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Hassane Chellai Hassane This article is protected by copyright. All rights reserved. copyright. This articleis protectedby doi: 10.1002/dep2.24 thisversionandthe between lead todifferences been through the copyediting, typesetting, and proofreading which may pagination process, This exposed in a coastal section ofthe Tarfaya Basin, Morocco. The black shales were deposited in the to date. This study reports on alarge limestone body that occurs within ablack shale succession documented including the Cenomanian to Turonian OAE2,which is among thebest studied examples marine black shales rich in organic carbon. Seve During theCretaceous major episodes of oceanic anoxic conditions triggered large scale deposition of ABSTRACT g f e c b a Smrzka Daniel carbonate deposit from theTarfaya Basin,Morocco Methane seepage in a Cretaceous gree Article type : Original Research Article 08-Feb-2017 : Date Accepted :08-Feb-2017 Date Revised :30-Nov-2016 Date Received PROF. JÖRN PECKMANN (Orcid ID : 0000-0002-8572-0060) d Department of Geology, Faculty of Sciences Semlalia, Cadi Ayyad University, Marrakech, Morocco Morocco Marrakech, University, Ayyad Cadi Semlalia, Sciences of Faculty Geology, of Department Geology Department, Faculty of Science, Tanta University, 31527 Tanta, Egypt Bundesst Hamburg, Geologie, Universität für Institut Department für Geodynamik und Sedimentologie, Universität Wien, 1090 Wien, Austria Shell Petroleum Development Company of Nigeria, Port Harcourt, Nigeria Nigeria Harcourt, Port Nigeria, of Company Development Petroleum Shell Lyell Centre, Heriot-Watt University, Edinburgh EH14 4AS, UK AcceptedSchool of Earth and Environment, University ofLeeds, Leeds LS2 9JT, UK Article article has been accepted for publication forpublication accepted article hasbeen a , Jennifer Zwicker Jennifer , f , Thomas Wagner a g , Sadat Kolonic , Sadat , Jörn Peckmann raße 55, 20146 Hamburg, Germany (Email: Germany joern.peckm Hamburg, 20146 raße 55, b , Daniel Birgel a,c ral oceanic anoxic events (OAEs) have been nhouse world recorded by an unusual unusual an by recorded world nhouse

and undergone full peer review buthasnot review undergone fullpeer and Version of Record. PleaseVersion cite thisarticle as c , Crispin T.S. Little T.S. , Crispin

d , Akmal M.Marzouk ann@uni- e , El enhanced nutrient flux from thecontinents increased primary production, enabled the accumulation of al., some periods of the Cretaceous compared to the present due to the warm, equable climate (Sames 1987; Kerr, 1998; Jenkyns, 2003; Meyer & Kump, 2008).Sea level was markedly elevated during oceanic anoxic events (OAEs, Schlanger & Jenkyns, 1976; Weissert phasesof their coeval andrepeatedoccurrence Phanerozoic inthe rock recordhave been referred toas Erba, 1999; Jones & Jenkyns, 2001). These organic-rich deposits have been termed black shales, and large scale accumulation of organic matter in ma The Cretaceous was aperiod inEarth history whenmajor episodes of oceanic anoxic conditions led to INTRODUCTION Keywords: seep site. sheds lightenvironmentalhow these on factorsinfl hydrocarbon seep that was situated within ashallow continental sea in the aftermath ofOAE 2,and productivity andepisodically euxinic bottom waters enclose the carbonate body, but the palaeoenvironment was overall mostly characterized by high environmental conditions became less reducing during the deposition of the background shales that inventories of the black shales and the macrofaunal assemblage ofthe carbonate body reveal that in situ remineralization of organic matter contained in the black shales. Nannofossil and trace metal sources than methane apart from admixed marine carbonate, indicating apotential contribution from seep. The lowest obtained microbially-mediated anaerobic oxidation of methane in the shallow subseafloor at ahydrocarbon depleted biphytanic diacids reveal that the carbonate deposit resulted, at least in part, from This article isprotected Allrights bycopyright. reserved. Accepted Articlepetrography, carbon and oxygen stable isotope ge formation in black shales, a combination of element geochemistry, palaeontology, thin section aftermath of OAE2in a shallow continental sea. To decipher the mode and causes ofcarbonate 2016 and references therein). The expansion of shallow epicontinental seas, where upwelling and Carbonate authigenesis, cold seeps, black shales, oceanic anoxic events, Tarfaya Basin. δ 13 C carbonate values of −23.5‰ are not lowenough toexclude other carbon rine sediments (Arthur & Sagemann, 1994; Larson & ochemistry andlipid biomarkers areused. The uenced carbonate formation and the ecology atthe . This study reconstructs the evolution of a et al., 1979; Schlanger et al., 13

C- et in stratified basins increased sequestration rates of organic carbon in Cretaceous marine sediments 2008). With supporting evidence for both scenarios, it is likely that both production andpreservation matter within restricted, stratified, oxygen-deficient basins (Mascle (Barron, 1983; Ingall accompanied by elevated atmospheric carbon dioxide responsible for the deposition ofblack shales are (1) pulses of enhanced primaryproductivity perturbations of redox-nutrient cycles and orbital forcing (Leine,1986; El Albani enabled the rapid accumulation of shales and limestones rich in organic carbon linked tocyclic slope along thenorthern parts of Algeria, Libya, Tunisia and Morocco were deprived ofoxygen, and Sinninghe Damsté & Köster, 1998; Handoh and, possibly, euxinic conditions even in the photic zone (Herbin of oxygen wasimpeded within these partially isolated basins, favouring the development ofanoxic shallow and partly closed connections to neighbouring oceans (Kuypers Tethys andAtlantic Oceans wereaffected by sluggish circulation of bottom waters caused by the proto southern North Atlantic and eastern Tethys Oceans (Lüning 2013). Black shales related to OAE2have been reported frommany partsof the world including the et al., by a significant turnover of ocean chemistry andextinctions of marine biota (Brumsack, 1980; Arthur evolution of ocean gateways –led to increasing at linked to the breakup ofGondwana with the formation of early ocean basins as carbon sinks andthe among thebest studied examples todate. High rates of seafloor spreading andvolcanic activity –both and references therein). The OAE2,orBonarelli event (Bonarelli, 1891; Schlanger OAE 1,theCenomanian to Turonian OAE2and the Coniacian toSantonian OAE3(Jenkyns, 2010 (Jenkyns This article isprotected Allrights bycopyright. reserved. Accepted Article 1977; Weissert,1981; Kuhnt organic carbon-richsediments waterof depths in 1985; Larson, 1991; Kaiho, 1994; Wagner & Pletsch, 1999; Gale Several OAEshave beendocumented during the Cretaceous including theAptian to Albian et al., 2007; Owens et al., 1993;Forster et al., et al., 1990; Arthur & Sagemann, 1994). processesTwo held primarily 2013). et al., et al., 2007), and(2) the increased preservation of organic several hundreds of metres (Hallam & Bradshaw, 1999). Large areas of the continental shelf and mospheric carbon dioxide concentrations followed concentrations and sea surface temperatures et al., et al., et al., 1986; Baudin, 1995; 2004). During OAE2the et al., et al., 1997; Meyer & Kump, 2000; McAnena 2002). Replenishment et al., et al., 1999a; 1987), is et al ., involved microorganisms mineralizing large amounts oforganic matter, as suggested by possibly limestones Tunisian the of genesis The Tunisia. Northern in Formation Bahloul the from mound-shaped carbonate structures associated with OAE 2within Late Cenomanian black shales formation below awater body witheutrophic, anoxic waters. Layeb OAE 1d.The fabric and texture of these limestones suggest the involvement ofmicrobes during their thrombolitic fabric and formed withinorganic-rich black shales deposited during the Late Albian buildups from theLower Cretaceous Fahdene Basin in Tunisia. These limestones reveal a aerobic methanotrophic bacteria (Birgel periods of enhanced bottom water oxygenation, supported by thepresence of molecular fossils of al., confirming that carbonate precipitation wasdriven by microbial oxidation ofmethane (Kauffman deposits are rich in chemosymbiotic macrofaunal communities and exhibit diagnostic carbonate bodies, collectively known asthe Tepee Buttes (Shapiro & Fricke 2002; Metz, 2010). These organic- Campanian The assemblage. faunal diversity petrography, macro-micropalaeontology, and ca aftermath of OAE2exposed along acoastal section carbonate cements and thrombolitic fabrics (Layeb This article isprotected Allrights bycopyright. reserved. (Kauffman chemosynthesis-based microbial activity, andinclude examples from theWestern Interior Seaway after the OAEs.Some ofthese deposits have been ascribed to carbonate precipitation related to teleconnections see Wagner Nederbragt & Fiorentino, 1999; Kolonic mineral fabricsand Accepted Article2012), and are characterized by shallow-water methane-seep deposits that formed during OAE2inwarm bottom waters (Kiel continental margins (Layeb 1996; Birgel This study reports on a large limestone body associated with black shales deposited in the The Cretaceous has yielded several unusual carbonate deposits occurring before, during and et al., et al., 1996; Metz, 2010; Kiel 13 C-depleted molecular fossils of the anaerobic oxidation of methane consortium, 2006). fossiliferous The TepeeButtelimestones possiblyformedduring et al., et al 13 ., 2013 and references therein). C-depleted carbonate mineral phases and ahigh-abundance but low- 2012, 2014). Limestones from theWestern Interior Seaway feature et al., et al et al., ., 2005; Poulton 2006). Layeb 2012) and the northern Tethyan and North African rbon and oxygen stable isotope and trace element et al et of the Tarfaya Basin, Morocco. A combination of rich Pierre Shales comprise numerous peculiar ., 2014). et al. et al (2012) documented carbonate ., 2015; for Atlantic-wide et al. et (2014) further reported on 13 C-depleted 13 C-depleted et al et ., 2B; ElAlbani southern North Atlantic with outer shelf to upper bathyal water depths of 200 to 300 m (Figs 1and to the West (Kolonic Tindouf Basin to the East, the Senegal Basin to the 2001). The TarfayaBasinsituated is tothesouth date, as well as one of the largest oil shale deposits in the world (Amblés This article isprotected Allrights bycopyright. reserved. km Tunisia (Figs 1and 2A;Lüning the Tarfaya Basin, oneof several palaeo-shelf basins located on the coasts of Senegal, Morocco and (Kolonic making them prolific petroleum source rocks (Leine, 1986) and high resolution climate archives thick successions of organic-rich shales and limestones (Kuhnt studied in Tunisia and Morocco. This is partly due to the fact that these regions feature up to 800 m Deposits from theCenomanian–Turonian (C/T) boundary inNorthern Africa have been intensively SETTING GEOLOGICAL seep fauna is likely tobeoutcompeted by heterotrophic background fauna. that seep deposits are difficult to identify inhi primary production and subsequent consumption of or and (2) the eutrophic palaeoenvironment in the aftermath of OAE2that favoured photosynthetic been caused by (1) low water depth – afactor known have resulted frommethane seepage. The lack ofobligate, endemic seep fauna is interpreted tohave features typical ofhydrocarbon seep carbonates and apparently noendemic seep fauna, it is shown to assessed. Although theAmma Fatma limestone body reveals only alimited number of lithological oceanographic andgeochemical conditions on the benthonic environment and faunal communities are precipitation within the mid-Cretaceous organic-ri that led to the unusual morphology ofthis limestone body. potential The triggers for carbonate geochemistry, aswell as lipid biomarkers has been used todecipher the mode ofcarbonate accretion

Accepted2 Article andfeatures the highest accumulation rates of organic matter from theC/T boundary known to

et al., et al., 2005; Kuhnt 1999b; Kuhnt et al., 2002). It hasbeen suggested that the basin was a distal section of the proto et al et al., ., 2005). The southern Moroccan passive continental margin includes et al., 2004; Kolonic 2001). It experienced intense upwelling, extended oxygen gh productivity settings, where chemosynthesis-based chemosynthesis-based where settings, productivity gh of theAnti-Atlas Mountains andextends the into ch deposits,the impact and of theprevailing South, and is bordered by the East Canary Ridge et al., to discriminateto againstseep taxa(Kiel,2010) – ganic matter by heterotrophs. This work reveals 2005). It covers an area ofaround 170,000 et al ., 2001; Kolonic et al., 1994; Kuhnt et al., 2002), et al.,

section of the basin where deposition of organic-rich approximately 8km tothe southwest of Mohammed Plage, the latter being awell-studied coastal middle shelf section at the northern edge of the Tarfaya Basin (Fig. 2).Amma Fatma Plage islocated palaeocoastlineAlbani (El This article isprotected Allrights bycopyright. reserved. (Kolonic flooding, and initiated the deposition of laminated biogenic sediments associated with OAE2 transgressional cycles during themid tolate Cretaceous that caused repeated and widespread ferruginous water-column conditions (Poulton pronounced redox cycles on orbital time scales that alternated between sulphidic and anoxic (Kuhnt & Wiedmann, 1995; ElAlbani minimumzones andrecurrent pulses of high primary production since at least the LateCenomanian of 5-10 cm acrossthe profile. Atotal of 20 samples were collected from various zones of the from afresh coastal exposure in direct proximity tothe carbonate body, and taken at regular intervals collected during afield trip in 2003. Samples from the studied sedimentary succession were recovered Rock samples from the carbonate body and from avertical profile at Amma Fatma Plage were Petrography, mineralogypalaeontology and ANDMETHODS MATERIAL platform (Kolonic Plage represent shallower, proximal successions deposited at the northwestern margin of the Sahara marine shelf setting withwater depths of 200 to 300m, whereas Mohammed Plage andAmma Fatma most proximal part at Mohammed Plage (Fig. 2B).Ex runs in SW toNEdirection andconnects its deepest and most distal part at wells S13 andS57 to its exploration wells S13, S57, S75and Mohammed Plage (cf. Kolonic Fatma Plage lies along a175 km long palaeotransect (hereafter referred to as cover bed). Thin sections (150 x 100mm, 100x75mm) weremade at the Acceptedcarbonate body, two further samples were collected from acarbonate bank covering thestructure Article

