Marine and Petroleum Geology 18 (2001) 287±306

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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. Mar®l a, R. Salas c, M.I. Benito d, A. Permanyer c, Ä a a, M.A. Caja a J.A. de la Pen
a

Âa y Geoquõ Âmica, Facultad de Ciencias Geolo  gicas, Universidad Complutense, 28040 Madrid, Spain Departamento de Petrologõ b Department of Geology, University of Kansas, Lawrence, KS 66045-7613, USA c Âmica, Universidad de Barcelona, 08028 Barcelona, Spain Departamento de Geoquõ d Âa, Universidad Complutense, Madrid, Spain Departamento de Estratigrafõ 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, Mar®l, Ä 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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C. Rossi et al. / Marine and Petroleum Geology 18 (2001) 287±306

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

È 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, & Mar®l, 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 pore¯uid 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, & Bjùrlykke, 1993; McLimans, 1991; Wilkinson, Lonergan, Fairs, & Herrington, 1998). Oil inclusions may also reveal relict migration pathways (Mann, 1994) and oil±water contacts (Lisk, Eadington, & O'Brien, 1998; Oxtoby, Mitchell, & Gluyas, 1995), and con®rm the effectiveness of a potential source-rock as an oil generator. The use of oil inclusions as geothermometers may be dif®cult, 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 re¯ect 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 Ân-Closas, & Roca, 1997; Salas, Guimera Â, Montsant, Martõ

Rossi et al. The second stage occurred during the latest Jurassic±Early Cretaceous in association with the opening of the North Atlantic. Restored cross-section of the Maestrat Basin during late Albian time.C. & Alonso. 2. The Alpine structure is not considered. The dashed lines represent the restored pre-Tertiary stratigraphy. The ®rst Mas. Martõ stage occurred during the Triassic and resulted in high-angle normal faults in the Palaeozoic basement. The Salzedella sub-basin. showing the Salzedella and nearby sub-basins (after Salas et al. Ân-Closas.. 1 for location. . Post-Hercynian restored stratigraphy of the Salzedella area. Fig. and created an extensional fault system which divided the basin into several sub-basins. 2001). showing the calculated magnitude of the post-Eocene erosion and the location of the sampled outcrop section. See Fig. which was the main depocenter of the Maestrat basin. 3. 2001). Mele  ndez. / Marine and Petroleum Geology 18 (2001) 287±306 289 Fig.

with rare wackestones and grainstones. resulting in the formation of a fold-and-thrust system known as the Iberian chain. The Ascla Formation is composed of calcareous mudstones and marlstones. 300 ppm for Fe. In the thick sections. FeCO3. Cement stratigraphy and geochemistry Three cement sequences were distinguished. and up to 500 m of late Cretaceous. Most epi¯uorescence photomicrographs were performed on very thin (. Several generations of fractures. Incident-light ¯uorescence microscopy employed Olympus BX-60 and Diastare epi¯uorescence systems. 1987). which were recorded in the order of increasing Th. cathodoluminescence (CL) microscopy of calcite cements was accomplished using a Technosyn MK4 system. Bartrina. 2). Guimera 1992). General texture and composition The analyzed samples are predominantly calcareous mudstones.. and sponge spicules (cf. cathodoluminescence or staining work to protect the FIs. silt-sized quartz. In addition to transmitted light microscopy. 1989).290 C. and thickens towards the centre of the sub-basin. are ®lled by generations of sparry calcite cements. hematitic pseudomorphs after authigenic pyrite. 2001). 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. It is overlain by a thick succession (up to 3500 m in the depocenters) of Tithonian-to-Albian synrift strata (Fig. MgCO3. 4. Rossi et al. 3) dominated by platform carbonates and deltaic siliciclastics. arenaceous foraminifera. Bioclasts include serpulids. where it reaches 800 m in thickness (Fig. . the extensional faults were inverted as a result of Alpine compressional tectonics. and disseminated hematitic pseudomorphs after authigenic pyrite. Detection limits are approximately 150 ppm for Ca. more common towards the top of the formation. 5. drusy calcite cement. 1996). 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. post-rift shallowmarine carbonates (Salas. 275 ppm for Mn. 100 ppm for Mg. 1994) to avoid reequilibration of FIs. Post-Eocene Â&A (Guimera erosion removed signi®cant portions of the Jurassic± Cretaceous sedimentary section of the earlier depocenters of the Salzedella sub-basin (Fig. Selected calcite-cement zones were micro-sampled using a microdrill mounted on a microscope. 1999).20 mm). deposited in a relatively deep platform setting (Salas. 1990. / Marine and Petroleum Geology 18 (2001) 287±306 represents a large. The micritic matrix is cathodoluminescent and ¯uorescent. 1992. From an initial set of 320 samples (Permanyer et al. Salas et al. which crosses eastern Spain in a NW±SE direction  lvaro.5% totals accepted). Samples were treated using `cold preparation techniques' (Goldstein & Reynolds.047E-08 A beam current. Isotopic enrichments were corrected for acid fractionation and the values are reported in ½ notation relative to VPDB standard. in part cut by vertical stylolites. 1972) for two minutes. extensional tectonics linked to the opening of the offshore Valencia trough led to the development of large grabens in nearby inshore and offshore areas  . During the Late Oligocene to Early Miocene. 2) (Salas & Guimera The late Kimmeridgian Ascla Formation was deposited in the depocenter of the Salzedella sub-basin. 5 mm beam size. Salas. BSE petrography on a JEOL JXA-8900 electron microprobe was used to further observe chemical variability of cements. and SrCO3. northwards-tilted block bounded by a  . and is less brightly luminescent in haloes bordering fractures and stylolites. 1989). (Vegas. Its thermocouple was calibrated using synthetic FI standards. and their oxygen and carbon isotopic compositions were determined at the University of Michigan using a Finnigan MAT 251 mass spectrometer. The results were normalized to 100 mol% CaCO3. in places.. deep-seated fault (Fig. miliolids. and. 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. During the Eocene± Oligocene. 2001).3 mole% FeCO3. and a single ®eld of view was selected for each chip for performing microthermometry. Cabrera. Methods The Ascla Formation was sampled in outcrops in its type locality near La Salzedella (Figs. with rare echinoderms. polished sections in order to improve de®nition of mineral ¯uorescence. which allowed for the optical detection of Fe-enriched growth bands in calcite cements with as little as 0. MnCO3. Thick sections were then cut into small chips. The petrographic and geochemical data of the different cement generations are summarized in Table 1. FI analyses were performed before any electron microprobe. The matrix typically contains small amounts of illite. The original intraparticle porosity in bioclasts is ®lled by: internal sediment. 3. 1 and 3) (Salas. Double-polished thin and thick sections were prepared from each sample. 3). Jurado. 31 samples were selected on the basis of the presence of visible cements. Low heating rates were used for measuring homogenization temperatures (Th). & Roca. 2. 100 ^ 3. cloudy calcite with dolomite and hematite inclusions.. and 250 ppm for Sr. and bivalves. recording the onset of the second rifting stage (Salas et al. A 490 nm excitation ®lter and a 520 nm barrier ®lter were used for most photographic work. 1989).

