Fluid Dynamics in a Thrust Fault Inferred from Petrology and Geochemistry of Calcite Veins: An Example from the Southern Pyrenees

Departament de Mineralogia, Petrologia i Geologia Aplicada, Facultat de Ciències de la Terra, Universitat de Barcelona (UB), Martí i Franquès s/n, 08028 Barcelona, Spain Group of Dynamics of the Lithosphere (GDL), Geosciences Barcelona, GEO3BCN-CSIC, Lluís Solé i Sabarís s/n, 08028 Barcelona, Spain UMR CNR GEOPS, Université Paris-Saclay, 91405 Orsay, France Department of Earth Science and Engineering, Imperial College London, London SW7 2BP, UK


Introduction
The study of outcrop analogues in fractured carbonate reservoirs is important to better understand the characteristics and evolution of synkinematic fracture systems and their control on fluid migration during crustal deformation [1][2][3][4]. In areas undergoing compressional regimes, the largest fluid fluxes, mass transfer, and heat transport commonly occur along the main thrust faults and related fracture networks because of the loading induced by thrust sheet emplacement [5][6][7]. By contrast, fluid flow rates in adjacent rock-matrix and poorly connected synkinematic fractures are commonly very low and fluid composition are often rock-buffered [6,8]. In some cases, the development of thrust systems may also inhibit vertical fluid transport inducing fluid overpressure [9][10][11] leading to hydraulic fracturing [12][13][14]. Whether a fault zone will constitute either a conduit or barrier to fluid migration depends, among other factors, on the architecture of the fault zone and the permeability associated with the developed structures [15,16]. Since the fault zone consists of a fault core, which is usually formed of low-permeability fault rocks, and a damage zone, which mainly includes extensional fractures and faults, overall permeability of the fault is conditioned by the amount, the spatial distribution, and the internal composition of these two fault zone elements [15,17]. Besides, such structural permeability is dynamic and may vary spatially and temporally across the fault zone due to successive episodes of fracture opening and cementation [18,19].
Although numerous studies based primarily on structural and numerical data have provided conceptual and analytical models on the architecture, mechanical properties, and fluid flow along fault zones [7,15,20], there exist only a few studies coupling field data and geochemistry of synkinematic minerals filling fractures that characterize the fluid migration through a thrust zone [21][22][23][24][25] and its spatial behavior as a conduit or barrier system [26,27]. An outstanding exposed thrust in the Southern Pyrenees was chosen as a case study to evaluate qualitatively the fault-related permeability and its control on the fluid flow within and around the fault zone. Here, we combine structural, petrological, and geochemical data of calcite veins and host rocks present in the studied thrust zone. Therefore, the main objectives of this paper are (i) to determine the origin, composition, and temperature of the vein-forming fluids and the timing of fluid migration in relation to the fracturing events and (ii) to discern the fluid pathways, the extent of fluid-rock interaction, and the transfer of fluids across a fault zone during thrusting. The field and lab results are then compared with other studies reporting fluid flow within fault zones in other geological settings to generalize our conclusions to fault zones in carbonate settings.

Geological Setting
The Pyrenees constitute an asymmetrical and doubly verging orogenic belt that resulted from the Alpine convergence between the Iberian and European plates from Late Cretaceous to Oligocene, causing the inversion of previous Mesozoic rift basins and their incorporation into the thrust system [28][29][30][31][32]. The Pyrenean structure consists of a central antiformal stack of basement-involved thrust sheets from the axial zone [30], flanked by two oppositely vergent fold-andthrust belts and their related Cenozoic Aquitaine and Ebro foreland basins [30,33] (Figure 1(a)).
The South Pyrenean fold-and-thrust belt comprises a piggy-back imbrication of south verging and east-west striking thrust sheets involving Mesozoic and Tertiary cover rocks detached above Late Triassic evaporites [34] and transported southwards over the Ebro foreland basin. From north to south, they are the Bóixols thrust sheet, emplaced during the Late Cretaceous to Paleocene, the Montsec thrust sheet, originated during the Paleocene to late Ypresian, and the Serres Marginals thrust sheet, formed during the Lutetian-Oligocene [35,36] (Figure 1(a)). In the frontal part of the Bóixols thrust sheet, a south verging and east-west trending fault-related anticline developed in relation to the propagation of the Bóixols thrust (the Sant Corneli-Bóixols anticline; Figures 1(b) and 1(c)). It is characterized by a gently dipping northern backlimb and a vertical to overturned southern forelimb [37].
Rocks cropping out along the Bóixols anticline comprise a large stratigraphic record ranging in age from Jurassic to Oligocene and deposited during the main tectonic events that affected the study area [38] (Figures 1(b) and 2). The stratigraphic sequence includes prerift Jurassic limestones and dolostones, synrift Lower Cretaceous limestones, marls and clays, preorogenic (postrift) Late Cenomanian to Santonian limestones, sandy limestones and marls and synorogenic Late Santonian to Oligocene marls and clays, sandstones, sandy limestones, and conglomerates ( [38] and references therein).
In the central part of this anticline, the southern tilted forelimb is offset by minor low-dipping south-directed thrusts developed after the main folding phase, as evidenced by the displacement of already folded beds [38][39][40]. Therefore, they have been interpreted as postfolding accommodation structures or as hanging wall splays of the main Bóixols thrust [39,40,42]. One of these minor thrust faults is well exposed 2 km southeast of the Bóixols village (15 km of the L511 road), in the southern-central Pyrenees (Figure 3), exhibiting a complex calcite-filled fracture network developed in the fault core and damage zone of both the footwall and hanging wall of this reverse fault. This outcrop represents an exceptional field analogue to observe in a 300 m long outcrop the variation in deformation mechanisms developed across a fault zone and its contribution as seal or conduit for fluids. In this area, the studied thrust juxtaposes the Upper Cretaceous Santa Fe Formation against the Collada Gassó Formation (Figures 2 and  3). The Collada Gassó Formation [43] is formed of Coniacian grainstones with the variable presence of quartz, marly limestones, and limestones with abundant fossil content and has a general thickness of 150 to 250 m [38]. The Santa Fe Formation [44] is basically constituted of Cenomanian-Turonian limestones with a general thickness of 20 m [38].

