Sulfur isotope analysis of microcrystalline iron sulfides using secondary ion mass spectrometry imaging: Extracting local paleo-environmental information from modern and ancient sediments

Bryant, Roger N.; Jones, Clive; Raven, Morgan R.; Gomes, Maya L.; Berelson, William M.; Bradley, Alexander S.; Fike, David A.

doi:10.1002/rcm.8375

Title: Sulfur isotope analysis of microcrystalline iron sulfides using secondary ion mass spectrometry imaging: Extracting local paleo-environmental information from modern and ancient sediments

Journal Article · Tue Dec 18 00:00:00 EST 2018 · Rapid Communications in Mass Spectrometry

DOI:https://doi.org/10.1002/rcm.8375· OSTI ID:1612250

^[1];

^[1]; Raven, Morgan R. ^[2]; Gomes, Maya L. ^[3]; Berelson, William M. ^[4]; Bradley, Alexander S. ^[1]; Fike, David A. ^[1]

Washington Univ., St. Louis, MO (United States)
Washington Univ., St. Louis, MO (United States); Univ. of California, Santa Barbara, CA (United States)
Johns Hopkins Univ., Baltimore, MD (United States)
Univ. of Southern California, Los Angeles, CA (United States)

Rationale: Sulfur isotope ratio measurements of bulk sulfide from marine sediments have often been used to reconstruct environmental conditions associated with their formation. In situ microscale spot analyses by secondary ion mass spectrometry (SIMS) and laser ablation multiple-collector inductively coupled plasma mass spectrometry (LA-MC-ICP-MS) have been utilized for the same purpose. However, these techniques are often not suitable for studying small (≤10 μm) grains or for detecting intra-grain variability. Methods: In this work, we present a method for the physical extraction (using lithium polytungstate heavy liquid) and subsequent sulfur isotope analysis (using SIMS; CAMECA IMS 7f-GEO) of microcrystalline iron sulfides. SIMS sulfur isotope ratio measurements were made via Cs⁺ bombardment of raster squares with sides of 20–130 μm, using an electron multiplier (EM) detector to collect counts of ³²S^- and ³⁴S^- for each pixel (128 × 128 pixel grids) for between 20 and 960 cycles. Results: The extraction procedure did not discernibly alter pyrite grain-size distributions. The apparent inter-grain variability in ³⁴S/³²S in 1–4 μm-sized pyrite and marcasite fragments from isotopically homogeneous hydrothermal crystals was ~ ±2‰ (1σ), comparable with the standard error of the mean for individual measurements (≤ ±2‰, 1σ). In contrast, grain-specific ³⁴S/³²S ratios in modern and ancient sedimentary pyrites and marcasites can have inter- and intra-grain variability >60‰. The distributions of intra-sample isotopic variability are consistent with bulk ³⁴S/³²S values. Conclusions: SIMS analyses of isolated iron sulfide grains yielded distributions that are isotopically representative of bulk ³⁴S/³²S values. Populations of iron sulfide grains from sedimentary samples record the evolution of the S-isotopic composition of pore water sulfide in their S-isotopic compositions. These data allow past local environmental conditions to be inferred.

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Research Organization:: Washington Univ., St. Louis, MO (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Biological and Environmental Research (BER); American Chemical Society

Grant/Contract Number:: SC0014613; 57548-ND2

OSTI ID:: 1612250

Journal Information:: Rapid Communications in Mass Spectrometry, Vol. 33, Issue 5; ISSN 0951-4198

Publisher:: WileyCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 14 works

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References (61)