2 11.07 0.03 0. CL.96 0.00 0. NL. and pseudosecondary ± ± C.4½ d 13C (VPDB) ± ± 1109 to 12.82 0. Rossi et al. bright luminescent.41 0.6½ ± ± ± 26.8 to 11.1 Fluorite C2. ± ± ± Aqueous: primary.0 to 28.05 0.3b C1.2 C3. Oil: pseudosec.7 to 20.3½ 28. and pseudosec.00 10. and FI data of the different cement generations. Oil: pseudosec. and pseudosecondary Aqueous: secondary.Table 1 Summary of the petrographic.9 to 25. non ¯uorescent Sequence Sequence 1 Cement Pyrite C1.83 ± 1.04 0.3a C1.59 CO3Fe ± 0.4 Dolomite Celestite Barite Sequence 2 C2.00 0.2 C.00 0. BL.02 0.01 0.36 ± 0. and pseudosecondary Aqueous: all liquid primary.2% 20.84 0.04 CO3Mn ± 0.3½ ± ± ± ± ± 25.02 0.02 0.3 ± 20.01 0. sec. and pseudosec.22 0. ± Aqueous: second.01 0.1 C3.2½ d 18O (VPDB) ± ± 20.2 C2.01 ± 0.4½ FIs ± ± Aqueous: all liquid primary. and pseudosec. Oil: primary.02 ± 0.37 ± ± ± 1. second.4 C3.37 ± ± ± 0. 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.04 0. ¯uorescence.76 1.02 0.03 0. DL.01 0.52 0.2 to 11.59 0.4 ± ± ± 26.02 0.00 0.2 to 10.1 C1.3½ ± 211 to 211. FL. Oil: pseudosec. and pseudosecondary Aqueous: secondary.20 0.01 ± ± ± 0.13 0.07 0.00 0./non-fer.01 0.14 0.02 0.85 1.9½ ± ± ± ± ± 11.01 0. and pseudosec. dull luminescent.02 0. non luminescent. ± Aqueous: second.3 C3.02 0.02 ± ± ± 0.05 0.05 CO3Sr ± 0.19 0.12 C1. Aqueous: secondary.00 0. geochemical.82 0.02 0. / Marine and Petroleum Geology 18 (2001) 287±306 291 . cathodoluminescence.49 0.2 Sequence 3 C3.80 0. green CO3Mg ± 1.5 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. NF.3a C1.04 0. Oil: pseudosec.40 0. ± Aqueous: secondary.49 1. Aqueous: second. and pseudosec.

1 fracture (arrow).1 to C1. E: same ®eld of view as D in blue-light epi-illumination. which appear as a drusy mosaic of spar crystals with abundant twin lamellae.2.1±C1. Note the presence of abundant oil FIs (bright spots) trapped along microfractures in both C1. F: ¯uorescence photomicrograph showing relict ®brousfan textures (center-left) in C1.3 show non-¯uorescent sectors. ¯uorescence and CL petrography of sequence-1 calcite cements ®lling intraparticle porosity in serpulids.292 C.2 with non-¯uorescent sectors and ®nally. followed by subordinate darker orange luminescent C1. D: CL photomicrograph showing C1. which is now replaced by hematite. .4 (center right).2 and C1.1. B: CL photomicrograph showing the predominantly bright orange luminescent C1. which is currently replaced by cloudy calcite.1 calcite. Both C1.2 (arrow).3).3 ®lling primary porosity. A: epi¯uorescence photomicrograph showing an initial predominantly non-¯uorescent generation of ®brous calcite (C1. followed by brightly ¯uorescent C1.3.1). 4. Pore is ®nally ®lled by non-¯uorescent ferroan calcite of C1. Transmitted-light.2 with prominent non luminescent sectors.4) and one generation of dolomite.1±C1. followed by three generations of non-ferroan calcite (C1. weakly ¯uorescent C1.4. Rossi et al. C: transmitted-light photomicrograph of C1. was the ®rst cement to precipitate.3. / Marine and Petroleum Geology 18 (2001) 287±306 Fig. oil-FI-bearing C2.3. 5. Pyrite.2 and C1. one generation of ferroan calcite (C1. Note the presence of small brightly ¯uorescent oil FI enclosed in the non-¯uorescent C2. which predated some internal sediment. Note (arrow) the presence of a thin fracture ®lled by luminescent. Notice that compaction breakage of grains predates precipitation of C1. Cement sequence 1 The ®rst cement sequence ®lled the primary porosity and some vertical fractures.

3 (see below). dull cathodoluminescent band which may represent a later calcite cement which overgrew the dedolomitized material. Note the presence of a less cloudy. both celestite and barite are preserved only as inclusions. a replacement product after original dolomite.982Mg0.0014)CO3).3 (C1. with a mean composition of (Ca0. C1.2½) and d 18O close to 0 (20.0002Sr0)CO3.1 to C1.0004)CO3. C1.0082Fe0.1 has a mean composition of (Ca0. The cloudy calcite typically has a bright.1 appears to include several subgenerations. 4A).4 are cross-cut by subvertical fractures. In the upper part of the formation. patchy luminescence in CL (Fig. Calcitic pseudomorphs after dolomite rhombs are also found enclosed in the micritic matrix. In places C2.0001Mn0.1 and the bright. They typically have small inclusions of dolomite and Fe-oxides. Luminescent sectors have mean composition of (Ca0.2. all consisting of relatively Mg-rich ferroan calcite usually containing oil FIs.984Mg0. In some fractures. 4B). 5. 5.1 is typically very thin and has a ®brous texture. celestite and minor Sr-rich barite cement postdated the original dolomite precipitation.0137Fe0. with timing of calcitization probably different from that of the dolomite cements.0001)CO3.3a has a mean geochemical composition of (Ca0. C1.3 is also sector zoned. It is best developed towards the top of the formation. C1. but in places it shows a less cloudy. d18 O ˆ 20:3† practically identical to C1. C1. 4B and D).9 to 12.988Mg0. The mean composition of the cloudy calcite is (Ca0. Although the more inclusion-rich areas were avoided for analysis.0108Fe0. Rossi et al. isolated or more commonly in the vicinity of fractures (Fig.2 has moderately positive d 13C values (11. 4F).0002Sr0. having a mean composition of (Ca0.0001Sr0.995Mg0.4 consists of ferroan.0013Mn0. which de®ne ghosts of rhombs. patchy luminescence of the cloudy calcite.2½).0002Sr0)CO3. 5B).0001Sr0. Non luminescent sectors show prominent triangular cross sections (Fig. but less bright orange under CL (Fig.2. 4F). / Marine and Petroleum Geology 18 (2001) 287±306 293 Fig. In these fractures.e.to yellowish ¯uorescent.0002Sr0. because they must be in¯uenced by the abundance of small dolomite and hematite inclusions.0005Mn0.C.0176Fe0Mn0. It is non-cathodoluminescent and non.1 1 C1.2 to 10. the Mg and Fe concentrations obtained probably do not re¯ect true concentrations in the calcite. and the original crystals have been replaced by ferroan calcite (Fig. C1.0008Mn0.0149Fe0. 4E). show the curved cleavages typical of saddle dolomite.0007Fe0. Cement sequence 1 is terminated by a distinctive generation of cloudy calcite.1 contains a prominent corrosion surface which is postdated by later C2. they are interpreted as calcitized matrixreplacive dolomite. C1. where it rims the primary porosity. C1. 4B±E) and are highly enriched in Sr and depleted in Mg. and terminated by a distinctive greenish band in blue-light epi- illumination (Fig.991Mg0. which reduces the fracture and the remaining primary porosity.2 is predated by `grain-breakage' compaction of bioclasts (Fig. dull orange cathodoluminescent calcite with a mean composition of (Ca0. 6B±C) with a geochemical composition identical to that of generation C3. The cloudy calcite is thus interpreted as dedolomite.982Mg0.2) and ®lled by cloudy calcite.to green ¯uorescent and bright orange in CL with sector zoning.0041)CO3.0001Sr0)CO3.0003)CO3 in the brighter sectors. 7. Thus. 6A). This calcite contains dolomite (arrows) and hematite inclusions. i.979Mg0. Cements of C1.1 cements containing primary oil FIs . which in places. C1.3a has an isotopic composition …d13 C ˆ 11:9. dolomite and hematite inclusions (Fig.0004Mn0. due to the high inclusion density. A: transmitted light photomicrograph of primary pore in the upper part of the Ascla Formation rimmed by ®brous calcite (C1. The Mg and Fe contents of sequence-1 calcites are summarized in Fig.0001Sr0.2 shows a relict ®brous-fan texture which can be seen under blue-light epi-illumination (Fig. In places.3b) is signi®cantly richer in Mg and Fe. These inclusions typically de®ne ghosts of rhombs.989Mg0. which usually cut across cement sequence 1. These pseudomorphs are of dark-cathodoluminescent. weakly ¯uorescent (Fig. 4F) or after slight etching. B: CL photomicrograph showing the ®brous and non luminescent nature of pore-rimming C1.0004Mn0. C1. which commonly is only visible under blue-light epi-illumination (Fig.0037Mn0. Cement sequence 2 Cement sequence 2 is virtually only found in fractures. with the darker luminescent sectors slightly enriched in Sr ((Ca0. Its cloudiness results from abundant ¯uid. non-¯uorescent (Fig.C2. In the lower part of the studied interval. non-ferroan calcite with a microspar texture. 5A).0196Fe0. darker luminescent band postdating the inclusion-rich patchy core.0085Fe0. It is predominantly yellow.

