximum burial depth and temperature, very likely during the Cretaceous to earliest Tertiary, and before the Eocene. Thus, oil migration occurred just before Alpine tectonics, which created the most obvious traps. Thus, the potential for oil accumulation in this particular part of the basin is probably low, unless pre-Alpine traps are preserved. The outcrop locality (La Salzedella) in which the Ascla has been found to have residual oil-generation potential is in a basin sector which suffered elevated erosion rates during the Paleogene (Fig. 3). It is therefore conceivable that similar conditions could have existed in the present-day offshore near Amposta eld. Unlike the Salzedella sub-basin, in this area, some Miocene subsidence could have caused a second phase of oil generation from the Ascla Formation. Even in this case, the effectiveness of the Ascla, as an oil generator, must have been limited because (1) the organic content of the Ascla source-rock intervals is relatively low, (2) its oilgeneration capabilities could have been partially exhausted during the Late Cretaceous to Earliest Tertiary, and (3) oil generation predated formation of most of the traps. 9. Conclusions Three distinct calcite cement sequences are distinguished in the Ascla Formation by their CL, uorescence, traceelement composition and cross-cutting relationships. (1) Cement sequence 1 precipitated during the Kimmeridgian-Valanginian burial stage and mainly lled the primary porosity. The rst sequence-1 zones precipitated from marine-derived waters. Subsequent sequence-1 calcites precipitated from reducing waters during increasing burial. Sequence 1 ended with the widespread precipitation of dolomite. This dolomite is currently replaced by inclusion-rich calcite. (2) Cement sequence 2 precipitated exclusively in fractures, very likely during the latest Cretaceous to earliest Tertiary burial when the Ascla Formation reached its maximum burial depth. Sequence 2 begins with the precipitation of ferroan calcite, which records oil generation and migration through the Ascla Formation via fractures. Both the FI

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and isotopic data can be interpreted to indicate that this calcite records the maximum temperatures reached by the Ascla, which are around 1178C. Widespread vertical fracturing postdated oil migration. The resulting fractures are mainly lled by non-ferroan calcite yielding geochemical data compatible with precipitation from marine-inuenced waters at elevated but potentially decreasing temperatures. (3) Sequence 3 is formed by alternating ferroan and nonferroan calcites, which precipitated exclusively in fractures during the Tertiary. The rst sequence-3 zones precipitated during or after the EoceneOligocene stage of compressional tectonics, whereas subsequent sequence-3 zones likely precipitated during the Neogene. The petrographic and FI characteristics, and the trace-element and isotopic compositions of sequence-3 indicate precipitation predominantly from meteoric waters in the low-temperature (less than about 508C) phreatic zone. The ferroan calcites of sequence 3 represent precipitation in relatively closed systems characterized by low uidrock ratios and reducing conditions, whereas the non-ferroan subzones represent the ingress of oxidizing waters perhaps related to episodes of fracture opening. Some of the latest sequence-3 zones may have formed in the vadose zone. Oil inclusions in sequence 2 provide evidence that light to medium gravity oils were generated in the Ascla Formation in the Salzedella sub-basin and migrated through fractures. Oil migrated before the Eocene, very likely when the formation reached its maximum burial depth during the Late Cretaceous to earliest Tertiary. As oil migration predated the Alpine tectonics, the potential for oil accumulations in this part of the basin is probably low, unless pre-Alpine traps are preserved. Acknowledgements Funding was provided by research projects DGICYT n Duro PB96-1236-C02-01/02 y PB95-1142-C02-01. Rube ndezis acknowledged for his eld work and Alfredo Ferna Larios for his technical assistance with the electron microprobe. The helpful comments of Jorge Navarro are also gratefully acknowledged. Norman Oxtoby and an anonymous reviewer are thanked for their careful reviews and critical comments. References
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