The carbonate body studied here crops out at Amma Fatma Plage, which is a coastal to et al., 2002, 2005; Gebhardt et al., 2002,2005; Kuhnt et al., 1999b; Kolonic et al., et al., 2004; Kuhnt et al., 1999a,b; Kolonic et al et et al., et 2009). ., 2015). through the Tarfaya Basin, together with shallow shales and carbonate beds occurred close to the ploration well S13 is interpreted to be an open- 2005).Both sites experienced a series of et al., 2009; Gertsch et al., et al., 2002, 2005), leading to 2002, 2005). The transect et al., 2010). Amma standard wasmeasured prior to sample analyses and a standard deviation of 0.005% was calculated. contents were determined at 550°C. ASynthetic Carbon Leco502-029 (1.01± 0.02 carbon%) standard (Co. Merck) was measured, revealing arelative standard deviation of 0.06%. The TOC This article isprotected Allrights bycopyright. reserved. Acceptedcarbon dioxide was released ata temperature of 1000°C. Prior to sample measurements apure CaCO All samples were ground to fine powder in an agate mortar prior to measurements. measureTo TC, state infrared detector at the Department ofEnvi determined using aLECORC-612 CarbonAnalyzer (St. Joseph, MI, USA),equipped with a solid- Total carbon (TC) and total organic carbon (TOC) co elements Inorganic geochemistry – Total organic carbon, carbon andoxygen stable isotopes and trace magnification of about 1250 times under both cross-polarized and phase-contrast illumination. described in Bramlette and Sullivan (1961) and Hay (1961, 1965). The slides were examined at a slabbed intervals. For the calcareous nannoplankton, smear slides were prepared using techniques assemblages were studied in 150samples with ahigh-resolution spacing of about 4-7 cm withinthe interpreted using the Panalytical software "X´Pert High score plus". Calcareous nannoplankton 0.0167.5 s per step) diffractometerArticle at the University analysed with a Panalytical PW 3040/60 X’Pert PRO(CuK hand-held microdrill at low tomedium rotational speed. For analysis,XRD powdered samples were (XRD) and carbon and oxygen stable isotope analyses were obtained from polished rock slabs using a dissolved in 0.1% hydrochloric acid (cf. Dickson, 1966). Powdered samples for X-ray diffraction several thin sections were stained with a mixture ofpotassium ferricyanide and alizarin red Ssolution analysis and camera control. To discriminate the different carbonate minerals under the microscope, were used for petrographic observations using the software Prog.Res Capture pro 2.8 for image coupled to aProg.Res Speed core XT 5 camera, as using the Leica Application Suite 4.4.0 software. Additionally, aNikon SMZ 1500 stereomicroscope Leica DM4500 Ppolarization microscope. Photogra University ofBremen and the University of Vien

ronmental Geosciences at the University of Vienna. na. Thin section microscopy was conducted using a well as a Nikon Optiphot-2 optical microscope of Vienna. X-ray diffraction patterns were phs were taken with aLeica DFC 450Ccamera ntents of the Amma Fatma carbonate body were α radiation, 40 kV, 40 mA, stepsize 3

of 3ml HNO standard reference material. ForICP-AES, about50mg ofsample powder wasdigested in amixture atomic emission spectrometry (ICP-AES). The XRF calibration curves were based oninternational fluorescence (XRF) spectrometry onfused-borate glass beads, andby inductively coupled plasma appropriate correction factors were applied. carefully removed by repetitive addition of 0.25 NHCl. The CaCO Geoscience Department, University ofBremen. contents ofblack shales were measured us 8.333. All black shale samples were carefully dried and ground in an agate mortar. The TIC andTOC trace elements were calculated according toBrumsack (2006): Relative standard deviations induplicate measurement were below 3%. Enrichment factors (EFs) of analysed with ICP-AES, andthe results were checked EF (precision ofmeasurements ±3%). The This article isprotected Allrights bycopyright. reserved. Carbonate (CaCO Franzens University, Graz. Effective accuracy was ±0.05 for analyses were performed at the light stable isotope laboratory of the Institute of Earth Sciences, Karl- obtained from polished rock slabsusing ahand-h body wereanalysed for their stable carbon and oxygenisotope content. Sample powders were followed by conventional isotope-ratio mass spectrometry. PDB) weredetermined on decalcified sediment samples using automated on-line combustion the residue was re-dissolved in0.5 ml HNO in closed vesselsTeflon (Heinrichs The

Acceptedelement Article δ 13 Trace metal compositions of black shales and limestones were determined using X-ray A total of 48sample powders from 12different samples throughout the Amma Fatma carbonate C and =(element/Al) 3 δ (65%), 2ml HF(40%) and 2ml HCl(36%) of suprapure quality at 200°C and30 kbar 8 O values are reported relative to V-PDB (standard deviation smaller than 0.04‰), and 3 %) contents were calculated according tothe equation: CaCO sample /(element/Al) et al., δ 13 1986). Sample powders were then dried by evaporation, and ing aLECOCS-300 carbon-sulphur analyser at the C average shale 3 TOC (65%)and 4.5ml deionized water. The solutions were values (±0.1‰ versus Vienna Pee Dee belemnite, V- Before determination, TOC inorganic carbon was eld microdrill. Stable carbon and oxygen isotope

with internationalstandard referencematerial. δ 13 C values and ± 0.11 for 3 contents were calculated as above 3 % = (TC – TOC) × × – = TOC) (TC % δ 18 O values. O values. chromatography. N,O- Alcohols pyridinewere derivatised and 100µl by adding 100µl were dried with sodium sulphate and the TLE of both extraction procedures were separated by column free fatty acids (FAs) to the organic solvent phase. Fo the solvents became colourless. The combined extracts were subsequently extracted via ultrasonication inDCM/methanol (MeOH) (3:1; v:v) fourtimes until methanol (MeOH) to release bond carboxylic acids. The supernatants were decanted and the residues After washing with clean water, the samples were saponified with 6% potassium hydroxide (KOH) in From here on, the extracts before and the extract after decalcification are treated in the same fashion. decalcificationbelow.extract after as the referred to extract is This a secondobtain TLE. to above carbonate wasdissolved. The remaining sample powder was centrifuged and extracted as described avoidtransesterificationTo reactions atlow again. In detail, doubly distilled water wasadded and 10% HClwas slowly poured onto the samples. This article isprotected Allrights bycopyright. reserved. Acceptedmolecular fossils, the residual sediment of the first extraction step was referred to as the extract before decalcification times until the solvents became colourless to get the first total lipid extract (TLE). This extract is bound compounds, the ground samples were extracted by ultrasonication in DCM:MeOH (3:1) nine the carbonate matrix fromArticle easily extractable compounds. Toobtain preferentially intercrystalline- fossils (cf. Thiel discriminate preferentially intercrystalline-bound from preferentially intracrystalline-bound molecular ground to fine powder. All carbonates were treated with a‘two-step extraction procedure’ to hydrochloricacid (HCl)andthen dichlorometh from eachof the zones 4, 3 and 1. The samples were cleaned repeatedly by washing with 10% Four carbonate rock samples were chosen for biomarker analysis, one from thecover bed andone Organic geochemistry –Lipid biomarkers average shale, respectively. element with an EFeither above orbelow 1is considered tobe enriched or depleted compared to Average shale refers to the composition of collected shale samples compiled by Wedepohl (1969). An et al., 1999; Guido et al., 2013), and to separate compounds tightly associated with pH, HCladdition was stopped when ~75% of the ane (DCM) to avoid any contamination, and then below. obtainTo preferentially intracrystalline-bound r gas chromatography (GC) analyses the extracts were thentreatedwith10% HClto transfer the

decalcified andthen extracted carboxylic acids were reacted with 1ml 14%boron trifluoride (BF injection. The alcohol fractions are not described below dueto the lack ofpristine compounds. Free mixture (C known isotopic composition prior to and after the run. Precision was checked with an derivatisation. Each measurement wascalibrated using several pulses of carbon dioxide (CO values of carboxylic acids (methyl esters) were corrected for additional carbon introduced after extracts were evaporated under a stream ofN FA methyl esters. After cooling, the mixture was extracted 4 times with 2ml specific carbon isotope values are given as as given are values isotope carbon specific spectrometer at the Department ofTerrestrial Ecosystem Research,University of Vienna. Compound- GC Ultra connected via a Thermo Fisher GC Isolink interface to a Thermo Fisher Delta VAdvantage mass spectra. 320°C (held 25 min) at 4°C/min. Compound assignme program forhydrocarbons and carboxylic acids was60°C (1min) to 150°C at 10°C/min, then to filmm thickness).mm x0.25 Helium i.d.,0.25µm wasused as the carrier gas. The GCtemperature carboxylic acid fractions. Both GCsystems were equipped with HP-5 MSUI fused silica columns (30 This article isprotected Allrights bycopyright. reserved. derivatised fraction was dried under a stream ofnitrogen (N bis(trimethylsilyl)trifluoracetramide (BSTFA) to the alcohol fraction at 70°C for30 min. The system.Internal standards used were 5 Quantification wasdone using GC-flame ionization detection (GC-FID) withan Agilent 7820 AGC Agilent 7890 AGCsystem coupled to an derivatised carboxylic acid fractions were analys and 4). The limestones are represented by (1) carbonate nodules mainly composed of mudstones and Acceptedfeatures cyclic alternations of black shales, siltstones and organic-rich, marly limestone beds (Figs 3 The complete section at Amma Fatma Plage measures approximately 14m fromtop to bottom and Amma Fatma section –Lithology, biostratigraphy and inorganic geochemistry RESULTS Article Compound-specificstable carbon isotopeanalysiswas performed with aThermoFisher Trace 14 to C to 38 ) of known isotopic composition. Analytical standard deviation was<0.7‰. α -cholestane for the hydrocarbon and 2-Me-C Agilent 5975C inert MSD mass spectrometer. δ values in permil (‰) relative to V-PDB. The 2 andredissolved in ed using GC-mass spectrometry (GC-MS) with an nt wasbased on retention times andpublished 2 ) and dissolved in n 3 -hexane before injection. The ) in MeOH at 70°C for1h to form n -hexane. Combined n -hexane prior to 18 n FA forthe -alkane δ 13 2 ) of C One exception is a 1 m thick bed3m above thebase of the profile featuring large carbonate nodules cm, respectively. Bedscomprising limestone nodules with chert measure up to 20 cm inthickness. and black shale beds alternate regularly, whereby their thicknesses measure 20 to 80 cm and60to 300 succession of 22beds is shown by thestratigraphic chart of the outcrop in Figures 3and 5. Limestone partly bioturbated. Adetailed microfacies analysis is included in ElAlbani calcispheres, molluscs including ammonites, brachiopods, variable amounts of quartz grains and are shown in Table 1. The characteristic positive 60 to90% and 4 to 9%, respectively. Calcium carbonate and valuesTOC throughout the section are with a corona made of chert. Calcium carbonate and TOC contents of the black shale beds vary from Krumbach (1986) to indicate that nannofossil distribution patterns can still largely be used for abundance of in two carbonate beds), and areknown to bevery good. moderate, except in the uppermost part of the se highly abundant calcareous nannofossil flora was observed inall samples studied. Preservation is in very high numbers and benthonic foraminiferal faunas are of lowdiversity. Ahighly diverse and placed at about 9.5 m abovethe (cf. Marzouk & Lüning, 2005). The position of the nannofossil zonal datum marker CC11/CC12 is and the placing the investigated sedimentary succession within the This article isprotected Allrights bycopyright. reserved. hummocky crossstratification (cf. ElAlbani wackestones that are aligned parallel to stratifica Acceptedof deposition. measuredThe the C/T boundary inadjacent sites is not found at Article Watznaueria barnesae Biostratigraphic data confirm thepositioning relative to theOAE2 carbon isotope excursion, coloradoense Watznaueria barnesae and nodosoides and δ 13 C helvetica TOC Eiffelithus turriseffeilii does not surpass 40%, a cut-off value proposed by Rothand values vary slightly between −26.2 and −27.8‰. ammonite zone of the upper part of the Lower Turonian stage and et al., δ nodosoides 13 ction (from 13.5 m onwards), where preservation is C tion and (2) discontinuous bioclastic storm bedswith Amma Fatma Plage, supporting apostOAEperiod resistant to solution. Although frequent, the TOC 1999b). The limestones contain Foraminifera, excursion that is prominently observed across are abundant throughoutsection the(except zones. Planktonic Foraminifera are present H. helvetica planktonic foraminiferal zone et al. (1997, 1999a). The This article isprotected Allrights bycopyright. reserved. which consists mainly ofmarly limestone and exhi togetherwithabsolute contents oftherespective to zone 4 (Table 3). AsEFs may beexaggerated due to varying Alcontent, they must be considered Zone 4reveals relatively high Alcontents, and all EFs are higher in the lower zones 1and 2compared zone 1hasan Alcontent that is half that of zone 4,which has a considerable effect oncalculated EFs. concentration of several major elements including Al, Mg, Feand Mn (Tables 1and 2).Particularly, to 4and the cover bed are shown in Tables 2and 3, respectively. Zone 1shows the lowest Mean trace metal concentrations and EFsof black shale and limestone beds that correspond to zones 1 deposition is influenced by bottom andporewater redo beds, and also within the black shale successions themselves. Calculated EFs of trace metals whose shales. Trace metal patterns vary across the section between alternating black shales and limestone enrichment is restricted to stratigraphic intervals that correspond to the organic carbon-rich black in Figure 5. identified nannofossil species and phosphorus content throughout the Amma Fatma section are shown Gartnerago segmentatum (Thierstein 1976; Hattner abundance fluctuations over afew centimetres ( having longer-term,gradual changes, with only also solution resistant. Cyclagelosphaera margerelii palaeoecological interpretations, despite diagenetic and syndepositional dissolution. Notably, Accepted Articleof the section. Other identified species distribution of uppermost parts of the studied section, and is absent in the interval in-between. Notably, the Eprolithus floralis Abundant species throughout the section include Total contents of all measured elements are shown in Table 1. Prominent trace metal The nannofossil distribution in the Amma Fatma section is characterised by many species E. floralis . R. splendens R. in thesection is characterised by similar abundance peaks at the base and top abundance peak between 7.5 and8m. Abundance anddistribution of all et al., shows asimilarly abundant distribution and, therefore, appears to be 1980) arenotablyrare throughout thesection.exceptionAn isa occurs in moderate and high abundances in the lowermost and Broisonia spp Tranolithus orionatus some species exhibiting stronger, high-frequency elements.particularly This is 14,bed the casefor Zygodiscus erectus bits low Alconcentrations. Chromium, Co andU . (except x conditions are plotted with depth inFigure 6. B. enormis , Rhagodiscus splendens , Zeugrhabdus diplogrammus ) and Gartnerago spp. and