Methodology
This study combines field structural data, including bedding and fracture orientation and dips, fracture type identification, 2 Geofluids  3 Geofluids kinematics, and crosscutting relationships, with petrological and geochemical analyses. Structural data were plotted in equal-area lower-hemisphere projections, and different fracture sets were established according to their type, strike, orientation respect to bedding, mineral infillings, and relative age deduced from crosscutting relationships. Representative samples of each fracture generation and related host rocks were sampled in order to perform petrological and geochemical analyses. Thin sections were prepared and studied under optical and cathodoluminescence microscopes at the Facultat de Ciències de la Terra of the Universitat de Barcelona, using a Zeiss Axiophot optical microscope and a Technosyn Cold Cathodoluminescence microscope, model 8200 Mk5-1 operating between 16-19 kV and 350 μA gun current.
Thirty-one samples of calcite cements and host rocks were sampled for carbon and oxygen isotopic analysis using a 500 μm-diameter dental drill. Around 50-100 μg of each sample was reacted with 100% phosphoric acid for two minutes at 70°C. The resultant CO 2 was analyzed with an automated Kiel Carbonate Device attached to a Thermal Ionization Mass Spectrometer Thermo Electron MAT-252 (Thermo Fisher Scientific) following the method of [45]. The International Standard NBS-18 and the internal standard RC-1, traceable to the International Standard NBS-19, were used for calibration. The standard deviation is ±0.03‰ for δ 13 C and ±0.05‰ for δ 18 O expressed with respect to the VPDB standard (Vienna Pee Dee Belemnite). Analyses were carried out at "Centre Científics i Tecnològics" of the Universitat de Barcelona (CCiTUB).
The elemental composition of the calcite cements and related host rocks (12 samples in total) was analyzed with a high-resolution inductively coupled plasma-mass spectrometer (HR-ICP-MS, model Element XR, Thermo Fisher Scientific). Around 100 mg of each sample was extracted with a 400/500 μm-diameter dental drill, and then, powdered samples were dried at 40°C for 24 h. Then, 100 mg of sample was acid digested in closed polytetrafluoroethylene (PTFE) vessels with a combination of HNO 3 + HF + HClO 4 (2.5 mL : 5 mL : 2.5 mL v/v). The samples were evaporated, and 1 mL of HNO 3 was added to make a double evaporation. Finally, the samples were redissolved and diluted with Milli-Q water (18.2 MΩ cm -1 ) and 1 mL of HNO 3 in a 100 mL volume flask. In order to improve the sensitivity of the ICP-MS, a tuning solution containing 1 g L -1 Li, B, Na, K, Sc, Fe, Co, Cu, Ga, Y, Rh, In, Ba, Tl, and U was used, and as internal standard, 20 mg L -1 of a monoelemental solution of 115 In was used. Reference materials are the BCS-CRM no. 393 (ECRM 752-1) limestone, JA-2 andesite, and JB-3 basalt. The precision of the results was expressed in terms of two standard deviations of a set of eight reference material measurements (reference material JA-2), whereas accuracy (%) was calculated using the absolute value of the difference between the measured values obtained during the analysis and the certified values of a set of eight reference material analysis (reference material BCS-CRM no. 393 for major oxides and JA-2 for trace elements). The detection limit (DL) was calculated as three times the standard deviation of the average of ten blanks. Analyses were performed at the Geochemistry Facility of labGEOTOP of Geoscience Barcelona (GEO3BCN-CSIC).
The 87 Sr/ 86 Sr isotope ratios were analyzed in calcite cements and host rocks (9 samples). Powdered samples were fully dissolved in 5 mL of 10% acetic acid. After centrifugation, the supernatant was dried and dissolved in 1 mL of 1 M HNO 3 . The resulted solid residue, generated after evaporation, was diluted in 3 mL of 3 M HNO 3 and loaded into chromatographic columns to separate the Rb-free Sr fraction, by using SrResin™ (crown-ether (4,4 ′ (5 ′ )-di-t-butylcyclohexano-18-crown-6)) and 0.05 M HNO 3 as eluent. After evaporation, samples were loaded onto a Re filament along with 1 μL of 1 M phosphoric acid and 2 μL of Ta 2 O 5 . Isotopic ratio analyses were carried out in a TIMS-Phoenix mass  [41]. The preorogenic (postrift) sequence, where the thrust was emplaced, is colored in green. The right panel shows a detail of the formations forming this sequence. Thickness and age of these formations are based on [38]. 5 Geofluids 0:000009 (standard deviation, 2σ). NBS 987 data have been used to correct the sample ratios for standard drift from the certified value. The analytical error in the 87 Sr/ 86 Sr ratio, referred to two standard deviations, was 0.01%, whilst the internal precision is 0.000003. Sr procedural blanks were always below 0.5 ng. Analyses were carried out at the "CAI de Geocronología y Geoquímica Isotópica" of the Universidad Complutense de Madrid.
The 143 Nd/ 144 Nd isotope ratios were also analyzed in calcite cements and host rocks (9 samples in total). Samples were weighed in Teflon® vessels, with enriched spike solution ( 149 Sm-150 Nd, Oak Ridge) and dissolved in 5 mL of ultrapure HF and 3 mL of ultrapure HNO 3 (Merck-Suprapur™). The PFA vessels were placed for 65 hours into an oven at 120°C. Then, cold vials were evaporated on a heat plate at 120°C. 4 mL of distilled 6N HCl was added to the dried samples and placed in an oven overnight at 120°C. The resulted solid residue, generated after evaporation, was dissolved in 3 mL of distilled and titrated 2.5N HCl. In order to separate the dissolved fraction from the residue, if any, samples were centrifuged for 10 minutes at 4000 rpm. Chromatographic separation of the total group of REE was performed using cation exchange resin DOWEX 50W-X8 200-400 mesh (previously calibrated). Then, recovered REE fractions were completely dried and again dissolved in 200 μL 0.18N HCl. These solutions were passed in a new chromatographic step (Ln-resin) in order to obtain a complete separation between the Nd and the Sm fractions (using 0.3N HCl and 0.4N HCl as eluent, respectively). Dried Sm and Nd samples dissolved with 2 μL of 0.05 M phosphoric acid were loaded onto a side rhenium (Re) filament of a triple Re filament arrangement. Nd ratios were analyzed in a mass spectrometer TIMS-Phoenix®, following a dynamic multicollection method, through 160 cycles at a stable intensity of 1 V for the 144 Nd mass. In turn, Sm ratios were analyzed in the same spectrometer, following a single static method through 112 cycles maintaining 1 V intensity for the 149 Sm mass. Nd measurements were corrected for possible 142 Ce and 144 Sm interferences and they were normalized to a constant ratio of 146 Nd/ 144 Nd = 0:7219 to correct the possible mass fractionation during the processes of loading and analyzing at the TIMS. Nd isotopic standard JNdi-1 was checked along with the samples to correct the sample ratios for standard drift from the certified value. The analytical error (2STD) in the 147 Sm/ 144 Nd ratio was 0.1% and in the 143 Nd/ 144 Nd ratio was 0.006%. Procedural blanks were always below 0.1 ng. Analyses were performed at the "CAI de Geocronología y Geoquímica Isotópica" of the Universidad Complutense de Madrid.
Clumped isotope thermometry was applied to four representative samples of the calcite cements Cc1 to Cc4 in order to determine the temperature and δ 18 O fluid in ‰VSMOW of the vein-forming fluids. Around 2-3 mg aliquots of powdered calcite cements was measured with an automated line developed at Imperial College London (the Imperial Batch Extraction system, IBEX). Samples were dropped in 105%   6 Geofluids phosphoric acid at 90°C and reacted for 30 minutes. The reactant CO 2 was separated with a Poropak Q column and transferred into the bellows of a Thermo Scientific MAT 253 mass spectrometer. The characterization of a single replicate consisted of 8 acquisitions in dual inlet mode with 7 cycles per acquisition. The total time of analysis per replicate is~2 hours, and each sample was replicated at least 3 times. The postacquisition processing was completed with software for clumped isotope analyses (Easotope) [46]. During phosphoric acid digestion, Δ 47 values were corrected for isotope fractionation with a phosphoric acid correction of 0.069‰ at 90°C for calcite [47]. The data were also corrected for nonlinearity applying the heated gas method [48] and projected into the reference frame of [49]. Carbonate δ 18 O values were calculated with the acid fractionation factors of [50]. Results were converted to temperatures applying the calibration method of [51].

