minerals Article Origin of the Coloured Karst Fills in the Neogene Extensional System of NE Iberia (Spain) Anna Travé 1 , Noelia Rodríguez-Morillas 2 , Vinyet Baqués 1 , Elisabet Playà 1 , Lluís Casas 3 , Irene Cantarero 1 , Juan Diego Martín-Martín 1 , Enrique Gómez-Rivas 1 , Mar Moragas 4 and David Cruset 4, * 1 Departament de Mineralogia, Petrologia i Geologia Aplicada, Facultat de Ciències de la Terra, Universitat de Barcelona (UB), 08028 Barcelona, Spain; atrave@ub.edu (A.T.); vinyetb@gmail.com (V.B.); eplaya@ub.edu (E.P.); i_cantarero@ub.edu (I.C.); juandiegomartin@ub.edu (J.D.M.-M.); e.gomez-rivas@ub.edu (E.G.-R.) 2 Repsol Technology Lab., 28935 Móstoles, Spain; noelia.rodriguez@repsol.com 3 Departament de Geologia, Universitat Autònoma de Barcelona (UAB), Edifici C, Cerdanyola del Vallès, 08193 Catalonia, Spain; lluis.casas@uab.cat 4 Group of Dynamics of the Lithosphere (GDL), Geosciences Barcelona (GEO3BCN-CSIC), Lluís Solé i Sabarís s/n, 08028 Barcelona, Spain; mmoragas@geo3bcn.csic.es * Correspondence: dcruset@geo3bcn.csic.es Abstract: Karst fills from the onshore Penedès Basin and offshore València Trough display red,  pink, orange and ochre colours. Their Mössbauer spectra indicate that Fe3+ contained in goethite  is the dominant species in reddish-pink fills, whereas Fe2+ contained in dolomite and clays is more Citation: Travé, A.; dominant in the orange and ochre ones. The lower δ13 C values and higher 87 Sr/86 Sr ratios of the Rodríguez-Morillas, N.; Baqués, V.; karst fills with respect to their host carbonates can reflect the input of soil-derived CO2 and an Playà, E.; Casas, L.; Cantarero, I.; external radiogenic source into the karst system. This geochemical composition, together with Martín-Martín, J.D.; Gómez-Rivas, E.; the non-carbonate fraction of the fills, consists of authigenic and transported illite, illite-smectite Moragas, M.; Cruset, D. Origin of the interlayers, as well as kaolinite, chlorite, pyrite, quartz, ilmenite, magnetite, apatite and feldspar, Coloured Karst Fills in the Neogene account for a mixed residual-detrital origin of fills. This polygenic origin agrees with that of the terra Extensional System of NE Iberia rossa sediments described worldwide. The different colours of karst fills are attributed to fluctuations (Spain). Minerals 2021, 11, 1382. in the water table, which control the Eh/pH conditions in the karst system. Thus, reddish colours https://doi.org/10.3390/min11121382 reflect low water table levels and oxidising episodes, and orange and ochre ones reflect high water table levels and more reducing episodes. The greenish colours of fills could be related to fluctuations Academic Editors: Georgia Pe-Piper and Roberta Di Febo in the Fe3+ /Fe2+ ratio. Received: 29 October 2021 Keywords: carbonate diagenesis; coloured karst fills; fracture and vug porosity; geochemistry Accepted: 30 November 2021 Published: 8 December 2021 Publisher’s Note: MDPI stays neutral 1. Introduction with regard to jurisdictional claims in Karst sediments register the evolution of karst systems developed in carbonate published maps and institutional affil- rocks [1]. In this regard, their geochemical composition can provide information about iations. changes in climate, groundwater level fluctuations and tectonic regimes within orogens and sedimentary basins [2–6]. Coloured sediments within karstified rocks are widely recognised worldwide. Red sediments such as terra rossa deposits and laterites have been widely attributed to residual Copyright: © 2021 by the authors. soil deposits due to rock weathering [7], although detrital inputs are also reported in terra Licensee MDPI, Basel, Switzerland. rossa sediments. Examples of such deposits have been documented in karst systems from This article is an open access article the Czech Republic and Slovenia [1], South Africa [8] and in the Northern Apennines [9,10]. distributed under the terms and Beige to pink rocks found in calcretes developed on quaternary karstic surfaces in the conditions of the Creative Commons Grand Cayman Island were interpreted as resulting from a porous mixture of dolomite, clay Attribution (CC BY) license (https:// and calcite due to the activity of plant roots and associated microorganisms [11]. Dark to creativecommons.org/licenses/by/ black colours are attributed to the presence of organic matter transported by groundwater 4.0/). Minerals 2021, 11, 1382. https://doi.org/10.3390/min11121382 https://www.mdpi.com/journal/minerals Minerals 2021, 11, 1382 2 of 28 flows, which hides their original red or brownish colour, as observed in the coastal caves of Mallorca Island [12]. The onshore Penedès Basin (Catalan Coastal Ranges) and the offshore València Trough (Western Mediterranean) are part of the same extensional system that affected the NE sector of Iberia during the latest Oligocene and Miocene [13]. Several diagenetic studies were carried out in these areas motivated by the oil exploitation potential of offshore carbonate reservoirs [3,14–18]. These authors deciphered the fracture and fluid flow history in structural highs and normal fault zones, defining different diagenetic events related to the tectonic evolution of the Penedès Basin and València Trough from the Mesozoic to the Neogene. Multiple karst events were identified in Mesozoic limestones and dolostones in close association with the Neogene extension [3,15–21]. Karstification comprises dissolution processes, calcite and dolomite cementation from meteoric fluids, and are characterised by carbonate karst fills displaying red, pink, orange, ochre and green colours. Despite the existing knowledge about the geology of the onshore Penedès Basin and the offshore València Trough, several questions about karst fills remain open: (1) the resid- ual vs. detrital origin of the fills, (2) their accurate mineralogical composition, (3) the redox conditions in which they were deposited and/or precipitated and (4) the significance of their variable colour. To shed light on these issues, we combined petrographic observa- tions with Mössbauer spectrometry, classical isotopic methods (δ18 O, δ13 C and 87 Sr/86 Sr) and elemental composition analyses (electron microprobe). The results enlighten the cur- rent knowledge of the evolution of karst systems in carbonate rocks from the Western Mediterranean Margin during the Neogene rift-related extension and equivalent systems worldwide. 2. Geological Setting The Penedès Basin and the València Trough are linked to the Palaeogene to Neogene tectonic evolution of the Catalan Margin, which consists of a portion of the Western Mediterranean Margin. This margin displays a horst and graben structure that formed during the latest Oligocene to Miocene extension [22,23], resulting from the reactivation of previous Eocene to late Oligocene compressional fractures [24–26] (Figure 1A). The Penedès Basin, together with its northeastern continuation, the Vallès Basin, as well as the El Camp and Amposta Basins, are all NE–SW half grabens that compartmentalised the onshore Western Mediterranean Margin and defined a system of NE–SW system of horsts known as the Catalan Coastal Ranges [13]. These ranges represent the northern margin of the València Trough, which is bounded to the south by the Betic orogen [27]. The offshore València trough displays a similar structure to the Catalan Coastal Ranges, with a system of structural highs limited by extensional basins (e.g., Tarragona and Barcelona Basins) [13]. In the Penedès Basin and València Trough, Upper Jurassic and Lower Cretaceous ma- rine limestones and dolostones act as structural highs and basement of the latest Palaeogene– Neogene sediments filling the extensional basins [13] (Figure 2). In general, the stratigraphy of the Penedès Basin comprises: (1) Aquitanian to lower Burdigalian alluvial and lacus- trine sediments, (2) middle Burdigalian sabkha–salina deposits, (3) upper Burdigalian to Langhian shelf deposits and (4) Langhian to middle Serravallian fan delta deposits, which laterally pass to continental complexes that were accumulated until the Tortonian [28,29]. These sediments are truncated by an erosive event related to the Messinian, which was followed by the deposition of Pliocene marine and alluvial sediments. A summary of the stratigraphy of the València Trough was presented by [15] (Figure 2). Rift-related sedimentation began with the deposition of Chattian to Aquitanian red beds, conglomerates and dolostones (Basal Tertiary Group), which are unconformably overlain by Burdigalian–Langhian dark to black argillaceous limestones with variable organic- carbon content (Casablanca Group). These sediments are the main source of rock of the Casablanca oil field in the València Trough [30,31]. Source rocks of the Casablanca Group are overlain by Serravallian turbidites of the Sant Carlos Group and/or limestones and marls of the Castellón Group, which in turn are overlain by Tortonian to Messinian shales. Minerals 2021, 11, x 3 of 28 Minerals 2021, 11, 1382 3 of 28 Group are overlain by Serravallian turbidites of the Sant Carlos Group and/or limestones and marls of the Castellón Group, which in turn are overlain by Tortonian to Messinian These shales shales. These acted shalesas a regional acted seal. Younger as a regional sediments seal. Younger consist sediments of Plio-Quaternary consist shelf of Plio-Quaternary sandstones and conglomerates of the Ebro Group [32]. shelf sandstones and conglomerates of the Ebro Group [32]. Figure 1. (A) Simplified geological map of the Catalan Coastal Ranges and location of the Casablanca-1A and Amposta Marino1.C2(A) Figure wells in the València Simplified Trough geological map(red stars). of the The Coastal Catalan red box Ranges indicatesand thelocation locationof ofthe Figure 1B. (B) Geological Casablanca-1A map of and Amposta Marino C2 wells in the València Trough (red stars). The red box indicates the location of Figure 1B. (B) Geological map the Penedès half-graben showing location of the Castellví, Olèrdola and Montjuïc outcrops (red stars). Redrawn from [3]. of the Penedès half-graben showing location of the Castellví, Olèrdola and Montjuïc outcrops (red stars). Redrawn from [3]. Minerals 2021, 11, 1382 4 of 28 Minerals 2021, 11, x 4 of 28 Figure 2. Lithostratigraphy of the offshore València Trough and onshore Penedès Basin. The stratigraphy of the València Trough is based on the lithostratigraphic panels of [15,16], as well as the cross-section of [33]. The stratigraphy of the Penedès Basin is based on the lithostratigraphic panel in [34]. Minerals 2021, 11, 1382 5 of 28 3. Study Areas The studied karst fills are found in the porosity of Mesozoic carbonate rocks in both the offshore València Trough and in the onshore Penedès Basin [3,15–18,21]. They were described by previous authors in the Casablanca-1A and Amposta Marino C2 wells (València Trough) and in the Montjuïc, Castellví and Olèrdola outcrops of the Penedès Basin (Figure 1). 