). This article isprotected Allrights bycopyright. reserved. 80% of the bulk rock volume (Figs 9and10A). Ma Acceptedoccur, whereby the former is themost abundant carbonate phase inzones 1and 2, making upatleast that makes upthematrix of theAmma Fatma carbonate body. Matrix micrite and peloidal micrite Micrite (i.e. microcrystalline calcite with a crystal isthe dominant size below 10 primaryµm) mineral The Amma carbonateFatma body – Petrography and mineralogy C), which corresponds to bed 14of the section (Figs 3 and 4A). the body iscapped by a15 to 20cm thick carbonate bank, referred to as a cover bed (Figs 4and 8A- yielded abundantmolluscan fossils,wellascylindricalas totubular trace fossilsof (Fig. top 8C). The features massive limestone blocks and nodules. Zone thickness separates zone 1 from 2(Fig. 7B).Zone 3comprises the middle part of the body, and numerous veins filled by secondary precipitates (Fig. 7). Acarbonate bank measuring 17to19 cm in lowermost part of the structure and feature concretionary and nodular carbonates penetrated by divided into 4zones, illustrated in a schematic sketch (Fig. 4B).Zones 1and 2comprise the base and Amma Fatma section, and measures 5.5 m inheight and 3.6m inwidth. The carbonate body was The carbonate body associated with black shales (Figs 3and4) is enclosed by beds 6to 14 of the The Amma carbonateFatma body Article with Ni andCd (Table 4). correlate well among eachother, these being (1)Cr with Cu,(2) Mo with Ni,Zn and V and (3) Zn better than the former. Trace metal correlations can be distinguished into three groups of elements that Table 4. onlyThe trace metals that exhibit correlation with Al are Cr and Co, with the latter correlated trace metals and Al, as well asbetween trace metals themselves were calculated and are shown in decrease steadily from bottom totopand fall below unity inbed 14.Correlation coefficients between 14 exhibits the lowest contents of most trace metals with the exception of U.Molybdenum/U ratios and Coin zone 3,which is not as apparent in respective EFsdue tohigh Alcontents in this zone. Bed concentrations in zone 1 and 4are almost equal. There is adistinct peak of all trace metals except Cr are the only trace metals whose concentrations increase from zone 1to4 (Table 2), whereas Mo

trix micrite is light to dark brown incolour, 4 is the topmost part of the carbonate body and This article isprotected Allrights bycopyright. reserved. equant calcite is the dominant void filling phase Acceptedcrystal fans showing oscillatory extinction patterns under crossed polarized light. Volumetrically, can also be found finely dispersed among theequant calcite crystals. Microquartz occasionally forms and typified by very small grain sizes reaching nomore than several microns in diameter. In places it and B). Microquartz ( rimmed bymicroquartz, followed by equant calc Matrix micrite or peloidal micrite represents the primary fabric of the rock. Cavities and veins are throughout zones 1 to 4.Cavities and veins show the same paragenetic mineral sequence in all zones: pale grey in colour and show welldefined crystal faces (Figs 9Band 10B). of idiomorphic crystals (Fig. 9B).Dolomite occurs within zones 1and 2. The dolomite crystals are measuring only several microns in size. In some rarecases pyrite also forms aggregates and clusters from theaforementioned micritic peloids. Pyrite occurs asvery small and finely dispersed grains in shape and indiameter. measure uptoTheir internal500 µm structure clearly distinguishes them oriented in different directions towards and away fro (Fig. 10B). The crescent-shaped canals are arranged in two groups around asymmetry plane, and are micrite. Articleunder UV light, suggesting that they areenriched inorganic matter compared to the surrounding Foraminiferawell as andradiolarianpeloids tests. The and scattered occurrencesof fine, dispersed equant calcite cement. Similar to the matrix micrite, the peloidal micrite exhibits structure and exhibit acloudy andheterogeneous fabric. Thespace between the peloids is occupied by peloids, which measure indiameter. 100 The peloids to500 µm donot show any obvious internal rock volume (Figs 10Cand 11B). Th Peloidal micrite is particularly abundant in zones 3 and 4,where it accounts for around 70% of the Foraminifera (Fig. 9B), large amounts of recrystallized bivalve andgastropod shell fragments (Fig. 9A),benthonic exhibits avery heterogeneous andpartly clotted texture andis rich in detrital material comprising The Amma Fatma limestone ispenetrated by numerous veins, cracks and large cavities Palaxius faecal pellets are present in all zones but are particularly common inzones 1 and2 sensu Palaxius Palaxius Knauth, 1994) is pale brown tobeige in colour (Figs 10C and11B,C), faecal pellets (Fig. 10B),radiolarians (Fig. 11A) and clay minerals. faecal pellets, gastropod, bivalve and ammonite shell fragments, as is micrite is characterized by abundant oval to spherically shaped in all four zones (Figs 10A,11C, 12A andB); its ite spar andmegaquartz (Figs 10C, D,11B,C,12A m thesymmetry plane. They areoval to spherical Palaxius faecal pellets are fluorescent

genus lucinid precludes further identification. The ammonites (n=5) are juveniles and adults belonging tothe Pycnodonte inoceramids (n=4; Fig. 14D) andgryphaeid oysters (n=6), which could belong tothe genus 14C). The bivalves belong to three taxa: a single might represent a neogastropod belonging tothe genera juveniles, but also afew adults up to 21mm high, and asingle, partially fragmented specimen that gastropodsThe comprise 23specimens of theaporrhaid This article isprotected Allrights bycopyright. reserved. Acceptedassemblage ofgastropods, bivalves and ammonites, together with The macrofossils collected from Zone 4of the carbonate body comprise a low diversity molluscan Macrofauna precipitates. Cavities contain microquartz and later formed equantcalcite spar (Fig. 13BandC). the cover bed is penetrated by numerous cracks and veins, which have been filled by secondary represented by mainly radiolarian and foraminiferan tests (Fig. 13A).Similar to the carbonate body, or peloidal textures and containsArticle minor dolomite crystals (Fig. 13). The fossil content is low, micrite of zones 1to 4,contains less detrital material. It is relatively homogeneous showing noclotted to 4of the carbonate body (Fig. 4). matrixThe comprises micrite, which, compared to the matrix light (Fig. 12C). homogenous, showing nodetrital inclusions. It show and fringes (Fig. 12Aand B). Seam micrite is da occurs exclusively along the outer rims ofveins and cavities, where it forms highly irregular patches rim ofmicrocrystalline calcite referred to as seammicrite (Fig. 12). It ispresent in all zones and 10C andD).An accessory peculiar carbonate phase present within fractures and voids is an authigenic megaquartz ( crystals measure up to 1mm indiameter. The last phase in the paragenetic phase sequence is Benueites The carbonate cover bed (Fig. 4)shows a quite similar paragenetic phase sequence tozones 1 . smallThe specimen sizes (<10 mm) ofthetwolatter taxa and the articulation of the sensu , including Knauth, 1994). Megaquartz crystals reach up to 1mm ormore in diameter (Fig. Benueites cf. benueensis rk brown, almost black in colour andis very articulated lucinid specimen (Fig. 14E), juvenile . s strong epifluorescence when excited with UV Drilluta Drepanocheilus , Bellifusus Palaxius sp. (Fig. 14A andB),mostly faecaland burrows. pellets or or Paleopsephaea (Fig. depleted than matrix micrite. Asample from zone 3revealed the only positive negative revealed the lowest depleted to different degrees throughout all zones of the carbonate body, including thecover bed.It −3.2 to −2.1‰ and −3.4 to −1.8‰, respectively. Zone 4matrix micrite displays more scattered are exclusively negative. Matrix micrites from zones 1,2and3 exhibit values from −2.9to−2.3‰, to −0.3‰. Zone 4micrite shows the largest scatter of wider range of values from−23.1 to −7.9‰, and zone 3 micrite more positive values between −11.0 δ values from −4.3to −1.7‰. Matrix micrite of the cover bedyielded values from −3.3to −2.6‰. The The −0.9 to −0.7‰, respectively. Samples from zone 4andthe cover bed show little heterogeneity andfall between −3.7to −1.5‰ and This article isprotected Allrights bycopyright. reserved. Results of carbon and oxygen stable isotope analyses are shown inFigure 15. Matrix micrite is Isotope geochemistry, TCandTOC The matrix micrite of the cover bedyielded Organic matter enclosed in the sediments of the Tarf Hydrocarbons Biomarkers 0.1%. zone 4to0.7% in zone 1. The cover bed exhibits asimilar contentTOC as the topmost zone 4of contentsTOC (Table 5). The content TOC increases significantly from topto bottom, from 0.1%in −1.7‰). cover bed is characterized by shortand long chain (Kolonic equant calcite were analysed from zones 3,4and the cover bed.Generally, equant calcite is less 18

AcceptedvalueO of equant calcite from zone 3and2 is −3.4‰. Equant calcite from zone 4shows the most Article A total of six samples from theAmma Fatma carbonate body wereanalysed for their TC and δ et al 18 O values from −6.2to −2.6.Equant calcite ofthe cover bed is less δ ., 2002; Sachse 18 O values of matrix micrite and equant calcite from allsections of the carbonate body δ 13 C values in zone 1, ranging from −23.5to−21.3‰. Zone 2 micrite yielded a et al .,2012). hydrocarbon The fraction before decalcificationfrom the δ 13 C values from −2.3to−0.4‰. The n -alkanes that range from C aya Basin has been shown to be of low maturity δ 13 C values, C falling between −22.9 and −1.3‰. 16 18 δ 13 O depleted (−2.3 and to C C value of1.6‰. δ 13 34 C values of of values C . The . The shorter- 13 δ 13 18 C- C- O (Fig. 16D)differs markedly from all other samples. Apart from short-chain atoms are accessory compounds. The carboxylic acid fraction after decalcification ofzone 1 limestone chain shown inFigure 16. The carboxylic acid fraction from thecover bed is dominated by saturated short Carboxylic acid fractions before and after decalcification from thecover bed and zone 1limestone are Carboxylic acids here. similar results were obtained for two carbonate samples ofzones 3 and 4, and are not further detailed before decalcification except that the overall intensities ofall compounds are greatly reduced. Very more abundant than pristane. Thehydrocarbon fraction after decalcification is similar to the fraction Pristane and phytane are the only non-alkane compounds detected in zone 1,with phytane slightly dominance of reduced compared to the fraction before decalcification. decalcification from thecover bedshows avery similar pattern, except that the contents are much pristane and phytane, with phytane more abundant than pristane. The hydrocarbon fraction after Apart from dominant over all other compounds. Additionally, dominate over C characterized by short-chained, C This article isprotected Allrights bycopyright. reserved. from thefraction before decalcification, with medium-chain very small amounts (Fig. 16A). carboxylicThe acid fraction after decalcification varies only slightly chained C AccepteddistributionC of all carboxylic acids) compared to the fraction before decalcification (Table 6), however, the the former(Fig. contents16B). The chainedof short Article n -fatty acids ranging from C