Nature of Host Rocks.
In the study area, two Upper Cretaceous sequences are present [38,42]: the Collada Gassó Formation, located in the footwall, and the Santa Fe Formation, located in the hanging wall.
The Collada Gassó Formation consists of massive to well-bedded dark grey to brown limestones with an E-W orientation and dipping 80°towards the north. The limestones consist of grainstones made up of bivalves, gastropods, echinoids, bryozoans, corals, miliolids, partially to totally micritized components (i.e., peloids), and locally quartz grains. The inter-and intraparticle porosity is cemented by calcite cement (Cc0) (Figure 4(a)). Under cathodoluminescence, the skeletal components show a dull to bright brown color, whereas the inter-and intraparticle calcite cement (Cc0) displays a bright yellow color (Figure 4(b)). This formation is characterized by the widespread presence of bedding-parallel compaction stylolites, developed during progressive burial prior to deformation.
The Santa Fe Formation consists of a massive succession of grey limestones with an E-W orientation and dipping 80-85°towards the north. The limestones are made up of wackestones, locally packstones, with a notably presence of calcispheres and planktonic foraminifera (Figure 4(c)). Under cathodoluminescence, it exhibits a very dark orange color ( Figure 4(d)).

Fault Zone
Structure. The studied fault zone exhibits a classical fault organization with a main slip plane, a fault core, and two surrounding damage zones within the footwall and hanging wall, respectively ( Figures 5 and 6). The slip plane   Figure 6: Spatial distribution and crosscutting relationships between veins developed within the studied thrust zone. Vein density increases towards the fault plane. In the footwall, three vein systems (F1, F2, and F3) (a, b, and c, respectively) evolve to randomly oriented veins (d) on approaching the fault core (e). In the hanging wall, only randomly oriented veins are observed, being more chaotic towards the fault plane (f). The yellow circle refers to sample location. 9 Geofluids grey to yellowish foliated cataclasite ( Figure 7). This foliated cataclasite is characterized by well-developed S-C shears forming sigmoidal lenses (imbricated lithons), a combination of host rock carbonate and calcite lenses within a fine-grained micritic matrix (Figure 7(b)) with abundant calcite cement (Figures 6(e) and 7). Imbricated lithons are bounded by well-developed pressure-dissolution seams or stylolites (Figure 7(a)). S-C shears and stylolites strike ENE-WSW, compatible with the NNW-SSE shortening direction. Orange to reddish clay minerals concentrate along pressure-dissolution surfaces and are locally scattered within the micritic matrix (Figure 7(c)).
The transition from the fault core to the hanging wall damage zone is marked by discrete S-C sigmoidal shears without the development of foliated cataclasite, or by a discrete, discontinuous slip plane mineralized with calcite ( Figure 5(c)).
Both the footwall and hanging wall damage zones comprise multiple sets of systematically and randomly oriented calcite-cemented fractures (i.e., veins) developed at both sides of the fault core ( Figures 5 and 6). Although in both cases, there is a progressive increase in deforma-tion and vein intensity from the protolith towards the fault core ( Figure 5(a)), the geometry of veins differs from one to another damage zone.
In the footwall damage zone, there are two areas showing different vein characteristics ( Figure 5   By contrast, in the hanging wall, the damage zone is narrower, only concentrated in the 15-20 meters near the fault core ( Figure 6(e)), and it is defined by randomly oriented calcite veins defining an incipient crackle breccia (proto-breccia) [52] (Figure 6(f)). Fracture density is lower than within the footwall damage zone.

Calcite Cements of Veins and
Breccias. The damage zones in the footwall and hanging wall not only differ in the type and distribution of fracture systems, as previously described, but also they also show different fracture-filling calcite cements, characterized by distinct petrological and geochemical features.
In the footwall, three calcite cement generations (Cc1 to Cc3) have been observed filling the fracture systems F1 to F3 and two of those calcite cements (Cc1 and Cc2) are also present in the mosaic to chaotic breccia (randomly oriented fractures).
Calcite cement Cc1 exhibits a milky to slightly brownish color in hand sample and consists of up to 1 mm-sized anhedral crystals showing mechanical twinning and featuring a blocky to elongated blocky texture, in which crystals grow syntaxially. This cement shows a dark to light orange cathodoluminescence (Figure 8(a)). Calcite Cc1 precipitated in fractures F1 and in the mosaic to chaotic breccia of the footwall.
Cc2 displays a white to translucent aspect in hand sample. It is formed of anhedral to subhedral calcite crystals, ranging in size from approximately 0.2 to 5 mm, with a blocky to elongated blocky texture. The elongated blocky Cc2 cement grows syntaxially from the fracture walls (Figures 8(a) and 8(b)). Crystals present abundant twin planes and show a nonluminescent to bright orange concentric zonation under cathodoluminescence in which the zoning pattern generally coincides with the crystal growth ( Figure 8(b)). Calcite Cc2 precipitated in fractures F2 as well as in fractures F1 and in the mosaic to chaotic breccia of the footwall after Cc1.
Cc3 exhibits a milky appearance in hand sample and is constituted of up to 0.5 mm anhedral blocky, locally elongated crystals. It has mechanical twinning and presents a dull orange luminescence (Figure 8(c)). Cc3 precipitated in fractures F3.
On the other hand, in the hanging wall and in the fault core, only one calcite cement (Cc4) is observed. Cc4 precipitated in the main fault plane and in randomly oriented fractures. This cement has a milky aspect in hand sample and is characterized by up to 1 mm anhedral crystals with a nonluminescent to dark brown luminescence (Figure 8(d)).

Oxygen and Carbon
Isotopes. The δ 18 O and δ 13 C isotopic composition of the calcite cements Cc1 to Cc4, adjacent host rocks, and fault rocks is summarized in Table 1 and presented in Figure 9. The calcite cement Cc0 in the interparticle porosity of the grainstone from the Collada Gassó Formation (footwall) has δ 18 O values between -7.2 and -6.7‰VPDB and δ 13 C values between -0.5 and +0.7‰VPDB. The micrite matrix of the wackestone from the Santa Fe Formation (hanging wall) shows δ 18 O values between -6.2 and -5.8‰ VPDB and δ 13 C values between +2.1 and +2.2‰VPDB. The carbonate micritic matrix from the cataclasite yields δ 18 O values between -7.1 and -6‰VPDB and δ 13 C values between +2.3 and +3‰VPDB.
The calcite cements in the footwall exhibit higher 87 Sr/ 86 Sr ratios with respect to the calcite cement (Cc0) cementing their adjacent host rock (Figure 11(a)). This ratio is 0.707707 for Cc1, ranges from 0.707695 to 0.707699 for Cc2, and is 0.707698 for Cc3. By contrast, the calcite cement Cc4 has a 87 Sr/ 86 Sr ratio similar to its adjacent host carbonate in the case of the crackle proto-breccia veins located in the hanging wall (0.707715) and more radiogenic than the host rock in the case of the fault plane (0.707771) (Figure 11(a)).   whilst the REY (REE and Y) pattern in the four cements follows a trend comparable to that of the adjacent host rock (Figure 12(c)).  (Figure 12(a)). The REY concentration of these cements (Cc1 to Cc3) is lower compared to that of the cement within the host rock (Cc0), but follows a similar flat trend, with a slight negative Ce anomaly (Figures 12(b) and 12(c)) and a slight positive Y anomaly (except for Cc2 that may exhibit either a positive or negative Ce anomaly) (Figure 12(c)).
In the fault core and hanging wall, Cc4 exhibits high Mg and Sr concentrations, intermediate Fe values, and low Mn contents. The REY pattern of Cc4 is also flat with a better defined negative Ce anomaly and a positive Y anomaly, which are also present in the hanging wall host rock. The REY concentrations are lower in cement Cc4 than in its adjacent host rocks, except for the calcite in the fault plane that exhibits higher concentrations (Figure 12(c)).
4.8. Neodymium Isotopes. Nine representative samples from calcite cements and related host rocks were also analyzed for Nd isotopic composition. However, although the Nd concentration is above the detection limit for all the analyzed samples (Table 3), the 143 Nd/ 144 Nd ratio could not be measured. This is attributed to both the low Nd concentration  13 Geofluids in the samples, ranging between 0.5 and around 10 ppm (Table 3), and the scarce quantity of sample that was possible to collect, generally around 30 mg, which was not enough for a dynamic multicollection method through 160 cycles at a stable intensity of 1 V.

