Skip to main content

Advertisement

SpringerLink
Log in

Preservation of 34S-enriched sulfides in fossil sulfate-methane transition zones: new evidence from Miocene outcrops of the northern Apennines (Italy)

  • Original
  • Published:
Geo-Marine Letters Aims and scope Submit manuscript

Abstract

We provide new evidence of the preservation of 34S-enriched signals in methane seep-impacted sediments from two onshore Miocene outcrops located in the northern Apennines (Italy). Selected outcrops include methane-derived authigenic carbonates (MDAC) with δ13C composition between − 42.3 and − 18.2‰. MDACs contain chemosynthetic clams and abundant pyrite indicative of formation close to or within a shallow sulfate-methane transition zone (SMTZ). This study aims to evaluate the relative contributions of background organic matter mineralization and anaerobic oxidation of methane (AOM) to sulfate consumption and to gain insight into the transport process (i.e., diffusion, advection) controlling the depth of the SMTZ. Host sediments were investigated by CHN elemental analysis coupled with total sulfur (TS) and sulfur isotopic measurements on bulk samples. Total organic carbon (TOC) measurements reveal a consistent and low amount of organic carbon (TOC< 0.5%), with no notable difference between the underlying turbidites and the stratigraphic intervals hosting the MDACs. The TS/TOC ratio of most samples is well above the baseline value of deposition under normal marine conditions, suggesting the excess TS here is due to enhanced sulfate reduction. The samples show bulk δ34S values commonly enriched (> 0‰ and up to + 17.1‰), which is characteristic of sulfides precipitated in association with AOM. We propose that advection of methane-rich fluids was responsible for maintaining the shallow depth of the studied paleo-SMTZs. AOM at paleo-SMTZ positions in the investigated seep-impacted sediments resulted in excess bicarbonate and sulfide production, favoring solid-phase MDAC and iron sulfide precipitation.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7
Fig. 8
Fig. 9

Similar content being viewed by others

References

  • Argentino C, Conti S, Crutchley GJ, Fioroni C, Fontana D, Johnson JE (2019a) Methane-derived authigenic carbonates on accretionary ridges: Miocene case studies in the northern Apennines (Italy) compared with modern submarine counterparts. Mar Pet Geol 102:860–872

    Google Scholar 

  • Argentino C, Lugli F, Cipriani A, Conti S, Fontana D (2019b) A deep fluid source of radiogenic Sr and highly dynamic seepage conditions recorded in Miocene seep carbonates of the northern Apennines (Italy). Chem Geol 522:135–147

    Google Scholar 

  • Argnani A, Ricci Lucchi F (2001) Tertiary silicoclastic turbidite systems of the Northern Apennines. In: Vai F, Martini I (eds) Anatomy of an Orogen: The Apennines and Adjacent Mediterranean Basins. Springer, Dordrecht, pp 327–349

    Google Scholar 

  • Bailey JV, Raub TD, Meckler AN, Harrison BK, Raub TM, Green AM, Orphan VJ (2010) Pseudofossils in relict methane seep carbonates resemble endemic microbial consortia. Palaeogeogr Palaeoclimatol Palaeoecol 285(1–2):131–142

    Google Scholar 

  • Baker PA, Kastner M (1981) Constraints on the formation of sedimentary dolomite. Science 213(4504):214–216

    Google Scholar 

  • Berner RA (1982) Burial of organic carbon and pyrite sulfur in the modern ocean: its geochemical and environmental significance. Am J Sci 282. https://doi.org/10.2475/ajs.282.4.451

  • Berner RA (1984) Sedimentary pyrite formation: an update. Geochim Cosmochim Acta 48:605–615

    Google Scholar 

  • Boetius A, Wenzhöfer F (2013) Seafloor oxygen consumption fuelled by methane from cold seeps. Nat Geosci 6:725–734

    Google Scholar 

  • Bohrmann G, Suess E, Greinert J, Teichert B, Naehr T (2002) Gas hydrate carbonates from Hydrate Ridge, Cascadia convergent margin: indicators of near-seafloor clathrate deposits. In: Fourth Intern. Conf. Gas Hydrates, Yokohama, Japan, pp 102–107

