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Paragenesis of Cretaceous to Eocene carbonate reservoirs in the Ionian fold and thrust belt (Albania): relation between tectonism and fluid flow
1. 2. 3. 4. 5. M. Van Geet1, R. Swennen1, C. Durmishi2, F. Roure3, PH. Muchez1

Article first published online: 15 AUG 2002

DOI: 10.1046/j.1365-3091.2002.00476.x Issue

Sedimentology
Volume 49, Issue 4, pages 697718, August 2002 Additional Information(Show All) How to CiteAuthor InformationPublication History

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Keywords:

Carbonate turbidites; diagenesis; dual porosity; fractures; layer-parallel shortening; stable isotopes

Abstract
ABSTRACT This paper examines the diagenetic history of dual (i.e. matrix and fracture) porosity reservoir lithologies in Cretaceous to Eocene carbonate turbidites of the Ionian fold and thrust belt, close to the oil-producing centre of FierBallsh (central Albania). The first major diagenetic event controlling reservoir quality was early cementation by isopachous and syntaxial low-Mg calcite. These cements formed primarily around crinoid and rudist fragments, which acted as nucleation sites. In sediments in which these bioclasts are the major rock constituent, this cement can make up 30% of the rock volume, resulting in low effective porosity. In strata in which these bioclasts are mixed with reworkedmicrite, isopachous/syntaxial cements stabilized the framework, and matrixporosity is around 15%. The volumetric importance of these cements, their optical and luminescence character (distribution and dull orange luminescence) and stable isotopic signal (18O and 13C averaging respectively; 05 VPDB and +2 VPDB) all support a marine phreatic origin. Within these turbidites and debris flows, several generations of fractures alternated with episodes of cementation. A detailed reconstruction of this history was based on cross-cutting relationships of fractures and compactional and layer-parallel shortening (LPS) stylolites. The prefolding calcite veins possess orange cathodoluminescence similar to that of the host rock. Their stable isotope signatures (18O of 386 to 085 VPDB and 13C of 014 to + 298 VPDB) support a closed diagenetic rock-buffered system. A similar closed system accounts for the selectively reopened and subsequently calcite-cemented LPS stylolites (18O of 181 to 114 VPDB and 13C of +152 to +256 VPDB). Within the prefolding veins, brecciated host rock fragments and complex textures such as crack and seal features resulted from hydraulic fracturing. They reflect expulsion of overpressured fluids within the footwall of the frontal thrusts. After folding and thrust sheet emplacement, some calcite veins are still rock buffered (18O of 096 to +02 VPDB and 13C of +079 to +137 VPDB), whereas others reflect external (i.e. extraformational) and thus large-scale fluid fluxes. Some of these veins are linked to basement-derived fluid circulation or originated from fluid flow along evaporitic dcollement horizons (18O around +30 VPDB and 13C around +15 VPDB). Others are related to the maturation of hydrocarbons in the system (18O around 71 VPDB and 13C around +93 VPDB). An open joint system reflecting an extensional stress regime

developed during or after the final folding stage. This joint system enhanced vertical connectivity. This open joint network can be explained by the high palaeotopographical position and the folding of the reservoir analogue within the deformational front. The joint system is preBurdigalian in age based upon a dated karstified discordance contact. Sediment-filled karst cavity development is linked to meteoric water infiltration during emergence of some of the structures. Despite its sediment fill, the karst network is locally an important contributor to reservoir matrix porosity in otherwise tight lithologies. Development of secondary porosity along bed-parallel and bed-perpendicular (i.e. layer-parallel shortening) stylolites is interpreted as a late-stage diagenetic event associated with migration of acidic fluids during hydrocarbon maturation. Development of porosity along the LPS system enhanced the vertical reservoir connectivity.

Introduction
Exploration in fold and thrust belts is a very challenging task. It necessitates a good understanding of pre-, syn- and post-tectonic processes, which can, to a degree, be inferred from the interpretation of seismic transects and from forward kinematic modelling (Roure & Sassi, 1995). In order to determine processes that might have affected potential reservoirs, such as cementation, fracturing, pressure solution and secondary porosity development, detailed diagenetic research is needed. It is well acknowledged that fluids play a major role in many geological processes and that episodic fluid expulsion occurs in tectonically active regimes (e.g. Oliver, 1986; Marquer & Burkhard, 1992). Based on an integrated approach combining petrography, stable isotope analysis and fluid inclusion data, it is often possible to reconstruct fluid flow through time (Muchez et al., 1991, 1994; Travet al., 1998). Additional techniques, such as the study of organic material, apatite fission tracks and clay minerals, can help to constrain the geological evolution better in tectonized areas (Pagel et al., 1996). Furthermore, it is of interest to investigate the stage in the deformation history at which fluids changed their characteristics. Muchez et al. (1995) and Henry et al. (1996) reported that synkinematic fractures are dominantly rock buffered, whereas open systems are more characteristic of large fluid fluxes and mass transfer along thrust and shear zones (see also Kerrich et al., 1984; Marquer & Burkhard, 1992). The aim of this paper is to unravel the diagenetic history of Cretaceous to Eocene deep-marine carbonates in the Ionian Zone (Albanian fold and thrust belt) and to determine the effects of diagenetic processes on reservoir properties. This is one of the first papers in which the relationships among diagenesis, tectonic features (e.g. joints and tectonic stylolites) and the porosity evolution of dual (i.e. matrix and fracture)-porosity reservoirs is addressed. Based on numerical and forward kinematic modelling data (Roure et al., 2001), it was possible to place the diagenetic evolution into the deformation history of the external Albanides. An understanding of such relationships is critical to unravelling the history of fluid circulation in fold and thrust belts. For this purpose, a surface analogue of the Ionian Zone carbonate reservoirs has been studied. This study is part of the SUBTRAP (SUBThrust Reservoir APpraisal) programme, during which similar studies have been carried out on outcrop analogues as well as on cores in the Salt Range (Pakistan), the Cordoba platform and Veracruz Basin (Mexico) and the Canadian Rocky Mountain fold and thrust belt near Calgary (Canada; e.g. Ferket et al., 2002; Ortuno Arzate et al., 2002).