Dissolution versus Precipitation
Zones. The studied fault zone has different brittle structures accommodating deformation both in the fault core and in the damage zone. Within the fault core, the presence of tectonic stylolites and S-C structures evidences processes of pressure solution and/or frictional sliding [54,55]. Such processes are associated with contractional stress concentration and slip accommodation imposed by the advancing thrust [64,65]. By contrast, within the damage zone, the widespread presence of veins represents dilational sites where calcite precipitated [66,67]. The mechanism of calcite precipitation was likely induced by the rapid fluid pressure drop due to fluid trapping in the fractures developed in the footwall and hanging wall [10,66,68,69]. The repartition of such structures, stylolites, S-C foliation, and veins, and therefore of zones of dissolution and zones of precipitation, is the result of a heterogeneous distribution of stress and the variation in deformation intensity across the fault zone [54].

Structural Context of Fracturing and
Veining. The main stress orientations responsible for the development of the studied thrust system have been calculated plotting the main plane orientation and related slickenlines (Figure 6(e)). The estimated stress field shows a SSE transport direction, compatible with the N-S to NNW-SSE shortening direction reported in the Pyrenees [28,30,39], and a vertical minimum principal stress (σ v = σ 3 ), characteristic of compressional regimes [9,10]. The studied vein systems are interpreted as developed during the thrust activity under the same compressional regime [8,42,70]. The synchronicity between fracturing. In the case of conjugated fracture systems F3, their bisector angle indicates a subhorizontal σ 1 and a subvertical σ 3 , and therefore, their formation is compatible with the prevailing stress field associated with thrusting (σ v = σ 3 ). Two mechanisms, a local variation of the stress axes as well as high fluid pressure conditions, are invoked to explain the formation of the steeply dipping F1 and F2 fractures in relation to the low angle reverse fault [72][73][74]. In the first case, the remote stress fields could have varied locally within a constant far-field compressional regime to become properly oriented for the development of these fractures [71,72,75]. Such a local variation of the magnitude and orientation of the remote stress fields is attributed to the formation of a process zone at the front of the fault tip during thrust (slip plane) propagation [71,76]. This occurs, firstly, because the fault tip acts as a stress concentrator amplifying the magnitude of the remote stress [76] and, secondly, because the main compressive stress (σ 1 ) exhibits different angles with the fault in compressive quadrants with respect to dilational quadrants in propagating faults [71,76].
Several observations, which are described below, indicate that the formation of the studied fractures occurred under high fluid pressure conditions, and therefore, it is associated with a hydraulic (over)pressure mechanism. Fluid overpressure may explain the high concentration of systematically oriented extensional (F1, F2) and extensional-shear (F3) veins, as well as the absence of any structural orientation of veins in the breccias [77]. Comparable fracture systems (systematic arrays of extensional and extensional-shear fractures) are expected to develop in compressional settings when the tensile overpressure condition is achieved, that is, when the pore fluid pressure exceeds the least compressive stress (P f > σ 3 ) [9,10,78]. Such a fluid pressure is common during the propagation of thrust faults in compressional regimes [9,12,67,79] and is attributed to the following: (i) the constraint stress field around the fault tip may generate overpressure of a confined fluid [80,81], (ii) the low dip of Table 2: Elemental composition (Ca, Mg, Fe, Mn, and Sr) of the different calcite cements (Cc1 to Cc4), the interparticle cement Cc0 in the footwall host rocks (FW), and the hanging wall rocks (HW). The calculated Mg/Ca and Sr/Ca molar ratios of the parent fluid using the distribution coefficient equation [57] are also shown.   thrusts prevents vertical flow [14,68], and (iii) it is because of sediment compaction induced by loading during thrust sheet emplacement [77,81].

Fluid History and Pathways.
The widespread presence of calcite cements in the different fracture sets indicates that these structures themselves were traps for fluids migrating during thrusting. Field observations based mainly on the macroscopic vein features and crosscutting relationships between them together with the above presented petrological and geochemical data evidence the formation of four calcite cementation phases (Cc1 to Cc4) that record the evolution of the fluid system during the thrust activity. Since the footwall and hanging wall exhibit different fracture systems and different calcite cements, the fluid system was compartmentalized [26,27,82,83].