2). 7.0002Sr0.2. The interpreted paragenetic sequence in this fracture is thus celestite-C2. Note that the celestite-replacive C3.4) have higher Fe and lower Mg contents (NL.3 calcite.3b. Late sequence-1 generations (C1. 8C and D).1 is altered and partially replaced by subsequent generations (Fig.1.0036Mn0.2) are Mg.977Mg0.3 calcite contains corroded celestite inclusions (arrows). darker-luminescent. As in C1. C2. C1. C2. In the bright sectors. and fractures which are in places parallel to the strati®cation. K-ferricyanide-stained prismatic pseudomorphs after celestite. 1.3 calcite.3. and hence postdates. C2. abundant planes of secondary aqueous FIs (Fig. the mean composition is (Ca0. 6.1) and later non-ferroan calcite (C2. 5. Minor amounts of ¯uorite have been observed postdating C2. The reactivation of this fracture allowed for the precipitation of oil-FI-bearing ferroan calcite (C2. C2. The pseudomorphs consist of ferroan C2. C: BSE image of another view of the same fracture shown in A.3 to 25.2 and C1. Where present.0183Fe0. A: calcite pseudomorphs after dolomite rhombs (arrows) are present on the borders of this fracture.1.0002)CO3. B: purple-coloured.2 is bright orange cathodoluminescent and shows prominent. inclusion-rich dolomite rhombs. having a mean composition of (Ca0. C2.3.0002Sr0.0002Mn0Sr0. Note the patchy aspect of the celestite-replacive ferroan calcite. the dark sectors in C2. and are enclosed in brighter-coloured (unstained by K-4ferricyanide) non-ferroan C3. Rossi et al. have small inclusions of dolomite and Fe-oxides. Cement sequence 3 Sequence 3 postdates a phase of compressive tectonics that produced vertical stylolites and extensive deformation structures. and overgrowths.and Sr-rich and Fe-poor. Sequence 3 cements ®ll those fractures. . Deformation appears to have continued Fig.2 reduces signi®cant amounts of porosity and is composed of non-ferroan prismatic calcite.004Fe0. Earlier cements (C1.1 has d 13C from 11. C2.0002Mn0. The pseudomorphs are of microspar. having a mean composition of (Ca0.2 calcite.0019)CO3. / Marine and Petroleum Geology 18 (2001) 287±306 Fig. it is predated and postdated by corrosion surfaces. (Fig. C2.3½ and d 18O from 25.0182Fe0. 8A and B). shows a mottled texture. irregularly shaped sectors (Fig. which cut across sequence 2 cements.9½.994Mg0.294 C.2 calcite-C3. The bright spots represent the sites of microprobe analyses.2 are depleted in Mg and enriched in Sr. Plot of Mg versus Fe for sequence-1 calcites.1 is slightly more magnesian than C1. 8C).0001)CO3. non luminescent). Deformation includes twin lamellae. 8C and B).2 is predated by fractures which cut across at low angles C2.1-bearing fractures.2 to 11. In some fractures.4. and are interpreted as a replacement after matrix-replacive.981Mg0.

indicating its later-stage compressional reactivation.1 is commonly formed by a ®ne-scale alternation of ferroan and non-ferroan bands (Fig. Note that C2. The earliest growth zones of sequence 3 contain extensive deformation twins and aqueous FI-bearing microcracks. which ®lled the residual porosity of this fracture (lower right). Cements are alternating ferroan and non-ferroan calcite. The non-ferroan cement zones typically luminesce greenish with concentric zones in blue-light epi-illumination. These cements are in turn affected by pressure solution along the borders of the reopened stylolite. 9F). Note the presence of trails of bright spots (upper right) representing aqueous FIs trapped along microcracks.4 is slightly ferroan.2. C3. which appears bright yellow under transmitted light (Figs. Rossi et al. and replaces celestite. Note the differences between the two darker-coloured.1) is more rich in inclusions and forms the central parts of the crystals.2 calcite and ®nally by C3. B: Transmitted light photomicrograph after staining. The formation of these pseudosecondary inclusions was postdated by the precipitation of sequence-3 calcites.1 ferroan calcite postdated by thicker and non-ferroan C2. whereas the younger growth zones are relatively clean of such features. 8.3 is predominantly ferroan and dully cathodoluminescent. / Marine and Petroleum Geology 18 (2001) 287±306 295 Fig. indicating precipitation after a local compression±extension cycle.1 to C3. prismatic C2. A: In this CL photomicrograph. dull luminescent. C3.1. relatively bright and dull orange luminescence and sector zoning. predominantly non cathodoluminescent but showing several bright hairlines. C: CL photomicrograph showing dark luminescent. The later part of sequence 3 is formed by two generations (C3.2 calcite with.2 calcite. Petrography of sequence-2 calcites. the earlier calcites are ferroan. Growth zones of sequence 3 are dif®cult to correlate between different samples. C3. during precipitation of sequence 3 calcite cements. D: CL photomicrograph showing sector and diffuse concentric zoning in C2. forms the outer parts of the crystals. This surface is covered by a layer of dark luminescent calcite (late C2. whereas the last ferroan calcite (C3. The ferroan zones typically do not luminesce in blue-light and luminesce dully in CL. green to dark and zoned under blue-light . and the next generation (C3. and dark green and zoned under blue-light epi-illumination. ferroan generations: the ®rst ferroan calcite (2.4 and C3. is commonly marked by an ironhydroxide-rich surface. C3. dull to bright yellow under CL. which is postdated by non-ferroan and lighter luminescent C2. sequence-3 cements ®ll a re-opened vertical stylolite. C3.5 is non-ferroan.C.5). and affected by a prominent corrosion surface.3.3) has a cleaner aspect. but ferroan zones typically give way to non-ferroan zones (Fig. and non luminescent or brightly subzoned in CL. Note also that C2. 9D±E).2 has abundant aqueous FIs which appear as trails of bright spots that terminate against a growth zone boundary (arrow). The transition between late C3. The early part of this sequence consists of three zones. oil-FI bearing.3 ferroan calcite. arrows) bearing primary oil inclusions. non-ferroan).1 (ferroan).1 is altered and partially replaced. In one sample. 9A±C).