Hydrocarbons in the extract before decalcification from zone 1are characterized by the The carboxylic acid fraction prior to decalcification of zone 1limestone (Fig. 16C) is 16 n to C to -alkanes, theonly compounds detected are minor amounts of the regular isoprenoids n -alkanes from C 20 12 12

, C . Unsaturated n -alkanes dominate over longer chain 16 and C 18 issimilar. 16 n toC -fatty acids and long-chained saturated 12 12 toC toC 30 . In. contrast to the cover bed,C 18 18

n . Most abundant -fatty acids. The C αβ n - and -fatty acids are markedly decreased (~50% of n -alkanes, whereby ββ n -fatty acids are C n -fatty acids up to C -hopanoic acids with 31 and 32 carbon 12 , C 16 andC 16 and C n -fatty acids are present in 18 n

n n -fatty acidsnumerous 16 -alkanes peak at -fatty acidsare 18 and C dominate over C 23 more abundant in 18 , which n -C 20 20 . . diacids and minor hopanoic acids, namely C higher tricyclic- (BP-3) biphytanic diacids. BP-2 isstrongly diacids, bicyclic biphytanicdiacid (BP-2)domin rings and one cyclohexane ring, according toits mass spectrum andretention time. Ofall biphytanic only contain cyclopentane rings, whereas the tricyc biphytanic diacids were only foundinzone 1 lime This article isprotected Allrights bycopyright. reserved. middle- tolong-chain compounds are abundant. These compounds include C for methane seepage is the presence of evidenceit that formed at ashallow-water seep in hydrocarbon-seep deposits in terms ofits faunal content (cf. Campbell, 2006), there is multiple geological setting andthe processes that triggered its formation. Although this deposit is unlike many The comprehensive data set obtained for the Amma Fatma carbonate body allows constraining of the The Amma carbonateFatma body – Ahydrocarbon seepdeposit ANDDISCUSSION INTERPRETATION shown in Table 6. 4 tozone 1.Contents and phase-specific stable carbon isotope values of the carboxylic acids are were found to be more tightly boundto the carbonate lattice. The amount of acids increases from zone decalcification. For the samples from zones 4,3and1 the ratio is reversed, where the carboxylic acids the amount of acids in the extract after decalcification is half that of the fraction before Biphytanic diacids with extreme 2016) and are membrane lipids of archaea including ANMEs (see Schouten diagenetic breakdown products of glycerol di anaerobic methane oxidizing archaea (ANMEs; Birgel 2012). GDGTs and biphytanic diacids are uncommon inMesozoic and Palaeozoic seep limestones, Acceptedenvironments (Schouten Article δ The total amount of carboxylic acids varies strongly between the samples. For the cover bed 13 C value of −22‰. et al., 2003; Birgel 13 C-depletions have beenreported from various methane-rich 13 C-depleted biphytanic diacids, which are molecular fossils of 32 et al., biphytanyl glycerol tetraethers (GDGTs; Liu Liu (GDGTs; tetraethers glycerol biphytanyl -17 ates over acyclic- (BP-0),monocyclic- (BP-1) and β ahigh productivity realm. The strongest indication 2008a; DeBoever stone. The mono- andbicyclic biphytanic diacids (H),21 lic biphytanic diacid contains two cyclopentane 13 C-depleted (−96‰), while BP-3 showsa et al β (H)-hopanoic acid. Acyclic to tricyclic ., 2008a). These compounds are putative et al., 2009; Natalicchio et al., 16 , C 18 2013 for a review). andC 22 et al α , ω et al., ., -

contrast to BP-2, BP-3 isderived from other sources, as indicated by its also reported for other Cenozoic andmodern methane-seep carbonates (Birgel Fatma deposit exhibit awide range of 1994) and detritus-rich matrix micrite (Kiel types can be distinguished including clotted (Peckmann 2015). Microcrystalline calcite (i.e. micrite) forms the matrix ofmost seep limestones, and several Savard, 1992; Campbell phasesthat enables thereconstruction processes of that governed their formation(Beauchamp & authigenesis, consistent with anaerobic methanotrophy contributing tocarbonate formation. are tightly boundto the carbonate lattice and consequently reflect environmental conditions during diacids were only detected within the carboxylic acids fraction after decalcification, these compounds carbonates, particularly oil-seep carbonates (Naehr possibly obscured by hydrocarbons and unresolvable complex mixtures, similar to somemodern seep diacids and other molecular fossils of hydrocarbon seepage suchas isoprenoid hydrocarbons are Interestingly, biphytanic diacids are only present in the lowermost zone 1,suggesting a heterogeneous composition ofthe Amma Fatma carbonate body. Inzones 2to4, however, biphytanic Schouten crenarchaeol-derived tricyclic biphytanes of planktonic Thaumarchaeota (Könneke This article isprotected Allrights bycopyright. reserved. dwelling ANMEs.Asimilar predominance of 2. Values as lowas −96‰ for BP-2 intheAmma Fatma deposit have only beenreported from seep- the Amma Fatma deposit. The most abundant biphytanic diacid in the Amma Fatma limestone is BP- to track methane oxidation in the rock record (Birgel and the more persistent irregular isoprenoids crocetane andpentamethylicosane (PMI) have beenused AcceptedWhiticar, 1989; Peckmann & Thiel, 2004). Biogenic and thermogenic methane, higher hydrocarbon varies over time anddepends on the degree of mixing between various carbon sources (Suess & Greinert Article Many ancient seep limestones are typified by adistinct paragenetic sequence of mineral et al., et al., 2001). composition The poolfromof thecarbon carbonates which precipitateseeps at 2013; Pearson et al., 2002; Peckmann et al ., 2016). δ 13 C values, apattern commonly foundfor seep limestones (cf. et al 13 C-depleted BP-2 among thebiphytanic diacids was et al., ., 2013; Tong et al., et al., 2002; Hagemann et al., 2009; Feng 2008b), but neither of these were found in 2002), peloidal (Roberts & Aharon, et al., 2016). Micrite of the Amma et al., δ et al., 13 C value similar to that of 2014). Sincebiphytanic 2013; Zwicker Zwicker 2013; et al., et al., 2008a). In 2012; et al.,

succession are slightly lower than the the seafloor (Xu and were attributed to biogenic methane production in the host sediments and its oxidation close to AOM didnot necessarily contribute substantially tocarbonate precipitation, although carbonate precipitation, but itdoes not explain the presence of large amounts of organic carbon buried during OAE2 may have consequently contributed to composition of the carbon pool, the carbonates that precipitate at seeps are usuallymore Peckmann & Thiel, 2004; Campbell microbially remineralisation-driven carbonate formation. The black shales themselves might have acted as a readily available source of organic carbon, causing may assess the impact of crude oil at ancient seeps with more confidence. Finally, theAmma Fatma light on the composition of fluids of the Amma Fatma seep (cf. Smrzka al., within the range ofcarbonates precipitating atmodern oil seeps (cf. Anderson This article isprotected Allrights bycopyright. reserved. whereby the carbonates inherit the methane (AOM) is considered to be the main process triggering carbonate precipitation at seeps, precipitation at ancient seeps thus remains problematic. Sulphate-dependent anaerobic oxidation of carbon pool of the parent fluid, and determining thecontribution of each source to carbonate compounds including crude oil and dissolved inorgani than the organic carbon sources due to an admixture of marine carbonate (Peckmann & Thiel., 2004). δ biphytanic diacids testify to thepresence ofmicrobial communities performing AOM. Slightly lower the presence ofoil at the ancient seep is missing, andit isonly supported by to carbonate formation at Amma Fatma. This notion, however, is rather speculative asevidence for 13

Accepted valuesC were obtained from seepdeposits associated with Jurassic black shales from Kilve, UK, Article 1999; Formolo

The lowest et al., et al., δ 13 C value of the Amma Fatmamatrix micrite of −23.5‰ therefore suggests that 2016). oxidationhigherof The hydroc 2004). Anew approach using trace and rare earth metal contents may shed 13 , C-depletion of the organic carbon sources (Ritger 2006). Regardless of the carbon source controlling the isotopic δ 13 C values of the authigenic carbonates. Remineralisation of c carbon from seawater all contribute to the arbon compounds may have contributed δ 13 13 C-depleted biphytanic diacids. C TOC values of the Amma Fatma et al., δ 2016), and future work 13 et al., C values that are 1983; Sassen 13 et al., C-depleted 13 C-enriched 1987; et mineralogy ofthe precipitate over time (Heany, presence of silica polymorphs suggests that changing silicic acid concentrations controlled the occluding large cavities (Fig. 10C andD) is typical of seep limestones (Smrzka occurring asthin linings along crack andcavity walls (Figs 11B,Cand12) and later megaquartz carbonate body (Fig. 11A) suggests abiogenic source of silica. The sequence of microquartz buriallatediagenesis (Keene,1975). abundance The radiolarian of within tests theAmmaFatma al., spicules (Lancelot, 1973; von Rad seep environments is derived from thedissolution of radiolarian tests, diatom frustules and sponge Smrzka al., This article isprotected Allrights bycopyright. reserved. 13 modern seep limestones, it lacks acarbonate phase that typifies many seepdeposits, namely banded concentrations haddecreased. with higher concentrations of silicic acid and megaquartz formed during alater stage when silica δ and botryoidal aggregates of fibrous aragonite ceme precipitated during increasing burial and progressive diagenesis, which agrees with theonly moderate al., & Thiel, 2004). Equant calcite is a typical, later-stage mineral phase of seeps limestones (Campbell of organic residue, agreeing withan involvement ofmicrobial activity in its formation (cf. Peckmann distinguishes it frommatrix andpeloidal micrite. The latter observation suggests an increased content micrite are indicative ofan in situ precipit walls andpredates later-stage calcite cements. The purity andmicrofabric of the Amma Fatma seam (2003) described asimilar phase in Eocene seep deposits from Washington State that also lines cavity 13 C-depletion of the AmmaFatma equant calcite.

C values, C reflecting its origin from AOM(Beauchamp & 1992; Savard, Roberts Accepted Article 2012), although dissolution of volcanic glass and cl 2002; Peckmann 2000; Himmler Authigenic silica minerals typifymany Mesozoic and Cenozoic seep limestones (Goedert Seammicrite is apeculiar carbonate phase of the Amma Fatma deposit. Peckmann Although the Amma Fatma deposit features mineral phases that are common in ancient and et al., 2015). Most of the dissolved silica required for quartz precipitation in seep and non- et al., et al., 2008; Peckmann 2003), and is interpreted 2003),andis abiotically-formedan tobe cement that et al., 1977; Bohrmann ation,intense andits epifluorescence (Fig.12C) et al ., 2011; Kuechler 1993), whereby microquartz prec nt. This type ofcement typically exhibits low ay minerals may alsobecome relevant during et al., 1994; DeMaster, 2002; Kuechler et al., 2012; Kiel et al., ipitated from fluids et al. et al., 2015). The , 1993; 2013; et al.

et et et et et 2010, Little seep taxa is acommon feature of shallow water seep faunas in the Mesozoic and Cenozoic (Kiel, Figs 7-10) as Nymphalucina obligate taxa, possibly apart from thelucinid, which might belong tothe seep obligate genus seep fauna contains mostly elements of normal marine background faunas, and lacks specialized (Busson aporrhaid gastropods are common elements inLate gryphaeid ( aporrhaid ( The benthonic macrofossil assemblage of the top part of the Amma Fatma carbonate body includes fauna Benthonic inoceramids (up to 35mm Fig. long, 14H).Further, species of same species of lucinid (Fig. 14FandG) in 2003 andnow housed in the collections of the Oxford University Museum, This UK. includes the concretions from belowthe carbonate body in bed 2 conditions. A taxonomicallyvery similar low diversity fauna is present in shell-rich micritic carbonate although the absence of large inoceramid andoyster water column andsediment during theformation of at least the upper part of the carbonate body, presence of this fauna suggests that oxygenated conditions were at least episodically present in the was most likely epifaunal, but without further taxono aporrhaid was an epifaunal/shallow infaunal suspension ordeposit feeder. The possible neogastropod chemosymbionts, by comparison with modern members of this family (Dando feeders, and the lucinid was aninfaunal taxon This article isprotected Allrights bycopyright. reserved. Accepted Articlefluids (cf.Peckmann Amma Fatma seepwas characterized by diffusive rather than advective seepage of hydrocarbon-rich Savard et al.