Methodology
A representative set of lithofacies was identified and sampled during field work in the study area south of the Patos field (FierBallsh, central Albania). Sampling emphasis was placed on lithotypes containing matrix porosity and particular diagenetic/deformation features, such as fractures and stylolites. Sixty-five thin sections were examined by conventional and cathodoluminescence (CL) petrography. CL petrography was carried out with a Technosyn Cold Cathodoluminescence model 8200, mark II. Operating conditions were 1620 kV gun potential, 420 A beam current, 005 Torr vacuum and 5 mm beam width. Stable isotope analysis was conducted on 05-g samples extracted with a 03-mm microdrill from 47 specimens. Preextraction petrographic examination was used to ensure sample purity and to identify diagenetic phases of cements. Stable isotope analysis of carbon and oxygen was performed on a Finnigan Mat delta E mass spectrometer. Carbonate powders were dissolved in 100% orthophosphoric acid at 25 C. All data were corrected according to procedures modified from Craig (1957) and are expressed in values in per mil () difference from the VPDB international standard. Reproducibility, determined by replicate analysis of NBS 19 and NBS 20, is better than 01 for oxygen and 005 for carbon. Doubly polished sections (100150 m thick) of two representative samples of each of the most common vein generations were prepared for fluid inclusion analysis on a Linkam heatingcooling stage. However, two-phase fluid inclusions were rare or absent in the prepared sections. Some of the rocks were also studied by microfocus X-ray tomography in order to visualize pore connectivity and quantify porosity. This non-destructive imaging technique produces threedimensional density images with resolution of the order of 15 15 15 m (Van Geet et al., 2000, 2001). Trace element analysis (Mg, Fe, Mn, Sr, Na) of all vein types was performed according to standard procedures by atomic absorption spectrometry (protocol is described in detail in Swennen et al., 1990). Thermal modelling has been carried out based on the results of the Thrustpack kinematic modelling of the thrust emplacement history taking faulting, flexural deformation, vertical movements, synorogenic sedimentation and erosion into account. For the thermal modelling, different reference points were taken to trace coeval burial and palaeotemperature curves for the Late Cretaceous to Eocene reservoirs from the end of the passive margin until the present. A purely conductive heat transfer was used, with a heat flow of 30 mW m2 and a surface temperature of 16 C.

Geological setting
A general map of the structural geology of Albania is shown in Fig. 1A. The major structural zones in the eastern Internal and western External Albanides possess a NNWSSE alignment. The thrust sheets are WSW oriented. They form the extension of the Dinarides in the north and the Hellinides in the south, which relates Albania to the Alpine orogeny. The Korabi and Mirdita Zones of the Internal Albanides mainly consist of ophiolites. Within the External Albanides, from east to west, the Krasta-Cukali, the Kruja, the Ionian and the Sazani Zones can be

differentiated (Velaj et al., 1999; Meo & Aliaj, 2000; Roure et al., 2001). These zones correspond to horst- and graben-like elements resulting from extensional tectonics, especially during Late Jurassic and Early to Middle Cretaceous times (Gealey, 1988), with platform carbonates (Kruja and Sazani Zones) alternating with basinal carbonates (Ionian Zone; Meo & Aliaj, 2000). These zones become more allochthonous towards the east. The Sazani Zone is autochthonous and forms the extension of the Apulia platform. North of the transversal VloraElbasan structural element, post-Eocene sediments of the peri-Adriatic depression cover the Ionian Zone. Most of the oil and gas fields occur in the transition area where the Ionian Zone plunges below the peri-Adriatic depression. Because well-developed surface analogues of fractured carbonate reservoirs with matrix porosity occur in the latter area, near the cities of Fier and Ballsh, research was focused in this area.

Figure 1. (A) General tectonic map of Albania. (B) General stratigraphy of the Ionian Zone (vertical scale is approximate as exact thicknesses are unknown). Figure 1B gives a general lithostratigraphic section of the Ionian Zone carbonates in the study area. According to Moorkens & Dhler (1994), the sequence can be split into three major lithological units:

1 Triassic to Lower Jurassic evaporites and dolomites. The lower part of the succession consists of mudrock, with thin evaporite intervals grading upwards to an alternation of dolomite and evaporite beds and then to massive dolomites. Deposition occurred in lagoonal to shallow platform conditions. Intracrystalline porosity developed within coarse crystalline dolomite intervals, and some evaporite collapse breccias may form potential reservoirs.

2 Lower Jurassic to Eocene fine-grained carbonates, reflecting mainly basinal depositional conditions. Several prolific hydrocarbon reservoirs (e.g. Ballsh, Krane, Gorisht, Delvina) occur in these strata. Their characteristics, especially those of the Upper Cretaceous to Palaeocene strata, are the focus of this paper.

3 Oligocene siliciclastic turbidites (flysch), locally overlain by coarse-grained porous Miocene and younger deposits (molasse). Important oil and gas reservoirs are especially prevalent in Messinian to Tortonian sands and Pliocene deltaic sands. Burdigalian to

Serravallian molasse sandstones lie above an angular unconformity surface, sometimes in contact with the eroded crests of the more frontal thrusts affecting the Ionian Zone carbonates (Fig. 2). During fieldwork for this study, corals and burrowing pipes of phollades and barnacle shells intermixed with reworked limestone pebbles were observed at this contact. These features suggest a beach setting (e.g. Davis, 1985).

Figure 2. Cross-section through the Selishta, Selenica and Kremenara structures in central Albania with an indication of the different regional disconformities.

Upper cretaceous to palaeocene carbonate reservoir


The best carbonate reservoir intervals, according to Albpetrol reservoir geologists, are situated in the fractured Upper Cretaceous to Palaeocene succession (Albpetrol, 1993). Locally, Eocene porcellaneous carbonates are also productive. This Albanian carbonate sequence is the time equivalent of the Scaglia carbonate reservoirs of the Adriatic Sea and onshore Italy (Cazzola & Soudet, 1993; Bosellini et al., 1999). The studied carbonates consist primarily of fine-grained calciturbidites. Individual beds in central Albania (near the city of Kremenara) are 1035 cm thick. The turbidites reflect deep-marine depositional conditions (Cazzola & Soudet, 1993) and commonly consist of pelagic foraminiferal and coccolith wackestone/mudstone. The thickest beds contain typical turbidite sequences, including basal coarser grained intervals overlain by parallel and convolute laminae. The coarser intervals are locally impregnated with hydrocarbons (Fig. 3A). Semi-continuous beds of chert nodules, which contain ghosts of pelagic foraminifera, are less common than in underlying Middle and Upper Jurassic porcellaneous carbonates. Within the Upper Cretaceous interval, several metre-thick massive debris flow units occur (Fig. 3B). Most of the clasts consist of resedimented rudist-dominated platform carbonates with macromoulds.