epi-illumination. A±B: transmitted light photomicrograph of ®ne-scale alternations of ferroan and non-ferroan zones in early C3. and C3. F: CL photomicrograph showing a C3. and the MnCO3 is typically below 0. E: CL photomicrograph of approximately the same view as D. Rossi et al.1 (lower part) from the non-ferroan C3. where the mole percent MnCO3 can be as high as 1.3 mole% except in some bright luminescent bands.2. but with a wide variation in Fe content.3. Thin-section petrography of sequence-3 calcites. Plane polarized light.1 showing the bright luminescence of the non-ferroan subzones. D: transmitted light photomicrograph of iron hydroxide-stained surface (arrow) separating the predominantly ferroan C3.to bright yellow luminescent. 10). The latest cements .8 to 11. 9.4. The earliest cements of sequence 3 (3. C: CL photomicrograph of early C3. There is a clear tendency for the sequence-3 cements to be less magnesian than sequence 2 (Fig.3-®lled vertical fracture crosscut by a horizontal fracture ®lled by C3. and typically includes one or two intervals of ¯uorescent microsparitic internal sediment.1) have d 18O from 28 to 28.1.6½ and d 13C from 10.1 and C3. re¯ecting the alternation of ferroan and non-ferroan subzones. and the dull luminescence of the ferroan ones.4 (bright yellow luminescent and zoned) and C3. these cements ®ll fractures that postdate C3.4½.5 (predominantly non-luminescent with orange hair-lines and internal sediment).296 C. which is non. As detailed in B.2 (upper part). / Marine and Petroleum Geology 18 (2001) 287±306 Fig. Sr contents are invariably below the detection limits.3. The ferroan zones appear darker as a result of selective staining by K-ferricyanide. In places. the non-ferroan zones host primary all-liquid aqueous FIs (arrow). showing the predominantly dullluminescent C3.

The yellow-¯uorescent inclusions are the only oil inclusion type in some microfractures. they are only found in one or two fracture ®llings per sample. 1984).5 mm (e. In one sample from the middle part of the formation. Oil inclusions are particularly abundant in samples from the basal part of the formation. 13B and C) that cut across the cement zones. FI petrography 6. abundant calcite-cemented fractures (less than 0.V. inclusions with a yellow ¯uorescence. C2. We interpret the variability in phase ratios of the oil inclusions as a consequence of endolithic biologic . In these fractures and groups microfractures. so they are interpreted as pseudosecondary in origin (sensu Roedder. 11). op. Here. 11. Some oil inclusions. hundreds of oil FIs per mm are observed even in very thin sections (Fig. 4F and 12). These ®laments have not been observed in other cement zones or in other samples. are primary in the ferroan calcites of sequence 2 (C2. In this diagram.C. 12). more typical of lower gravity oils (McLimans. Oil inclusions Oil inclusions have been observed in seven samples.1. 12 and 4F). In samples from the basal part of the formation. In this cement generation. cit. the ®laments are seen to penetrate oil inclusions. in places. The yellow¯uorescent oil inclusions are typically very small and all liquid. 13B).4½. apparently causing leakage of the oil inclusion and partial ®lling of the bacterial or fungal ®lament mould by oil (Fig. Plot of Mg versus Fe content in sequence-2 and sequence-3 calcites. Fig.). Rossi et al. epi-illumination. the calcites of both sequences are distinguished by their different Mg contents. are typically larger. or contain very small vapour bubbles. 13A). whose stratigraphic position is shown in Fig. which is commonly characteristic of light oils (McLimans. Some of these inclusions also contain a visible aqueous phase (Fig. however. oil inclusions are signi®cantly more scarce and.1 cement is.g.5 mm in thickness) and groups of closely spaced microfractures are crowded with small oil inclusions (Figs. a single microfracture: Fig. they coexist with the blue ones.e. These oil-bearing fractures are typically thicker that 0. oil FIs are restricted to the last growth zone and elongate in the direction of growth (Fig. 10. 12 and 13A). 13C). but not in later cements.1 contains primary blue-¯uorescent oil inclusions which show extremely variable gas-to-oil ratios. but vary widely from one assemblage to another. are present in small amounts. 13A). 8A). 1991). most have the appearance of two-phase oil-gas inclusions. Most oil inclusions ¯uorescence blue in U. In places. while in others.5) have d 18O ˆ 26. The oil-bearing zones in this sample are crowded with possible fungal or bacterial ®lament moulds (Fig. when present.3½ and 6. of sequence 3 d 13C ˆ 26. In samples located upsection. 13D). which is the interval showing the best source-rock characteristics (Fig. 4E.1) (Figs. and ratios of gas to liquid appear relatively consistent within a given FI assemblage (i. ranging from all liquid to small amounts of liquid with large bubbles. / Marine and Petroleum Geology 18 (2001) 287±306 297 Fig. marked by abundant oil inclusions. Abundant oil inclusions are present in microfractures that cut across the cements of sequence 1 (Figs. The relative timing of the entrapment of these two oils is unclear. and their oil-inclusion density is usually very low (tens of inclusions per mm in thick sections). The blue-¯uorescent ones. however. further indicating a primary origin (Fig. (3. The corrosion surface that predates late-stage C2.