    Google Scholar 

  • Bojanowski MJ, Kędzior A, Porębski SJ, Radzikowska M (2019) Origin and significance of early-diagenetic calcite concretions and barite from Silurian black shales in the East European Craton, Poland. Acta Geol Pol 69(3):403–430

    Google Scholar 

  • Borowski WS, Paull CK, Ussler W III (1996) Marine pore-water sulfate profiles indicate in situ methane flux from underlying gas hydrate. Geology 24(7):655–658

    Google Scholar 

  • Borowski WS, Rodriguez NM, Paull CK, Ussler W (2013) Are 34S-enriched authigenic sulfide minerals a proxy for elevated methane flux and gas hydrates in the geologic record? Mar Pet Geol 43:381–395

    Google Scholar 

  • Böttcher ME, Smock AM, Cypionka H (1998) Sulfur isotope fractionation during experimental precipitation of iron (II) and manganese (II) sulfide at room temperature. Chem Geol 146(3–4):127–134

    Google Scholar 

  • Brand U, Veizer J (1980) Chemical diagenesis of a multicomponent carbonate system; 1, Trace elements. J Sediment Res 50(4):1219–1236

    Google Scholar 

  • Burdige DJ (2007) Preservation of organic matter in marine sediments: controls, mechanisms, and an imbalance in sediment organic carbon budgets? Preservation of organic matter in marine sediments: controls, mechanisms, and an imbalance in sediment organic carbon Bud. Chem Rev 107:467–485

    Google Scholar 

  • Caldwell SL, Laidler JR, Brewer EA, Eberly JO, Sandborgh SC, Colwell FS (2008) Anaerobic oxidation of methane: mechanisms, bioenergetics, and the ecology of associated microorganisms. Environ Sci Technol 42:6791–6799

    Google Scholar 

  • Canfield DE (1993) Organic matter oxidation in marine sediments. Interact. C, N, P S. Biogeochem Cycles Glob Chang I:333–363

  • Canfield DE, Thamdrup B (1994) The production of 34S-depleted sulfide during bacterial disproportionation of elemental sulfur. Science 266(5193):1973–1975

    Google Scholar 

  • Capozzi R, Picotti V (2010) Spontaneous fluid emissions in the Northern Apennines: geochemistry, structures and implications for the petroleum system. Geol Soc Lond Spec Publ 348(1):115–135

    Google Scholar 

  • Carminati E, Doglioni C (2012) Alps vs. Apennines: the paradigm of a tectonically asymmetric Earth. Earth-Sci Rev 112(1–2):67–96

    Google Scholar 

  • Cavalazzi B, Barbieri R, Cady SL, George AD, Gennaro S, Westall F, Lui A, Canteri R, Rossi AP, Ori GG, Taj-Eddine K (2012) Iron-framboids in the hydrocarbon-related Middle Devonian Hollard Mound of the Anti-Atlas mountain range in Morocco: evidence of potential microbial biosignatures. Sediment Geol 263:183–193

    Google Scholar 

  • Chatterjee S, Dickens GR, Bhatnagar G, Chapman WG, Dugan B, Snyder GT, Hirasaki GJ (2011) Pore water sulfate, alkalinity, and carbon isotope profiles in shallow sediment above marine gas hydrate systems: a numerical modeling perspective. J Geophys Res Solid Earth 116(B9)

  • Conti S, Fontana D, Lucente CC (2008) Authigenic seep-carbonates cementing coarse-grained deposits in a fan-delta depositional system (Middle Miocene, Marnoso-arenacea Formation, Central Italy). Sedimentol 55(2):471–486

    Google Scholar 

  • Conti S, Fontana D, Mecozzi S, Panieri G, Pini GA (2010) Late Miocene seep-carbonates and fluid migration on top of the Montepetra intrabasinal high (Northern Apennines, Italy): relations with synsedimentary folding. Sediment Geol 231:41–54

    Google Scholar 

  • Conti S, Fioroni C, Fontana D (2017) Correlating shelf carbonate evolutive phases with fluid expulsion episodes in the foredeep (Miocene, northern Apennines, Italy). Mar Pet Geol 79:351–359

    Google Scholar 

  • Curtis C (1987) Mineralogical consequences of organic matter degradation in sediments: inorganic/organic diagenesis. Mar Clastic Sedimentol 6:108–123

