Native sulfur at the seafloor: Composition and origin

Vesselin M. Dekov; Andrea Koschinsky; Toshiro Yamanaka; Sven Petersen; Sophie A.L. Paul; Charlotte Kleint; Ewan Pelleter; Gert J. de Lange; Victoria Kürzinger; Dieter Garbe-Schönberg; Monika Ilieva; Yves Fouquet; Olivier Rouxel

doi:10.1016/j.chemgeo.2024.122295

Native sulfur at the seafloor: Composition and origin

Vesselin M. Dekov^*, Andrea Koschinsky, Toshiro Yamanaka, Sven Petersen, Sophie A.L. Paul, Charlotte Kleint, Ewan Pelleter, Gert J. de Lange, Victoria Kürzinger, Dieter Garbe-Schönberg, Monika Ilieva, Yves Fouquet, Olivier Rouxel

^*Corresponding author for this work

Research output: Contribution to journal › Article › Academic › peer-review

Abstract

Mineralogy, geochemistry and sulfur (S) isotope composition of native sulfur (S⁰) precipitated at intraoceanic and intracontinental back-arc rift, submarine and subaerial volcanic arc, sediment and sediment-free mid-ocean ridge, hot spot, accretionary wedge, and submarine and continental cave settings were investigated with a main goal to understand the mode of formation of all the types of native S at the modern seafloor. Native S occurs as various depositional forms: chimneys, colloform flows, liquid ponds, slabs; fills in cavities and pore space of the sediment, vesicles and cracks in volcanic rocks; cements and coats the sediment; stains the conduits or fills in pores of the sulfide chimneys; forms fine-grained layers within the sediment; coats the walls, stalactites and stalagmites in the caves. Mineralogically, the native S from the seafloor is pure rhombic S⁰ with negligible impurities of metal sulfides, aluminosilicates, and carbonates inferred from the chemistry data. Mineral interrelations and S isotope data suggest that native S from different geologic settings has different origin. In the sulfide chimneys and mounds at the mid-ocean ridges, native S appears to be a result of oxidative alteration of primary pyrrhotite. The native S from back-arc rifts, volcanic arcs and hot spots can be a result of either disproportionation of magmatic SO₂ (δ³⁴S < 0 ‰), or synproportionation of magmatic SO₂ and H₂S (δ³⁴S > 0 ‰). The native S from the sediments in anoxic brine-filled deeps (accretionary wedge setting) is a result of bacterial sulfate reduction and consequent sulfide (δ³⁴S < 0 ‰) oxidation. The native S coating the cave walls and forms also has a bacterial origin (δ³⁴S < 0 ‰).

Original language	English
Article number	122295
Number of pages	18
Journal	Chemical Geology
Volume	668
Early online date	25 Jul 2024
DOIs	https://doi.org/10.1016/j.chemgeo.2024.122295
Publication status	Published - 20 Nov 2024

Bibliographical note

Publisher Copyright:
© 2024 Elsevier B.V.