the early sequence 3 cements contain either secondary or pseudosecondary FIs similar to those in C2. These inclusions are too small to use for microthermometry. these `primary' aqueous inclusions are extremely rare. they have small bubbles. although locally. and Bitzer (2000b).2.3. showing the location of the oil-FI-bearing samples and their estimated relative abundance of oil inclusions (RAOI). Most ¯uorescent oil inclusions are in microfractures that cut across C1. some of the earliest growth zones contain very small primary all-liquid inclusions. / Marine and Petroleum Geology 18 (2001) 287±306 Fig. Aqueous inclusions Cement C1. but in places. concentrated along cloudy growth zones and typically elongated in the direction of growth (Fig. 11. 9A and B). 6. .1 and pseudosecondary in C1.2 typically contains very small primary aqueous inclusions. Most of the aqueous inclusions are trapped in microfractures. In addition. Aqueous inclusions are abundant in healed microfractures in C2. Rossi et al.1. which also has higher TOCs and the best source-rock characteristics according to Permanyer et al.2. Therefore. Fig. the microcracks terminate against the base of sequence 3 cements (Fig. Stratigraphic distribution of the studied samples.2 precipitation or after. 1994). are best interpreted as primary. In C2. 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. Epi¯uorescence photomicrograph showing abundant ¯uorescent oil inclusions (bright spots) in a very thin (.298 C. (2000b). The oil inclusions are therefore interpreted as primary in C2. leading to their alteration. which are predominantly all liquid. These inclusions are predominantly all liquid. but before C3. These aqueous inclusions are generally very small. they are associated with primary oil inclusions in the same cement. suggesting heterogeneous entrapment of a liquid and gas phase at a low temperature. but locally.1 and also contain ¯uorescent oil inclusions. probably at outcrop. These microfractures are aligned with fractures (arrows) ®lled by C2.2±1. Goldstein & Reynolds. penetration of the FIs. Salas. they contain small bubbles. In sequence 3. Some of the microfractures are clearly ®lled with a cement. They are predominantly all liquid. Note that the samples with higher RAOIs are from the basal part of the formation. and in places. 12. Commonly.2.20 mm) section of a sample from the basal part of the Ascla Formation. they have bubbles and highly variable vapour-to-liquid ratios. and are thus interpreted as pseudosecondary in origin (sensu Roedder.1.2 and C1.3. suggesting an originally low-temperature origin and later thermal reequilibration of variable magnitude or metastability of the all-liquid inclusions (cf. but not within the surrounding calcite. the inclusions formed during the end of C2. The total organic content (TOC) values are from Permanyer. so inclusions trapped within them. 1984). 8C).

and 6 ice ®nal melting temperatures on aqueous inclusions (Tm ice). 14). or FIAs with inclusions of highly variable vapour-toliquid ratio. however. Within individual FIAs. B: ¯uorescent FIs in C1. blue-¯uorescent inclusions trapped in microfractures ®lled with C2.78C.7 and 23.118C (4 FIAs).1. For those in secondary or pseudosecondary inclusions in Sequence 3. Note that all FIs are two phase and contain similar ratios of vapour to liquid.1.3. between 18 and 248C (4 FIAs). C: Three-phase inclusion mostly containing ¯uorescent oil.C. 14). 14). most of them from oil inclusions. The measured Th in oil inclusions are from primary and pseudosecondary. D: all-liquid oil inclusion. containing secondary FIs.0 to 20. the overall range of Th is very wide.100 mm) sections using a combination of epi¯uorescence and transmitted light.2.98C (Fig. measured Tm ice values are high and relatively consistent from 0.0 to 20. Tm ice values ranged from 0. the range of Th is narrower but also variable: . from 84. but in places. and more rarely higher (2 FIAs) (Fig. Tm ice values measured in these inclusions are 22. A: assemblage of primary oil FIs de®ning a growth zone in a late growth zone of C2. 7. We avoided microthermometry on oil inclusions suspected to have been altered by biologic processes.1 fracture-®lls along with oil FIs. with a gas bubble and a small rim of aqueous liquid visible in the uppermost tip. / Marine and Petroleum Geology 18 (2001) 287±306 299 Fig. it was extremely dif®cult to get microthermometric measurements from them. from 45 to 115. Data could be obtained only from two FIAs.28C. Because the aqueous inclusions of some generations were so small.1. these oil inclusions occur within a narrow fracture. They are aligned along what would normally be interpreted as a healed microcrack. ®lled with C2.1. Note the presence of possible endolithic fungal or bacterial ®lament moulds (arrows). one with only one measurable inclusion (Th ˆ 1148C). In these inclusions. .5 to 117.28C. and the other showing a wide range of Th variation. Photomicrographs illustrating oil FIs in thick (. they have bubbles and highly variable vapourto-liquid ratios. Rossi et al. In CL and blue-light epi-illumination. surrounded by possible endolithic fungal or bacterial ®lament moulds partially ®lled by ¯uorescent oil (arrows). The aqueous inclusions with measured Th are primary inclusions trapped in the C2.28C (Fig. 13. FI microthermometry We obtained 61 homogenization temperatures. In the pseudosecondary aqueous inclusions present in generation C2. indicating the inclusions are actually primary in origin and were trapped after precipitation of sequence 1 and during precipitation of C2.

Although a transient thermal event cannot be disproved for C2. This would indicate that at least some of C2. temperatures had dropped to very low values. we conclude that the oil inclusions must have been trapped broadly during the time of precipitation of C2. and that thermal reequilibration of the aqueous inclusions was unlikely. if oil inclusions are buried after entrapment and overheated above their entrapment temperatures. because the liquid-vapour phase envelopes for light oils often show major variation for only small variations in composition (cf. higher temperature Th at 1178C.1 and pseudosecondary in cement sequence 1. / Marine and Petroleum Geology 18 (2001) 287±306 Fig. it remains possible that the variation in Th is merely the result of secular compositional variation of the oils entrapped.508C. Another explanation could be that the range in Th re¯ects true variation in entrapment temperature.1 precipitation. These Th tend to coincide with the uppermost Th data measured from the oil inclusions measured in the same FIAs.2 precipitated at low temperature (less than . If it is true that neither the aqueous nor petroleum inclusions have reequilibrated. then the coincidence of the petroleum and aqueous.1 time. Discussion 8. However. 1987. 14. And ®nally. 1989.2 are dominated by all-liquid FIs.2 precipitation. Goldstein & Reynolds. Thus. but seems unlikely. This is possible. . 1994).2 are dominated by all-liquid inclusions.1-®lled microfractures. the internal pressures are less likely to rise signi®cantly above the external pressure than aqueous inclusions. Episodic fracturing may have allowed overpressure release.2 and the beginning of C3.1 also are variable. 55±618C. which suggests that these cements precipitated at relatively low temperatures. The meager data on Th in the aqueous inclusions trapped along with the oil in C2. the variability in Th is most easily explained by pressure or compositional variations. Homogenization temperatures of blue-¯uorescent oil and aqueous FIs in unaltered C2. Goldstein & Reynolds. however. This would be consistent with the lightness of the trapped oils (as deduced from their blue ¯uorescence). p. which seems likely given the basinal lithology and complex fracturing history in the system. 1994. and thus oil inclusions are less prone to thermal re-equilibration (Burruss. Primary aqueous FIs in cements of sequence 3 are allliquid. Other FIAs are more wide-ranging and could have been altered by thermal reequilibration. The Ascla Formation is composed of low-permeability marly limestones that could have developed overpressure during C2. The oil inclusions are primary in C2. The variability in Th could easily be explained by variable amounts of thermal reequilibration. Thus. Rossi et al. Goldstein & Reynolds. 1994). 50± 598C. given the apparent restriction of oil entrapment to a single position in the paragenesis.1. pseudosecondary FIs in C2.1.1. The variability in Th of the oil inclusions needs to be explained. 39).300 C. This shows that between the end of C2. as argued above. and 63±748C. 8. Another possibility is that the variation in Th re¯ects entrapment at similar temperatures but under variable pressures. indicates a period of FI entrapment in which both phases were saturated with respect to the gas phase. Some FIAs are narrowly distributed and thus a reliable indicators of minimum entrapment temperatures of 45±498C. This suggests that C1. the simplest hypothesis would be that temperatures decreased after C2.1 precipitated at 1178C in the presence of gas-saturated oil. Interpretation of FI data The primary aqueous inclusions in C1.