    Google Scholar 

  • Fan LF, Lin S, Hsu CW, Tseng YT, Yang TF, Huang KM (2018) Formation and preservation of authigenic pyrite in the methane dominated environment. Deep Sea Res Part I Oceanogr Res Pap 138:60–71

    Google Scholar 

  • Feng D, Chen D, Qi L, Roberts HH (2008) Petrographic and geochemical characterization of seep carbonate from Alaminos Canyon, Gulf of Mexico. Chin Sci Bull 53(11):1716–1724

    Google Scholar 

  • Folk RL (1974) The natural history of crystalline calcium carbonate; effect of magnesium content and salinity. J Sediment Res 44(1):40–53

    Google Scholar 

  • Formolo MJ, Lyons TW (2013) Sulfur biogeochemistry of cold seeps in the Green Canyon region of the Gulf of Mexico. Geochim Cosmochim Acta 119:264–285

    Google Scholar 

  • Froelich P, Klinkhammer GP, Bender ML, Luedtke NA, Heath GR, Cullen D, Dauphin P, Hammond D, Hartman B, Maynard V (1979) Early oxidation of organic matter in pelagic sediments of the eastern equatorial Atlantic: suboxic diagenesis. Geochim Cosmochim Acta 43(7):1075–1090

    Google Scholar 

  • Greinert J, Bohrmann G, Suess E (1999) Gas hydrate-associated carbonates and methane-venting at hydrate ridge: classification, distribution, and origin of authigenic lithologies. In: Paul CK, Dillon WP (eds) Natural Gas Hydrates: Occurrence, Distribution, and Detection, Geophys Monogr, vol 124, pp 99–114

    Google Scholar 

  • Grillenzoni C, Monegatti P, Turco E, Conti S, Fioroni C, Fontana D, Salocchi AC (2017) Paleoenvironmental evolution in a high-stressed cold-seep system (Vicchio Marls, Miocene, northern Apennines, Italy). Palaeogeogr Palaeoclimatol Palaeoecol 487:37–50

    Google Scholar 

  • Hensen C, Zabel M, Pfeifer K, Schwenk T, Kasten S, Riedinger N, Schulz HD, Boetius A (2003) Control of sulfate pore-water profiles by sedimentary events and the significance of anaerobic oxidation of methane for the burial of sulfur in marine sediments. Geochim Cosmochim Acta 67:2631–2647

    Google Scholar 

  • Hu CY, Frank Yang T, Burr GS, Chuang PC, Chen HW, Walia M, Chen NC, Huang YC, Lin S, Wang Y, Chung SH, Huang CD, Chen CH (2017) Biogeochemical cycles at the sulfate-methane transition zone (SMTZ) and geochemical characteristics of the pore fluids offshore southwestern Taiwan. J Asian Earth Sci 149:172–183

    Google Scholar 

  • Irwin H, Curtis C, Coleman M (1977) Isotopic evidence for source of diagenetic carbonates formed during burial of organic-rich sediments. Nature 269(5625):209

    Google Scholar 

  • Johnson CA, Slack JF, Dumoulin JA, Kelley KD, Falck H (2018) Sulfur isotopes of host strata for Howards Pass (Yukon–Northwest Territories) Zn-Pb deposits implicate anaerobic oxidation of methane, not basin stagnation. Geology 46(7):619–622

    Google Scholar 

  • Jørgensen BB, Kasten S (2006) Sulfur cycling and methane oxidation. Mar Geochem 2:271–310

    Google Scholar 

  • Jørgensen BB, Böttcher ME, Lüschen H, Neretin LN, Volkov II (2004) Anaerobic methane oxidation and a deep H2S sink generate isotopically heavy sulfides in Black Sea sediments. Geochim Cosmochim Acta 68:2095–2118. https://doi.org/10.1016/j.gca.2003.07.017

    Article  Google Scholar 

  • Judd A, Hovland M (2009) Seabed Fluid Flow: the Impact on Geology, Biology and the Marine Environment. Cambridge University Press

  • Judd A, Noble-James T, Golding N, Eggett A, Diesing M, Clare D, Silburn B, Duncan G, Field L, Milodowski A (2019) The Croker Carbonate Slabs: extensive methane-derived authigenic carbonate in the Irish Sea-nature, origin, longevity and environmental significance. Geo-Mar Lett:1–16. https://doi.org/10.1007/s00367-019-00584-0