3.1. Casablanca-1A Well The Casablanca oil field is 1 km wide and 11 km long and is located in a structural high formed by Mesozoic carbonate rocks. This palaeohigh is limited by normal faults in its northwestern and southeastern margins [20]. In the Casablanca oil field, the main reservoir rocks are Upper Jurassic and Lower Cretaceous shallow marine limestones and dolostones. The study of the diagenetic evolution of the Casablanca oil field was carried out by [15] in samples from the Casablanca-1A well. This well cuts 100 m of karstified Upper Jurassic (Kimmeridgian) dolostones, where karstic matrix- and clast-supported collapse breccias, vug and fracture porosities are filled with ochre and red dolomite fills (RD2 sediment according to the terminology used in [15]). According to these authors, the Jurassic host rocks forming the Casablanca oil field were affected by three main diagenetic stages: (1) karstification and karst fill accumulation, (2) dolomitisation of both host carbonates and karst fills and (3) calcite cementation and oil emplacement. 3.2. Amposta Marino C2 Well The Amposta oil field consists of a 25 km long Mesozoic structural high, bound by normal faults and covered by Neogene sediments [35]. In the Amposta Marino C2 well, samples from 1874 m to 1957 m depth were studied. This well cuts locally-karstified Barremian–Aptian limestones that are overlain by Miocene clays, sandstones and con- glomerates. In the Barremian–Aptian limestones, several fracture, cementation and karstic events were reported by [16]. According to these authors, in the Amposta Marino C2 well, three main types of fracture systems (A–C) and four types of calcite cement are present. Fractures A and B are completely filled with calcite cement. Fractures A correspond to pre-Alpine structures, whereas fractures B are attributed to being developed during the late Eocene-early Oligocene Alpine compression. Fractures C, developed during the Neogene extension and enlarged by subaerial exposure, are filled with karst fills constituted of microsparite, clays and blocky calcite cement, which are postdated by kaolinite, pyrite, barite and oil. 3.3. The Penedès Basin In the onshore Penedès Basin, Upper Jurassic and Lower Cretaceous carbonate se- quences are well exposed at the tilted fault blocks, where their uppermost is affected by fractures enlarged by karstic dissolution, vug porosities and large caverns. Several palaeokarst horizons developed onshore since the lower Eocene [3,7,36,37]. Vug, cavern and fracture porosities described by previous authors are occluded with reddish to ochre laminated fills and by sparite calcite cement. These karst fills and cements are summarised and described in detail by [3,17,18]. For the present study, we chose the Montjuïc, Castellví and Olèrdola outcrops, where excellent exposures of karst fills are observed. The Montjuïc outcrop is constituted by Barremian lacustrine limestones, the Castellví outcrop corresponds to the Thitonian–Berriasian Garraf Upper Dolomites Formation and the Olèrdola outcrop corresponds to marine limestones of the lower Aptian Farreny Formation [36]. In these three outcrops, the studied karst fills are filling randomly- oriented fractures (Castellví and Olèrdola) and vugs (Castellví), as well as the intraclast porosity of fault breccias (Montjuïc) and breccias that result from the collapse of randomly- oriented fractures (Olèrdola). Minerals 2021, 11, 1382 6 of 28 4. Materials and Methods Part of the results presented in this study was already presented in [3,15–18]. These results are combined with new petrographic, spectral and isotopic and elemental composi- tions and are summarised in Table 1. A description of the different petrographic, spectral and elemental and isotopic methods of analysis are presented in this section. Table 1. List of analytical methods used in this work and the areas where they were applied. Data from this work and from previous authors are also indicated. Studied Optical and Cathodolumi- SEM, Mössbauer Electron Microprobe, 87 Sr/86 Sr XRD Outcrop/Well nescemicroscope TEM Spect. δ18 O, δ13 C València Trough Casablanca-1A [15] This work [15] This work [15] [15] Amposta [16] - - - [16] [16] Marino C2 Penedès Basin Castellví [3], this work - This work This work [3] [3] Olèrdola This work - - - This work - Montjuïc This work - This work This work This work - A total of thirty-one samples from the Casablanca-1A well core at depths between 2660 m and 2760 m; twenty-three samples from the Amposta Marino C-2 well, at perforation depths between 1874 and 1957 m; and more than 240 samples from the Penedès Basin outcrops were carefully studied in order to identify the diagenetic phases and their spatial and temporal relations. The selected karst fills for this study are in Jurassic and Early Cretaceous carbonates, although they are interpreted to have occurred during the Neogene rift-related extension affecting the North Eastern Margin of Iberia [3,15–21]. Thin sections were examined using optical and cathodoluminescence (CL) microscopy (Technosyn Cold Cathodoluminescence Model 8200 MkII (Technosyn Limited, Cambridge, UK) operating at 10–18 kV gun potential and 250–350 µm beam current). For scanning electron microscopy (SEM), an ESEM Quanta 200 FEI, XTE 325/D8395 device (FEI Europe B.V., Eindhoven, The Netherlands) with an energy dispersive spectrometer (EDX) and equipped with backscatter image technology was used. For Transmission electron microscopy (TEM), a JEOL 1010 + Orius (Gatan) device with a CCD camera was used. For the detailed study of the non-carbonate fraction, the bulk rock was leached with HCl 10% at room temperature. The resulting non-carbonate fraction was analysed with X-ray diffraction (XRD), with a diffractometer Siemens D-500 (Bruker AXS, Karlsruhe, Germany) working at 40 kV and 30 mA, and equipped with a graphite monochromator. The whole rock mineralogy of the non-carbonate fraction was obtained from non-oriented powdered preparations. The mineralogy of the clay fraction was obtained from oriented aggregates in air-dried etilenglicol (ETG) and heated at 550 ◦ C preparations. Selected samples of host rocks and dolomite and calcite, contained in the ochre, reddish, green and orange karst fills were used to characterise the oxidation state of Fe by determining the Fe2+ /Fe3+ ratio by Mössbauer spectrometry (MS). The 57 Fe Mössbauer spectra were acquired at room temperature by means of a conventional spectrometer with an operation geometry of transmission and radioactive source of 57 Co in an Rh matrix. The spectra were calibrated with a standard iron foil. The isomeric shifts are given with respect to the isomeric shift of this sample standard. In order to analyse major, minor and trace element composition (Ca, Mg, Mn, Fe, Sr and Na) of the diagenetic products, eight C-coated double-polished thin sections were investigated. The analyses were performed using a CAMECA SX-50 electron microprobe (CAMECA SAS, Gennevilliers, France), equipped with four vertically oriented WD X-ray spectrometers and operating at 20 kV of excitation potential, with 10 µm of beam diameter and 10 nA of current intensity for the Ca and Mg analyses, and 50 nA for Mn, Fe, Sr and Na. The detection limits are 495 ppm for Ca, 493 ppm for Mg, 131 ppm for Mn, 128 ppm Minerals 2021, 11, 1382 7 of 28 for Fe, 161 ppm for Sr and 128 ppm for Na. Na and Mn are mostly under the detection limit in all the identified diagenetic products. Standards used were calcite for Ca, periclase for Mg, albite for Na, celestite for Sr, iron oxide for Fe and rhodonite for Mn. Precision on major element analyses averaged 6.86% standard error at 3σ confidence level. For carbon- and oxygen-isotope analyses, samples were prepared using a 500 µm-thick microdrill to extract 60 ± 10 µg of powder from trims containing carbonate host rocks and karst fills. The carbonate powder was reacted with 100% phosphoric acid for two minutes at 70 ◦ C for calcite. The resultant CO2 was analysed using an automated Kiel Carbonate Device attached to a Thermal Ionization Mass Spectrometer Thermo Electron (Finnigan) MAT-252 (Thermo Fisher Scientific, Bremen, Germany) following the method of [37]. The obtained results were corrected using the standard technique from [38,39], expressed in ‰ with respect to the VPDB (Vienna Pee Dee Belemnite) standard. The standard deviation is ±0.01‰ for δ13 C and ±0.05‰ for δ18 O. Samples of 100% calcite and dolomite were analysed for 87 Sr/86 Sr. Samples were fully dissolved in 5 mL of 10% acetic acid and introduced in an ultrasonic bath for 15 min. After this time, samples were centrifuged for ten minutes at 4000 rpm and dried. The resultant product was reacted in 1 mL of 3 M HNO3 and dried. Finally, the sample was digested again in 3 mL of 3 M HNO3 and introduced in chromatographic columns. For the chromatographic separation of Sr, an extraction resin type SrResinTM was used (Trisken International, London, UK) (crown ether (4.40 (50 )-di-t-butylcyclohexano-18-crown-6). The Sr was recovered with HNO3 0.05 M as eluent. The fraction where Sr is concentrated was dried, charged on a Re single filament with 1 µL of H3 PO4 1 M and 2 µL of Ta2 O5 and analysed on a TIMS-Phoenix mass spectrometer (Isotopx, Cheshire, UK). The data acquisition method consisted of dynamic multicollection during ten blocks of 16 cycles each one, with a beam intensity in the 88 Sr mass of 3 V. Analyses were corrected for possible interferences of 87 Rb. The 87 Sr/86 Sr ratios were normalised with respect to the measured mean value of the ratio 86 Sr/88 Sr = 0.1194 of the isotopic standard NBS-987 in order to correct possible mass fractionation during filament charge and instrumental analyses. The precision of the analytical standard error or internal precision is 0.000003. 