and isotopic composition (Fig. . The dolomite not only ®lled porosity but also partially replaced the host limestone. 8.3b. Rossi et al. 1. 15). Fig. Composition is consistent with precipitation from marine water. 1991). because it ®lled remaining primary porosity. Meyers. indicating more reducing waters consistent with progressive burial and a different ¯uid composition (cf. The dolomite must have precipitated relatively early in the diagenetic history. / Marine and Petroleum Geology 18 (2001) 287±306 301 Fig. as suggested by their paragenetic position before and just after initial compaction. Data for meteoric calcites in the Catalan Coastal ranges are from Trave et al. The presumably marine. Rectangular ®elds represent mean values ^ one standard deviation for each zone. where the original primary porosities were higher due to the predominance of shallower-water facies (Salas. Fe-poor cements (C1.and Sr-rich. 16). Moreover. 1989). especially the relatively high overall Mg and Sr content. The abundance of dolomite increases up section. Summary of Mg and Fe contents of the different calcite generations.2 is common in modern and ancient marine calcite cements. (1998). 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. relict ®brous texture of both C1.4. and low-temperature FIs. 15). C1. This suggests that the original abundance of dolomite was controlled by depositional facies.1. 16. 15. Oxygen and carbon isotopic compositions of individual calcite cement zones. Sequence 1 ended with the precipitation of dolomite. low Fe content (Fig.2. which ®lled the remnant primary porosity and some new fracture porosity.1 and C1. especially towards the top of  Fig.C.2) were followed by non-¯uorescent generations with higher Fe and lower Mg contents (C1. Mg.

Rossi et al. 3. the second explanation (multistage dolomitization) is consistent with the association with faults.6½VPDB) indicates that C2. The relatively positive d 13C values (Fig. It postdates the dolomite. then the dolomites in the Ascla would have precipitated at burial depths of less than about 1000±1500 m (Fig. 8. 17). which could have acted as conduits for hot ¯uids. However. 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. & Salas. Timing has been interpreted as predating deposition of the upper part of the Valanginian.8½SMOW (Friedman & O'Neil. 17). which is consistent with a basinal brine enriched in 18O from evaporation or ¯uid±rock interaction. the Ascla Formation grades upwards into an extensive unit of dolomitized carbonate (the Talaies Dolomite. / Marine and Petroleum Geology 18 (2001) 287±306 Fig. 2000. Generalized paragenetic sequence of the Ascla Formation. The location of dolomitization in the Talaies is related to normal faults. 3).5±6 wt% NaCl eq.1 precipitated from a water with d 18O ˆ 19. cit).1 hosts primary oil inclusions. Martõ & Roca. the formation. 1987) that replaces the Tithonian to Berriasian Bovalar Formation and the top of the Ascla Formation (Nadal. In the Salzedella area.). because the dolomites were partly eroded during development of a late Berriasian-to-late Valanginian unconformity (Fig.1 and abundant fracturing during this stage is consistent with timing beginning during rapid Barremian±Albian rift subsidence or Late Cretaceous post-rift subsidence and ending with maximum burial during the latest Cretaceous or earliest Tertiary (Fig.3. 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 relationship between the Ascla and Talaies dolomites could not be evaluated further because the Ascla dolomites have been almost completely calcitized. Salas. The ®rst explanation is consistent with the relatively small depth of burial for dolomite precipitation inferred by Nadal (2000). C2. which is consistent with its observed paragenetic position (Fig.1) ferroan calcite. The dolomitization of Sr-rich marine carbonates might have released the Sr necessary for the precipitation of the celestite that postdated dolomite. or (2) multiple events of dolomite precipitation at variable temperatures. 17. Burial-thermal modelling shows that the Ascla . 2000). Unfortunately. and with the evidences of zoning described by Nadal (op. 16) are also consistent with such a ¯uid. Mas. so oil migration must have taken place during or after the late Valanginian. If the dolomites in the Ascla and Talaies Formations are equivalent. Ân-Closas. Querol. sensu Salas. Assuming a precipitation temperature of 1178C. which may predate the late part of the Valanginian. Guimera Â. The high-temperature FIs in C2. The Tm ice data indicate that C2. 1994.1 precipitated from waters slightly more saline than sea water (4. Interpretation of cement sequence 2: main burial stage and oil migration Sequence 2 begins with the precipitation of syntectonic (C2. 1977). from all liquid to two-phase with inconsistent Th (80±1258C). Aurell. If the reported FIs are primary and have not suffered necking down after a phase change.302 C. 1995). Melendez. Nadal (2000) has reported in the Talaies dolomites the presence of FIs with variable densities. Nadal. the oxygen isotopic data (d 18O ˆ 25.