et al., Drepanocheilus Pycnodonte et al., , 1996). The lack ofthis phase together with the dominance ofmicrite suggests that the Lucina fallax (Kiel, 2013), although is also similar to the lucind figured in El Qot (2006,Plate 14, 1999; ElQot, 2006; Ayoub-Hannaa 2015). Other examples include the slightly older Cenomanian Tropic Shale seep et al. sp.) bivalves. The small inoceramids andgryphaeids were epifaunal filter , 2009). Forbes, 1846 from theLate Cenomanian ofEgypt. This paucity ofobligate sp.) and possible neogastropod gastropods, lucinid, inoceramid and Drepanocheilus that almost certainly had sulphide-oxidizing Cretaceous faunas from across North Africa et al., specimens may hintat challenging environmental at Amma Fatma Plage, collected by AndrewGale mic information its diet cannot be inferred. The 2014). This indicatestheAmma that Fatma sp. (Fig. 14I), butalso much larger Pycnodonte , inoceramids, lucinids and et al., 1986). The least episodically oxygenated at that time. The absence ofthe diagnostic assemblage of the upper part of the Amma Fatma deposit suggests that the entire water column was at an early Turonian age based onthe ammonite fauna and planktonic foraminifera. The macrofaunal (Collignon, 1967). El Albani Tarfaya Basin. belongs to the ammonites belonging to the genus The Amma Fatma carbonate body isnot older than Lower Turonian in age. Thepresence of of theAmma formationcarbonateof Mode Fatma deposit availability, sustaining dense populations of crustaceans. Palaxius water carbonate deposits of northern Africa (Senow strongly resemble 2015). The number and shape of the crescent shaped canals in the Amma Fatmamicrocoprolites Peckmann Daryan microcoprolites are common inPalaeozoic and Mesozoic shallow water limestones (Senowbari- microcoprolites, which are today produced by callianassid decapod crustaceans. OAE 2,andis consistent with biostratigraphic evidence. observed for OAEs confirms that the black shales and the carbonate body formed in the aftermath of This article isprotected Allrights bycopyright. reserved. Accepted Articlecontains numerous specimens of the Paleocene Panoche Hills seep deposit from California, USA(Schwartz examples of the neogastropod of the bivalve genera faunas from southern Utah, USA(Kiel et al.,

The microcoprolites in theAmma Fatma body suggests high productivity and organic matter et al., Palaxius 1992, Schweigert nodosoides Benueites 2007; Senowbari-Daryan Palaxius decemlunulatus faecal pellets found throughout the Amma Fatma carbonate body are Inoceramus species,including Zone, theyoungest zone of the Lower Turonian, as elsewhere in the et al. Paleopsephaea et al., Nymphalucina and Benueites (2001) described the laminated marls at Amma Fatma anddeduced Nymphalucina 1997) and other methane-seep deposits (Kauffman et al., et al., , which has previously been found in Cretaceous shallow benueensis in zone 4 shows that the upper part of theseep deposit 2012), which are dominated by mostly small specimens and and less common aporrhaid gastropods (Kiel, 2013). 2007; Taviani Callianassa bari-Daryan & 1992). Kuss, The high density of , the gastropod genus , are associated with decapod claws. Ayounger example is et al., 2013, 2015; Zwicker δ 13 Drepanochilus et al., C isotope excursion excursion isotope C Mammites nodosoides Palaxius 2003), which

, rarer et al., et al., 1996;

pore water that transports the necessary solutes to the locus of precipitation (Raiswell & Fischer, subsurface but close to the seafloor. Large concretionary bodies require a constant andlarge supply of accretion of the Amma Fatma carbonate body, and that carbonate precipitation occurred in the that concretionary growth accompanied by compaction evidence for an ancient hardground or firmground, as cementing epifauna are absent. It isconceivable bottom watersas observed today inthe Black Sea (Peckmann conditions, the carbonate bodymay have projected into thewater column during episodes of sulphidic indicates that the deposit was elevated above the seafloor. Given the changing environmental cover bed is much thinner directly ontopof the seep deposit, and thickens readily away from it, bed as seen during pockmark formation (cf. Agirrezabala on the seafloor during the time ofdeposition. Such ascenario is in contrast to a thickening ofacover out around the top of the carbonate body (Fig. 8Aand the carbonates precipitated during or after their deposition. crosses almost the entire section of laminated shales and limestones, making itdifficult to ascertain if beds of the host marls wrap above andbelow the outside of the concretions. The Amma Fatma deposit diagenesis before significant compaction occurred, as fossils were well preserved andsurrounding in direct proximity tothe Amma Fatma carbonate body. These concretions formed during early al., concretions that precipitated within the organic carbon-rich limestones and black shales (El Albani laminated strata from Amma Fatma and Mohammed Plage feature isolated, nodular, diagenetic carbonate body clearly stands out from thehost successions. Apart from this large carbonate deposit, Liang 1993; Coleman & Raiswell, 1995;Sellés-Martínez, 1996; Seilacher, 2001; Marshall & Pirrie, 2013; common inMesozoic strata, andtypically stand out from thehostsediment after erosion (Coleman, and Miocene deposits ofItaly (Conti resembles some ofthe exhumed Oxfordian seep deposits from Beauvoisin (Peckmann This article isprotected Allrights bycopyright. reserved. Accepted Article 1997, 1999a). El Albani et al., The cover bed capping the Amma Fatma deposit sheds light on the mode ofaccretion. It thins The Amma Fatma deposit is atall, concretionary carbonate body, andin this respect 2016). What is most indicative of concretionary growth is that the Amma Fatma et al. (2001) described lower Turonian, elongated carbonate concretions et al., 2004). Concretions of various shapes and sizes are B), which agrees with the presence of a relief ofthe host sediment were the main modes of et al., et al., 2013).circumstance The the that 2001). However, there is no et al., 1999) et apparently lower, resulting ingradually less negative The impact of methane-bearing fluids oncarbonate precipitation in the upper zones 3and 4 was hotspot of hydrocarbon-driven authigenesis that apparently continued during ongoing sedimentation from thehost black shales associated with OAE2. changed from isotopically lighter, seepage-derived hydrocarbons to heavier organic matter derived microbial activity asevidenced by the occurrence of hydrocarbon-rich fluids from below. Zone 1waspos mode ofaccretion remain speculative. Seep carbonate formation is fuelled by asource of reduced, pervasive growth, outward, downw challenging, as the preferential growth direction of the Amma Fatma deposit is not obvious. Neither the sole occurrence ofbiphytanic diacids and the highest TOC content. Explaining these patterns is This article isprotected Allrights bycopyright. reserved. experienced much elevated temperatures during burial diagenesis (cf. Campbell calcite donot differ substantially from thoseof the matrix micrite, suggesting that neither phase (Hudson & Friedman, 1974; Raiswell & Fisher, 2000). The isotope compositions are common forconcretions that fostered compaction and cementation of the Turonian black shales andmarly limestones. most likely mechanism that sustained concretionary growth over long timescales that subsequently 2004; Mozley & Davis, 2005). Diffusive and advective transport of solutes by seeping fluids is the Acceptedzone 1(Fig. 15) is interesting. bottom The zone 1not only showsthe highest Articlenegative did not experience large temperature shifts or meteoric water input that would have produced more et al., limestones that precipitated inequilibrium with Cretaceous seawater at Mohammed Plage (cf. Kuhnt −2.9‰ also point towards precipitation close to the seafloor, as they arewithin the range ofvalues for 2009). They showno appreciable deviation throughout the body, suggesting thatpore waters In contrast, the trend toward lower Mean δ 18 O values (Hudson, 1978; Astin & Scotchman, 1988). Such fairly homogeneous oxygen δ 18 O values of the predominantly authigenic matrix micrite ranging between −2.6and ard, nor upward growth can be excluded, and assumptions on the δ 13 C values from thetopmost zone 4 to the lowermost clogged upthe pore space and reduced permeability. of organic material, and zone 1 remained the sibly affected most by these fluids, which drove 13 δ C-depleted biphytanic diacids. Fluid seepage 13 grew inshallow sediments close to the seafloor C carbonate δ 18 O values of the later-stage equant values as the dominant carbon source 13 C depletion, but also et al., 2002). seep deposit formed. macrofaunal assemblage, help to reconstruct the environmental conditions in which the Amma Fatma Amma Fatma section (Fig. 5). These observations, together with the characterisation of the higher abundances of shelf. This interpretation is supported by pronounced peaks inphosphorus content that coincide with upwelling of relatively cool, intermediate water occurred during the lower Turonian along the Tarfaya waters (Kuhnt conditionspresence isthe of top of the section within agenerally highly productiv intensification of upwelling conditions, possibly marking high productivity phases at the base and the nannoplankton, whereby ecological preferences of some species are already partly known (Eshet& trophic resources are considered the most important factors affecting thedistribution ofcalcareous (= palaeoecologically significant Foraminifera species identified at Amma Fatma are identified as high productivity-prone is conditions throughout the entire section consistent with overall high carbon burial. Another species Fatma section and lacks any systematic distributional changes, suggesting persistent high productivity Krumbach, 1986; Erba (= water productivity (Holbourn assemblages in combination with the occurrence of Almogi-Labin, 1996; Mattioli, 1997; Lüning This article isprotected Allrights bycopyright. reserved. (Holbourn suggested by theforaminiferal assemblages andsmectite-dominated clay mineral assemblages The depositional environment of Amma Fatma Plage was most likely anouter shelf setting, as Methane seepage andcarbonate precipitation in the aftermath of OAE 2

Accepted Zeugrhabdotus ArticleZeugrhabdotus et al., et al., 1999)macrofossilthe aswell as contenttheofdepositseep (see above). three The ) ) erectus erectus 2001). The co-occurrence of these three species suggests that intensified Eprolithus floralis et al., is interpreted as an indicator forhigh productivity (Roth, 1981,Roth & , Rhagodiscus splendens Eprolithus floralis 1992; Herrle,1992;2003). Thisspecies isabundant throughoutAmma the et al., 1999; ElAlbani Rhagodiscus splendens and Rhagodiscus splendens et al., , which is also considered to be an indicator for cooler and and radiolarians anddiatoms suggest high surface 1998; Herrle, 2003). The foraminiferal et al., e setting. Anadditional argument forupwelling Eprolithus floralis 1999b). Specifically, . This may indicate further at the bottom andtop parts of the . Generally, temperature and Zygodiscus Zygodiscus

concentrations between zones 1and 4(Tables 2 and 3). Rhenium EFsare the highest on average of sensitivity towards hydrogen sulphide leads to high EFs, aswell as to the large spread in EFs and total either during orshortly after deposition of the host strata, and vital information on the environmental suggest lower levels of oxygen compared to the upper part. presenceThe of productivity environment. The absence ofbenthonic macrofauna in the lower part of the body might dominated and out-competed any specialized seep-specific taxa in this shallow water and high periods of oxygenated conditions. The occurrence of marine background fauna suggests that it concentrations (Rosenthal phase and can be just as easily enriched in barely reducing conditions at very low hydrogen sulphide behaviour towards dissolved hydrogen sulphide, except that it accumulates as a separate sulphide incorporatedbe co-precipitated and byiron sulphides (Helz Mo to reduced thiomolybdate, which can bemuch more readily deposited either on organic species, or waters is linked to the presence of hydrogen sulphide that causes aspeciation change from oxidized Molybdenum, Cd,Reand U exhibit the highest EF magnitudes, which argue for changing environmental conditions during deposition (Table 3). consequently omitted from thediscussion below. Black shalebeds 7 to 13 show EFs ofvarying of the black shales as it shows the strongest correlation with Al of all trace metals, and will be marine sediments (Tribovillard analysis has been cautioned, asit is to a large degree of detrital provenance and is highlymobile in is due togeochemical changes inbottom andpore waters. The use ofCr in palaeoenvironmental – with the exception of Cr and Co–donot correlate with Alconfirms that their authigenic enrichment (Calvert & Pedersen, 1993; Algeo & Maynard, 2004; and Re,whereby the modes andmechanisms ofenrichment differ somewhat between these elements Organic-rich shales are distinctly enriched in trace metals including Cr,Mo,U,Ni, Zn, Cd,Co Cu,V, conditions can be derived by analysing the trace metal content of host black shales andlimestones. This article isprotected Allrights bycopyright. reserved. Accepted Articleanoxia (Forster & Graf, 1992; Anderson does not contradict this notion, as callianassid decapod crustaceans can tolerate extended periods of Carbonates from zone 4andthe cover bed formed underthe influence of more prolonged et al., et al., 1995). The ease of Cd1995).of ease enrichment The inanoxic sedimentshigh andits 2006). Cobalt mainly resides within the alumosilicate fraction et al., 1994; Bromley, carbonate1996). The bodyformed s. Molybdenum behaviour in sedimentary pore Brumsack, factall2006). The thatmetals trace et al., 1996). Cadmium exhibits asimilar Palaxius in the lower part part lower the in This article isprotected Allrights bycopyright. reserved. offset between authigenic minerals and the host sediment decreases the more the redox zonation is Acceptedwithin redox zones in the sediment (cf. Kasten et al., 2003; Reitz et al., 2004). However, this age via direct precipitation from bottom waters,and enrichment via theprecipitation of solid phases elements are enriched. It can therefore bedifficult to discriminate between enrichment oftrace metals a strong offset between the age ofauthigenic precipitates and the age of the sediment in which the boundaries in the sediments that often lie substantially below the sediment surface, whichmay leadto conditions, as well as sedimentary redoxconditions. Redox-sensitive metals precipitate at redox between these elements, and their lack of correlation to Al(Table 4). authigenic enrichment of Mo, Ni,Zn, and V Cdis supported by the strong positive correlation throughout zones 1 to 4 (cf. Hetzel enrichment of V, Zn, Ni and Mosuggest at least temporal euxinia at the sediment-water interface marine sediments, and does notnecessarily require dissolved sulphide. However, the combined Maynard, 2004). Vanadium canalso accumulate efficiently within the nitrate reduction zone of effectively under euxinic conditions and reside inNi-and Fe-sulphides, respectively (Algeo & conditions in zone 1 to more mildly anoxic conditions in zone 4.Nickel and Zn accumulate most combined with the concomitant increaseArticle in Ucontent fromzone 1to4 suggests a trend from euxinic Tribovillard, 2009). The decrease in Mo/U ratios, conditions, whereas the reverse is the case when pore waters are strongly sulphidic (Algeo & Emerson, 1999). It hasbeen argued that preferential U over Mouptake is an indicator for suboxic reduction zone, before or, more likely, periodically anoxicbottom waters. carbonates of zones 1 to 4 formed wereall characterized by avery shallowoxygen penetration depth potential of the ambient water (Morford presence of free hydrogen sulphide or Feor Mn (oxy)hydroxides, and is solely controlled by the redox accumulates in anoxic sediments (Crusius any trace metal. This is due toits very low crustal concentrations and the ease with which it Trace metal contents ofblack shales and limestones are governed by bottom water redox Inmodern sediments Uenrichment isobserved at redox potentials present within the Fe