  • Larson AC, Von Dreele RB (1994) General Structure Analysis System (GSAS). Report LAUR, 86–748

  • Lash GG (2015) Pyritization induced by anaerobic oxidation of methane (AOM)–An example from the Upper Devonian shale succession, Western New York, USA. Mar Pet Geol 68:520–535

    Google Scholar 

  • Lash GG (2018) Significance of stable carbon isotope trends in carbonate concretions formed in association with anaerobic oxidation of methane (AOM), Middle and Upper Devonian shale succession, Western New York State, USA. Mar Pet Geol 91:470–479

    Google Scholar 

  • Latour P, Hong W, Sauer S, Sen A, Iii WPG (2018) Dynamic interactions between iron and sulfur cycles from Arctic methane seeps. Biogeosci Discuss 2018:1–48

    Google Scholar 

  • Libes SM (2009) Introduction to Marine Biogeochemistry, 2nd edn. Elsevier, Academic Press, pp 169–324

  • Lin Q, Wang J, Taladay K, Lu H, Hu G, Sun F, Lin R (2016) Coupled pyrite concentration and sulfur isotopic insight into the paleo sulfate-methane transition zone (SMTZ) in the northern South China Sea. J Asian Earth Sci 115:547–556

    Google Scholar 

  • Lyons TW, Berner RA (1992) Carbon-sulfur-iron systematics of the uppermost deep-water sediments of the Black Sea. Chem Geol 99(1–3):1–27

    Google Scholar 

  • Mambelli S, Brooks PD, Sutka R, Hughes S, Finstad KM, Nelson JP, Dawson TE (2016) High-throughput method for simultaneous quantification of N, C and S stable isotopes and contents in organics and soils. Rapid Commun Mass Spectrom 30(15):1743–1753

    Google Scholar 

  • Meyers PA (1994) Preservation of elemental and isotopic source identification of sedimentary organic matter. Chem Geol 114(3–4):289–302

    Google Scholar 

  • Milucka J, Ferdelman TG, Polerecky L, Franzke D, Wegener G, Schmid M, Lieberwirth I, Wagner M, Widdel F, Kuypers MMM (2012) Zero-valent sulphur is a key intermediate in marine methane oxidation. Nature 491:541–546

    Google Scholar 

  • Naehr TH, Rodriguez NM, Bohrmann G, Paull CK, Botz R (2000) Methane-derived authigenic carbonates associated with gas hydrate decomposition and fluid venting above the Blake Ridge Diapir. Proc Ocean Drill Program Sci Results 164:285–300

    Google Scholar 

  • Paytan A, Kastner M, Campbell D, Thiemens MH (1999) Sulfur isotopic composition of Cenozoic seawater sulfate. Science 282:1459–1462

    Google Scholar 

  • Peckmann J, Thiel V (2004) Carbon cycling at ancient methane–seeps. Chem Geol 205(3–4):443–467

    Google Scholar 

  • Peckmann J, Reimer A, Luth U, Luth C, Hansen BT, Heinicke C, Hoefs J, Reitner J (2001) Methane-derived carbonates and authigenic pyrite from the northwestern Black Sea. Mar Geol 177(1–2):129–150

    Google Scholar 

  • Peketi A, Mazumdar A, Joshi RK, Patil DJ, Srinivas PL, Dayal AM (2012) Tracing the Paleo sulfate-methane transition zones and H2S seepage events in marine sediments: an application of C-S-Mo systematics. Geochem Geophys Geosyst 13(10):1–11

    Google Scholar 

  • Peketi A, Mazumdar A, Joao HM, Patil DJ, Usapkar A, Dewangan P (2015) Coupled C-S-Fe geochemistry in a rapidly accumulating marine sedimentary system: diagenetic and depositional implications. Geochem Geophys Geosyst 16:2865–2883

    Google Scholar 

  • Phillips SC, Johnson JE, Miranda E, Disenhof C (2011) Improving CHN measurements in carbonate-rich marine sediments. Limnol Oceanogr Methods 9(5):194–203