Fluid
System in the Footwall. The evolution of the fluid system in the footwall during thrusting is inferred from the geochemical data of calcite cements Cc1, Cc2, and Cc3. Calcite cement Cc1 is observed within fractures F1 and within the mosaic to chaotic breccia located in the footwall. This cement has δ 18 O (-8.2 to -6.5‰VPDB) and δ 13 C values (-2 to -1.5‰VPDB) similar or slightly more depleted with respect to those of the interparticle calcite cement (Cc0) in the adjacent host rocks (Figures 9(a) and 9(b)). This fact, together with the observed positive Y anomaly in both Cc1 and Cc0, indicates buffering of the vein-forming fluids by the adjacent host carbonates due to fluid-rock interaction [84]. The fluid-rock interaction is also recorded in the δ 18 O fluid obtained from clumped isotopes, yielding values between -1.8 and -0.1‰VSMOW. These values may result from interaction between meteoric waters, which have typically negative δ 18 O values, and marine carbonates, with δ 18 O values around 0‰PDB [64]. This fact is supported by the calculated Mg/Ca and Sr/Ca molar ratios, indicating the involvement of meteoric fluids, and the diluted elemental composition in Cc1 with respect to Cc0, showing lower REY concentration and lower Mg, Mn, and Sr contents (Figure 12(a)). Likewise, the 87 Sr/ 86 Sr ratio of Cc1 is slightly more radiogenic than Cc0 but is still between the ranges of Cretaceous marine carbonates ( Figure 11). The homogeneous orange luminescence of Cc1 is interpreted as constant precipitation rates during a single precipitation event, and the presence of a negative Ce anomaly suggests precipitation in an oxic environment [84] (Figures 12(b) and 12(c)). Finally, the temperature of Cc1, also obtained from clumped isotope thermometry, ranges between 42 and 51°C. The presence of meteoric fluids and the relatively low temperatures could indicate shallow burial depths, probably less than 1 km if we consider a normal geothermal gradient of 25-30°C/km and a surface temperature of 20°C. Therefore, Cc1 precipitated from meteoric fluids (Figure 13(a)) with a composition strongly buffered by the Cretaceous host carbonates.
Calcite cement Cc2 is found in fractures F1 and F2 and within the mosaic to chaotic breccia from the footwall. This cement has similar 87 Sr/ 86 Sr ratios and δ 18 O values to Cc1 but precipitated at higher temperatures (between 64 and 78°C) and from heavier δ 18 O fluid (between +3.7 and +5.9‰ VSMOW). These higher temperatures and the δ 18 O fluid imply hot formation waters. However, the low δ 13 C values (Figure 9), the diluted Mg, Sr, and REY concentrations (Figure 12), and the calculated Mg/Ca and Sr/Ca molar ratios of Cc2 reveal the involvement of meteoric fluids with increasing influence of organic-derived carbon [85][86][87][88][89] (Figure 12(b)). The CL zonation of Cc2, alternating between non-and bright luminescent zones, the presence of positive and negative Ce anomalies (Figures 12(b) and 12(c)), and the oscillations in the Fe and Mn contents (Figure 12(a)) indicate oxidizing-reducing fluctuation, typical of the meteoric environment [6,[90][91][92][93]. These facts indicate that Cc2 precipitated from formation fluids that likely evolved from heated meteoric waters during the development of the second fracturing event (F2). The evolution of these fluids probably involved water-rock interactions during progressive increase in burial depths and temperatures linked to thrust sheet emplacement [94][95][96].
Calcite cement Cc3, occluding fractures F3, shows an 87 Sr/ 86 Sr ratio similar to cements Cc1 and Cc2 (Figure 11), δ 13 C within the same range of values of Cc2 (Figure 9(a)), and a lighter δ 18 O than the previous cement generations and the adjacent host carbonates (Figures 9(a) and 9(b)). Such depletion is related to hotter precipitation conditions (between 105 and 117°C). On the other hand, the δ 18 O fluid (between +3.2 and +5.2‰VSMOW), the high Sr, Mn, and Fe contents (Figure 12(a)), and the calculated Mg/Ca and Sr/Ca molar ratios for the vein-forming fluids are within the range of formation waters [57,87,95]. The homogeneous bright-orange luminescence points to complete precipitation of Cc3 during a single precipitation event [97], and the presence of a negative Ce anomaly indicates oxic precipitation conditions [84] (Figure 12(b)).
In conclusion, the progressive depletion in δ 18 O values from Cc1 to Cc3, as well as the continuous increase in precipitation temperatures and enrichment in δ 18 O fluid and in the elemental composition, evidences a progressive change in the fluid regime during ongoing deformation. This change may result from a continuous shift in the fluid composition, due to the evolution of the meteoric waters, or from a progressive change in the fluid origin, from percolation of diluted meteoric waters to the upflow of hotter formation fluids. The evolution of the fluid system is also attested by the disequilibrium between Cc3 and its adjacent host rocks (Figure 9(b)) and may be indicative of a continuous opening of the fluid system, which is in turn attributed to the increase in fracture density and superposition of different fracturing events [4,[98][99][100][101][102]. Previous contributions reported the relationships between folding, fracturing, and fluid migration in the eastern part of the Sant Corneli-Bóixols anticline (around the Coll de Nargó area, Figure 1(b)) [37]. During the latest stages of deformation in the frontal part of the anticline, these authors also reported a change in the fluid origin and composition, that is, from percolation of meteoric waters, circulating at approximately 40°C, to migration of hotter formation fluids, at temperatures around 90°C [103]. Consequently, the comparison between both studies suggests a common fluid behavior during the latest-folding to postfolding stages of deformation in the whole anticline. 18 Geofluids