Mo accumulation occurs under more reducing conditions (Morford & et al., et al., 2009). The notion that ambient water mass chemistry lead to et al., 2005). This suggests that the sediments inwhich 1996). Rhenium enrichment does notrequire the total Mo concentrations and Mo, CdandReEFs, This article isprotected Allrights bycopyright. reserved. influenced the mode of seepage inthe Cretaceous Tarfaya Basin include differential compaction and Acceptedchanges in sedimentation rates (Judd & Hovland, 2007; Suess, 2014). Relevant factors that may have seafloor sediments, including tectonic processes, thermohaline convection, sea-level changes, and the mineralogy ofauthigenic carbonate at the Amma Fatma seepas well. of the black shales did consequently not only govern the mode ofaccretion, but apparently influenced 2010; Nöthen & Kasten, 2011). The environmental conditions as constrained by trace metal analyses under the influence of strongly reducing porewaters with low sulphate concentrations (Haas botryoidal aragonite cement. Calcite precipitation at seeps is favoured over aragonite precipitation mineralogy oftheAmma Fatma seepdeposits is almost exclusively calcite, lacking any bandedand for the wider Tarfaya palaeo-shelf area (Kolonic were the shallow sediments where carbonate precipitation occurred, consistent with reconstructions assemblages to temporarily colonize the seep. Bottom water conditions were temporarily sulphidic, as interrupted by sporadic oxygenation during formation of zone 4 that enabled macrofaunal their survival altogether. Euxinic conditions occurred during all stages of carbonate precipitation, macrofaunal species at the Amma Fatma seepwere at the very least challenging, ifnot precluding distance, indicating that mostArticle of these molluscs did not live at the seep. Environmental conditions for in thin sections are severely fragmented andwere most likely transported to the site over some (Campbell & Bottjer, 1995; Kiel & Peckmann, 2007;Little compared tomost Phanerozoic seep deposits, which are usually replete in shelly macrofauna conditions, which would have hampered the formation of black shales in bed 13. within the shales and limestones. Zone 4carbonates formed underat least episodically oxygenated 4. This questions the proposition that the carbonate body grew inits entirety and simultaneously hydrogen sulphide content of the water mass, from higher contents inzone 1 to lower contents in zone euxinic bottom waters. More importantly, the distribution of Mo, U,Cdand Reimplies changes in enrichment argue for a formation ofblack shale and marly limestone beds 7 to 14 under episodic compressed in the sediment like in the case of anoxic bottom waters. Analyses of trace metal At passive continental margins various proces Despite the occurrence of macrofossils inzone 4,the Amma Fatma body ispoor in fossils et al ses control the mechanismses control the fluidof flowfrom ., 2005;Poulton et al., 2015). Most of the shells identified et al et ., 2015). The carbonate et al.,

al., reduced fluids from theunderlying organic carbon-rich source rocks towards the seafloor (cf. Suess et sediment loading onthe continental slope that can lead topore water overpressure, whichsqueezes reconstructions, all estimates reflect high sedimentation rates. Such high sedimentation rates increase 1.6 cm/kyr atMohammed Plage (Kolonic been above 10cm/kyr (Kuhnt margin sediments. Sedimentation rates in the Tarfaya Basinduring OAE2wereestimated to have Broisonia enormis due to the comparatively low pressure of the water column. presence The of shallow water species shelf water depths at Amma Fatma, which should ha ephemeral buildup of Antarctic ice sheets during that time. This is in accord with the inferred outer lowermost Turonian at Mohammed Plage wascharacterized by asea-level lowstand, linked to the the highest during theCretaceous (Haq, 2014). However, Kuhnt culminated during the earliest Turonian where sea This article isprotected Allrights bycopyright. reserved. Acceptedsea-level development during thelate Early Turonian also suggested by Hardenbol this observation as evidence for afalling sealevel through thesection corresponding tothe eustatic al. al., Articlesubsidence (Gebhardt continuously during theCenomanian due to a combination of eustatic sea-level rise andshelf early Turonian in age, and studies from the Tarfaya Basin have demonstrated that the sea level rose hemipelagic background sediments (cf. El Albani Amma Fatma Plage are indicated by intercalations of bioclastic storm bedsinto the marly, fluid flow towards the seafloor (Carson & Screaton, 1998). High-frequency sea-level changes at hydraulic2003), asthe pressure needsto exceed th sea level. Low sea levels promote seepage of fluids through thesediment column (Teichert pore water overpressure, both ofwhich are in turn controlled by sedimentation rates and changes in 2014). Taken together, favourable conditions for seepage over long timescales were apparently (1997) noted an upward increase in the frequency and thickness of the storm beds,and interpreted 1980) further suggests that a short-term shallowing event may have occurred. Finally, ElAlbani Apart from sea-level changes, sedimentation rates also affect seepage dynamics in continental and the abundance peak of et al., al., et 2004; Mort et al., 2005), or correspond to4.8 cm/kyr atwellS13 (see Fig. 2) and et al., et al., Gartnerago segmentatum 2008; Kuhnt 2005).differencesDespite the inthese et al. al. et levels were possibly upto 250 m higher thantoday, e pressure of the water column toenable upward ve promoted seepage ofhydrocarbon-rich fluids 1999b). AmmaThe Fatma coastal section is et al., et al. 2009). This sea-levelrise (2009) inferredthe that (Thierstein, 1976; Hattner et al. (1998). et al., et et et deposits formed athydrocarbon seeps, and to constrain themodes of carbonate formation. such an environment, only a combination of methods serve as an example on how toidentify seep deposits in high productivity, shallow water settings. In outcompete obligate, endemicchemosymbiotic se advantage of the vast amounts of organic matter derived from photosynthetic primary production and Diagnostic signals are masked by high primary pr marine environment. Identifying seepdeposits in point towards a high productivity setting with recurrent episodes of euxinia that shaped the shallow However, nannofossil distribution and pronounced enrichments of trace metals within the host strata Their presence testifies to the sporadic occurrence of oxygenated conditions in the bottom water. macrofossils, and those present in the uppermost zone 4are all Cretaceous shallow water species. and preservation of black shales rich in organic matter. The Amma Fatma deposit is poor in considerable length of time. High productivity andpa sedimentation rates. AmmaThe Fatma deposit formed during theaftermath ofOAE 2over a limestone formation. Persistent seepage wasprobably favoured by asea-level lowstand and high of organic matter residing in thehost black shales may have beenan additional source of carbon for anaerobic oxidation ofmethane was not the only trigger for carbonate precipitation. Remineralization This article isprotected Allrights bycopyright. reserved. Accepted Articleauthigenic carbonate formation.With of microbial communities that performed anaerobic oxidation of methane and contributed to characterizes many otherseep deposits is absent. Nonetheless, lipid biomarkers testify to the presence The Amma Fatma carbonate body isan unusual seep deposit, as seep-endemic macrofauna that CONCLUSIONS large amounts of authigenic carbonate at the Amma Fatma seep. favoured by a relative sea-level fall and high sedimentation rates, which facilitated theprecipitation of δ 13 C values ofmatrix micrite as low as −23.5‰ it appears that such a shallow water setting poses achallenge. oduction favouring heterotrophic taxa, which take ep fauna. The Amma Fatma carbonate body may will allowtoascertain that authigenic carbonate rtly euxinic conditions resulted in the deposition This article isprotected Allrights bycopyright. reserved. Anderson, R.K., Scalan, R.S., Parker, R.L., Amblés, A., Halim, M.,Jacquesy, J.C., Vitorovic, D., Algeo, T.J. Agirrezabala, L.M., Kiel, S., Blumenberg, M.,Schäfer, N., References referee are gratefully acknowledged. Comments by Sabine Kasten andthe two journal reviewers Nicolas Tribovillard and ananonymous and Eliza Howlett for access to specimens curated in the Oxford University Natural History Museum. Squires, Andrew Gale, Steffen Kiel and Jim Kennedy foradvice about macrofossil identifications, carbonate samples. CTSLthanks Louella Saul, and Matthias Zabel for help withelement analysis, and Sylvain Richoz for stable isotope analyses of sections, Susanne Gier for XRD measurements, Petra Körner for LECO measurements, Sabine Kasten ACKNOWLEDGEMENTS Arthur, M.A., Dean,W.E., AcceptedArthur, M.A., Dean,W.E., Anderson, S.J., Taylor, A.C., Algeo, T.J. Article Fuel kerogen from Timahdit shale (Y-layer) based on multistage alkaline permanganate degradation. on molybdenum-uranium covariation. W.S. Broecker.) 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, This article isprotected Allrights bycopyright. reserved. lithologies and their corresponding thickness. (Right) CaCO lines (cf. Fig. 4).(Centre) Lithostratigraphic chart of the Amma Fatma coastal section showing dashed red lines; the Amma Fatma carbonate body lies within beds 6 to 14delimited by the thick red Figure 3 and Kolonic Amma Fatma, MB=Mohammed Plage, S13,S57and S75 =drill cores described by Leine Africa. (B) Palaeogeographic map ofthe Tarfaya Basin (modified from Kolonic (B) and the small inset map inthe upper left, which indicates the location of the studied section in margin (modified from Kolonic et al., 2005). Yellow containing black shales (grey) from theC/T boundary along the northwestern African continental Figure 2 (modified from Kuypers epicontinental seas, brown areas represent dry land.Brown, thick lines delineate palaeocoastlines Tarfaya Basin, Morocco. Light blueareas represent continental plates covered by shallow Figure 1 table captionsFigure and Zwicker, J., Smrzka, D.,Gier, S.,Goedert, J.L., Acceptedhighlighting thefour zones from bottom to top and the cover bed capping thebody. arrows amongst thebeds shown inFig. 3.(B)Schematic sketch of the Amma Fatma body Figure 4 content and its carbon stable isotope composition within the corresponding beds. Article State (USA). are part of the uppermost plumbing system ofOligocene methane-seep deposits, Washington (Left) Photograph ofthe Amma Fatma outcrop section showing beds5 to 14separated by (A)Locality mapshowing the distribution of unfolded Mesozoic and Cenozoic Basins Palaeogeographical map ofthe mid-Cretaceous (~94 Ma) showing the study sitewithin the (A)Photograph of theAmma Fatma carbonate body with its four zones highlighted by et al. (2005). Mar. Petrol. Geol. et al., 2002). , 66 , 616–630. and and stars indicating the Amma Fatma section in (A), Peckmann, J. 3 content, total organic carbon (TOC) (2015) Mineralized conduits et al., 2005); AF=