5. Petrology of Host Carbonates and Karst Fills The paragenetic sequence of fracture-filling calcite and dolomite cement, as well as karst, fills in the offshore València Trough and onshore Penedès Basin was already established by [3,15–18]. With the aim of facilitating the comparison with previous studies, this work uses the same terminology used by [16] and [3,17,18] for the Amposta Marino C2 well, and for the Castellví and Olèrdola outcrops in the Penedès Basin, respectively. For the Casablanca C1 well, the dolomite host rocks and karst fills described by [15] are called Dolomite 1 (RD1) and Dolomite 2a and 2b (RD2) in this study. For the Montjuïc outcrop in the Penedès Basin, the orange matrix made of orange pisoids described by [3] is called OP1 in this study. The host rocks and karst fills are listed in Table 2. Table 2. List of host rocks and karst fills from the offshore València Trough and the onshore Penedès Basin. Area Studied Outcrop/Well Fill Host Rock Colour Mineralogy València Trough Casablanca-1A Dolomite 2b Dolomite 2a Red and ochre Dolomite València Trough Amposta Marino C2 CS3r Limestones Red Calcite València Trough Amposta Marino C2 CS3g Limestones Green Calcite Penedès Basin Castellví DS2 RD1 Orange Dolomite Penedès Basin Castellví DS3 RD1 Pink to red Dolomite Penedès Basin Castellví CS1 RD1 Pink Calcite Penedès Basin Olèrdola CS2 Limestones Orange Calcite Penedès Basin Olèrdola CS3 Limestones Red Calcite Penedès Basin Montjuïc OP1 Limestones Orange Calcite Minerals 2021, 11, 1382 8 of 28 5.1. Casablanca-1A Well The diagenetic study of the Casablanca-1A well was carried out by [15]. The origi- nal host rock porosity was totally occluded in this well by multiepisodic dolomitisation processes. At present, the porosity is estimated to range between 7% and 12% [33], with most being of secondary origin (vug, intercrystalline, fracture and mouldic). Vug porosity up to 2 cm can be partially filled with dolomitised fills displaying geopetal structures. Fracture porosity corresponds to vertical fractures totally or partially occluded by calcite and dolomite cement, or karst fills. The Upper Jurassic (Kimmeridgian) host dolostones are formed by replacive dolomite with a crystal size of 10 µm to 80 µm. Dolomite 1 forms hypidiotopic crystal mosaics and shows a penetrative and destructive fabric. The crystals are non-homogeneous bright red under cathodoluminescence (Figure 3A,B). Dolomite 1 is only preserved as centimetric patches isolated between Dolomite 2a. Dolomite 2a replaces Dolomite 1. It consists of a mosaic of hypidiotopic crystals, with a size from 20 to 140 µm, and with a penetrative and non-destructive fabric. Dolomite 2a crystals are zoned, with dark cores and clear outer zones, and have dull red cathodo- luminescence (Figure 3A,B). Some crystals have a core with a luminescence typical of Dolomite 1. Replacive Dolomite 2b replaces the karst fills in the fracture and vug porosity within the host dolostone. It consists of euhedral crystals, 40 µm to 450 µm in size and planar-e borders, forming a dense fabric-selective idiotopic mosaic (Figure 3C,D). The crystals have a dark nucleus and clear outer zones, and dull red luminescence. Only locally, some of the zones are bright orange. Two types of Dolomite 2b, characterised by two different colours, fills fracture and vug porosity. The first one evolves from pink to red colour, travelling through to reddish-brown (Figure 3E). The second has a very pale brown or clear grey olive colour (Figure 3F). In this work, the first one is called a reddish fill, and the second one is an ochre fill. Dolomite 2b is only present in the uppermost 15 m of the Casablanca-1A well [15]. SEM and TEM microscopy reveal that the non-carbonate fraction of Dolomite 2b consists of illite, pyrite and goethite, although XRD performed previously by [15] also indicates the presence of illite/smectite (Figure 4A). Illite is observed in both the ochre and red fills and occurs as (1) clay coatings of dolomite flaky crystals with irregular shape (Figure 5A,B) and (2) as lath-shaped crystals (Figure 5C). Pyrite and ilmenite are also observed in the ochre and reddish fills, occluding growth cavities of dolomite or disseminated between dolomite crystals (Figure 5D,E). Goethite and magnetite are also identified in the reddish Dolomite 2b (Figure 5F), whereas apatite is observed in the ochre one. 5.2. Amposta Marino C2 Well The fluid flow history of the Amposta oil field rocks was deciphered by [16]. In this well, the Lower Cretaceous host limestones (usually brecciated) are wackestones to packstones of benthic foraminifera, silicified sponge spicules, green algae and echinoderm fragments that show a dull-red luminescence. Foraminifera mainly consists of Orbitolinop- sis, Nautiloculina, Pseudocyclamina, Choffatella and miliolids. The uppermost part of the sampled interval is a wackestone of charophytes–Atoporochara, ostracoda and dasy- cladacea algae characterising freshwater and shallow marine facies. Small framboidal pyrites are disseminated in the host-limestones or concentrated in the stylolitic planes as insoluble residue. Minerals 2021, 11, 1382 9 of 28 Minerals 2021, 11, x 9 of 28 Figure 3. Figure 3. Optical Optical and and cathodoluminescence cathodoluminescence microscope microscope (CL)(CL) and and hand hand sample sample photographs photographs from from [15] [15] showing showing the the main main features of features ofDolomite Dolomite1,1,2a 2aand and2b2bininCasablanca-1A Casablanca-1A well. well. (A,B) (A,B) CLCL photomicrographs photomicrographs showing showing thethe contact contact between between Dolo- Dolomite 1mite and12aand that2aare that cutare bycut by younger younger calcite calcite cementcement filling fractures. filling fractures. (C,D) CL(C,D) CL photomicrographs photomicrographs showingshowing DolomiteDolomite 2b 2b karst fill karst fill in a vug developed in Dolomite 1. (E) Polished slab showing reddish Dolomite 2b postdating Dolomite 2a. (F) in a vug developed in Dolomite 1. (E) Polished slab showing reddish Dolomite 2b postdating Dolomite 2a. (F) Polished slab Polished slab showing ochre Dolomite 2b filling fracture porosity within Dolomite 2a. showing ochre Dolomite 2b filling fracture porosity within Dolomite 2a. Minerals 2021, 11, 1382 10 of 28 rals 2021, 11, x 10 of 28 Figure 4. Air-dried, ETG and heated ◦ C) XRD diagrams of the non-carbonate fraction of Dolomite 2b fills in the Figure 4. Air-dried, ETG (550 and heated (550 °C) XRD diagrams of the non-carbonate fraction of Dolo- Casablanca-1A well, mite DS2 in 2b fills and theDS3 dolomite fills Casablanca-1A in Castellví well, outcrop DS2 and DS3 and orange dolomite pisoids inoutcrop fills in Castellví the Montjuïc outcrop. For and orange Dolomite 2a, XRD spectra pisoids in theare redrawn Montjuïc from [15]. outcrop. For Dolomite 2a, XRD spectra are redrawn from [15]. Minerals 2021, 11, 1382 11 of 28 Minerals 2021, 11, x 11 of 28 Figure 5. SEM Figure 5. SEM and and TEM TEM images images ofof the the non-carbonate non-carbonate fraction fraction of of Dolomite Dolomite 2a 2a and and 2b 2b in in the the Casablanca-1A Casablanca-1A well. well. (A) (A) SEM SEM microphotograph of Dolomite 2b coated by flaky particles of illite (white arrows). (B) TEM microphotograph microphotograph of Dolomite 2b coated by flaky particles of illite (white arrows). (B) TEM microphotograph of an irreg- of an irregular flaky particle ular flaky of illite. particle (C) TEM of illite. microphotograph (C) TEM microphotographof lath-shaped crystals of lath-shaped of illiteofinillite crystals Dolomite 2B. (D)2B. in Dolomite SEM(D)microphotograph SEM micropho- tograph of pyrite of pyritewithin placed placedgrowth withincavities growthofcavities of dolomite. dolomite. (E) SEM microphotograph (E) SEM microphotograph of pyrite disseminated of pyrite disseminated between between dolomite dolomite(F) crystals. crystals. (F) TEM microphotograph TEM microphotograph of goethiteofcrystals goethitewithin crystals withinDolomite reddish reddish Dolomite 2b. 2b. 5.2. Amposta Marino C2 In the Amposta Well C2 well, the aforementioned type C fractures display sharp Marino and undulating The fluid flow history of enlarged walls, locally the Amposta by dissolution, andwas oil field rocks are totally or partially deciphered filled by [16]. by In this calcite fills and younger calcite cement (Figure 6A). The calcite fill is constituted well, the Lower Cretaceous host limestones (usually brecciated) are wackestones to pack- of reddish (CS3r; Figure stones 6A) and of benthic greenish (CS3g; foraminifera, Figure silicified 6B) microsparite sponge spicules, greenandalgae clay minerals. Calcite and echinoderm fills and cements locally display geopetal structures, with the cement fragments that show a dull-red luminescence. Foraminifera mainly consists of Orbito- occluding the upper linopsis, Nautiloculina, Pseudocyclamina, Choffatella and miliolids. The uppermost8 part part of fracture porosity (Figure 6C). Individual calcite crystals range in size between and 40 µm (Figure 6C,D) and show dull orange to bright orange luminescence of the sampled interval is a wackestone of charophytes–Atoporochara, ostracoda