Process zone deformation
Fractures F1 and mosaic to chaotic breccia. Calcite cement Cc1 Process zone deformation Fractures F2 and mosaic to chaotic breccia. Calcite cement Cc2 Remote stress fields reorientation P r o c e s s z o n e  (F1-F2), the remote stress field varied locally within the process zone to generate steeply dipping fractures. (c) As the thrust developed, fractures F3 were formed in the footwall damage zone. The orientation of these fractures reflects the far-field stress regime unaltered by faulting. The fluid involved in this stage evidences the continuous increase in precipitation temperatures due to burial during thrust emplacement. From this stage, the thrust drained fluids that only infiltrated in the hanging wall. These fluids were likely expelled from underlying Cretaceous carbonates due to rock compaction during thrusting. 19 Geofluids 5.3.2. Fluid System in the Hanging Wall. Calcite cement Cc4 precipitated within the main fault plane, within the fault core, and within the randomly oriented fractures (crackle protobreccia) located in the hanging wall. The similarity between δ 13 C values in Cc4 and its host carbonates, together with the high Mg contents and the REY pattern showing a welldefined negative Ce anomaly and a positive Y anomaly, similar to that of the host rocks, indicates buffering of the precipitating fluid by the hanging wall carbonates (Figures 9 and 12). This buffered composition of the fluids is also recorded in the δ 18 O fluid obtained from clumped isotopes and yielding values between +0.7 and +1.9‰VSMOW. However, the depletion in δ 18 O values in Cc4 in relation to the adjacent rocks suggests that the system was opened to advection of the vein-forming fluid (Figures 9(a) and 9(b)). The Mg/Ca and Sr/Ca molar ratios calculated for the fluid that precipitated Cc4 reveal the presence of formation waters, which precipitated at temperatures between 93 and 96°C (according to clumped isotope thermometry). The 87 Sr/ 86 Sr ratio of Cc4, similar to that of the hanging wall host rock (0.707718) in the crackle proto-breccia (0.707715), but more radiogenic in the fault plane (0.707771) (Figure 11), reveals a channelized ascending fluid migrating through the thrust plane towards the hanging wall, where it progressively increased the fluid-rock interaction. Cretaceous evaporated seawater is the most probable source for these formation fluids, if we take into account that (i) Cretaceous carbonates are broadly present around and underlying the studied thrust, (ii) the 87 Sr/ 86 Sr ratios of Cc4 are consistent with Cretaceous seawater and the δ 18 O fluid is slightly more enriched with respect to marine values (Figure 10), and (iii) during the Late Cretaceous, there was a transition from marine to lagoonal and thus more restricted and evaporative conditions [104]. Upward migration of Cretaceous connate seawater was also reported during the postfolding stages of evolution in the eastern part of the Sant Corneli-Bóixols anticline [37].

Thrust Zone
Evolution. The successive deformation stages, associated with different fracture systems, record an episodic evolution of the studied thrust zone. We interpret this evolution to result from an upward propagation of the fault tip leading to distributed deformation within the process zone before propagation of the fault [71,89,105,106].
During initial fault growth, deformation at the fault tip, i.e., within the process zone, was dominated by concentration of dilatant (extensional) fracturing, giving rise to fractures F1 and the mosaic to chaotic breccia from the footwall (Figure 13(a)). The fluid associated with this initial deformation stage responsible for precipitation of calcite cement Cc1 was a host-rock buffered meteoric fluid. Meteoric fluids probably infiltrated the system on high structural reliefs that were likely elevated during growth of the Sant Corneli-Bóixols anticline (Figure 13(a)). These fluids warmed up tõ 50°C at depth by a normal geothermal gradient and then migrated through diffuse deformation developed in the process zone before the growth and propagation of the thrust slip plane (Figure 13(a)) [71,89,105]. As deformation continued, new dilatant fractures F2 developed, and F1 fractures reopened and randomly oriented fractures from the breccia con-tinued forming. This synchronicity is evidenced by the presence of the same calcite cement (Cc2) in the aforementioned fractures. The second fluid flow event, associated with the second deformation stage, was characterized by the progressive evolution of meteoric fluids due to water-rock interactions at increasing depths and temperatures (Figure 13(b)). During these two initial stages of deformation, the remote stress fields varied locally in the process zone, allowing for the formation of steeply dipping fractures (F1 and F2) (Figures 13(a) and 13(b)).
Finally, the thrust slip plane propagated through the process zone. Frictional processes occurred along the thrust surface as well as the progressive weakening of the fault zone, which led to the formation of the foliated cataclasite, characterized by S-C shear fabric, pressure solution seams, calcite mineralization, and carbonate fine-grained matrix. This micritic matrix is petrographically similar to that of the hanging wall protolith (Figures 4(c) and 7(b) and 7(c)) and displays comparable isotopic composition ( Figure 9). These observations indicate that the cataclasite matrix derived from the hanging wall carbonates. During this period of thrust sheet emplacement, fractures F3 developed. We interpret that the orientation of these fractures represents the farfield stress regime unaltered by faulting (Figure 13(c)). The calcite cement Cc3, precipitated in fractures F3, reflects the presence of formation fluids and the progressive increase in precipitation temperatures, up to~117°C, which could indicate progressive burial during fault growth from calcite cement Cc1 to Cc3 [107].