Figure 3. (A) Parallel-laminated interval in the lower part of a fining-upward turbidite with welldeveloped matrix porosity and oil impregnation (dark laminae). (B) Debris-flow deposit. Note oil impregnation between clasts along stylolites (arrows). (C) Interval with widespread development

of oil-impregnated matrix porosity in the lower part of fining-upward turbidites. Lines trace some of the oil-impregnated strata, which are black. The total length of the outcrop shown is about 5 m. (D) Photomicrograph of packstone/grainstone with (oil-filled) interparticle porosity. Note equant calcite cement bordering many of the intergranular pores next to crinoid ossicles and rudist fragments. Development of syntaxial cements (arrows) is also common. Scale bar is 90 m. (E) Photomicrograph of packstone/grainstone with inter- and intraparticle porosity after hydrocarbon removal. Reworked micrite particles form the dominant rock constituent. Notice the virtual absence of cements. Scale bar is 90 m. (F) SEM photomicrograph of equant calcite bordering interparticle cavity walls after removal of hydrocarbons. Note absence of corrosion on the crystal faces. Scale bar is 10 m.

Turbidite matrix porosity


Lithologies with well-developed matrix porosity are present in some of the outcrops. Three dominant lithotypes can be recognized in the turbidite sequence: (1) porous packstones/grainstones; (2) non-porous bioclastic packstones/grainstones; and (3) mudstones/wackestones. The porous intervals occur dominantly in the lower portions (but not necessarily at basal contacts) of fining-upward turbidite sequences, where they locally comprise more than 30% of the sequences (Fig. 3C). Porous intervals are composed of bioclastic pack- and grainstones consisting of an accumulation of broken bioclasts such as crinoids, foraminifera and rudist and shell fragments. Small reworked and rounded clasts of mudstones and peloidal wackestones are also present. Clast and particle size ranges from 100 to 250 m. Sorting exerts an important control on porosity, with high initial interparticle porosity being the dominant type in well-sorted lithologies (Fig. 3D). Intraparticle porosity occurs only within foraminifera (Fig. 3E). In crinoid- and rudist-rich intervals of lithotype 2 bioclastic packstone/grainstone, syntaxial rim cements are pervasive, greatly reducing porosity (Fig. 3E). Up to 30% of the rock volume in such intervals can be made up of this cement showing dull orange luminescence. In porous lithotype 1 packstone/grainstone lithologies, crinoid and rudist components are less frequent, and these bioclasts as well as peloids occur in a micrite matrix. Syntaxial rim cements also developed in these packstones/grainstones, but do not occlude all the pores. It can thus be classed as framework stabilizing. These intervals are heavily oil impregnated (Fig. 3D). Other components are either cemented by equant calcite cement or not cemented (Fig. 3E). Lithologies rich in mixed micrite and bioclast components are generally not cemented. Equant calcite cement occurs as an isopachous cement and locally also borders biomoulds, but seldom exceeds 15 vol%. A microfocus X-ray tomography three-dimensional representation of the porosity network is shown in Fig. 4A. Based on the study of six porous samples by this technique, average porosity is 16%. Finally, in lithotype 3 mudstone/wackestone lithologies, compaction destroyed all porosity.

Figure 4. (A) Microfocus X-ray tomography view of a porous carbonate turbidite after removal of hydrocarbons. Matrix porosity has been enhanced by thresholding and is green, as is the border of the plug. Non-porous (i.e. calcite) pixels are transparent. A two-dimensional plane is also shown where faint differences in blue-green colour visualize minor variations in porosity (sample diameter is 6 mm; pixel size is of the order of 15 m in three dimensions). (B) Photomicrograph of a debris-flow clast cut by an oil-stained stylolite (white arrows). The clast, which makes up the entire right and middle part of the photomicrograph, is composed of biomoulds partially to completely cemented by drusy calcite. Remaining mouldic porosity is oil filled. The outlines of bioclasts are still discernible because of the presence of micrite envelopes (black arrows). Scale bar is 90 m. (C) Macroscopic view of the cross-cutting relationship of compactional (1) and layer-parallel shortening stylolites (2). Scale bar is 6 mm. (D) SEM photomicrograph of secondary porosity along a stylolite after oil has been removed. Notice the vertical stylolite striations (black arrows). Scale bar is 100 m. (E) Photomicrograph of calcite cement post-dating extension of an LPS stylolite. The bedding is subvertical (see alignment of bioclasts indicated by an arrow). Scale bar is 90 m. (F) Photomicrograph of an LPS stylolite with pores (arrows) and microsparitic calcite cement (M). A vein crosses the middle of the photo and has an LPS component. Bedding is subvertical. Scale bar is 90 m. Lithologies with porosities of the order of 15% and containing <15% syntaxial and equant calcite and/or rim cement possess carbon and oxygen isotopic signatures similar to those of non-porous wackestones and mudstones (18O = 05 PDB; 13C=+2 PDB; Fig. 5). The analysed Ionian samples with early diagenetic calcite cement do not record any shift in isotopic signature with respect to time-equivalent mudstones/wackestones that contain little or no cement, but are interpreted as being composed almost entirely of marine components. The oxygen and carbon isotopic composition of these limestones is within the range of marine CretaceousPalaeocene carbonates reported in the literature (Table 1). Therefore, the syntaxial and equant calcite cements are most likely also of marine origin, in agreement with their textural and volumetric distribution. However, in contrast to marine cementation in platform settings, no internal marine sediments occur upon these cements, which suggests that they formed below the sedimentwater interface.