and (Figure 6E,F). dasycladacea algae characterising freshwater and shallow marine facies. Small framboidal pyrites are disseminated in the host-limestones or concentrated in the stylolitic planes as insoluble residue. In the Amposta Marino C2 well, the aforementioned type C fractures display sharp and undulating walls, locally enlarged by dissolution, and are totally or partially filled by calcite fills and younger calcite cement (Figure 6A). The calcite fill is constituted of reddish (CS3r; Figure 6A) and greenish (CS3g; Figure 6B) microsparite and clay minerals. Calcite fills and cements locally display geopetal structures, with the cement occluding the upper Minerals 2021, 11, x 12 of 28 Minerals 2021, 11, 1382 part of fracture porosity (Figure 6C). Individual calcite crystals range in size between 8 28 12 of and 40 μm (Figure 6C,D) and show dull orange to bright orange luminescence (Figure 6E,F). Figure Figure 6. The 6. The mainfeatures main featuresof ofhost host limestones limestones andandreddish reddishCS3r and CS3r and greenish CS3g greenish karst CS3g fills fills karst in theinAmposta Marino the Amposta C2 Marino well (A to D photographs are from [16]). (A) Hand sample of CS3r filling fracture porosity within Lower C2 well (A to D photographs are from [16]). (A) Hand sample of CS3r filling fracture porosity within Lower Cretaceous Cretaceous lime- stones. (B) Hand sample with CS3g filling fracture porosity. (C) Photomicrograph of geopetal structure filled with CS3r limestones. (B) Hand sample with CS3g filling fracture porosity. (C) Photomicrograph of geopetal structure filled with CS3r and younger calcite cement (plane polarised light). (D) Photomicrograph of a brecciated host-limestone partially cemented andby younger CS3g and calcite cement calcite (plane cement (crosspolarised polarisedlight). light).(D) Photomicrograph (E,F) of a and Plane polarised light brecciated host-limestone(CL) cathodoluminescence partially imagescemented with by CS3g filling and calcite cement fracture (cross porosity polarised in Lower light). (E,F) Cretaceous Plane polarised light and cathodoluminescence (CL) images with limestones. CS3g filling fracture porosity in Lower Cretaceous limestones. 5.3. Penedès Basin The complete fracture and diagenetic history of the Penedès Basin during the Meso- zoic extension, Palaeogene compression and Neogene extension periods were defined by [3,17,18]. However, this study focuses on those Neogene karst fills that were identified in the Castellví, Olèrdola and Montjuïc outcrops. In the Castellví outcrop, there are three different karst fills: dolomite DS2 and DS3 and calcite CS1. Dolomite fills are found in randomly oriented fractures affected by strong 5.3. Penedès Basin The complete fracture and diagenetic history of the Penedès Basin during the Meso- zoic extension, Palaeogene compression and Neogene extension periods were defined by [3,17,18]. However, this study focuses on those Neogene karst fills that were identified in Minerals 2021, 11, 1382 13 of 28 the Castellví, Olèrdola and Montjuïc outcrops. In the Castellví outcrop, there are three different karst fills: dolomite DS2 and DS3 and calcite CS1. Dolomite fills are found in randomly oriented fractures affected by strong dissolution. Specifically, DS2 fills channel dissolution. channel and vug vug porosities porosities generated generated by this this process, process, and DS3 and DS3 isis observed observed in in aa rubble rubble floatbreccia floatbreccia produced producedby byfracture fracturewall wallcollapse. collapse. Dolomite Dolomite DS2 is DS2 is red red toto orange orange in in colour colour (Figure (Figure 7A,B) 7A,B) and and consists consists of ofmicro-fragments micro-fragments of of the the host host dolostone RD1. dolostone RD1. This non-luminescent non-luminescent to to orange orange luminescent luminescent fill fill is is cemented cemented by bydolomite dolomite (Figure (Figure7C,D), 7C,D),which whichisisarranged arrangedinina arim rimposition positionatatthe walls the wallsof of thethefracture fracture or surrounding or surround- the ing host dolomite the host dolomite fragments. fragments. The non-carbonate The non-carbonate fraction fractionofofDS2 DS2isisconstituted constitutedof of illite, illite, kaolinite kaolinite andand quartz quartz (Figure (Figure4B).4B). Dolomite DolomiteDS3 DS3isis aa pink pink to to red red laminated laminated fill fill (Figure (Figure 7A,B) 7A,B) and and consists consists ofof bright bright orange orange luminescent luminescent euhedral euhedral dolomite dolomite crystals crystals (Figure (Figure 7C,D).7C,D). ThisThis fill fill contains contains abundant abundant iron iron oxides, oxides, which which are are not not detected detected by XRD. However, However, as as with with DS2, the the spectra spectra ofof the the non-carbonate non-carbonate fraction fraction of of DS3 DS3 reveal reveal the the presence presence of of illite, illite, kaolinite kaoliniteand and quartz (Figure 4B). Pink and laminated calcite CS1 surrounds calcite quartz (Figure 4B). Pink and laminated calcite CS1 surrounds calcite cement precipitated cement precipitated between between spelean spelean pisoids, pisoids, which which form form layers layers parallel parallel toto the the main main normal normal fault fault (Figure (Figure 7E). 7E). This fill consists This fill consistsof ofnon-luminescent non-luminescentblocky blocky anhedral anhedral calcite calcite crystals, crystals, 4–104–10μm in µmsize in (Fig- size (Figure ure 7F).7F). Figure 7. Figure 7. Main Main features features of of host host dolostones dolostones RD1 RD1 and and DS2, DS2, DS3 DS3 and and CS1 CS1 karst karst fill fill in in the the Castellví Castellví outcrop (C,D photographs are from [3]). (A) Field photograph of DS2 and DS3 within fractures outcrop (C,D photographs are from [3]). (A) Field photograph of DS2 and DS3 within fractures in in RD1. (B) Field photograph of DS2 and DS3 filling a karst cavity within RD1. (C,D) Optical (plane RD1. (B) Field photograph of DS2 and DS3 filling a karst cavity within RD1. (C,D) Optical (plane polarised light) and CL images of the relationships between DS2, DS3 and dolomite cement. (E) polarised light) and CL images of the relationships between DS2, DS3 and dolomite cement. (E) Field photograph of CS1 bounding fragments of RD1. (F) Photomicrograph of CS1 bounded by calcite cement in contact with RD1 fragment (cross polarised light). The host rocks of the Olèrdola and Montjuïc outcrops are Lower Cretaceous limestones. Two types of karst fills are present in fractures of the Olèrdola outcrop. The first fill consists of orange calcite CS2 (Figure 8A,B), constituted by subhedral microsparite crystals showing zoned red to orange luminescence (Figure 8C,D). Calcite cement associated with CS2 is Field photograph of CS1 bounding fragments of RD1. (F) Photomicrograph of CS1 bounded by cal- cite cement in contact with RD1 fragment (cross polarised light). The host rocks of the Olèrdola and Montjuïc outcrops are Lower Cretaceous lime- Minerals 2021, 11, 1382 stones. Two types of karst fills are present in fractures of the Olèrdola outcrop. The 14 of 28 first fill consists of orange calcite CS2 (Figure 8A,B), constituted by subhedral microsparite crystals showing zoned red to orange luminescence (Figure 8C,D). Calcite cement associ- ated with CS2byisnon-luminescent constituted constituted by tonon-luminescent to orange orange luminescent luminescent zoned euhedral crystalszoned euhedral arranged crystals in a rim position at the fracture walls. The second fill is a locally laminated red calcite lami- arranged in a rim position at the fracture walls. The second fill is a locally nated CS3red calcite CS3 constituted constituted by bright by bright red to orange red to orange luminescent micriteluminescent and abundant micrite and abun- iron oxides dant iron 8A–D). (Figure oxides (Figure 8A–D). Figure 8. Main Figure features 8. Main of Lower features Cretaceous of Lower Cretaceoushost hostlimestones, CS2and limestones, CS2 andCS3 CS3karst karst fills fills in the in the Olèrdola Olèrdola outcrop. outcrop. (A,B)(A,B) Field Field photograph photograph of CS2 and CS3 within fractures in Lower Cretaceous limestones. (C,D) Optical (plane polarised light)light) of CS2 and CS3 within fractures in Lower Cretaceous limestones. (C,D) Optical (plane polarised and and cathodoluminescence image of the relationships between CS2, CS3 and calcite cement. Note the microsparite and cathodoluminescence image of the relationships between CS2, CS3 and calcite cement. Note the microsparite and micrite micrite textures of CS2 textures andand of CS2 CS3,CS3, respectively. respectively. Lower Lower Cretaceouslimestones Cretaceous limestones from fromthethefootwall of of footwall a normal faultfault a normal are in contact are with with in contact Neogene siliciclastic sediments of the hangingwall at the Montjuïc outcrop. Neogene siliciclastic sediments of the hangingwall at the Montjuïc outcrop. The fault zoneThe fault zone consists of a cataclasite (Figure 9A), which is surrounded by fractures filled with consists of a cataclasite (Figure 9A), which is surrounded by fractures filled with collapse- collapse-breccias with an orange fill made of pisoids (OP1) (Figure 9B). Breccia fragments breccias with an orange fill made of pisoids (OP1) (Figure 9B). Breccia fragments are de- are derived from adjacent host rocks and are supported by the orange fill, which displays rived from adjacent(Figure red luminescence host rocks and 9C,D). Theare supported by non-carbonate the orange fraction of OP1 fill, which consists displays red of chlorite, luminescence (Figure kaolinite, illite 9C,D). (Figure and feldspars The non-carbonate 4C). fraction of OP1 consists of chlorite, kao- linite, illite and feldspars (Figure 4C). Minerals Minerals x 11, 1382 2021, 2021, 11, 15 of 28 15 of 28 Figure 9. (A)9.Neogene Figure normal (A) Neogene faultfault normal plane showing plane a cataclasite showing formed a cataclasite formedduring duringthe the movement movement ofof the the fault. fault. (B) (B) Frac- Fractures filled tures with filled collapse-breccias and the orange with collapse-breccias and thefill madefillofmade orange pisoids (OP1). (OP1). of pisoids (C,D) Optical (plane(plane (C,D) Optical polarised light)light) polarised and and cathodo- luminescence images of OP1 fill. cathodoluminescence images of OP1 fill. 6. Geochemistry of the Karst Fills and Host Rocks 6. Geochemistry of the Karst Fills and Host Rocks The Mesozoic carbonate host rocks and Neogene karst fills of the offshore Casablanca andThe Mesozoic Amposta carbonate oil fields, host as well rocks as of and Neogene the onshore karst Penedès fills Basin, of the were offshore studied Casablanca in terms of andtheir Amposta oil fields, as well as of the onshore Penedès Basin, were studied oxidation state and their elemental and isotopic composition. Analyses were carried in terms of their outoxidation state andspectrometry, using Mössbauer their elemental and microprobe electron isotopic composition and δ18 O, δ(Tables 13 C and 3–6). 