Funding

This research was supported by a Renewed Research Stay Fellowship (Alexander von Humboldt Foundation) to V. M. Dekov. M. Ilieva acknowledges the support from the SPIRIT TNA Programme (grant #056). Sincere thanks go to numerous colleagues who generously gave us native S samples from a range of seafloor and continental sites: Dr. T. Tomiyama (JAMSTEC, Japan; for Ryukyu VA, Mariana VA, and Okinawa BAB samples), Prof. G. Chazot (Universit\u00E9 de Bretagne Occidentale, France; for Vulcano and Kawah Ijen samples), Prof. R. Mills [University of Southampton, UK; for South Sandwich VA (Kemp Caldera) sample; collection of this sample was with RRS James Cook in Jan/Feb 2010 and the cruise was funded by the Natural Environment Research Council consortium grant NE/D01249X/1 to Tyler, Connelly, Mills et al.], Prof. W. Bach (University Bremen; for samples from the Manus Basin collected during R/V Sonne cruise SO216 in 2011), Dr. R.A. Koski (USGS; for Escanaba Trough and Guaymas Basin samples, and information on their appearance and mineralogy), Dr. W.C. Shanks (USGS; for Yellowstone Lake samples and information on their appearance), Prof. T. Pinegina (Institute of Volcanology and Seismology, Russia; for Ebeco sample), Mr. A. Mocchiutti (Geomok S.r.l. Italy; for Grotta di Cala Fetente sample), Mr. D. Davis (Denver, USA; for Shoshone Canyon Conduit Cave sample), and Mr. H. DuChene (Englewood, USA; for Lechuguilla Cave and Cueva de Villa Luz samples). The Dutch Science Foundation (NWO) is acknowledged for financial support for the expedition of R/V Logatchev to the Urania Basin (Mediterranean Sea). Captain, crew, and scientific team on board R/V Logatchev are thanked for collection of core SL108PC (Urania Basin) and G. Nobbe, R. Knoop, A. Filippidi for analytical assistance. This research was supported by a Renewed Research Stay Fellowship ( Alexander von Humboldt Foundation ) to V. M. Dekov. M. Ilieva acknowledges the support from the SPIRIT TNA Programme (grant # 056 ). Sincere thanks go to numerous colleagues who generously gave us native S samples from a range of seafloor and continental sites: Dr. T. Tomiyama (JAMSTEC, Japan; for Ryukyu VA, Mariana VA, and Okinawa BAB samples), Prof. G. Chazot (Universit\u00E9 de Bretagne Occidentale, France; for Vulcano and Kawah Ijen samples), Prof. R. Mills [University of Southampton, UK; for South Sandwich VA (Kemp Caldera) sample; collection of this sample was with RRS James Cook in Jan/Feb 2010 and the cruise was funded by the Natural Environment Research Council consortium grant NE/D01249X/1 to Tyler, Connelly, Mills et al.], Prof. W. Bach (University Bremen; for samples from the Manus Basin collected during R/V Sonne cruise SO216 in 2011), Dr. R.A. Koski (USGS; for Escanaba Trough and Guaymas Basin samples, and information on their appearance and mineralogy), Dr. W.C. Shanks (USGS; for Yellowstone Lake samples and information on their appearance), Prof. T. Pinegina (Institute of Volcanology and Seismology, Russia; for Ebeco sample), Mr. A. Mocchiutti (Geomok S.r.l., Italy; for Grotta di Cala Fetente sample), Mr. D. Davis (Denver, USA; for Shoshone Canyon Conduit Cave sample), and Mr. H. DuChene (Englewood, USA; for Lechuguilla Cave and Cueva de Villa Luz samples). The Dutch Science Foundation (NWO) is acknowledged for financial support for the expedition of R/V Logatchev to the Urania Basin (Mediterranean Sea). Captain, crew, and scientific team on board R/V Logatchev are thanked for collection of core SL108PC (Urania Basin) and G. Nobbe, R. Knoop, A. Filippidi for analytical assistance.

Funders	Funder number
Nederlandse Organisatie voor Wetenschappelijk Onderzoek
Cueva de Villa Luz samples
South Sandwich VA
Mariana VA
Ryukyu VA
Université de Bretagne Occidentale
Alexander von Humboldt-Stiftung	056
Natural Environment Research Council	NE/D01249X/1, SO216

Keywords

Alteration
Back-arc rifts
Disproportionation
Mid-ocean ridges
Native S
Synproportionation
Volcanic arcs

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10.1016/j.chemgeo.2024.122295

1-s2.0-S0009254124003759-mainFinal published version, 31.8 MBLicence: Taverne

Cite this

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title = "Native sulfur at the seafloor: Composition and origin",

abstract = "Mineralogy, geochemistry and sulfur (S) isotope composition of native sulfur (S0) precipitated at intraoceanic and intracontinental back-arc rift, submarine and subaerial volcanic arc, sediment and sediment-free mid-ocean ridge, hot spot, accretionary wedge, and submarine and continental cave settings were investigated with a main goal to understand the mode of formation of all the types of native S at the modern seafloor. Native S occurs as various depositional forms: chimneys, colloform flows, liquid ponds, slabs; fills in cavities and pore space of the sediment, vesicles and cracks in volcanic rocks; cements and coats the sediment; stains the conduits or fills in pores of the sulfide chimneys; forms fine-grained layers within the sediment; coats the walls, stalactites and stalagmites in the caves. Mineralogically, the native S from the seafloor is pure rhombic S0 with negligible impurities of metal sulfides, aluminosilicates, and carbonates inferred from the chemistry data. Mineral interrelations and S isotope data suggest that native S from different geologic settings has different origin. In the sulfide chimneys and mounds at the mid-ocean ridges, native S appears to be a result of oxidative alteration of primary pyrrhotite. The native S from back-arc rifts, volcanic arcs and hot spots can be a result of either disproportionation of magmatic SO2 (δ34S < 0 ‰), or synproportionation of magmatic SO2 and H2S (δ34S > 0 ‰). The native S from the sediments in anoxic brine-filled deeps (accretionary wedge setting) is a result of bacterial sulfate reduction and consequent sulfide (δ34S < 0 ‰) oxidation. The native S coating the cave walls and forms also has a bacterial origin (δ34S < 0 ‰).",

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doi = "10.1016/j.chemgeo.2024.122295",

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AU - Dekov, Vesselin M.