Figure 5. Carbon and oxygen isotope cross-plot of porous grainstone/packstone with equant and syntaxial calcite and non-porous carbonate mudstone/wackestone. The cements do not seem to exert any effect on the marine isotopic composition of the mudstones/wackestones, which suggests an early diagenetic marine origin for the cements. Table 1. Stable isotope composition of Cretaceous and Palaeocene marine constituents and carbonates. 18O VPDB 13C VPDB Shackleton & Kennett (1975) 05 to 17 +02 to +14 (Late Palaeocene foraminifera) Veizer & Hoefs (1976) 10 to 42 00 to +31 (major population Cretaceous carbonates) Scholle & Arthur (1980) 25 +25 to +40 (AptianAlbian carbonates) Moldovanyi & Lohmann (1984) 20 +40 (Lower Cretaceous carbonates) Shackleton (1986) 00 to 05 +10 to +35 (Palaeocene carbonates) Jrgensen (1987) 05 to 20 +05 to +30 (Upper Cretaceous chalk) Swennen & Dusar (1997) 125 to 263 +196 to +240 (Maastrichtian chalk) Frank & Arthur (1999) 17 to +10 +05 to +22 (Upper Maastrichtian)

Debris-flow matrix porosity


A wide spectrum of clast sizes (decimetre to submillimetre) are present within the debrisflowdeposits, some of which display intraclast porosity. Nearly all clasts consist of a mixture of platform bioclasts (mainly rudists), with partially to completely cemented biomoulds. The biomoulds are easily discernible because of the presence of micrite envelopes (Fig. 4B). Most of the debris-flow clasts or biomoulds are cemented by isopachous, syntaxial and dogtooth calcite. Drusy calcite cement typically fills biomoulds (Fig. 4B). These cemented biomoulds are regularly truncated at clast edges, suggesting that dissolution and subsequent cementation

occurred in platform settings before reworking and transportation to the deep-marine environment. The porosity of many of these partially cemented clasts is dominantly noneffective. However, because many of these clasts are surrounded by stylolites and some secondary porosity developed along stylolites (described below), intraclast pores contain some hydrocarbons. Thus, debris flows contribute, to some degree, to the total hydrocarbon content of the sequence (Fig. 4B).

Porosity development along stylolites


At least two major types of stylolites can be recognized. Relatively high-amplitude stylolites (centimetre size) parallel to bedding are the oldest set and are interpreted as compactional in origin. The second set of stylolites is also characterized by relatively high amplitudes; however, they have a subvertical orientation with indentations parallel to bedding (Fig. 4C). These stylolites are believed to have formed during layer-parallel shortening (LPS) when tectonic compression affected the carbonates (Ramsay & Huber, 1983). Both sets of stylolites are commonly stained with oil, filling secondary porosity (Fig. 4D). Interconnected small cavities locally link the larger (30 by 10 m) cavities. Calcite cemented LPS stylolites also exist. Both sides of cemented LPS stylolites still fit into each other, indicating extension of the stylolite before cementation. The cement consists of either a microsparitic calcite (Fig. 4E and F) or a blocky spar with orange luminescence. Because these calcite-cemented LPS stylolites are uncommon, their development is considered to be a local phenomenon. Within several of the debris flows, contacts between clasts and matrix contain microstylolites, which are locally impregnated by hydrocarbons (Figs 3B and 4B).

Karst infill matrix porosity


Large (up to 10 by 10 cm), oil-impregnated sediment-filled pockets occur within non-porous limestones. The pockets display the outline of former cavities that became filled with either poorly sorted, sub- to well-rounded carbonate grains or layered carbonate detritus. The layering in these cavities is not parallel to the host rock bedding, indicating post-deformational infilling. The layers are mainly composed of small micritic carbonate particles (< 5 m) alternating with poorly sorted reworked carbonate allochems (mainly wackestones) and biochems. Locally, they contain detrital quartz grains, which are the only non-carbonate constituents present in otherwise pure carbonates. Nannoplankton assemblages of Langhian age (determination by C. Muller, IFP) were isolated from the cavity sediment fill. In the study area, Burdigalian sandstones occurred discordantly upon an anticlinal crest in Cretaceous to Eocene carbonates. The cavities are therefore interpreted as karstic in origin and the layered sediments as infiltrated carbonate detrital infill. The sediment is not cemented by calcite but is instead impregnated by hydrocarbons. Consequently, sediment cavities retain an important interparticle porosity. These sediment-filled cavities are present 200250 m below the regional unconformity. The vertical distribution of these pockets has not been established, so it is not yet possible to determine whether they become more abundant towards the discordance surface.

Joint and fracture development

As discussed above, most of the Albanian carbonate reservoirs are fractured reservoirs (Albpetrol, 1993; Velaj et al., 1999). The highest density of fractures and joints occurs at the top of anticlinal structures, with a clear relationship to the lithology. In general, joint density is highest in porcellaneous fine-grained carbonate lithofacies where joints are still open. In coarser grained turbidites, fracture density is still high, but many of the fractures are cemented by calcite, reducing both porosity and permeability. Within debris-flow units, fractures are less frequent and generally cemented. Most of the fractures and joints have a subvertical orientation, independent of lithofacies. Several generations of cemented fractures, henceforth called veins, were recognized based on field observations, mutual cross-cutting relationships and petrographical characteristics. Vein organization with respect to stylolites is particularly important. Cathodoluminescence petrography reveals that luminescence characteristics of the different vein generations and the host rock are similar. A first vein generation (V1) is displaced and cut by compactional stylolites, indicating that it predates them. V1 veins are normally < 1 mm wide and are filled with orange-luminescent blocky calcite that often shows sector zonation under CL. The second vein generation (V2) cuts the compactional stylolites but is itself cut by LPS stylolites. Different subtypes of veins can be differentiated, such as blocky calcite veins that contain large, broken host rock fragments (Fig. 6A), which either float in the cement or have a geopetal arrangement. The calcite cement shows orange luminescence with sector zonation. The brecciated nature of the host rock and the fact that clasts are often different from the immediate neighbouring vein wall suggest that these V2 veins formed by hydraulic fracturing (V2H). There are four other varieties of second-generation veins: V2B, which are filled by one or several generations of blocky calcite cement (Fig. 6B); V2CS, which are composite veins with crack and seal textures, indicating alternating episodes of fracturing and cementation; V2F, which are fibrous antitaxial veins with elongated calcite crystals, and V2C, which are composite veins (Fig. 6C) with stretched calcite fibres and characteristic saw-tooth contacts between the briquette structure inside the crystals. The fibres contain regular inclusion bands, which are parallel to the vein wall. Twin plane development in the vein cements is common in most of these V2 vein types. All second-generation veins possess a weak orange-brown luminescence. At the contact between veins and host rock, LPS stylolites developed locally (Fig. 6A) and also cross-cut the calcite cement (Fig. 6D).