87 Sr/Analyses 86 Sr were carried isotope out using Mössbauer spectrometry, electron microprobe and δ O, δ13C and analysis. 18 87Sr/86Sr isotope analysis. 6.1. Fe Oxidation State (Mössbauer Spectrometry) The Mössbauer 6.1. Fe Oxidation Statespectra of carbonate (Mössbauer host rocks and karst fills of the offshore Casablanca- Spectrometry) 1A well and onshore Penedès Basin are shown in Figure 10, and the results are listed in The3.Mössbauer spectra of carbonate host rocks and karst fills of the offshore Casa- Table blanca-1A well and onshore Penedès Basin are shown in Figure 10, and the results are 6.1.1. listed inCasablanca-1A Table 3. Well Mössbauer spectra of the host Dolomite 2a in contact with Dolomite 2b show two dou- blets partially overlapped. Those doublets with higher values of isomer shift and quadrupo- lar splitting (δFe = 1.24 mm/s, ∆ = 1.45 mm/s and δFe = 1.17 mm/s, ∆ = 1.58 mm/s, re- spectively), are attributed to high spin Fe2+ , whereas the doublets with lower values (δFe = 0.21 mm/s, ∆ = 0.36 mm/s and δFe = 0.31 mm/s, ∆ =0.46 mm/s) arise from the presence of Fe3+ . With respect to the relative content in Fe species, although Fe2+ is the dominant species in both cases, the Fe2+ / Fe3+ ratio is 4.3 for Dolomite 2a in the host rock in contact with the reddish Dolomite 2b and 1.9 for Dolomite 2a in contact with ochre Dolomite 2b. Minerals Minerals 11, x11, 1382 2021,2021, 16 of 2816 of 28 Figure Figure 10. 10. Mössbauer Mössbauer spectraofofDolomite spectra Dolomite 2a 2a (in (in contact contactwith withred oror red ochre Dolomite ochre 2b) and Dolomite Dolomite 2b) and 2b in the Dolomite Casablanca 2b in the Casablanca 1A well, 1A oil oil well, as well as well asas dolomiteDS2 dolomite DS2in in Castellví Castellví outcrop outcropand andthe orange the fill fill orange made of pisoids made in Montjuïc of pisoids outcrop in Montjuïc from the outcrop from the Penedès Penedès Basin Basin (OP1). (OP1). Table Table 3. Hyperfine 3. Hyperfine parameters parameters ofofMössbauer spectra. ГΓ (mm/s): Mössbauerspectra. (mm/s): full full width width at at half half maximum maximumpeak; δFe(mm/s): peak;δFe (mm/s):isomer isomer shift; shift; ∆ (mm/s): quadrupolar splitting; 2ε (mm/s) quadrupolar shift; B (T): hyperfine Δ (mm/s): quadrupolar splitting; 2ε (mm/s) quadrupolar shift; Bhf (T):hfhyperfine field. field. Г Γ (mm/s)δFe δFe 2ε 2ε Fe2+ /Fe3+Fe2+/Fe3+ Sample Description/Colour ∆ (mm/s) Bhf % Interpretation Sample Description/Colour Δ (mm/s) (mm/s) Bhf (mm/s) % Interpretation Ratio (mm/s) (mm/s) (mm/s) Ratio Casablanca-1A Casablanca- well 1A well NR1 Dolomite 2a 0.22(-) 0.21(4) 0.36(7) - 19 Fe3+ 2+ 4.3 (host rock) 0.35(-) 1.24(2) Dolomite 2a 0.22(-) 0.21(4) 0.36(7) 1.45(4) - 19- 81 Fe3+ Fe NR1 NR2 Reddish Dolomite 2b 0.44(6) 0.26(3) 0.38(4) - 43.5 Fe3+ 4.3 (host rock) 0.35(-)0.29(3) 1.24(2) 1.25(1) 1.45(4) 1.41(2) - 81- Fe 2+ 1.3 (karst fill) 56.5 Fe2+ Dolomite2a 3+ Reddish Dolomite 2b 0.44(6)0.22(-) 0.26(3) 0.31(2) 0.38(4) 0.46(4) - - 43.5 34 Fe3+ Fe NR2 NR3 (host rock) 0.35(-) 1.17(2) 1.58(4) - 66 2+ Fe2+ 1.9 1.3 (karst fill) Ochre Dolomite 2b 0.29(3)0.22(2) 1.25(1) 0.31(1) 1.41(2) 0.58(2) - 56.5 - 36 Fe Pyrite NR4 - Dolomite2a (karst fill) 0.22(-)0.25(2) 0.31(2) 1.21(1) 0.46(4) 1.52(2) - 34- 64 Fe Fe3+ 2+ NR3 Penedès Basin (host rock) 1.9 0.35(-) 1.17(2) 1.58(4) - 66 Fe2+ Castellví Ochre Dolomite DS22b 0.22(2)0.60(5) 0.31(1) 0.35(2) 0.58(2) 0.55(3) - 36- 34 Pyrite Pyrite? NR4 VCV24 - - (karst fill) (karst fill) 0.25(2) - 1.21(1) 0.39(2) 1.52(2) −0.19(3) - 64 DIST 66 Fe2+ Hematite/Goethite. Montjuïc Penedès VMJ17 OP1 0.22(8) 0.38(2) 0.55(3) - 100 Pyrite? - BasinVMJ14B OP1 0.36(6) 0.32(2) 0.54(4) - 49 Pyrite? Castellví 1.26(6) 1.13(2) 1.59(3) - 51 Fe2+ DS2 0.60(5) 0.35(2) 0.55(3) - 34 Pyrite? VCV24 - (karst fill) - 0.39(2) -0.19(3) DIST 66 Hematite/Goethite. Montjuïc VMJ17 OP1 0.22(8) 0.38(2) 0.55(3) - 100 Pyrite? - VMJ14B OP1 0.36(6) 0.32(2) 0.54(4) - 49 Pyrite? 1.26(6) 1.13(2) 1.59(3) - 51 Fe2+ Minerals 2021, 11, 1382 17 of 28 Mössbauer spectra for reddish Dolomite 2b have two doublets partially overprinted (Table 3). Again, the doublet with higher values of isomer shift and quadrupolar splitting (δFe = 1.25 mm/s, ∆ =1.41 mm/s), is attributed to high spin Fe2+ , whereas the doublet with minor quadrupolar splitting (δFe = 0.26 mm/s, ∆ = 0.38 mm/s) is attributed to Fe3+ . With respect to the relative content in Fe species, for this karst fill, Fe2+ is still dominant, but the Fe2+ / Fe3+ ratio is very low, with a value of 1.3. Mössbauer spectra for ochre Dolomite 2b also show two doublets partially over- lapped (Table 3). The first doublet, with higher quadrupolar splitting (δFe = 1.21 mm/s, ∆ = 1.51 mm/s), is attributed to undetermined Fe2+ . Despite having values within the known range of Fe3+ , the hyperfine parameters of the second doublet match very well with low spin Fe2+ of pyrite. Therefore, iron from ochre Dolomite 2b would be mostly present as Fe2+ . 6.1.2. Penedès Basin The orange-reddish fills of the Castellví and Montjuïc outcrops from the onshore Penedès Basin were analysed. The results of the Mössbauer spectra are less clear than those in the offshore Casablanca oil field. At the Castellví outcrop, only the Mössbauer spectrum for the orange-reddish in DS2 fills was measured. The corresponding spectrum contains a doublet and a distribution of magnetic sextets (Table 3). The doublet (δFe = 0.35 mm/s, ∆ = 0.55 mm/s) could be attributed to pyrite as in ochre Dolomite 2b (Casablanca-1A well), but the quadrupolar is slightly too small so it could be interpreted as Fe3+ . The magnetic sextet contains two separate distributions (DIST) of hyperfine fields on the one hand, from 19 to 27 T, with a maximum at 21.6 T and on the other hand from 33 to 53 T, with two maxima at 28 T and 49.6 T. Considering the negative value of quadrupolar shift (∆ = −0.19 mm/s), this wide and complex distribution can be interpreted as the size distribution of microcrystalline hematite including nanosized particles. A contribution of goethite to the observed hyperfine field distribution cannot be excluded. Two samples of OP1from the Montjuïc outcrop were analysed. One of them has a single peak (δFe = 0.38 mm/s, ∆ = 0.55 mm/s), which again could be interpreted either as pyrite, although its quadrupolar is slightly too small, or simply Fe3+ . The other sample, although macroscopically similar to the previous one, shows two dou- blets partially overlapped (Table 3). The one with the smaller hyperfine parameters (δFe = 0.32 mm/s, ∆ = 0.54 mm/s) would be again pyrite or simply Fe3+ , whereas the widest (δFe = 1.13 mm/s, ∆ = 1.59 mm/s) is attributed to Fe2+ . 6.2. Minor and Trace Elements Content The Mg, Mn, Fe and Sr content of the carbonate host-rocks and karst fills of the offshore Casablanca C1 and Amposta Marino C2 oil wells, as well as of the Castellví, Olèrdola and Montjuïc outcrops of the onshore Penedès Basin, are summarised in Figure 11 and Table S1. 6.2.1. Casablanca-1A Well Dolomite 1 has Mg contents between 122,215 and 118,742 ppm, Fe content between 2514 and 2950 ppm and Sr content between 397 and 479 ppm. The Mn content is below the detection limit. Dolomite 2a has Mg content between 128,604 and 118,800 ppm, Fe content from below the detection limit up to 8341 ppm and Sr content from below the detection limit to 677 ppm. The Mn content is below the detection limit. Dolomite 2b replacing the ochre fills has Mg content between 122,661 and 122,545 ppm, Fe content between 1959 and 7051 ppm, Sr content from below the detection limit to 672 ppm and Mn content below the detection limit. Minerals 2021, 11, 1382 18 of 28 Minerals 2021, 11, x 19 of 28 Figure 11. Maximum, minimum and mean Mg, Mn, Fe and Sr contents in ppm of the karst fills and host carbonates in the Casablanca and Amposta oil wells and in the Penedès Basin. Figure 11. Maximum, minimum and mean Mg, Mn, Fe and Sr contents in ppm of the karst fills and host carbonates in the Casablanca and Amposta oil6.2.2. wellsAmposta and in theMarino PenedèsC2 Well Basin. Lower Cretaceous host-limestones have Mg and Sr contents from 1013 to 4909 ppm andδbetween 6.3. 18O, δ13C 355 and and 87Sr/ 1407 ppm, respectively. 86Sr Isotope Geochemistry Their Mn contents are below the detection limit.ForThethe host carbonates and karstfrom Fe content displays values below fills of the detection the offshore limit to 1813 Casablanca-1A andppm. The Amposta reddish calcite CS3r fill has Mg and Sr contents ranging from 2619 Marino C2 oil wells, as well as in the Castellví, Olèrdola and Montjuïc outcrops of the to 4038 ppm and 640 to 1053 ppm, respectively. Its Fe content range from below the detection onshore Penedès Basin, their δ18O and δ13C are plotted in Figure 12 and summarised in limit and 721 ppm, whereas Table S2.the TheMn content 87Sr/ is below 86Sr isotopic the detection ratios are plotted limit. The Mg in Figure 13and andSrsummarised contents of the greenish in Table S3. calcite CS3g fill vary from 1052 to 5461 ppm and from 491 to 1259 ppm, respectively. Its Fe content 6.3.1. range fromWell Casablanca-1A below the detection limit and 2701 ppm, whereas Mn is below the detection limit. Dolomite 1 has δ18O ranging between −10.8 and −7.6‰ VPDB, and δ13C between +1.1 and 6.2.3.