Later, the thrust acted as a preferential pathway for fluids that only infiltrated in the hanging wall block (Figure 13(c)) as indicated by the presence of the same calcite cement (Cc4) along the thrust slip plane, in the fault core and within the crackle proto-breccia from the hanging wall. Thus, this observation corroborates the compartmentalization of the fluid system. As proposed in other settings where faults compartmentalize fluid flow between the footwall and hanging wall, the presence of veins without a preferred structural orientation (i.e., randomly oriented veins) is indicative of overpressured fluid migrating during deformation. Pressured fluids were likely expelled from Cretaceous carbonates due to sediment compaction during thrust sheet emplacement [77] (Figure 13(c)).
The interpreted evolution of the studied fault zone is similar to models already proposed in other extensional settings during upward propagation of normal faults deforming carbonate rocks [71,80,89,105,108,109]. Therefore, the comparison between these studies allows us to provide insights into deformation processes and mechanisms related to propagation of faults in different geological settings. Interestingly, all these contributions reported an initial stage of fault nucleation related to the development of a process zone (in the fault tip) before individualization of the fault plane. This period was characterized by the formation of hydraulic extension fracturing and brecciation and the presence of a fluid in chemical equilibrium with the host rocks. Finally, the progressive deformation resulted in the propagation of the fault (slip plane) through the process zone and the circulation of external fluids along the main slip surfaces (i.e., 20 Geofluids longitudinal fluid migration). These studies also reported an evolution of the fracture connectivity, a continuous opening of the fluid regime, and a progressive change in the fluid composition and origin during the evolution of the fault zone [80,89,105].
5.5. Structural Permeability: Thrust Sealing Capability and Fluid Pressuring. The petrology and geochemistry of the studied calcite cements indicate that the thrust separates two compartments with different deformation and fluid flow patterns. It is therefore likely that the thrust acted as a transversal barrier for fluids migrating between the footwall and hanging wall. The barrier role of the thrust is attributed (i) to the poor permeability of the foliated cataclasite and its micritic carbonate matrix with concentration of clay minerals associated with pressure-solution surfaces and (ii) to the nonporous character of the hanging wall carbonates (i.e., wackestones). In the latter case, although it has not been measured, the permeability is likely lower in the hanging wall wackestones with respect to the footwall grainstones. Therefore, the thrust acted as a transversal barrier and a longitudinal drain from fluids [15]. Additionally, considering the footwall damage zone as a high fractured compartment, its structural permeability is qualitatively evaluated. In this compartment, systematically oriented fractures (F1 to F3) were cemented by three generations of calcite cement (Cc1 to Cc3) and the randomly oriented fractures were cemented by Cc1 and Cc2. This evidences that the structural permeability was transient and that successive episodes of fracturing added new pathways to fluids that were rapidly occluded by calcite precipitation and sealing [18,70]. According to theoretical models, the presence of existing fractures appropriately oriented for reactivation prevents the formation of new fracturing events [10]. Therefore, a new fracturing episode developed when the previous fracture system regained cohesive strength by calcite precipitation [10]. The fact that the calcite cements Cc1 to Cc3 vary geochemically through time demonstrate that the fluid pathways, path lengths (associated with different fracture sizes), and the extent of fluid-rock interaction changed during the thrust nucleation (process zone development) and growth (thrust slip plane propagation), which has been corroborated by the different fluid compositions and temperatures obtained from clumped isotopes. In the same location, a previous study [42] documented the distribution of fractures developed in the footwall and discussed the permeability properties of the footwall damage zone in terms of porosity creation and occluding processes based on structural analysis and crosscutting relationships between veins. These authors also concluded that the footwall damage zone had to be considered as a low-quality reservoir analogue because any porosity developed during fracturing was rapidly sealed by cementation processes [42].
The comparison between the above described scenario and the model proposed in the Oman Mountains [26] highlights that fluid behavior during thrusting greatly varies in different geological settings. In particular, the analysis of calcite cements precipitated across the fault zone in both studies reveals that the thrust faults acted as transversal barriers to fluid migration but were preferential paths for channelized fluids along the thrust planes (longitudinal drains). In the studied outcrop, fluids in the footwall did not reach the hanging wall because of the impermeable fault core rock (foliated cataclasite) and a different fluid migrated upwards along the thrust plane and towards the hanging wall. By contrast, in the outcrop of Oman [26], fluids migrated along the thrust fault and towards the footwall, the only block in which syntectonic fractures developed. Our contribution and that of [26] highlight the importance of a good understanding of the timing of fracturing and the associated fluids in order to characterize the hydraulic behavior of a fault zone.