Figure 6. (A) Photomicrograph of a hydraulically fractured interval with large fragments and fine debris, geopetally filling the void and cemented by blocky calcite. Bedding is subvertical (arrow indicates sample top). An LPS stylolite borders one side of the fracture (outline enhanced by white traces). Scale bar is 90 m. (B) Cathodoluminescence photomicrograph of the secondgeneration vein V2B, filled by two orange-luminescent blocky calcite cement phases (I and II), which both possess a well-developed sector zonation. Scale bar is 85 m. (C) Photomicrograph of vein V2C under cross-polarized light with stretched calcite fibres and characteristic saw-tooth contacts between, and briquette structure inside, the crystals. Note the presence of regular inclusion bands (arrows), which parallel the vein wall. Scale bar is 90 m. (D) Photomicrograph of an LPS stylolite cutting a V2 vein. Note the presence of pores along the stylolite (arrows). The burning of the impregnating resin during cathodoluminescence caused the brown colour. Bedding is subvertical, as indicated by the alignment of the foraminifera. Scale bar is 85 m. (E) Open joint system (here enhanced by surface weathering). Note the presence of LPS stylolites (arrows). A 7-cm pen is present as scale. (F) Oil seeps along open joints. Coin diameter is 18 cm. Arrow indicates stratigraphic up direction. A third generation of calcite-filled veins (V3) consists of thin fractures (< 2 mm in width) that were affected by LPS and display a zigzag pattern (Fig. 4F). From a petrographical point of view, they are equivalent to the LPS-cemented stylolites described above. Generations V2 and V3 are synorogenic, as they both predate and develop subsequent to LPS. A fourth vein generation post-dates the folding stage (V4) because it cuts fold structures and LPS stylolites. It was filled with blocky calcite showing yellow to orange luminescence. Finally, an open joint system developed (Fig. 6E), along which most of the oil seeps occur (Fig. 6F). Trace element analysis of these veins reveals low Mg (values below 3000 p.p.m.), Fe (values below 1000 p.p.m.), Mn (values below 600 p.p.m.), Na (values below 300 p.p.m.) and Sr (values below 600 p.p.m.) concentrations, with large variations occurring within one class of vein types and without any systematic difference between the different vein types.

Stable isotope results


Figure 7 summarizes carbon and oxygen isotope data for the different vein generations. Vein generation V2 possesses 13C values between 014 and +298 VPDB and 18O values between 085 and 386 VPDB. These variables show a covariant trend (Fig. 7). The 3 spread in oxygen isotope values of V2H veins could indicate that several hydraulic subgenerations exist. Most 13C values plot within, or are close ( 1) to, that of the host rock, so it is likely that the 13C signature was buffered by the host rock. No significant additional carbon source seems to have been present. The 13C values that are slightly more negative than most of the host rock could be explained by the temperature-related fractionation effect (Emrich et al., 1970). This may also explain why these slightly 13C-depleted samples have the most negative 18O values. The shift in 13C of 1 corresponds with a temperature increase of only 2530 C, supporting the interpretation that calcite precipitation did not occur at elevated temperatures. Otherwise, as these veins post-date compactional stylolites, involvement of depleted carbon derived from decarboxylation reactions could be an alternative explanation.

Figure 7. Carbon and oxygen isotope cross-plot of different vein generations in the Upper Cretaceous to Eocene turbidites. For reference, the stable isotope composition of the host rock is circled (data from Fig. 4). One can speculate about the fluid type involved by combining isotope data and assuming a precipitation temperature using the fractionation equation of O'Neil et al. (1969). Unfortunately, the fluid inclusion data are not reliable because it was not possible to measure systematic Th and/or Tm values on a large number of inclusions. In fact, only one V2H sample provided a Th value averaging around 52 C and Tm values between 3 and 0 C. Using this measurement and assuming that the majority of the observed small single-phase aqueous inclusions do not reflect metastable conditions, formation temperatures were relatively low (< 50 C: Sabouraud et al., 1980; <70 C: Touret, 1994). Calculated 18Owater values would then fall between +3 and +6 SMOW at 50 C. Vein type V3 13C and 18O values plot around +2 06 and 15 05 VPDB respectively. The 13C values all fall within the field of the host strata, suggesting that the system was buffered by the host rock. The 18O signature also seems to have been controlled by the surrounding carbonates, which might reflect low waterrock interaction. The involvement of enriched fluids at higher temperatures could also explain the oxygen isotope signature, but then one would expect to see some influence on the carbon isotopic signature. Stable isotope values of the post-folding vein system (V4) vary greatly in carbon and oxygen isotope values. Some possess values similar to the host rock and the former vein generations and can be explained in a similar way. The subpopulation of 18O values averaging +3 VPDB is, however, best explained by an influx of external fluids. A fluid system influenced by clay diagenesis (i.e. smectite/illite conversion; Boles & Franks, 1979) could be invoked. The fact that these calcite veins are non-ferroan could then relate to thermal sulphate reduction in which pyrite is formed or by involvement of oxygenated fluids. The latter, however, does not seem very likely based on the absence of pyrite. Fluids may also have been derived from the Triassic evaporites, which acted as a dcollement horizon (Velaj et al., 1999; Roure et al., 2001). Basement-derived fluids may also explain the isotopic signature. Two samples of vein generation V4 were rather negative in 18O (values around 71 VPDB) and positive in 13C (around +93 VPDB). Carbonate cements with such high 13C values are genetically linked to biodegradation fermentation of hydrocarbons (Dimitrakopoulos & Muehlenbachs, 1987). The depleted 18O signature suggests that either high temperature or 18O-depleted fluids, such as meteoric waters, were involved. However, no Th measurements could be carried out to resolve the formation temperature.

In an additional set of veins sampled (about 60 samples), for which the structural relationships were less clear (and therefore the data are not reported here), 18O-enriched/13C-host rock-like and 18 O-depleted/13C-enriched veins both make up about 10% of the analysed population. The other 80% displays rock-buffered characteristics similar to V2 veins.