+1.7‰ PenedèsVPDB. BasinDolomite 2a has δ18O ranging between −10.4 and −6.8‰ VPDB, δ13C between Karst +1.0 fillsandand+2.4‰ VPDBofand host rocks thean 87Sr/ 86Sr ratio of 0.708607. Dolomite 2b show δ18O Penedès Basin have higher Mn contents than those values similar to Dolomite 2a, of the Casablanca-1A and Amposta Marino-C2 or slightly heavier oilinwells. the ochre fills,Fe The Mg, and andδ13Sr C contents ranging be- do tween +1.0 and +1.4‰ VPDB. The 87 Sr/ 86 Sr ratios for the reddish not show a clear trend. The elemental composition of replacive dolomite RD1 and DS2, and ochre fills of dolomite 2b DS3areand0.709137 CS1 karst andfills 0.709202, respectively. was measured in samples from the Castellví outcrop. For RD1, Mg ranges between 130,202 and 125,280 ppm and between 129 and 316 ppm in Sr. Its Fe content 6.3.2. rangesAmposta from belowMarino C2 Well limit to 1181 ppm. The Mn content is below the detection the detection limit.Lower Cretaceous For DS2, the Mg limestones content rangeshavefromδ18O 120,843 values from −4.2 toppm, to 105,966 −2.2‰ andVPDB, the Mnδ13Ccontent values between ranges from+0.9below and +1.5‰ VPDB and the detection limitSr/ 87 andSr 86 235 ratios ppm;ranging the Fe from ranges 0.70748 from 52to to 0.70763. 6927 ppmThe δand 18O the andSrδcontent 13C values of CS3r between 177range fromppm. and 1250 −9.9 to For−5.6‰ DS3, Mg VPDB andbetween ranges from −1.4 to +0.3‰ 120,083 and VPDB, 107,265,respectively. Mn between Its Sr/ 86346 11587and Sr ratio ppm, ranges Fe betweenfrom213 0.70857 to 0.70888, and 1866 with an average and Sr between 237 and 1228 ppm. value For CS1, of 0.70871. the Mg CS3g content shows δ18Oisvalues from 1915 to 3620 ranging ppm, from −8.7thetoMn content −4.1‰ is from VPDB, andbelow δ13C the detection between limit+0.5‰ −1.2 and to 128 VPDB. ppm, the OnlyFe one content 87 Sr/is Sr 86 between 212 measured ratio was and 2885 ppm and with in CS3g, the Sra rangesoffrom value 292 and 0.70861. The 686 δ13Cppm. and 87Sr/ 86Sr values of CS3g are similar to that of CS3r, whereas their The δ18OMghascontent slightlyofmore host depleted limestones from the Olèrdola outcrop ranges between 231 and values. 5103 ppm, the Mn content is between 231 and 478 ppm, the Fe content is between 578 and 1253 ppm 6.3.3. and Basin Penedès the Sr content is below the detection limit. For CS2, the Mg content ranges fromReplacive 1672 to 923 ppm, and dolomite RD1theofMntheand Fe contents Castellví outcroprange fromδ239 yields 18O to 287 and values fromfrom −2.1530 to to 916 ppm, +1.2‰ VPDB,respectively. The Sr δ13C values from +1content to +2.3‰ is VPDB below and the detection an 87Sr/ 86Srlimit. ratioFor CS3, the Mg, of 0.707417. The Minerals 2021, 11, 1382 19 of 28 Minerals 2021, 11, x 20 of 28 Mn and Fe contents range from 2018 to 3200 ppm, from 239 and 478 ppm and from 627 to 1784 ppm, respectively. The Sr content is below the detection limit. DS2 karst fill ofThethehost samelimestones outcrop hasfrom δ18O the Montjuïc values varyingoutcrop have from −1.8 Mg content to +0.1‰ VPDB, δfrom 13C 2020 to 2652, Mn content ranging from from 108 −4.2 to −2.9‰ VPDBto and 126 an ppm,87Sr/Fe content 86Sr ratio offrom 1078For 0.708761. to 1127 ppm the DS3 and karst fill,Sr content from the δ18O 430 varies fromppm. to 444 −2 toOP1 +0.7‰ hasVPDB, the δ13from Mg content C ranges from 522 to −3.1 1602 to +0.1‰ ppm, VPDB,below Mn content and the detection the 87Sr/ 86 Sr ratio is 0.708855. CS1 has δ 18O values ranging from −8.6 to −8.5‰ VPDB and limit, Fe content from 478 to 2056 ppm and Sr content from 179 to 297 ppm. δ13C from −7.8 to −7.6‰ VPDB. Only theδ18 6.3. δ18O, O δand 13 C δand 13C 87 wasSr/measured in Geochemistry 86 Sr Isotope samples from the Olèrdola and Montjuïc outcrops. δ18O and δ13C of CS2 from the Olèrdola outcrop range from −6.3 to −5.9 and from For the host carbonates and karst fills of the offshore Casablanca-1A and Amposta −4.7 to −4.4‰ VPDB, respectively. For CS3, the δ18O and δ13C values range from −4.2 to Marino C2 oil wells, as well as in theThe −3.8 and from −4.1 to −3.2‰ VPDB, respectively. Castellví, Olèrdola and Montjuïc outcrops of the OP1 from the Montjuïc outcrop has onshore Penedès Basin, their δ18 O and δ13 C are plotted in Figure 12 and summarised in δ O values ranging from −7,1 to −4,4 ‰ VPDB and δ C values from −10,3 to −8,5 ‰ 18 13 87 86 VPDB. Table S2. The Sr/ Sr isotopic ratios are plotted in Figure 13 and summarised in Table S3. Figure 12. δ18 O vs. δ13 C of the karst fills and host carbonates in the Casablanca and Amposta oil wells and in the Penedès Basin. Minerals 2021, 11, x 21 of 28 Minerals 2021, 11, 1382 20 of 28 Figure 12. δ18O vs. δ13C of the karst fills and host carbonates in the Casablanca and Amposta oil wells and in the Penedès Basin. Figure13. Figure 13.The The8787Sr/ Sr/ 86 86Sr Sr ratios ratios of of the the karst karst fills and host fills and host carbonates carbonates in inthe theCasablanca Casablancaand andAmposta Amposta oil wells as well as in the Castellví outcrop in the Penedès Basin compared with values of Late Ju- oil wells as well as in the Castellví outcrop in the Penedès Basin compared with values of Late Jurassic– rassic–Early Cretaceous and Burdigalian–Langhian seawater. Seawater ratios are from the LOWESS Early Cretaceous and Burdigalian–Langhian seawater. Seawater ratios are from the LOWESS curve curve of [40]. of [40]. 6.3.1. Casablanca-1A Well 7. Discussion Dolomite 7.1. Detrital Versus δ18 O ranging 1 hasResidual Origin between −10.8 and −7.6‰ VPDB, and δ13 C between of Karst Fills +1.1 and +1.7‰ et VPDB. Dolomite 18 −10.4 −6.8‰ Lomando al. [20] reported2athat hasthe O ranging δ fill between of the fracture and vug and porosity VPDB, of the Cas- 13 C between +1.0 and +2.4‰ VPDB and an 87 Sr/ 86 Sr ratio of 0.708607. Dolomite 2b show δablanca-1A well is composed of dolomitised micrite. These authors noted that this 18 O values similar to Dolomite 2a, or slightly heavier in the ochre fills, and δ13 C ranging fill was δred at the uppermost part of the wells and86green at the bottom and reported the lower between +1.0oxidant limit of the and +1.4‰ VPDB. conditions The 87 Sr/ between Sr ratiosAccording both colours. for the reddish to theand ochre fills col- characteristic of dolomite 2b are 0.709137 and 0.709202, respectively. our, they called them terra rossa and terra verde fills. 6.3.2. The termsMarino Amposta terra rossa C2 (and Well terra verde) imply genetic conditions. According to the def- inition proposed by [41], the term terra rossa refers to meter-thick sequences of clays with Lower Cretaceous limestones have δ18 O values from −4.2 to −2.2‰ VPDB, δ13 C kilometre extension that develop at the Earth surface associated with limestone karstifica- values between +0.9 and +1.5‰ VPDB and 87 Sr/ 86 Sr ratios ranging from 0.70748 to tion. Two different theories were proposed to explain the origin of these formations: a 0.70763. The δ18 O and δ13 C values of CS3r range from −9.9 to −5.6‰ VPDB and from residual vs. a detrital origin. The residual origin hypothesis considers the terra rossa de- −1.4 to +0.3‰ VPDB, respectively. Its 87 Sr/ 86 Sr ratio ranges from 0.70857 to 0.70888, with posits as the insoluble residue that results from carbonate dissolution during karstification an average value of 0.70871. CS3g shows δ18 O values ranging from −8.7 to −4.1‰ VPDB, [42,43]. The main problem of this theory is the low content of clays and other insoluble and δ13 C between −1.2 and +0.5‰ VPDB. Only one 87 Sr/ 86 Sr ratio was measured in CS3g, minerals in limestones, which make it difficult to explain the large volumes of these fill with a value of 0.70861. The δ13 C and 87 Sr/ 86 Sr values of CS3g are similar to that of CS3r, accumulations. Contrarily, the detrital origin model assumes that the terra rossa sediment whereas their δ18 O has slightly more depleted values. is composed of clayey detrital material, volcanic ash and/or aerial transported dust accu- mulated 6.3.3. in pre-existent Penedès Basin karst [44–46]. This theory, however, does not explain the close relationship between terra rossa and karsts and their simultaneous development. The au- Replacive dolomite RD1 of the Castellví outcrop yields δ18 O values from −2.1 to thors of +1.2‰ [41] proposed VPDB, a third δ13 C values from theory in which +1 to +2.3‰ terra VPDB rossa and an is produced 87 Sr/ from 86 Sr ratio the authigenic of 0.707417. The DS2 karst fill of the same outcrop has δ18 O values varying from −1.8 to +0.1‰ VPDB, δ13 C ranging from −4.2 to −2.9‰ VPDB and an 87 Sr/ 86 Sr ratio of 0.708761. For the DS3 karst Minerals 2021, 11, 1382 21 of 28 fill, the δ18 O varies from −2 to +0.7‰ VPDB, the δ13 C ranges from −3.1 to +0.1‰ VPDB, and the 87 Sr/ 86 Sr ratio is 0.708855. CS1 has δ18 O values ranging from −8.6 to −8.5‰ VPDB and δ13 C from −7.8 to −7.6‰ VPDB. Only the δ18 O and δ13 C was measured in samples from the Olèrdola and Montjuïc outcrops. δ18 O and δ13 C of CS2 from the Olèrdola outcrop range from −6.3 to −5.9 and from −4.7 to −4.4‰ VPDB, respectively. For CS3, the δ18 O and δ13 C values range from −4.2 to −3.8 and from −4.1 to −3.2‰ VPDB, respectively. The OP1 from the Montjuïc outcrop has δ18 O values ranging from −7.1 to −4.4 ‰ VPDB and δ13 C values from −10.3 to −8.5 ‰ VPDB. 7. Discussion 7.1. Detrital Versus Residual Origin of Karst Fills Lomando et al. [20] reported that the fill of the fracture and vug porosity of the Casablanca-1A well is composed of dolomitised micrite. These authors noted that this fill was red at the uppermost part of the wells and green at the bottom and reported the lower limit of the