(1986) This article isprotected Allrights bycopyright. reserved. light. Accepted(mq);stained thin section, plane-polarized light. microquartz (miq) and equant calcite (ec); centre of the cavity is filled by large megaquartz crystals thin section, plane-polarized light. (C) Large cavity surrounded by matrix micrite (mm), rimmed by (B) Detailed view of a cavity filled by equant calcite (ec), several mm thick clay layers (cl) to the left; plane-polarized light. Figure 10 (arrows). crystals showing peloidal micrite with faecal pellets (fp), pyrite aggregates (py) andgrey, unstained dolomite micrite (mm) surrounding agastropod shell filled by peloidal micrite (pm). (B) Stained thin section Figure 9 southwest, hammerfor scale.(C) capping thebody bends upwards, hammer forscale Figure 8 ArticleConcretionary carbonate fromzone 2penetrated by numerous carbonate veins, hammer forscale. carbonate body. (B) Acarbonate bank separating zone 2from zone 1,hammer for scale. (C) Figure 7 outline zones 1 to 4and the cover bed (cf. Fig. 4,5). lines delineate upper and lower boundaries of the Amma Fatma carbonate body; dashed red lines Figure 6 lines outline zones 1 to 4and the cover bed (cf. Fig. 4). Solid red lines delineate upper and lower boundaries of the Amma Fatma carbonate body; dashed red Figure 5 Photomicrographs ofzone 1 limestones; plane-polarized light. (A) Detritus-rich matrix Photographs from thetopmost part of the body. (A)Viewfrom northeast, the cover bed (A)Bottomof the view Amma Fatma body.The width of the image is4 m atthebase of the Trace metal enrichment factors and Mo/U ratios across the Amma Fatma section. Solid red Distribution chart of nannofossils and phosphorus content across the Amma Fatma section. Photomicrographs ofzone 2 limestones. (A) Matrix micrite (mm) surrounding alarge Palaxius faecalpelletwith rhombohedral dolomitecrystals (arrows);stained Tubular fossils from zone 4of the carbonate body, coinfor scale. (D) Same photograph as (C) in crossed-polarized (cf. Fig. 4A). (B) Same as (A), view from This article isprotected Allrights bycopyright. reserved. of right valve (KX.15696). (I) Adult Note well-developed lunule andcalcified ligament right valve (KX.15683). (G) Lucinid; detail of dorsal ma (D) Juvenile inoceramid. (E) Lucinid; right valve with partially fractured anterior margin. (F) Lucinid; outcrop had siphon broken from (but still closely associated with) the main part of the body whorl. Adult Amma Fatma section: (F-I) from collections of the Oxford University Museum, (KX U.K. codes). (A) Figure 14 cavity surrounded by matrix micrite (mm) andfilled bymicroquartz (miq) and equant calcite (ec). brown, fine-grained micrite pervaded by several veins filled by secondary equant calcite. (C) Large micrite featuringdolomite crystals (arrow)foraminifera and tests,stained thin section.Dark(B) Figure 13 calcite; plane-polarized light. (C) Same detail as (B) under fluorescent light. Close-up view ofthe seammicrite (sm), pm =peloidal micrite, miq =microquartz, ec= equant by equantcalcite (ec), arrows indicate seam micrite (sm) lining the cavity; plane-polarized light. (B) Figure 12 Close-up view ofavein rimmedmicroquartz by (miq) and filled by equant calcite (ec). surrounding veins and cracks rimmed bymicroquartz (miq) andfilled by equant calcite (ec). (C) matrix featuring abundant radiolarian tests (arrow). Figure 11 z4) andthe cover bed (cb). All values are relative to V-PDB. Figure 15 Accepted Article Drepanocheilus Representative macrofossils from Amma Fatma Plage. Carbonate body: (A-E); bed2 Photomicrographs ofzone 4 limestones. (A) Peloidal micrite (pm) surrounding avoid filled Photomicrographs ofzone 3 limestones; plane-polarized light. (A) Microcrystalline calcite Carbon and oxygen stable isotope cross-plot of Photomicrographs of the cover bed; plane-polarized light. (A) Close-up view ofmatrix sp. (B) Juvenile Drepanocheilus Drepanocheilus (KX.15684). (H)Inoceramid, oblique dorsal view (B) Peloidal micrite with faecal pellets (fp) sp. (KX.15683). All scales = 5mm. sp. (C) Possible neogastropod; specimen at rgin ofarticulated specimen, anterior to right. carbonate phases from zones 1to 4 (z1 to This article isprotected Allrights bycopyright. reserved. decalcification; numbers 0 to 3refer to the biphytanic diacids BP-0 toBP-3, their Carboxylic acids from 1before zone decalcification. (D) Carboxylic acids from zone 1after cover bedbefore decalcification. (B) Carboxylic ac decalcification (intracrystalline compounds), IS = samples before decalcification (intercrystalline compounds) and from theresidual powders after Figure 16 indicated in parentheses and areversus V-PDB. Accepted Article Gas chromatograms (total ion currents) of the carboxylic acid fractions from total rock internal standard. (A) Carboxylic acids from the ids from the coverids fromafterthe bed decalcification. (C) δ 13 C values are total organic carbon (TOC) content (both in %). This article is protected All rights bycopyright. reserved. 1. Table Depth [m] Depth

Accepted8.20 8.39 8.67 9.35 9.91 10.2 10.4 10.6 10.7 10.8 10.9 11.1 11.2 11.7 12.1 12.3 12.4 12.9 13.0 13.1 Article13.3 13.4 13.5 Total concentrations of all measured elements of the Amma Fatma black shale section. All data are given in ppm except depth (i CaCO 31.7 21.9 11.3 3.62 3.48 14.0 34.0 47.4 49.1 28.4 21.2 37.6 28.8 29.7 33.3 36.4 19.5 27.7 19.9 18.9 34.6 10.0 2.7 3 [%] TOC [%] 0.064 0.093 0.068 0.231 6.03 3.45 2.37 5.09 6.46 6.54 6.07 5.67 5.43 3.78 4.37 5.32 6.28 2.51 5.59 5.47 4.13 5.66 3.62 1006 1066 1065 1786 1158 60.0 779 918 498 170 116 597 785 647 793 833 473 550 421 614 501 426 342 Ti 11637 13497 10620 12000 13631 14505 13377 22793 11564 15361 11928 7031 2556 1695 7754 9490 7043 9047 9278 8446 6792 6342 967 Al Al 76.1 80.8 55.6 37.7 76.5 53.4 76.2 63.3 72.1 85.0 88.5 82.4 85.2 64.2 60.0 57.7 81.5 54.3 60.6 52.3 43.7 108 664 Ba Ba 242917 239388 279359 303607 346508 245794 229982 244942 234427 251781 253042 240279 188394 363527 243988 276795 263207 211050 264626 252778 284508 279035 293386 Ca Ca 11925 5315 6821 3260 3220 4745 4457 6510 5493 6787 6123 5638 2912 4937 8242 4559 6346 4474 3381 2946 548 781 523 Fe 5620 5831 3950 1959 1229 4770 5950 4428 5709 6760 6767 6743 9355 5432 4008 4656 7054 4146 5416 4613 4069 3567 513 K 19351 23383 14793 30725 17944 10286 12893 13487 12459 14798 18824 14622 16448 10626 8324 6814 3699 8186 9411 7795 9189 8796 9149 Mg Mg 59.6 75.9 54.0 27.7 31.5 70.2 60.0 49.0 65.3 65.9 66.6 70.0 38.4 58.9 36.3 42.4 81.5 38.4 44.7 46.1 35.0 41.7 102 Mn Mn 1103 1419 683 613 609 142 131 262 469 557 505 616 830 633 612 122 522 613 724 735 438 528 716 P 59.5 41.1 31.6 18.2 6.61 21.7 46.9 51.9 63.9 59.3 62.2 53.9 58.8 4.61 46.1 39.7 40.6 43.4 46.6 40.8 34.5 35.3 28.6 Cr 19.1 13.0 5.18 2.27 3.44 3.57 9.46 15.9 18.9 8.54 13.2 17.1 18.6 3.00 22.7 13.2 26.4 23.3 23.4 23.9 20.7 22.6 10.3 Mo Mo 52.9 42.5 19.2 5.86 5.30 26.5 56.7 73.2 82.6 52.3 45.7 54.5 56.0 6.89 68.8 55.8 78.0 59.8 62.4 63.1 53.8 67.5 44.6 Ni 87.7 45.2 14.5 13.9 55.9 84.9 10.7 78.3 79.8 75.5 40.2 127 136 190 197 114 150 115 119 133 146 111 139 Zn 24.6 11.9 5.28 5.66 3.08 8.11 12.1 18.4 23.0 15.3 18.0 17.5 15.5 1.90 15.4 11.9 13.4 11.3 12.7 11.6 10.7 13.7 10.6 Cu Cu 48.3 13.8 31.8 86.2 97.7 93.1 148 150 127 135 160 127 170 185 160 106 161 246 192 206 183 154 38 V 2.99 2.77 3.27 1.56 1.17 1.54 2.89 3.06 4.00 2.73 3.22 3.31 4.30 1.04 2.95 2.11 2.59 3.12 2.32 2.42 1.76 2.04 2.07 Pb Pb 11.6 13.0 9.52 5.67 11.5 7.68 12.4 10.8 13.3 10.3 11.9 11.4 15.1 3.06 9.22 7.11 7.31 9.04 8.87 9.41 7.38 7.13 7.19 As As 1.62 1.47 3.07 1.83 1.38 1.37 2.97 3.96 3.89 2.25 1.70 4.96 2.67 1.02 2.39 2.80 3.12 1.76 3.03 2.10 2.14 2.55 1.36 Cd Cd n m), CaCO 2.29 2.67 2.90 1.14 1.13 2.13 2.45 2.48 3.13 3.05 3.06 2.72 4.58 1.06 2.49 1.97 2.27 3.13 1.95 2.51 2.12 2.00 1.97 Co Co 0.050 0.020 0.030 0.030 0.040 0.020 0.030 0.030 0.060 0.040 0.050 0.040 0.030 0.020 0.090 0.060 0.110 0.020 0.050 0.060 0.040 0.100 0.050 Re Re 3 and 0.756 7.67 6.41 6.37 5.20 1.86 6.39 7.31 9.58 9.04 5.07 6.34 7.96 5.54 9.39 8.99 8.47 6.14 8.01 9.15 8.73 9.05 9.93 U This article is protected All rights bycopyright. reserved. 2.42 2.47 2.52 2.62 2.65 3.14 3.48 3.62 3.91 4.08 4.23 4.55 4.75 4.78 4.85 4.92 5.44 5.82 5.93 6.05 6.88 6.94 7.00 7.13 7.22 7.45 7.69 7.87 8.07 Accepted Article6.5 7.8 59.3 56.9 57.1 37.9 37.8 5.70 20.6 17.9 36.0 29.1 37.4 14.7 37.1 72.8 38.0 61.2 11.7 29.5 33.0 23.2 44.3 70.9 90.3 43.4 21.3 10.8 15.4 17.9 25.1 21.8 5.5 6.90 5.75 6.61 3.75 5.11 1.05 4.02 3.20 5.01 6.10 6.10 1.46 4.29 6.73 4.48 8.09 1.12 4.77 6.34 4.96 1.00 5.26 6.45 8.00 5.94 4.08 1.17 4.15 5.20 7.63 6.51 1405 1508 1557 1130 1623 1139 1057 1029 888 335 918 549 423 193 506 467 251 351 509 920 570 422 220 972 969 846 485 995 452 526 602 20537 21271 22446 13315 16500 23868 16723 13538 13799 15136 14450 13749 14959 11967 14670 10743 4713 8718 6121 3026 7904 7096 4097 5401 7378 8509 6315 3212 7054 6305 9544 81.0 94.2 92.1 77.5 63.0 66.4 56.0 61.0 58.7 44.5 55.4 82.0 61.6 58.2 39.5 85.1 80.3 79.2 85.1 84.7 81.4 55.8 96.0 79.3 112 117 114 124 124 107 134 180636 180611 169364 220796 222161 348899 209749 280049 258689 294824 307471 336650 304941 296750 330172 300061 312712 260758 291161 303839 354767 247997 246417 243523 245875 277504 301984 236752 289013 259113 268301 10620 11811 12514 11962 6738 8856 2432 8198 6963 3456 2695 1400 3895 3893 1950 2429 3433 6191 3829 2701 1272 7506 7215 6853 7350 4594 2927 6152 2794 4782 3827 7893 8226 8565 5278 6632 1764 8254 5923 4864 3196 2839 1634 3588 3377 2190 2891 3224 5599 3824 3090 1392 5896 5654 5450 5747 4909 3015 5843 3134 4902 4640 15405 16347 17283 12784 15091 16204 13293 14672 12375 10794 14255 13140 11185 10053 18177 7141 7015 7314 6612 7617 8959 9423 7684 7409 5525 9233 9414 9045 7930 8169 9738 70.7 80.2 82.3 58.9 68.3 40.0 93.5 81.8 61.5 33.8 33.8 41.6 53.6 45.8 31.7 32.0 50.9 66.6 41.8 35.6 40.7 59.3 54.8 49.5 54.0 52.9 43.0 68.2 36.4 41.0 43.7 1083 1122 850 846 974 628 730 198 501 504 604 482 704 358 662 956 574 753 250 515 550 610 199 857 930 695 197 426 583 688 825 55.3 71.7 55.7 35.1 43.7 13.3 80.6 41.1 46.6 40.6 41.1 15.2 37.1 45.1 38.8 48.6 19.5 49.1 36.4 38.2 11.9 55.5 55.0 59.3 55.8 46.0 19.1 53.7 38.2 59.7 51.0 36.7 37.5 35.1 21.4 27.0 4.46 16.2 14.0 21.4 19.0 14.2 3.67 19.8 28.3 16.9 22.7 5.40 16.8 15.7 13.9 3.74 25.4 31.4 36.7 25.1 10.6 6.01 10.8 13.1 23.6 19.2 122.0 84.6 84.5 84.4 58.7 73.3 15.0 44.7 39.9 61.4 51.0 63.9 18.5 64.1 94.6 62.5 96.5 17.2 53.3 63.4 52.6 12.6 78.6 99.2 85.5 44.9 14.0 32.1 40.2 55.2 47.4 22.8 82.5 71.5 59.0 46.8 92.9 22.1 85.2 43.3 61.7 71.6 87.2 238 228 229 152 151 144 117 150 149 292 152 245 118 132 177 284 361 174 101 20.2 18.6 19.3 12.2 16.1 4.10 15.4 12.1 13.8 13.5 13.2 4.98 11.9 15.9 11.2 16.0 5.33 13.8 14.7 12.5 4.29 17.4 20.3 25.0 19.8 11.8 6.67 13.0 13.2 19.2 16.5 78.4 83.2 40.4 88.2 64.6 57.5 98.8 389 414 428 296 362 190 157 199 150 124 194 231 161 173 121 108 254 322 403 247 121 107 167 135 5.03 4.61 4.76 3.05 4.11 1.81 4.00 3.20 3.67 3.79 2.79 2.24 3.08 3.34 2.72 3.25 2.13 3.19 3.14 2.53 1.54 4.46 4.21 4.27 4.03 2.48 2.01 3.10 2.10 3.14 2.69 17.5 18.4 18.7 10.4 13.8 5.71 17.0 12.9 11.2 8.14 7.10 4.18 6.95 8.76 5.43 7.90 6.66 11.1 7.80 7.17 4.88 13.0 12.6 12.3 11.9 8.63 7.05 9.98 7.82 10.7 8.86 4.93 4.93 6.54 2.79 3.60 0.98 2.13 2.04 4.18 3.02 4.57 1.72 5.29 7.55 4.80 5.75 1.90 3.01 3.29 2.56 1.42 4.32 6.89 8.24 4.87 5.10 1.32 1.52 1.64 1.69 1.60 3.90 4.20 4.18 2.82 3.32 1.56 4.05 3.02 2.93 2.02 2.14 1.51 2.39 2.50 1.96 2.18 2.27 3.04 2.31 2.16 1.38 3.23 3.42 3.55 3.62 2.87 1.55 2.56 1.74 2.09 1.90 0.030 0.030 0.110 0.060 0.030 0.020 0.040 0.010 0.050 0.020 0.050 0.020 0.050 0.050 0.050 0.060 0.020 0.030 0.050 0.060 0.020 0.160 0.220 0.150 0.080 0.030 0.002 0.040 0.020 0.040 0.040 8.98 9.19 9.49 5.86 7.12 1.64 5.41 5.16 6.93 7.12 8.24 2.54 5.96 7.76 6.80 8.54 1.70 5.20 6.48 7.66 1.97 9.70 9.57 12.2 9.35 5.95 2.40 5.61 7.87 10.1 9.77 This article is protected All rights bycopyright. reserved. 0.030 0.730 0.920 0.960 0.990 Accepted Article1.02 1.15 1.18 1.24 2.09 2.14 2.23 2.33 44.9 21.5 35.5 42.0 71.5 53.9 87.1 42.6 59.0 52.1 52.1 41.7 29.6 4.43 4.75 5.87 5.15 6.32 5.09 6.10 4.81 5.83 7.33 8.47 6.90 4.99 1148 1428 1708 1538 1459 1534 1479 1424 1333 672 649 624 652 16750 21727 26651 23965 23156 24136 23513 22475 20823 10629 10269 9153 8907 89.4 76.6 74.0 75.6 92.3 107 116 109 105 109 108 103 101 207076 184326 156833 193622 186532 192277 186148 203908 199540 257256 257396 268239 272670 11082 12810 10423 10952 11533 11410 10222 10035 6587 3916 4016 4562 4273 5357 6854 8534 7714 7669 7682 7741 7184 6974 4515 4293 3946 4067 13574 20359 19272 21246 19396 22088 18097 19995 10505 9817 7951 6995 7994 57.9 72.0 80.0 73.0 75.9 75.2 80.7 65.7 71.9 38.8 35.9 44.6 47.3 1329 440 554 473 651 513 722 466 621 484 510 849 706 67.20 54.8 53.4 66.2 63.8 65.4 65.3 59.1 62.8 48.6 47.5 37.5 35.4 28.76 10.0 25.2 30.6 34.9 27.6 36.9 25.1 31.4 22.4 30.8 29.6 18.3 86.6 47.4 68.0 72.6 82.0 71.5 85.6 53.5 67.9 78.4 88.5 67.6 44.1 86.0 180 142 168 286 216 349 170 236 209 208 167 118 23.2 14.8 16.5 19.1 19.9 18.0 20.0 17.0 18.1 16.6 18.6 16.7 11.3 302 106 274 299 343 306 380 299 332 244 267 222 198 5.74 3.11 4.24 4.99 4.98 4.88 5.02 4.92 4.53 3.21 3.22 3.49 2.90 22.3 12.2 16.3 17.7 16.2 16.9 16.6 17.4 14.6 10.7 10.0 9.78 8.26 4.27 1.70 3.22 3.38 6.46 5.01 7.03 2.80 5.21 3.75 4.38 3.75 2.23 4.70 3.08 3.83 4.39 3.86 4.24 4.18 3.40 3.49 2.27 2.34 2.06 2.05 0.040 0.020 0.040 0.030 0.030 0.020 0.020 0.002 0.010 0.090 0.070 0.070 0.050 6.71 9.73 7.99 5.48 6.20 5.31 6.54 4.49 5.46 8.40 8.37 9.17 6.57 This article is protected All rights bycopyright. reserved. comparison. 2. Table 10 Beds Accepted6 Article 13 14 9 ̶ 8 ̶ 12 Mean element concentrations in ppm of black shale beds. The stratigraphically corresponding zones of the carbonate body are in Cover bed Zone 1 2 3 4 11504 11066 5817 9541 4794 Al 34.0 41.2 43.2 50.5 24.9 Cr Cr 16.1 15.5 19.9 16.5 3.72 Mo Mo 58.9 56.5 65.2 45.1 12.5 Ni 89.3 29.9 157 114 164 Zn 10.9 13.6 15.0 16.4 5.47 Cu Cu 87.4 147 106 210 134 V 4.50 2.96 4.60 1.59 2.45 Cd Cd 2.13 2.50 2.81 2.21 2.02 Co Co 0.042 0.047 0.095 0.035 0.030 Re Re 5.55 6.45 7.30 7.91 5.78 U dicated for 592 558 726 636 376 P 0.625 Mo/U Mo/U 2.79 2.49 2.54 2.07 This article is protected All rights bycopyright. reserved. The stratigraphically corresponding zones of the carbonate body are indicated for comparison. 3. Table