Discussion
The paragenetic sequence of the Ionian sections examined is summarized in Figure 8. Major diagenetic events affecting Upper Cretaceous to Palaeocene carbonates can be subdivided into the following stages: (1) early diagenetic (i.e. eogenetic stage sensuChoquette & Pray, 1970); (2) mesogenetic burial; (3) telogenetic pre-emergence (pre-Burdigalian); and (4) second mesogenetic burial during flysch and molasse deposition (post-Burdigalian). The first mesogenetic stage is subdivided according to the relationship between veins and the two major types of stylolites.

Figure 8. Schematic paragenesis of the Cretaceous to Eocene strata in the Ionian Zone (Albania). In the eogenetic realm, a differentiation has tobe made between the cementation history occurring in the platform settings, of which the debris flows record some signal, and the cementation affecting the turbidites, which reflects cementation in a deep-marine setting. Rapid marine cementation is one of the characteristic features of shallow-water platform sedimentary settings (Longman, 1980; Sandberg, 1985; Moore, 2001). During temporary emergence of the platform, unstable components, especially aragonitic bioclasts, may easily dissolve. Consequently, the saturation index for calcite rises, and cementation occurs within and around the biomoulds and other suitable substrates. Some of these cemented platform strata may become undercut because of slope failure, and early diagenetically cemented blocks, clasts and uncemented platform sediments may be incorporated into deep-marine debris-flow deposits and turbidites. As observed within the lower portion of the Albanian turbidite sequences, these resedimented particles created a porous deposit. This might result from a high initial porewater pressure, resulting from rapid sedimentation and fast sealing of these sediments by finer grained lithologies. A similar explanation was given to explain the porous nature of Cretaceous carbonates in the Ekofisk field (central North Sea) by Oakman & Partington (1998). Because mineralogically unstable carbonate phases are present in the platform deposits, it is likely that some were transported to depth by turbidity currents. Within the cold, deep-marine setting, these

unstable grains would have undergone dissolution, producing the observed biomoulds. Because deposition of the turbidites was very fast, it is likely that any dissolution occurred below the sedimentwater interface. As a consequence, supersaturation with respect to low-Mg calcite would occur, resulting in cementation by syntaxial rim and equant cements. The unstable grains may have been aragonite components from the platform that were resedimented below the aragonite compensation depth (Halley et al., 1984). Owing to the particularly high pCO2 during the Cretaceous, calcite and aragonite compensation depths in oceanic basins were rather shallow (Berger & Winterer, 1974; Van Andel, 1975). A model invoking rapid aragonite dissolution and calcite precipitation during early diagenesis of platform sediments redeposited in a deep-marine environment is favoured to explain the cementation of coarser turbidite lithologies. A similar model was proposed by Malonne et al. (1990) from recent periplatform sediments deposited in the Indian Ocean at depths of 500 m, with complete dissolution of unstable carbonate phases and subsequent cementation by about 160 m of burial in <6 Myr. In the Albanian carbonates, a clear substrate selectivity with respect to cementation existed, with monocrystalline crinoid and rudist fragments acting as ideal nucleation sites. Where the lithology was dominantly composed of rudists and crinoids, cementation was pervasive. In samples in which these bioclasts were more dispersed and intermixed with reworked micritic particles, syntaxial rim cements also developed and stabilized the rock matrix, which resisted later compaction. The other rock constituents, especially micrite, were less vulnerable to cementation. Here, isopachous equant calcite cement developed locally. Hendry et al. (1996) proposed a comparable model for low-Mg calcite cementation in Cretaceous sandstone reservoirs from the North Sea Basin. They explicitly stated that bioclast aragonite dissolution and low-Mg calcite cementation should not automatically be regarded as evidence for uplift and meteoric diagenesis. In the Albanian carbonate turbidites, meteoric water interaction during early diagenesis can be excluded because these deep-marine strata were deeply buried and tectonically deformed before they were uplifted and exposed to meteoric water during the Late Oligocene/Lower Miocene. After early diagenetic cementation, these turbidites, debris flows and pelagic wackestones/mudstones underwent compaction with dramatic porosity loss, especially in finegrained lithologies. At this stage, bedding-parallel (i.e. compactional) stylolites developed. Assuming that the Lower Oligocene structural regime was purely flexural (Roure et al., 2001), compactional stylolites and V1 veins in the foreland developed before or during the Lower Oligocene. The V1 veins most likely link to normal faults, which developed along the foreland flexure. This interpretation is partly based on deduced depths reported in previous studies examining the development of bed-parallel stylolites (Dunnington, 1967; Nicolaides & Wallace, 1997). LPS stylolitic planes record a prefolding deformation stage on the basis of their overall distribution on stereonets (Fig. 9). They were grossly orthogonal to the direction of maximum stress and, thus, they trend mostly parallel to the fold axes. Because large thickness variations and growth-fold strata had already formed in the Upper Oligocene, this period has to be considered as synorogenic. This implies that LPS stylolites developed between the Lower and Upper Oligocene, in the footwall of the frontal thrust, immediately before tectonic accretion of pelagic carbonate reservoir units into the allochthon. This period was also characterized by the development of different fracturing episodes (V2 and V3 veins). V2H fracturing was associated with the generation of fluid overpressuring in the sediments that extend to some distance from

the fault plane into the footwall block and its release during tectonic fracturing. The fact that many of the vein cements display complex patterns, such as crack and seal features and the development of twin planes, reflects their deformation history. The twin planes observed correspond to type 1 crystal twins according to Burkhard (1993), who indicated that factors that influence twin plane development (e.g. differential stress, strain, strain rate, crystal size, crystal orientation) were not necessarily responsible for the type of twins developed. Twin type is thought to be mainly a function of deformation temperature, with type 1 twins forming at temperatures <200 C. Depending on the position within the outcropping anticlinal structure, temperature never exceeded 100 C (Fig. 10).

Figure 9. Structural map of the northern part of the Kremenara anticline, with selected microtectonic sites outlining the prefolding origin of the LPS stylolitic features. Note the overall coaxiality between footwall LPS features and subsequent fold axis orientation.