this remains a possibility.1 and ®lled with non-ferroan calcite of C2. after the inversion of the Maestrat basin and its transformation into an emergent fold and thrust belt.3½VPDB) indicates precipitation from a water with d 18O from about 25. 2001). 1996. If C2.3½ SMOW (Friedman & O'Neil.2 does represent cooling of the unit. 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. 2000). Later sequence3 compressive structures could be Middle Miocene.5 (Fig.C. 1992.2.1±C1. Rossi et al. when the area suffered a subordinate compressional tectonic pulse  . Interpretation of cement sequence 3: Tertiary uplift Sequence 3 typically ®lls fractures that cut the sequence-2 fractures at high angles.2) are geochemically similar. 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. In the Ä agolosa sub-basin (Fig.2. 1977). and the events of oil migration that predate it must have taken place before the Eocene. as indicated by the presence of abundant all-liquid primary FIs (Goldstein & Reynolds. consistent with precipitation from marine-derived water.2 and the ®rst cements of sequence 1 (C1. they must postdate at least one compressional and one extensional tectonic event. However.. Zn±Pb deposits are not known and there is no evidence that such high temperatures had been reached.. we interpret that sequence 3 precipitated from low-temperature meteoric water. Similar maximum temperatures (1118C) have been obtained by Permanyer et al. 16) is also compatible with precipitation during a phase of erosional unroo®ng. Given the fractured nature of the unit and the evidence for a change in pore ¯uid composition. If one were to assume a temperature of 80± 1008C for precipitation of C2. when the Ascla reached its maximum burial depth and presumably maximum temperature. hydrothermal circulanearby Pen tion resulting in Zn±Pb mineralization (with local presence of ¯uorite).2½VPDB would indicate precipitation from a water with d 18O from about 0 to 12½ SMOW (Friedman & O'Neil.1 (28. then the its d 18O of 211.4½) of the last sequence-3 zone (C3. 1994) (Fig. it makes sense to interpret that C2. 15). at temperatures as high as 1508C. which suggests ®nely alternating reducing and oxidizing conditions compatible with a meteoric origin. & (the Betic compression of Calvet. Vegas. Asmerom. Both are Mg-rich. The low d 13C is consistent with the incorporation of soil-derived CO2. & Labaume. which are about 1178C.. Soler. Another explanation could be that the unit was cooled by deeply circulating pore ¯uids. suggesting a radical change in the stress ®eld. Assuming a precipitation temperature of 30±408C. occurred during the early Paleocene (Grandia.3½) and d 13C (26. Sequence 3 is typically formed by alternating ferroan and non-ferroan calcites. Thus. and if it predates compressional tectonism and its related unroo®ng. 2000a).2 is deformed by compressional structures. then the d 18O of C3. The carbon isotopic composition of 20. this trace-element composition could be consistent with precipitation from marine-derived waters. In the Salzedella sub-basin. 17). from C3. 1992).2 to 20. Some sequence-3 zones may have precipitated during the Late Oligocene to Early Miocene. indicating further compression. Because they ®ll re-opened vertical stylolites. These cements are cut across by further vertical stylolitization. Finally. Cardellach. Trave  . 1).5) are typical of meteoric calcites precipitated at lowtemperature in open systems.e. Roca.2. The low trace element content and moderately light d 18O (26. Calvet.2 to 23.1±C1. Soler. The resulting fractures were partly cemented by ferroan calcites of C2. Getty. i.e. 1977). i.2 represents part of the cooling path of this unit. C2.4. & Canals. suggesting increasingly less reducing conditions or limited Fe availability. The overall trend of the carbon and oxygen isotopic compositions of sequence 3.2.1 records the maximum temperatures reached by the Ascla. the relatively positive carbon isotopic composition (10. but there are no deformation features that would indicate this change in stress ®eld until after C2.8 to 11. 9B). in which cooler and more soil-in¯uenced waters progressively . These relationships suggest that sequence 3 precipitated during and after the Eocene±Oligocene (Fig. Therefore. 8. Labaume. and must then re¯ect ¯uid±rock interaction in a setting distal from the soil zone. one must question why the cooling has occurred. C2. Trave Sequence-3 cements are characterized by low Mg and Sr contents relative to sequences 1±2 (Fig. Our data are consistent with this. (2000a) from vitrinite re¯ectance values using empirical calibrations. the cooling could easily be related to decreasing heat ¯ow in the basin. consistent with meteoric-derived water. to meteoric waters in sequence 3.2 precipitation.1 to C3. Widespread vertical fracturing predated and postdated oil migration. Fe-poor and have Sr-enriched sectors (Fig. C2. The FI data suggest that C2. at least at a local scale. The earliest sequence-3 calcites precipitated at lowtemperature (less than about 508C). As in C1. / Marine and Petroleum Geology 18 (2001) 287±306 303 Formation in the study area probably entered the oil window during the Cenomanian (Permanyer et al.2 might have been preceded by the maximum temperatures and clearly were postdated by low temperatures.4½VPDB) is not consistent with the incorporation of soil-derived carbon. Thus. 15). One possibility would be that some compression and uplift coincided with C2. The onset of compressive tectonics and basin inversion has been interpreted as Eocene in age (Salas et al.7½VPDB is also compatible with marinederived waters. The FI data indicate that C2. when the area suffered its ®rst major stage of compressional tectonics. This suggests a change from predominantly marine-derived waters in sequences 1 and 2. 1998). but the least equivocal FI data suggest oil generation and migration continued during the latest Cretaceous or earliest Tertiary. The cements of sequence 3 are syntectonic.2 precipitation.

40 km to the west of Salzedella (Fig. 8. in the Tarragona Trough (Fig. The Amposta oil has unique geochemical characteristics and is not correlated with the other oils in the Tarragona offshore basin. This migration. 3). The ®rst sequence-1 zones precipitated from marine-derived waters. Therefore. which have their source in Miocene rocks deposited  s et al. These inclusions are essentially fresh water with extremely inconsistent gas to liquid ratios. Thus.. 1). 1990). in this area. oil migration occurred just before Alpine tectonics. 1986. Seemann et al. Sequence 1 ended with the widespread precipitation of dolomite. and the oil inclusions are only found in fractures showing low oil-FI densities.. Both the FI . which could point to entrapment during late sequence 3. however. near-surface origin. very likely during the Cretaceous to earliest Tertiary.. The possible contribution of oils generated in the Ascla Formation to the Amposta oil ®eld has been a matter of  s et al. the effectiveness of the Ascla.304 C. traceelement composition and cross-cutting relationships. Seemann et al. the isotopic compositions of sequence-3 calcites are similar to the values reported by  et al. and (2) the higher abundance of oil inclusions in the basal part of the Ascla. The results of the present study indicate that oil indeed migrated from the Ascla Formation. 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. 1983). Seifert debate (Albaige et al. took place when the formation was at or near maximum burial depth and temperature. which created the most obvious traps. Implications for oil potential The oils observed as inclusions in the Ascla Formation were likely generated in the organic-rich intervals of the formation. comm. Subsequent sequence-1 calcites precipitated from reducing waters during increasing burial. the overall abundance of oil FIs is perhaps lower than one should expect for a very rich source-rock. as an oil generator. This is suggested by (1) the absence of other feasible source rocks in this part of the basin. (1998) for Tertiary fracture-®lling calcites of Trave meteoric-water origin in the nearby Catalan Coastal Ranges (Fig. Some of the latest sequence-3 zones may even have formed in the vadose zone.. 1986). (2) Cement sequence 2 precipitated exclusively in fractures. and have variable compositions as indicated by their ¯uorescence (blue and yellow). ¯uorescence. Sequence 2 begins with the precipitation of ferroan calcite.. at least in the sampled location. the oil inclusions likely represent trapping along a migration route in close association with the source-rock. (2) its oilgeneration capabilities could have been partially exhausted during the Late Cretaceous to Earliest Tertiary. which records oil generation and migration through the Ascla Formation via fractures. Rossi et al. 1) (Albaige It has been argued that the Ascla Formation cannot be the source for the Amposta oil. It is therefore conceivable that similar conditions could have existed in the present-day offshore near Amposta ®eld. (2) the source-rock potential. However.. 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. compatible with trapping in the vadose zone. 1990. Moreover. 1999). Overall.5. These characteristics suggest trapping along a migration route through fractures. is not particularly high (Permanyer et al. must have been limited because (1) the organic content of the Ascla source-rock intervals is relatively low. This ®eld is located offshore. 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. and (3) oil generation predated formation of most of the traps. 1990) and in outcrops near la Salzedella (Permanyer et al. 11). 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. and reservoirs oil in Paleogene-aged karst developed in Lower Cretaceous carbonates (Seemann et al. The age of the trap and seal is Miocene. some Miocene subsidence could have caused a second phase of oil generation from the Ascla Formation. In samples from this part of the formation. oil inclusions are abundant in fractures and especially in clusters of microfractures (Fig. samples bearing oil inclusions are scarce. pers. However. (1) Cement sequence 1 precipitated during the Kimmeridgian-Valanginian burial stage and mainly ®lled the primary porosity. 12). very likely during the latest Cretaceous to earliest Tertiary burial when the Ascla Formation reached its maximum burial depth. Unlike the Salzedella sub-basin.). the trapped oils are restricted in composition. / Marine and Petroleum Geology 18 (2001) 287±306 predominated. which contains the richer potential source rocks (Fig. 16)... The earliest cements in sequence 3 contain the most abundant fresh-water inclusions along healed fractures. Conclusions Three distinct calcite cement sequences are distinguished in the Ascla Formation by their CL. unless pre-Alpine traps are preserved. the potential for oil accumulation in this particular part of the basin is probably low. even in the richer intervals. These features are typical in source rocks which have generated oil (Norman Oxtoby. 1999). when the area experienced an important rifting phase. (1990) found geochemical similarities between Ascla-source-rock extracts and the Amposta crude. This dolomite is currently replaced by inclusion-rich calcite. and before the Eocene.. In the middle and upper parts of the Ascla. as suggested by the crystal silt internal sediments coinciding with precipitation. 1986). Thus. Possible causes are: (1) The studied samples are from limestones. 9. and the richer source beds are the interbedded marls. Even in this case.