Determination of the absolute32S/34S ratio of IAEA-S-1 reference material and V-CDT sulfur isotope standard Ding, Tiping; Bai, Ruimei; Li, Yanhe Science in China Series D: Earth Sciences, Vol. 42, Issue 1 https://doi.org/10.1007/BF02878497	journal	August 1999
Sulfur Isotope Analysis of Sulfide and Sulfate Minerals by Continuous Flow-Isotope Ratio Mass Spectrometry Grassineau, N. V.; Mattey, D. P.; Lowry, D. Analytical Chemistry, Vol. 73, Issue 2 https://doi.org/10.1021/ac000550f	journal	January 2001
Opaque Oxides and Sulphides in Common Igneous Rocks Newhouse, W. H. Geological Society of America Bulletin, Vol. 47, Issue 1 https://doi.org/10.1130/GSAB-47-1	journal	January 1936
Sulfur isotope insights into microbial sulfate reduction: When microbes meet models Johnston, David T.; Farquhar, James; Canfield, Donald E. Geochimica et Cosmochimica Acta, Vol. 71, Issue 16 https://doi.org/10.1016/j.gca.2007.05.008	journal	August 2007
Measurement of light stable isotope ratios by SIMS: Riciputi, Lee R.; Paterson, Bruce A.; Ripperdan, Robert L. International Journal of Mass Spectrometry, Vol. 178, Issue 1-2 https://doi.org/10.1016/S1387-3806(98)14088-5	journal	October 1998
Multistage Sedimentary and Metamorphic Origin of Pyrite and Gold in the Giant Sukhoi Log Deposit, Lena Gold Province, Russia Large, R. R.; Maslennikov, V. V.; Robert, F. Economic Geology, Vol. 102, Issue 7 https://doi.org/10.2113/gsecongeo.102.7.1233	journal	November 2007
Reprint of “The effect of biogeochemical processes on pH” Soetaert, Karline; Hofmann, Andreas F.; Middelburg, Jack J. Marine Chemistry, Vol. 106, Issue 1-2 https://doi.org/10.1016/j.marchem.2007.06.008	journal	July 2007
Measurement of bacterial sulfate reduction in sediments: Evaluation of a single-step chromium reduction method Fossing, Henrik; J�rgensen, BoBarker Biogeochemistry, Vol. 8, Issue 3 https://doi.org/10.1007/BF00002889	journal	November 1989
Investigation of the quasi-simultaneous arrival (QSA) effect on a CAMECA IMS 7f-GEO: Investigation of the QSA effect on a CAMECA IMS 7f-GEO Jones, Clive; Fike, David A.; Peres, Paula Rapid Communications in Mass Spectrometry, Vol. 31, Issue 7 https://doi.org/10.1002/rcm.7828	journal	March 2017
High-precision EA-IRMS analysis of S and C isotopes in geological materials Grassineau, Nathalie V. Applied Geochemistry, Vol. 21, Issue 5 https://doi.org/10.1016/j.apgeochem.2006.02.015	journal	May 2006
Mineralization and paragenesis of the Huanzala Mine, central Peru Imai, Hideki; Kawasaki, Masashi; Yamaguchi, Mitsuo Economic Geology, Vol. 80, Issue 2 https://doi.org/10.2113/gsecongeo.80.2.461	journal	April 1985
Questioning the biogenicity of Neoproterozoic superheavy pyrite by SIMS Cui, Huan; Kitajima, Kouki; Spicuzza, Michael J. American Mineralogist, Vol. 103, Issue 9 https://doi.org/10.2138/am-2018-6489	journal	September 2018
Multiple sulfur isotopes of sulfides from sediments in the aftermath of Paleoproterozoic glaciations Papineau, D.; Mojzsis, S. J.; Coath, C. D. Geochimica et Cosmochimica Acta, Vol. 69, Issue 21 https://doi.org/10.1016/j.gca.2005.07.005	journal	November 2005
Modeling atmospheric O2 over Phanerozoic time Berner, R. A. Geochimica et Cosmochimica Acta, Vol. 65, Issue 5 https://doi.org/10.1016/S0016-7037(00)00572-X	journal	March 2001
Pyrite sulfur isotopes reveal glacial−interglacial environmental changes Pasquier, Virgil; Sansjofre, Pierre; Rabineau, Marina Proceedings of the National Academy of Sciences, Vol. 114, Issue 23 https://doi.org/10.1073/pnas.1618245114	journal	May 2017
Particle Settling Times for Gravity Sedimentation and Centrifugation: A Practical Guide for Palynologists Lentfer, C. J.; Cotter, M. M.; Boyd, W. E. Journal of Archaeological Science, Vol. 30, Issue 2 https://doi.org/10.1006/jasc.2001.0786	journal	February 2003
In situ multiple sulfur isotope analysis by SIMS of pyrite, chalcopyrite, pyrrhotite, and pentlandite to refine magmatic ore genetic models LaFlamme, Crystal; Martin, Laure; Jeon, Heejin Chemical Geology, Vol. 444 https://doi.org/10.1016/j.chemgeo.2016.09.032	journal	December 2016