Figure 10. Burialtemperature curves of the Cretaceous reservoir derived from basin modelling along a regional transect from the autochthonous foreland to the surface outcrops of the Kremenara anticline (i.e. presently outcropping unit in figure). The subsurface units correspond to (1) Selishta, (2) Selenica and (3) Kremenara duplex units (Fig. 2) (Roure et al., 2001). Numbers refer to burial temperatures in C. The cements that occur within LPS stylolites probably do not reflect a regional extensional episode. Outcrop evidence suggests that these open and cemented joints resulted from selective reactivation of LPS surfaces during folding as extrados (i.e. extensional features developed during folding) joints. This was deduced from the preservation of closed LPS features with exactly the same directions and characteristics in close association with reactivated ones (Fig. 11). However, it is unclear whether the reactivated fractures relate to the first, major folding episode, which occurred in Late OligoceneAquitanian time, or to an episode of moderate thrust reactivation that occurred during the PlioceneQuaternary. Open joints, which are of utmost

importance for the reservoir, formed during this folding episode. The presence of the basal Burdigalian unconformity on top of the anticlinal structures is also important for timing the folding event in the study area. Depending on the structural evolution during the Oligocene (growth strata surrounding the fold or folded flexural sediments), maximum burial would have been reached at different times for different segments of the folded structures. This is well expressed by burialtemperature curves of the reservoir computed using basin modelling tools at key points along a regional transect from the autochthon up to the surface exposures of the Kremenara anticline (Fig. 10). In places, the post-unconformity Neogene sediments were not as thick as former Oligocene flysch series, and maximum burial therefore occurred during the Lower Oligocene for the top of anticlinal structures. For the flanks of the same structures, however, maximum burial dates from any time from the Oligocene to the present. Timing depends on the balance between erosion of the Oligocene flysch and the deposition of Neogene series.

Figure 11. (A) Outcrop of the Cretaceous reservoir unit in the northern part of the Kremenara anticline, showing the distribution (regular spacing, trending grossly parallel to the fold axis) of early footwall LPS features. Approximately one in five to 10 of these microstructures has been reopened as an extrados (i.e. extensional) fracture during subsequent folding of the structure. A 7-cm pen for scale. (B) Detail of (A) showing open (1) and cemented (2) fractures. Along the open LPS features, a surface relief develops within the outcrops. A 7-cm pen for scale. The anticlinal structure studied was emergent after creation, as evidenced by the beach-type deposits of most likely Burdigalian age, which presently occur at its topographic crest. It is during this emergence that karstification occurred, with subsequent sediment infill in the karst cavities. The quartz grains present in some of these cavities might relate to the siliciclastic transgression that buried the reservoirs. Oil migration was probably coeval with fracturing and folding and, consequently, part of the charge could be as old as OligoceneAquitanian. This was deduced from thermal modelling assuming that Toarcian Posidonia Shale was the source rock in the study area (Roure et al., 2001). It is unclear whether any of this early oil was washed out as a result of early erosion andcirculation of meteoric water beneath the Burdigalian unconformity. However, no oilimpregnated erosion products were recognized in the beach-type conglomerates overlying the palaeoerosion surface at the anticline crest. Ultimately, the last charge could be Neogene (primarily Pliocene), which would be related to renewed tectonic thickening in nearby underthrust synclines. As documented by Roure et al. (2001), the more external parts of the Ionian allochton entered successively into the oil window as the foreland synclines became progressively underthrust beneath more distal anticlinal structures.

From the above description, it is clear that the two major sets of stylolites were essential in distinguishing different vein types. They also play an important role in reservoir character because porosity development along them caused interconnection of bed-parallel matrix porosity with open joint networks. The type and timing of fluid circulation responsible for porosity development along these stylolites is unclear. However, it must post-date LPS stylolite development. Matrix dissolution was not observed adjacent to any of the vein types, suggesting that the veins were already cemented. The dissolution may have been related to migration of acidic fluids formed during hydrocarbon maturation (e.g. Schmidt & MacDonald, 1979; Surdam et al., 1984). Giles & Marshall (1986) and Giles (1997) stressed the buffering capacity of carbonates, which might explain why dissolution was essentially restricted to stylolites. Why these aggressive acidic fluids did not enter the porous turbidites and thus did not enhance matrix porosity, by dissolving some of the cements, is not clear. No dissolution features were observed in this lithology, even in large pores. A possible explanation is that turbidites and open joints were rapidly charged with oil, whereas in less permeable strata, aggressive fluids circulated along preferential pathways such as stylolites. The V2 to V4 vein systems, if not reactivated, did not enhance reservoir volume because they were cemented before oil emplacement. From the geochemical results of the different vein systems, it appears that most type V2 and 3 veins were buffered by the host rock, implying low waterrock interaction. The fluid systems seem to have been mainly diagenetically closed, with dominantly intrastratal transfers. This is in agreement with the findings of Bradbury & Woodwell (1987), who described fluid flow in foreland terrains and concluded that each thrust sheet acted as a separate hydrodynamic unit. Marquer & Burkhard (1992) and Muchez et al. (2000) also noted that most pre- and syntectonic veins are geochemically similar to the surrounding wall rocks. The brecciated nature of hydraulic veins in this study (V2H) may have resulted from episodic fluid release caused by tectonically induced overpressuring. This is in agreement with the findings of Behrmann (1991), who concluded that episodic fracturing and release of fluids resulted from periodic movement of the thrust sheet in a series of earthquakes in the Barbados accretionary prism. Such a mechanism could also explain the development of crack and seal fractures (V2CS). As noted previously, it was only after the development of vein type V4 (after folding in the Late OligoceneAquitanian) that open system fluid advection became involved in the diagenesis of Ionian fold belt rocks. During this stage, the reservoir started to preserve evidence of exotic fluid transfers (i.e. isotopic data), suggesting the creation of a vertical network of discontinuities allowing channelled fluid flow from below. Basement or evaporite-related fluids and CO2-charged fluids derived from the thermal maturation of hydrocarbons circulated preferentially along open fractures. It was only after cementation of these fractures that the present open joint system developed. Hydrocarbon migration most likely post-dates this phase of fracturing. The model of Sassi & Faure (1997), which is based upon numerical modelling of a thrust propagation sand-box model (Fig. 12), is in agreement with the above observations. They addressed the different stress regimes as a function of their location with respect to the thrust zone. The study area can be considered to have undergone several stress regimes based on their modelling. V1 vein development occurred in the frontal zone where an extensional stress regime developed. The different V2 vein systems related to the propagation of the strike-slip regime developed ahead of the thrust zone. Once topographic relief was created in the hinterland,

gravity-driven meteoric fluid flow with periodic vertical fluid release controlled by tectonism occurred in the footwall. As discussed above, syntectonic V3 veins were rock buffered and are of limited volumetric importance. According to Sassi & Faure's (1997) numerical model, V4 veining developed in the compressive regime of the thrust zone in relation to fluids released from the deeper subsurface. Involvement of deeply sourced fluids during late syntectonic deformation was also recognized by Heijlen et al. (2000) along the Variscan thrust front in Belgium. Subsequently and, from a reservoir point of view, most importantly, an extensional stress regime developed in the uplifted and folded zone. This resulted in the formation of the open joint system, which allowed hydrocarbon emplacement. Finally, a karst system developed on emergent structures. However, the importance of the karst cavity network, which was infilled by sediment, is uncertain as it was not studied in detail.