    Google Scholar 

  • Picotti V, Capozzi R, Bertozzi G, Mosca F, Sitta A, Tornaghi M (2007) The Miocene petroleum system of the Northern Apennines in the central Po Plain (Italy). In: Thrust Belts and Foreland Basins. Springer, Berlin, Heidelberg, pp 117–131

    Google Scholar 

  • Roberts HH (2001) Fluid and gas expulsion on the northern Gulf of Mexico continental slope: mud-prone to mineral-prone responses. Geophys Monogr 124:145–161

    Google Scholar 

  • Sassen R, Brooks JM, Kennicutt MC, MacDonald IR, Guinasso NL Jr (1993) How oil seeps, discoveries relate in deepwater Gulf of Mexico. Oil Gas J (United States) 91(16)

  • Sato H, Hayashi K, Ogawa Y, Kawamura K (2012) Geochemistry of deep sea sediments at cold seep sites in the Nankai Trough: insights into the effect of anaerobic oxidation of methane. Mar Geol 323:47–55

    Google Scholar 

  • Strauss H (1997) The isotopic composition of sedimentary sulfur through time. Palaeogeogr Palaeoclimatol Palaeoecol 132(1–4):97–118

    Google Scholar 

  • Teichert BMA, Johnson JE, Solomon EA, Giosan L, Rose K, Kocherla M, Connolly EC, Torres ME (2014) Composition and origin of authigenic carbonates in the Krishna–Godavari and Mahanadi Basins, eastern continental margin of India. Mar Pet Geol 58:438–460

    Google Scholar 

  • Tinterri R, Magalhaes PM (2011) Synsedimentary structural control on foredeep turbidites: an example from Miocene Marnoso-arenacea Formation, Northern Apennines, Italy. Mar Pet Geol 28(3):629–657

    Google Scholar 

  • Titschack J, Goetz-Neunhoeffer F, Neubauer J (2011) Magnesium quantification in calcites [(Ca, Mg) CO3] by Rietveld-based XRD analysis: revisiting a well-established method. Am Mineral 96(7):1028–1038

    Google Scholar 

  • Turner S (2018) Tracking sulfur diagenesis in methane rich marine sediments on the Cascadia Margin: comparing sulfur isotopes of bulk sediment and chromium reducible sulfur (Unpublished master's thesis). University of New Hampshire, Durham, NH, U.S.A.

  • Wakeham S, Canuel E, Volkman J (2006) Degradation and preservation of organic matter in marine sediments. Mar Org Matter 2N:295–321

    Google Scholar 

  • Wang M, Cai F, Li Q, Liang J, Yan GJ, Dong G, Wang F, Shao HB, Hu GW (2015) Characteristics of authigenic pyrite and its sulfur isotopes influenced by methane seep at Core A, Site 79 of the middle Okinawa Trough. Sci China Earth Sci 58:2145–2153

    Google Scholar 

Download references

Funding

This work has been supported by an IAS Post-Graduate Grant 2nd session 2017 (International Association of Sedimentologists) and by the University of Modena and Reggio Emilia PhD student research grant. We are indebted to the reviewers for helpful suggestions and comments.

Author information

Author notes

  1. C. Argentino

    Present address: CAGE - Center for Arctic Gas Hydrate, Environment and Climate, Department of Geosciences, UiT The Arctic University of Norway, 9037, Tromsø, Norway

Authors and Affiliations

  1. Department of Chemical and Geological Sciences, University of Modena and Reggio Emilia, 41125, Modena, Italy

    C. Argentino, S. Conti, C. Fioroni & D. Fontana

  2. Department of Earth Sciences, University of New Hampshire, Durham, NH, 03824, USA

    J. E. Johnson

Authors
  1. C. Argentino
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. J. E. Johnson
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. S. Conti
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. C. Fioroni
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. D. Fontana
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to C. Argentino.

Additional information

Publisher’s note

Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Electronic supplementary material

ESM 1

(PDF 369 kb)

ESM 2

(PDF 459 kb)

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Argentino, C., Johnson, J.E., Conti, S. et al. Preservation of 34S-enriched sulfides in fossil sulfate-methane transition zones: new evidence from Miocene outcrops of the northern Apennines (Italy). Geo-Mar Lett 40, 379–390 (2020). https://doi.org/10.1007/s00367-020-00644-w

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s00367-020-00644-w

Keywords

Search

Navigation