AU - Koschinsky, Andrea

AU - Yamanaka, Toshiro

AU - Petersen, Sven

AU - Paul, Sophie A.L.

AU - Kleint, Charlotte

AU - Pelleter, Ewan

AU - de Lange, Gert J.

AU - Kürzinger, Victoria

AU - Garbe-Schönberg, Dieter

AU - Ilieva, Monika

AU - Fouquet, Yves

AU - Rouxel, Olivier

PY - 2024/11/20

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N2 - Mineralogy, geochemistry and sulfur (S) isotope composition of native sulfur (S0) precipitated at intraoceanic and intracontinental back-arc rift, submarine and subaerial volcanic arc, sediment and sediment-free mid-ocean ridge, hot spot, accretionary wedge, and submarine and continental cave settings were investigated with a main goal to understand the mode of formation of all the types of native S at the modern seafloor. Native S occurs as various depositional forms: chimneys, colloform flows, liquid ponds, slabs; fills in cavities and pore space of the sediment, vesicles and cracks in volcanic rocks; cements and coats the sediment; stains the conduits or fills in pores of the sulfide chimneys; forms fine-grained layers within the sediment; coats the walls, stalactites and stalagmites in the caves. Mineralogically, the native S from the seafloor is pure rhombic S0 with negligible impurities of metal sulfides, aluminosilicates, and carbonates inferred from the chemistry data. Mineral interrelations and S isotope data suggest that native S from different geologic settings has different origin. In the sulfide chimneys and mounds at the mid-ocean ridges, native S appears to be a result of oxidative alteration of primary pyrrhotite. The native S from back-arc rifts, volcanic arcs and hot spots can be a result of either disproportionation of magmatic SO2 (δ34S < 0 ‰), or synproportionation of magmatic SO2 and H2S (δ34S > 0 ‰). The native S from the sediments in anoxic brine-filled deeps (accretionary wedge setting) is a result of bacterial sulfate reduction and consequent sulfide (δ34S < 0 ‰) oxidation. The native S coating the cave walls and forms also has a bacterial origin (δ34S < 0 ‰).

AB - Mineralogy, geochemistry and sulfur (S) isotope composition of native sulfur (S0) precipitated at intraoceanic and intracontinental back-arc rift, submarine and subaerial volcanic arc, sediment and sediment-free mid-ocean ridge, hot spot, accretionary wedge, and submarine and continental cave settings were investigated with a main goal to understand the mode of formation of all the types of native S at the modern seafloor. Native S occurs as various depositional forms: chimneys, colloform flows, liquid ponds, slabs; fills in cavities and pore space of the sediment, vesicles and cracks in volcanic rocks; cements and coats the sediment; stains the conduits or fills in pores of the sulfide chimneys; forms fine-grained layers within the sediment; coats the walls, stalactites and stalagmites in the caves. Mineralogically, the native S from the seafloor is pure rhombic S0 with negligible impurities of metal sulfides, aluminosilicates, and carbonates inferred from the chemistry data. Mineral interrelations and S isotope data suggest that native S from different geologic settings has different origin. In the sulfide chimneys and mounds at the mid-ocean ridges, native S appears to be a result of oxidative alteration of primary pyrrhotite. The native S from back-arc rifts, volcanic arcs and hot spots can be a result of either disproportionation of magmatic SO2 (δ34S < 0 ‰), or synproportionation of magmatic SO2 and H2S (δ34S > 0 ‰). The native S from the sediments in anoxic brine-filled deeps (accretionary wedge setting) is a result of bacterial sulfate reduction and consequent sulfide (δ34S < 0 ‰) oxidation. The native S coating the cave walls and forms also has a bacterial origin (δ34S < 0 ‰).

KW - Alteration

KW - Back-arc rifts

KW - Disproportionation

KW - Mid-ocean ridges

KW - Native S

KW - Synproportionation

KW - Volcanic arcs

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DO - 10.1016/j.chemgeo.2024.122295

M3 - Article

AN - SCOPUS:85201780544

SN - 0009-2541

VL - 668

JO - Chemical Geology

JF - Chemical Geology

M1 - 122295

ER -

Native sulfur at the seafloor: Composition and origin

Abstract

Bibliographical note

Funding

Keywords

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