Conclusions
The studied thrust displaces a subvertical Upper Cretaceous carbonate succession located in the southern limb of the Sant Corneli-Bóixols anticline, in the Southern Pyrenees. Structural data together with petrological and geochemical analyses of synkinematic calcite veins developed within the fault zone constrain the evolution of the structural permeability and the thrust sealing capability and provide insights into the paleofluid system at the time of thrusting: (i) The heterogeneous distribution of deformation mechanisms across the thrust zone resulted in strong host rock dissolution within the fault core and calcite precipitation in veins within the damage zone (ii) The evolution of the thrust zone resulted from the upward propagation of the fault tip, producing distributed deformation in the process zone and subsequent propagation of the fault (slip plane), similar to the models already proposed for normal faults deforming carbonate rocks. During this evolution, the different deformation and fluid flow histories in the footwall and hanging wall indicate that the fault core acted as a transversal barrier due to its low permeability associated with the foliated cataclasite arrangement and matrix cementation. In the footwall, three systematically oriented fracture systems (F1 to F3) and randomly oriented fractures developed during progressive deformation. The structural permeability in the footwall damage zone was transient, and successive episodes of fracturing added new pathways to fluids but were rapidly occluded by calcite precipitation. By contrast, in the hanging wall, only randomly oriented fractures are present (iii) Three calcite cements (Cc1 to Cc3) precipitated within the fracture systems developed in the footwall. The petrology and geochemistry of Cc1 to Cc3 reveal a progressive change in the fluid origin and/or composition from percolation of meteoric fluids at temperatures between 42 and 51°C to upward migration of hotter formation waters at temperatures between 105 and 117°C. On the other hand, only one calcite cement (Cc4) precipitated in the hanging wall and in the fault core from hot 21 Geofluids formation waters at 95°C. These formation fluids were probably expelled from Cretaceous carbonates and migrated along the thrust plane towards the hanging wall during deformation. The comparison between the present study and previous data reported in the eastern part of the Sant Corneli-Bóixols anticline reveals the same fluid regimen and evolution of the fluid system during the postfolding stages of deformation in the whole anticline

Data Availability
All data used to support the findings of this study are included within the article.

Conflicts of Interest
The authors declare that there is no conflict of interest regarding the publication of this paper.