Figure 12. Modified view of the thrust propagation sand-box model of Sassi & Faure (1997) linked to the different reported vein systems of this study. J, joint network; V14, vein generations 14 described in the text. Black arrows indicate compression direction. This Albanian study, but also other cases currently being studied (e.g. Mexico: Ferket et al., 2002; Ortuno Arzate et al., 2002), show that, in geologically complex areas such as fold and thrust belts, it is extremely helpful to study reservoir outcrop analogues. Many of the complex relationships between diagenetic phases (e.g. matrix porosity, veins, stylolites, karst cavities) could never be studied in such detail in core material because of limitation in the vertical extent and size of the cores.

Conclusions
Hydrocarbon exploration in fold and thrust belts such as the outer Albanides is a high-risk operation. Understanding the types of fluids that have circulated through the system and affected the reservoir units might help to reduce this risk. This study has focused on outcrops of Upper Cretaceous to Eocene carbonates, which are outcrop analogues of the reservoir in adjacent petroleum fields and producing reservoirs in the Adriatic Sea and onshore Italy. The following major diagenetic stages were recognized:

1 An eogenetic stage, characterized by dissolution of unstable sedimentary components (deposited in basinal settings) and development of isopachous and syntaxial low-Mg calcite cements in the coarser grained lower portions of turbidite beds. Beds enriched in favourable nucleation sites, such as crinoid ossicles and rudist fragments, became pervasively cemented. Where reworked micrite particles were mixed with bioclasts, cement development around the bioclasts stabilized the framework, preserving some primary porosity. These isopachous and syntaxial cements are characterized by uniform dull orange luminescence, similar to that of the host rock. The abundance of the cements

(up to 30%) and their stable isotopic signature (18O and 13C averaging 05 VPDB and +2 VPDB respectively), which is within the field of time-equivalent marine carbonates, suggests that the cements formed in a marine phreatic environment.

2 A preorogenic, compactional mesogenetic stage during flexural loading of the foreland. Porosity decrease as a result of physical and chemical compaction especially affected fine-grained turbidites. Bed-parallel stylolites developed during this prefolding stage. The stylolites cut subvertical veins that formed in association with normal faults developed during extension.

3 A synorogenic deformational stage, affecting the footwall of the frontal thrusts, characterized by the development of LPS stylolites. Complex vein textures (e.g. calcite infill with brecciated rock fragments, crack and seal features) formed during the expulsion of overpressured fluids. Development of crystal twin planes is typical within all these cements, as is a dull orange luminescence similar to the host rock. A rockbuffered (i.e. closed) diagenetic system is suggested by the stable isotopic signal of these veins (18O of 386 to 085 VPDB and 13C of 014 to +298 VPDB). Some of the LPS stylolites opened during deformation and subsequently became calcite cemented. Luminescence characteristics (same as the host rock) and isotope composition (18O of 181 to 114 VPDB and 13C of +152 to +256 VPDB) of these cements support the theory of rock buffering.

4 A synorogenic deformational stage with development of folds, major faults and fractures. Some of the calcite veins still reflect a closed diagenetic system (18O of 096 to +02 VPDB and 13C of +079 to +137 VPDB), whereas others reflect large-scale fluid circulation. Circulation of basement-derived fluid, which interacted with shale deposits and/or Triassic evaporites, is indicated by calcite veins, which typically possess 18O values of +30 VPDB and 13C of around +15 VPDB. Other veins with depleted 18O (average 71 VPDB) and enriched 13C signatures (average +93 VPDB) indicate involvement of fluids affected by maturation of hydrocarbons. Acidic fluids generated during this diagenetic stage were responsible for secondary porosity development along stylolites.

5 A late synorogenic extensional stage in uplifted areas, with the formation of open joint networks. These joints are of major importance for oil production.

A post-orogenic telogenetic stage, which has been dated as pre-Burdigalian based on the discordant (karst) contact at the anticlinal crest. During this stage, a karst cavity network developed, which subsequently became infilled by sediment. Because these sediments were not lithified, they have high porosity and permeability and are oil impregnated. These different diagenetic stages fit well with modelled numerical experiments of thrust propagation systems. Regarding reservoir quality, it is clear that storage is mainly within the turbidite matrix pores. However, vertical connectivity within this layer-cake turbiditic reservoir is guaranteed by the presence of a vertical late synorogenic joint network and vertical LPS stylolites along which secondary porosity developed.

Acknowledgements
M.V.G and R.S. would like to thank T. Moorkens for introducing them to the geology of the Ionian Zone in Albania. We also thank several Albpetrol geologists, especially Shaqir Nazai, Luan Zaim, Kristaq Mushka and Maksim Zako, for their help. We thank H. Nijs for preparing the thin sections. Isotope analysis was carried out under the direction of E. Keppens at the Free University of Brussels (Belgium). E. Franseen, P. Mozley, Emily Albouy and an anonymous reviewer are especially thanked for the constructive remarks they made on a former version of the manuscript. The SUBTRAP Consortium partners are thanked for their help and financial support. The microfocus X-ray tomography research was carried out in the framework of projects INM/950330 and IWT/SB/971060 of the Flemish Institute for the Promotion of Scientific and Technological Research in Industry (IWT). The scanning electron microscopic study and the laser ablation-induced coupled mass spectrometric analysis were supported by grants 2003891 and n G.030097, respectively, from the National Fund for Scientific Research of Belgium. The colour plates have been subsidized, i.e. uitgegeven met de steun van de Universitaire Stichting van Belgi en het Francqui Fonds. P.M. was until recently a senior research associate of the Fund for Scientific Research of Flanders (Belgium).

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