Bartrina. & Labaume. The resulting fractures are mainly ®lled by non-ferroan calcite yielding geochemical data compatible with precipitation from marine-in¯uenced waters at elevated but potentially decreasing temperatures. U±Pb dating of MVT ore-stage calcite: implications for ¯uid ¯ow in a Mesozoic extensional basin from Iberian Peninsula. S. 239±245. FracturaCalvet. & Salas. Mann. J. Lisk. Norman Oxtoby and an anonymous reviewer are thanked for their careful reviews and critical comments.. (12 pp. Burruss.) Goldstein. Paleotemperatures from FIs. (1986). Bulletin de la Societe Karlsen. Calcite cement stratigraphy: an overview. A. Rossi et al. References  s. McCulloh. Dorronsoro. Geological society special publications 144 (pp. U. Luminescence microscopy: quantitative and qualitative aspects.. 377±380. R. In C. R.. Soler. The petrographic and FI characteristics. 369± evolucio 396. P. Roca. C. In J. mica (pp. J. Brasil. New York: Springer.. Cabrera. England... H. (Cuenca del Maestrazgo. M. J. S. unless pre-Alpine traps are preserved. 339±348. N. T.. Dolomõ  sico superior±Creta  cico inferior en la subcuenca de la Salzedella Jura  rica). (2000). which are around 1178C. D.C. R.. In L. W. & Rossi. 199±202). (1995). Algaba. U.. J. whereas subsequent sequence-3 zones likely precipitated during the Neogene. Rio de Janeiro. (3) Sequence 3 is formed by alternating ferroan and nonferroan calcites. 18. qualitative and quantitative applications. J. C. P.. (1989). Spain).... 10. 247±252. 219±247. 51. 119±131). M. Naeser & T. Mar®l. 78. C. K.. (1998). C. 42. E. & Grimalt. burial history. Guimera Evolution of the central Catalan margin of the Valencia trough (western Mediterranean).. Mas. Permanyer. very likely when the formation reached its maximum burial depth during the Late Cretaceous to earliest Tertiary. Melendez. K. R. D. An integrated approach to the study of primary petroleum migration.. Compilation of stable isotope fractionation factors of geochemical interest. 441±450. J. In M. B.. 1715± 1718. K. Parnell.). Kopp. 69±70 (1±3). 31 (199 pp. M. A. J. 233±260. Calcite staining: semiquantitative determination of ferrous iron. W.. Matias & M.. (1987). R. & O'Brien. Cuadernos de Geologõ Âa Ibe  rica.. Rube  ndezis acknowledged for his ®eld work and Alfredo Ferna Larios for his technical assistance with the electron microprobe. J. Clavell.. In 31st International Geological Congress. Trave  n y migracio  n de ¯uidos durante la evolucio  n tecto  nica neo  gena en el cio Sector Central de las Cadenas Costero Catalanas. Geo¯uids: origin.  nsito Jura  sico± Aurell. In N. methods and case histories (pp. the potential for oil accumulations in this part of the basin is probably low.. & A  volution de la compression Guimera  rique et la Chaine cotie  re catalane (Espagne). Luminescence microscopy and spectroscopy. Asmerom. SEPM short course. R. R. (1972). 20. Geological Society Special Publication. (1991). & Roca.. The geochemistry of reservoirs. (2000). Journal of Geochemical Exploration. Geotemas. 141±157. & Canals. E. Dating and duration of ¯uid ¯ow and ¯uid-rock interaction. and petroleum migration using luminescence microscopy. (1991). A.. Structure et e  . (1996). Geogaceta. y Basto. Salas. J. M. A. Brasil. J. Organic Geochemistry. Widespread vertical fracturing postdated oil migration. In C. A. Tectononophysics. Permanyer. & Bitzer. Hydrocarbon composition of authigenic inclusions.. (1977). El tra  cico en la Cordillera Ibe  rica: relacio  n tecto  nica-sedimentacio Ân y Creta  n paleogeogra  ®ca.S. G. 57. Petroleum Albaige geochemistry of the Tarragona Basin (Spanish Mediterranean offshore). Acknowledgements Funding was provided by research projects DGICYT  n Duro PB96-1236-C02-01/02 y PB95-1142-C02-01. Potencial petrolõ  sico superior) en la Cuenca del Maestrazgo. & Bjorlykke. Jurado. Burruss. J. Y. Barker & O. Data of Geochemistry (6th ed. 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.. Cubitt & W.). . Mitchell. Âas relacionadas con fallas durante la etapa de rift Nadal. 477±481. 189±203). W. / Marine and Petroleum Geology 18 (2001) 287±306 305 and isotopic data can be interpreted to indicate that this calcite records the maximum temperatures reached by the Ascla. & O'Neil. which precipitated exclusively in fractures during the Tertiary. 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. Mineralogical Magazine. E. (Jura  rico de geoquõ ÂM. (1994). advances in theory and technique. A. G. Journal of Sedimentary Petrology. (2000). (1994). A. M. & Reynolds. Unravelling complex ®lling histories by constraining the timing of events which modify oil ®elds after initial charge. 3641±3659. H. Eadington.. J. 1 (2). Kopp. Feisher (Ed. & Mar®l. Barker & O. Rio de Janeiro. The ®lling and emptying of the Ula Oil®eld: FI constraints. Organic geochemistry and sequence stratigraphy: an example in the Kimmeridgian-Tithonian from the Maestrat Basin (Eastern Iberian Chain. 203. A.). A. Geochimica et Cosmochimica Acta. Salas. migration and evolution of ¯uids in sedimentary basins.. (1992). Oil migrated before the Eocene. application to elucidation of petroleum reservoir ®lling history. J. Larter. Getty. R. whereas the non-ferroan subzones represent the ingress of oxidizing waters perhaps related to episodes of fracture opening. F. R. L... Meyers. Lindholm. A. The ®rst sequence-3 zones precipitated during or after the Eocene±Oligocene stage of compressional tectonics. In J. C.. 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