oxidant conditions between both colours. According to the characteristic colour, they called them terra rossa and terra verde fills. The terms terra rossa (and terra verde) imply genetic conditions. According to the definition proposed by [41], the term terra rossa refers to meter-thick sequences of clays with kilometre extension that develop at the Earth surface associated with limestone karsti- fication. Two different theories were proposed to explain the origin of these formations: a residual vs. a detrital origin. The residual origin hypothesis considers the terra rossa deposits as the insoluble residue that results from carbonate dissolution during karsti- fication [42,43]. The main problem of this theory is the low content of clays and other insoluble minerals in limestones, which make it difficult to explain the large volumes of these fill accumulations. Contrarily, the detrital origin model assumes that the terra rossa sediment is composed of clayey detrital material, volcanic ash and/or aerial transported dust accumulated in pre-existent karst [44–46]. This theory, however, does not explain the close relationship between terra rossa and karsts and their simultaneous development. The authors of [41] proposed a third theory in which terra rossa is produced from the authigenic replacement of limestones by means of a reaction front of small dimensions. In this study, we did not use the terms terra rossa and terra verde in order to avoid any genetic implication and because the mineralogical and petrological characteristics of the studied fills in the Penedès Basin and València Trough do not fit with the original definition of terra rossa due to their high carbonate content. The homogeneity of the mineralogy and petrology of the studied karst fills of the Casablanca and Amposta oil wells and of the Penedès Basin, as well as their proximity, make it unlikely that they were formed as independent materials and/or from different host rocks. The carbonate fraction of these fills is considered to have originated from the erosion of the host rock, either limestones or dolostones, which occurred during subaerial exposure during the Neogene extension period. This suggests a residual origin for the karst fills. Likewise, the fact that the non-carbonate fraction of the host limestones and fills of the Casablanca-1A well are constituted by the same minerals (illite, illite/smectite, quartz, pyrite and Ti oxides; [15]) also point out to a residual origin. There are two additional points in favour of this theory. The first one is that the bulk composition of the fills is enriched in the immobile elements (Ti and Al) with respect to the host limestone, according to the previous authors. The second point is the morphology of lath-shaped illite crystals as observed from the TEM images of Figure 5C, which do not show signs of mechanical deformation due to mineral transport. This could indicate that this mineral may have formed within the karst fills during diagenesis. In the same way, kaolinite in the Amposta Marino C2 well possibly precipitated from acidic fluids prior or during oil emplacement [16], whereas quartz and chlorite content could also provide from the dissolution of limestones. However, there is multiple evidence that indicates a detrital origin of the karst fills. For instance, the enrichment in immobile elements, such as Ti and Minerals 2021, 11, 1382 22 of 28 Al of the fills with respect to their host carbonates is also interpreted as the input of external material during the formation of the fills [46]. Additionally, the illite coatings of Dolomite 2b in the Casablanca-1A, well described by [15], are characteristic of the mechanical input of clays according to [47]. The presence of irregular flaky illite crystals in Dolomite 2b supports this scenario. The presence of feldspar, quartz and irregular pyrite grains also accounts for a detrital influence during the accumulation of karst fills [15]. Similarly, feldspar grains in OP1 are identified by means of XRD at Montjuïc outcrop of the onshore Penedès Basin. The presence of illite, kaolinite and chlorite at this outcrop and in DS2 and DS3 from the Castellví outcrop could be of detrital origin. In such case, the source of feldspars, quartz and possibly clay minerals such as illite, kaolinite and chlorite could be the Palaeogene thrust sheets composed of Palaeozoic igneous rocks and metasediments of the Catalan Coastal Ranges (Figure 1). The unroofing of these thrust sheets fed the alluvial and fluvial systems filling the half grabens of the Catalan Margin [48–50]. The difference in the non-carbonate fraction content between the karst fills of the offshore València Trough and of the onshore Penedès Basin, and their host carbonates (from 2 to 9% for the fills vs. up to 1% for the host carbonates; [15]) suggest a detritic origin for the fills [10]. This implies the dissolution of an important volume of host limestone or dolostone and the subsequent accumulation of carbonate fills together with the input of external detrital non-carbonate minerals. The higher 87 Sr/ 86 Sr ratios of the studied fills with respect to their host rocks account for this scenario (Figure 13). Therefore, based on all the aforementioned observations, we propose a polygenic origin for the studied fills, similar to the polygenic nature of the terra rossa fills [1,45,46,51]. 7.2. Significance of the Colour of the Karst Fillls The reddish colour of rocks is due to the presence of Fe oxides and hydroxides either as free or forming a coating in clay minerals [52–54]. Contrarily, dark and grey colours are normally attributed to the presence of organic matter and /or Fe sulphides, whereas green colours are normally attributed to the Fe2+ /Fe3+ ratio in chlorite and illite when other pigment phases are absent [12,52,55]. With respect to the clay minerals, especially those with a 2:1 structure as illite, Fe can be found as (1) Fe2+ and Fe3+ occurring in octahedral positions replacing Al, and (2) adsorbed in the surface of clay particles as Fe oxides and hydroxides [56–59]. The colours of the studied karst fills of the Casablanca and Amposta oil fields, as well as in the Penedès basin, are attributed to their non-carbonate fraction. In these fills, no mineralogical or petrological differences were observed, except for the punctual presence of goethite crystals and the higher total Fe content in the reddish fills (Table 1). This Fe can be distributed between dolomite, pyrite, goethite and clays. The data obtained by Mössbauer spectrometry on samples from the Casablanca oil field (Table 3) indicate that the predominant oxidation state of the Fe in host Dolomite 2a and Dolomite 2b fills is Fe2+ . However, the Fe2+ /Fe3+ ratio in the reddish Dolomite 2b is lower than in host Dolomite 2a, suggesting that Fe2+ is from the dolomite host and Fe3+ from the non-carbonate fraction of the karst fills. Nanometre size particles of hematite (or hematite with a content lower than the detection limit of the analytical techniques that we use), which are disseminated or absorbed in the clay surface as red coatings, could be the source of the Fe3+ [58,60]. This is supported by the presence of goethite crystals identified with TEM in the reddish Dolomite 2b [15]. The Fe2+ of the ochre Dolomite 2b is similar to that of its adjacent host Dolomite 2a, indicating that Fe2+ could be derived from dolomite crystals. However, this does not rule out the contribution of illite. These results point out the high Fe2+ content of dolomite and possibly illite and, indirectly, the lack of pigment minerals such as hematite and goethite, as the main responsible of the ochre Dolomite 2a and 2b [52,55,58,59]. Intense red, pink and orange fills are found in the karstic formations of the onshore Penedès Basin. In general, DRX and Mössbauer spectra reveal the presence of hematite and goethite. Mössbauer spectrometry applied to the reddish DS2 dolomite from samples of the Minerals 2021, 11, 1382 23 of 28 Castellví outcrop indicates the presence of hematite/goethite and possibly pyrite, although this can also be interpreted as Fe3+ . The presence of such minerals, and possibly Fe3+ , indicates a likely common origin for the reddish colours of fills of the onshore Penedès basin and the offshore València Trough (e.g., Casablanca and Amposta oil fields). Accordingly, OP1 of the Montjuïc outcrop shows similarities with the ochre fills in the Casablanca oil field. Mössbauer spectra of this fill indicate the presence of Fe2+ and pyrite, probably ruling out the presence of Fe3+ and pigment minerals such as hematite and goethite. The greenish fills of the Amposta oil field (CS3g) could indicate variations in the Fe2+ /Fe3+ ratio in chlorite and illite in the absence of other pigment phases [52,55]. 