Accepted 10 Article Beds Beds 6 13 14 9 12 ̶ 8 ̶ Mean major and trace element enrichment factors of black shale beds. Cover bed Cover bed Zone 1 2 3 4 6.06 6.06 4.52 3.60 4.69 5.67 Cr 94.6 94.6 59.4 53.7 54.3 27.5 Mo Mo 13.6 13.6 8.48 6.71 5.69 3.25 Ni Ni 26.0 26.0 12.0 11.8 7.95 5.61 Zn 3.85 3.85 3.06 2.50 3.09 2.90 Cu 18.2 18.2 8.00 11.9 8.63 12.5 V 87.9 87.9 37.1 43.1 17.2 63.4 Cd 0.956 0.956 1.81 1.81 1.29 1.22 1.99 Co 67.5 67.5 51.5 64.2 28.7 70.4 Re 24.4 24.4 18.6 14.5 18.7 35.0 U This article is protected All rights bycopyright. reserved. The stratigraphically corresponding zones of the carbonate body are indicated for comparison. 4. Table Beds Beds 6 10 12 13 14 9

Accepted8 ̶ Article ̶ Mean correlation coefficients of major and trace elements of black shale beds. Cover Zone bed 1 2 3 4

Al:Cr 0.27 0.27 0.91 0.98 0.35 0.95

Al:Mo -0.25 -0.25 0.39 0.39 0.93 0.84 0.85

-0.18 -0.18 -0.25 Al:Ni 0.24 0.24 0.85 0.99

Al:Zn 0.24 0.24 0.44 0.74 0.01 0.99

Al:Cu -0.06 -0.06 0.29 0.29 0.41 0.89 0.51

0.26 0.26 0.93 0.79 0.27 0.99 Al:V

Al:Cd -0.67 -0.67 0.37 0.37 0.41 0.79 0.99

Al:Co 0.92 0.92 0.99 0.96 0.95 0.99

Al:Re -1.00 -1.00 -0.62 0.19 0.19 0.73 0.29

-0.98 -0.98 -0.58 0.10 0.10 0.91 0.80 Al:U

Cr:Cu Cr:Cu 0.98 0.98 0.00 0.94 0.77 0.76

Mo:Ni Mo:Ni 0.97 0.97 0.20 0.99 0.94 0.90

Mo:Zn Mo:Zn 0.96 0.96 0.74 0.97 0.70 0.91

Mo:V Mo:V 0.95 0.95 1.00 0.99 0.75 0.75

Ni:Zn Ni:Zn 0.97 0.97 0.81 0.97 0.86 1.00

0.99 0.99 Zn:V 0.89 0.89 0.73 0.74 0.96

Zn:Cd 0.93 0.93 0.96 0.96 1.00 0.38 0.97 This article isprotected Allrights bycopyright. reserved. Accepted Article bed. 5. Table Sample M-17 M-17 M-11 M-20 M-06 M-03 M-01

Total organic carbon (TOC) content of the zones of the carbonate body including the cover Cover Bed Cover Bed Zone 1 Zone 3 Zone 4 Zone

TOC% 0.59 0.59 0.69 0.45 0.13 0.13 0.12

TIC% 7.65 7.65 7.59 7.75 8.02 8.23 8.36

TC% 8.24 8.24 8.28 8.20 8.15 8.36 8.48

This article is protected All rights bycopyright. reserved. relative percentages of all carboxylic acids, 6. Table

Hopanoic acids ( acids Hopanoic Accepted 2322.2 rock] [ng/g of all acids Sum carboxylic Article Iso- Short-chain Short-chain Long-chain Long-chain Short-chain Short-chain Long-chain Long-chain Biphytanic diacids (bp 0-3) diacids Biphytanic decalcification Before/after & Contents and compound-specific stable carbon isotope values of carboxylic acids. Summed up values are in ng/g rock, grouped li anteiso- n n Sample α α Others Others fatty acids (15 & 17) -fatty acids (26-32) acids -fatty -fatty acids (14-18) acids -fatty , , αβ ω ω -diacids (25-28) -diacids -diacids (14-24) -diacids 31/32 & ββ 31/32) 87% (−30‰)87% 5% (n.m.) Before 8% δ 0 0 0 0 0 13 C values in parentheses are in ‰ relative to V-PDB. V-PDB. to relative ‰ in are parentheses in values C Cover Bed Cover Bed 58% (−30‰)58% <1% (n.m.) <1% 3% (n.m.) 4% (n.m.) 2% (n.m.) 4% (n.m.) 1117.3 1117.3 After 29% 0 88% (−30‰)88% 2% (n.m.) 2235.4 2235.4 Before 10% 0 0 0 0 0 Zone 4 58% (−31‰)58% 9% (−31‰)9% 2% (n.m.) 3% (n.m.) 3% (n.m.) 1% (n.m.) 4640.5 4640.5 After 25% 0 76% (−31‰)76% 5% (−32‰)5% 1% (n.m.) 3149.1 3149.1 Before 18% 0 0 0 0 Zone 3 31 (−31‰) 28 (−30‰) 4886.9 4886.9 After 40 0 0 0 0 0 68% (−30‰)68% 6% (−31‰)6% 2% (n.m.) 1% (n.m.) 3191.8 3191.8 Before 23% 0 0 0 pid contents are in Zone 1 17% (−31‰)17% (−30‰)35% 3% (−66‰)3% 1% (n.m.) 5% (n.m.) 3% (n.m.) 5925.5 5925.5 After 36% 0 This article isprotected Allrights bycopyright. reserved. Accepted Article

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