The incorporation of trace elements into pyrite during diagenesis of black shales, Yorkshire, England Raiswell, R.; Plant, J. Economic Geology, Vol. 75, Issue 5 https://doi.org/10.2113/gsecongeo.75.5.684	journal	August 1980
Global niche of marine anaerobic metabolisms expanded by particle microenvironments Bianchi, Daniele; Weber, Thomas S.; Kiko, Rainer Nature Geoscience, Vol. 11, Issue 4 https://doi.org/10.1038/s41561-018-0081-0	journal	March 2018
Online Sulfur-Isotope Determination Using an Elemental Analyzer Coupled to a Mass Spectrometer Giesemann, A.; Jaeger, H. -J.; Norman, A. L. Analytical Chemistry, Vol. 66, Issue 18 https://doi.org/10.1021/ac00090a005	journal	September 1994
Origin of mass flow sedimentary structures in hemipelagic basin deposits: Santa Barbara Basin, California Borderland Thornton, Scott E. Geo-Marine Letters, Vol. 6, Issue 1 https://doi.org/10.1007/BF02311691	journal	March 1986
Isolation of Pyrite Spherules from Recent Sediments Vallentyne, J. R. Limnology and Oceanography, Vol. 8, Issue 1 https://doi.org/10.4319/lo.1963.8.1.0016	journal	April 1963
Sulfur isotopic compositions of individual sulfides in Martian meteorites ALH84001 and Nakhla: implications for crust–regolith exchange on Mars Greenwood, James P.; Mojzsis, Stephen J.; Coath, Christopher D. Earth and Planetary Science Letters, Vol. 184, Issue 1 https://doi.org/10.1016/S0012-821X(00)00301-0	journal	December 2000
Sulfur isotope's signal of nanopyrites enclosed in 2.7 Ga stromatolitic organic remains reveal microbial sulfate reduction Marin-Carbonne, J.; Remusat, L.; Sforna, M. C. Geobiology, Vol. 16, Issue 2 https://doi.org/10.1111/gbi.12275	journal	January 2018
Sulfur isotope fractionation in pyrite during laser ablation: Implications for laser ablation multiple collector inductively coupled plasma mass spectrometry mapping Zhu, Zhi-Yong; Jiang, Shao-Yong; Ciobanu, Cristiana L. Chemical Geology, Vol. 450 https://doi.org/10.1016/j.chemgeo.2016.12.037	journal	February 2017
Measurement of Sulphur Isotopic Compositions of Sulphide Minerals Using New Continuous He-Flow EA-MS Technology Grassineau, N. V. Mineralogical Magazine, Vol. 62A, Issue 1 https://doi.org/10.1180/minmag.1998.62A.1.284	journal	January 1998
Rethinking the Ancient Sulfur Cycle Fike, David A.; Bradley, Alexander S.; Rose, Catherine V. Annual Review of Earth and Planetary Sciences, Vol. 43, Issue 1 https://doi.org/10.1146/annurev-earth-060313-054802	journal	May 2015
Onset and demise of Cretaceous oceanic anoxic events: The coupling of surface and bottom oceanic processes in two pelagic basins of the western Tethys Gambacorta, G.; Bersezio, R.; Weissert, H. Paleoceanography, Vol. 31, Issue 6 https://doi.org/10.1002/2015PA002922	journal	June 2016
Coupling between sedimentary dynamics, early diagenetic processes, and biogeochemical cycling in the Amazon–Guianas mobile mud belt: coastal French Guiana Aller, Robert C.; Heilbrun, Christina; Panzeca, Caterina Marine Geology, Vol. 208, Issue 2-4 https://doi.org/10.1016/j.margeo.2004.04.027	journal	August 2004
SQUID-SIMS is a useful approach to uncover primary signals in the Archean sulfur cycle Fischer, W. W.; Fike, D. A.; Johnson, J. E. Proceedings of the National Academy of Sciences, Vol. 111, Issue 15 https://doi.org/10.1073/pnas.1322577111	journal	April 2014
NIH Image to ImageJ: 25 years of image analysis Schneider, Caroline A.; Rasband, Wayne S.; Eliceiri, Kevin W. Nature Methods, Vol. 9, Issue 7 https://doi.org/10.1038/nmeth.2089	journal	June 2012
A theoretical model of the stable sulfur isotope distribution in marine sediments Jorgensen, Bo Barker Geochimica et Cosmochimica Acta, Vol. 43, Issue 3 https://doi.org/10.1016/0016-7037(79)90201-1	journal	March 1979
Accurate determination of sulfur isotopes ( δ ³³ S and δ ³⁴ S) in sulfides and elemental sulfur by femtosecond laser ablation MC-ICP-MS with non-matrix matched calibration Fu, Jiali; Hu, Zhaochu; Li, Jianwei Journal of Analytical Atomic Spectrometry, Vol. 32, Issue 12 https://doi.org/10.1039/C7JA00282C	journal	January 2017
Variability in the Raman Spectrum of Unpolished Growth and Fracture Surfaces of Pyrite Due to Laser Heating and Crystal Orientation Bryant, Roger N.; Pasteris, Jill D.; Fike, David A. Applied Spectroscopy, Vol. 72, Issue 1 https://doi.org/10.1177/0003702817736516	journal	October 2017