7.3. Depositional Environment of Karst Fills The isotopic and elemental composition of karst fills compared with that of their host carbonates reflect the input of external fluids and organic components as well as diagenetic processes. Their δ13 C and 87 Sr/ 86 Sr isotope geochemistry are, in general, different from that of their adjacent Mesozoic host carbonates (Figures 10 and 11). For example, karst fills from the Amposta Marino C2 well and Penedès Basin have depleted δ13 C values with respect to their adjacent host rocks (Figure 12), probably indicating the input of soil-derived CO2 during the subaerial exposure of Mesozoic carbonates [61,62]. This interpretation agrees with the study of [61], which concluded that paedogenic carbonates have δ13 C values between −10 and +2‰ VPDB. Accordingly, the lighter δ13 C of fills in the exposed outcrops of the Penedès Basin supports a meteoric scenario for their accumulation, whereas the values of fills in the offshore Amposta well are also within the range of paedogenic carbonates. Contrarily, the similar δ13 C values of dolomite 1, 2a and 2b from the Casablanca oil well are interpreted by [15] as the result of a similar dolomitising fluid interacting with host rocks and karst fills. The 87 Sr/ 86 Sr ratios of all the karst fills show higher ratios than their adjacent host rocks and Late Jurassic–Early Cretaceous seawater, suggesting the influence of a more radiogenic source or Burdigalian–Langhian seawater, as indicated in Figure 13. Alternatively, the higher 87 Sr/ 86 Sr ratios of Dolomite 2a and 2b from the Casablanca-1A well with respect to those of Dolomite 1 could be the result of clay leaching during dolomitisation of these fills, according to [15]. The δ18 O isotopic composition of most of the karst fills has similar values to that of their adjacent host rocks, indicating a local origin of the carbonate fraction. Contrarily, CS3r and CS3g in the Amposta oil well and CS1 in the Castellví outcrop have more depleted δ18 O values than those of their host carbonates. This depletion is interpreted at the Amposta oil well as resulting from the recrystallisation of CS3r and CS3g fills from evolved meteoric waters [16], although an influence of hot fluids cannot be ruled out. Contrarily, [3] interpreted that CS1 of the Castellví outcrop precipitated from meteoric fluids, based on a large dataset of geochemical data of fracture-filling carbonates and karst fills sampled throughout the Penedès Basin. Regarding the elemental composition of karst fills, the higher Mn content of the fills from the onshore Penedès Basin with respect to those of the offshore Casablanca and Amposta oil wells could indicate a greater influence of meteoric fluids onshore [63]. Moreover, the decrease in Mg of the Castellví outcrop from RD1 to CS1 could indicate a progressive increase in meteoric fluids or a change in the host-carbonate feeding the karst system. The oxidation state of Fe in a rock is indicative of the Eh–pH conditions of the depo- sitional/diagenetic medium in which karst fills accumulated. The high total Fe content, together with the presence of Fe3+ , in the structure of illite or possibly in oxides and iron hydroxides, suggests that reddish fills were formed under oxidising (and perhaps slightly acidic) conditions (Figure 14A). On the other hand, the dominance of Fe2+ in ochre fills responds to reductive conditions (Figure 14B), leading to reduction and dissolution of oxides and hydroxides and partial leaching of Fe3+ contained in the structure of illite. The change in redox conditions affecting the oxidation state of Fe in the karst fills could be related to water table fluctuations. A similar scenario was inferred to explain different calcite cement generations during the early-middle Miocene in syn-rift deposits filling the onshore Penedès half-graben [64]. acidic) conditions (Figure 14A). On the other hand, the dominance of Fe2+ in ochre fills responds to reductive conditions (Figure 14B), leading to reduction and dissolution of ox- ides and hydroxides and partial leaching of Fe3+ contained in the structure of illite. The change in redox conditions affecting the oxidation state of Fe in the karst fills could be Minerals 2021, 11, 1382 related to water table fluctuations. A similar scenario was inferred to explain different 24 of 28 calcite cement generations during the early-middle Miocene in syn-rift deposits filling the onshore Penedès half-graben [64]. Figure 14. Sketch showing the two scenarios of karst fill accumulation in carbonates in the Penedès Basin and Amposta Marino C2 and Casablanca-1A oil wells. (A) Low water table level characterised by oxidising conditions and accumulation of red to pink fills. (B) High water table level characterised by more reducing conditions and accumulation of yellow to ochre fills. In both scenarios, carbonate dissolution and meteoric and detrital input occur. Later dolomitisation of karst fills of the Casablanca- 1A well is not represented in this figure. The penetration of the karst system at depth is based on the distribution of karst fills from the Casablanca-1A and Amposta Marino C2 wells [15,16]. Another parameter affecting the changes in the Eh–pH conditions that facilitated the release of Fe cations controlling the colour of karst fills of the Penedès Basin and València Trough could be the presence of organic matter. Suboxic and moderately acidic conditions in specific areas of the karst system, below the water table level, and where groundwaters become stagnant (e.g., in unconnected siphons or pothooks), facilitated the leaching of Fe3+, the lack of host carbonate dissolution and the preservation of organic matter trapped in rocks. After dissolution and karst development due to a change in the karst system dynamics, organic matter can be accumulated in karstic cavities. The existence of suboxic and reducing environments in karstic systems could explain the accumulation of greenish fills, as described by [65]. This scenario would be compatible with the presence of Jurassic dolostones in the Garraf Horst bounding the onshore Penedès Basin, with a total organic carbon content (TOC) between 0.02 and 0.82% [66]. These organic-rich dolostones are equivalent to those described in the Casablanca C1 and Amposta Marino C2 oil wells. 8. Conclusions The origin of the colour of karst fills of the onshore Penedès Basin and offshore València Trough as well as their detrital vs. residual origin, and the depositional environment was deciphered integrating spectral, mineralogical and geochemical methods, leading to the following conclusions: Minerals 2021, 11, 1382 25 of 28 1. Karst fills of the Penedès Basin and València Trough have red to pink, ochre, green and orange colours. The main mineralogy of these fills is calcite and dolomite, with minor contents of illite, smectite, kaolinite, chlorite, quartz, feldspar and pyrite; 2. Mössbauer spectrometry of karst fills and adjacent host carbonates indicate that, in general, Fe3+ from goethite is the dominant species in reddish fills, whereas Fe2+ from dolomite is dominant in the ochre to orange fills; 3. The carbonate fraction of karst fills is considered to have originated from the erosion of their host carbonates (limestones and dolostones). The non-carbonate fraction, which consists of illite (authigenic and as grain coatings), kaolinite, smectite, pyrite (authigenic and of irregular shape), quartz and feldspar, accounts for a polygenic origin of the karst fills (detrital and residual); 4. The lower δ13C values and higher 87Sr/6Sr ratios of most of the karst fills with respect to their adjacent host rocks could indicate the input of soil-derived CO2 together with the input of an external radiogenic source into the karstic system; 5. The higher Mn content of the onshore Penedès Basin fills with respect to those of the offshore Casablanca and Amposta oil wells could indicate a greater influence of meteoric fluids in the former. The decrease in Mg in the Castellví outcrop from RD1 to CS1 can also be interpreted as a progressive increase in meteoric percolation in the karst system or a change in the host-carbonate feeding the karst system; 6. The reddish colours of the fills result from the presence of pigment minerals such as hematite and goethite, as well as the dominance of the Fe3+ species, whereas the ochre and orange colours are attributed to the dominance of Fe2+. The greenish colours could result from fluctuations in the Fe3+/Fe2+ ratio; 7. The variation in colour of the karst fills is attributed to fluctuations in the water table, which control the Eh/pH conditions in the karst system. Thus, reddish colours are attributed to lower water table level and oxidising episodes, and orange and ochre ones to high water table level and more reducing episodes. Supplementary Materials: The following are available online at https://www.mdpi.com/article/ 10.3390/min11121382/s1, Table S1: Mg, Mn, Fe and Sr contents in ppm of the karst fills and host carbonates in the Casablanca and Amposta oil wells and in the Penedès Basin. Table S2: δ18 O and δ13 C values of the karst fills and host carbonates of the Casablanca and Amposta oil wells and of the Penedès Basin. Table S3: 87 Sr/86 Sr ratios of the karst fills and host carbonates of the Casablanca and Amposta oil and of the Castellví outcrop in the Penedès Basin. Author Contributions: Conceptualisation, A.T. and E.P.; methodology, A.T., E.P., N.R.-M., V.B., D.C., L.C. and J.D.M.-M.; software, D.C.; validation, D.C. and A.T.; formal analysis, N.R.-M. and V.B.; investigation, V.B. and N.R.-M.; writing—original draft preparation, N.R.-M. and A.T.; writing— review and editing, D.C., I.C., M.M. and E.G.-R.; supervision, E.P. and A.T.; funding acquisition, A.T. and E.P. All authors have read and agreed to the published version of the manuscript. Funding: The presented research was supported by the DGICYT Spanish Project PGC2018-093903- B-C22 and PID2020-118999GB-I00 and by the Catalan Council to the Grup Consolidat de Recerca “Geologia Sedimentària” (2017SGR-824). EGR acknowledges the funding provided by the Spanish Ministry of Science, Innovation and Universities (“Ramón y Cajal” fellowship RYC2018-026335-I). Acknowledgments: This research was performed within the framework of DGICYT Spanish Projects PGC2018-093903-B-C22 and PID2020-118999GB-I00 funded by the Ministerio de Ciencia, Innovación y Universidades/Agencia Estatal de Investigación/Fondo Europeo de Desarrollo Regional. EGR acknowledges the funding provided by the Spanish Ministry of Science, Innovation and Universities (“Ramón y Cajal” fellowship RYC2018-026335-I). The isotopic, electron microprobe and XRD analyses and the SEM and TEM observations were carried out at “Centres Científics i Tecnològics” of the Universitat de Barcelona. Mössbauer spectroscopy analyses were carried out at Institut de Ciència de Materials de Barcelona. Strontium isotope analyses were carried out at “CAI de Geocronología y Geoquímica Isotópica” of the Universidad Complutense de Madrid. Minerals 2021, 11, 1382 26 of 28 Conflicts of Interest: The authors declare no conflict of interest. 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