Environmental insights from high-resolution (SIMS) sulfur isotope analyses of sulfides in Proterozoic microbialites with diverse mat textures Gomes, M. L.; Fike, D. A.; Bergmann, K. D. Geobiology, Vol. 16, Issue 1 https://doi.org/10.1111/gbi.12265	journal	October 2017
Orbitally induced limestone/marlstone rhythms in the Albian—Cenomanian Cismon section (Venetian region, northern Italy): Sedimentology, calcareous and siliceous plankton distribution, elemental and isotope geochemistry Bellanca, A.; Claps, M.; Erba, E. Palaeogeography, Palaeoclimatology, Palaeoecology, Vol. 126, Issue 3-4 https://doi.org/10.1016/S0031-0182(96)00041-7	journal	December 1996
Oxidation of detrital pyrite as a cause for Marcasite Formation in marine lag deposits from the Devonian of the eastern US Schieber, Juergen Deep Sea Research Part II: Topical Studies in Oceanography, Vol. 54, Issue 11-13 https://doi.org/10.1016/j.dsr2.2007.04.005	journal	June 2007
Sulphur cycling in a Neoarchaean microbial mat Meyer, N. R.; Zerkle, A. L.; Fike, D. A. Geobiology, Vol. 15, Issue 3 https://doi.org/10.1111/gbi.12227	journal	January 2017
Integrated Pb- and S-isotope investigation of sulphide minerals from the early Archaean of southwest Greenland Whitehouse, Martin J.; Kamber, Balz S.; Fedo, Christopher M. Chemical Geology, Vol. 222, Issue 1-2 https://doi.org/10.1016/j.chemgeo.2005.06.004	journal	October 2005
Variability of sulphur isotope ratios in pyrite and dissolved sulphate in granitoid fractures down to 1km depth – Evidence for widespread activity of sulphur reducing bacteria Drake, Henrik; Åström, Mats E.; Tullborg, Eva-Lena Geochimica et Cosmochimica Acta, Vol. 102 https://doi.org/10.1016/j.gca.2012.10.036	journal	February 2013
D/H variation in terrestrial lipids from Santa Barbara Basin over the past 1400years: A preliminary assessment of paleoclimatic relevance Li, Chao; Sessions, Alex L.; Valentine, David L. Organic Geochemistry, Vol. 42, Issue 1 https://doi.org/10.1016/j.orggeochem.2010.09.011	journal	January 2011
Use of heavy liquid density separation to remove pyrite from sediment samples for radiocarbon dating Proske, Ulrike; Wood, Rachel; Fallon, Stewart Quaternary Geochronology, Vol. 25 https://doi.org/10.1016/j.quageo.2014.10.002	journal	February 2015
δ ³⁴ S Measurements of Sulfur by Multicollector Inductively Coupled Plasma Mass Spectrometry Clough, Robert; Evans, Peter; Catterick, Tim Analytical Chemistry, Vol. 78, Issue 17 https://doi.org/10.1021/ac060875h	journal	September 2006
The use of chromium reduction in the analysis of reduced inorganic sulfur in sediments and shales Canfield, Donald E.; Raiswell, Robert; Westrich, Joseph T. Chemical Geology, Vol. 54, Issue 1-2 https://doi.org/10.1016/0009-2541(86)90078-1	journal	January 1986
MC-ICP-MS measurement of δ34S and ∆33S in small amounts of dissolved sulfate Paris, Guillaume; Sessions, Alex L.; Subhas, Adam V. Chemical Geology, Vol. 345 https://doi.org/10.1016/j.chemgeo.2013.02.022	journal	May 2013
Early oxygenation of the terrestrial environment during the Mesoproterozoic Parnell, John; Boyce, Adrian J.; Mark, Darren Nature, Vol. 468, Issue 7321 https://doi.org/10.1038/nature09538	journal	November 2010
Burial of organic carbon and pyrite sulfur in the modern ocean; its geochemical and environmental significance Berner, R. A. American Journal of Science, Vol. 282, Issue 4 https://doi.org/10.2475/ajs.282.4.451	journal	April 1982
In situ sulfur isotope analysis of sulfide minerals by SIMS: Precision and accuracy, with application to thermometry of ∼3.5Ga Pilbara cherts Kozdon, Reinhard; Kita, Noriko T.; Huberty, Jason M. Chemical Geology, Vol. 275, Issue 3-4 https://doi.org/10.1016/j.chemgeo.2010.05.015	journal	August 2010
Sulfur isotope measurement of sulfate and sulfide by high-resolution MC-ICP-MS Craddock, Paul R.; Rouxel, Olivier J.; Ball, Lary A. Chemical Geology, Vol. 253, Issue 3-4 https://doi.org/10.1016/j.chemgeo.2008.04.017	journal	August 2008
Unprecedented ³⁴ S-enrichment of pyrite formed following microbial sulfate reduction in fractured crystalline rocks Drake, Henrik; Whitehouse, Martin J.; Heim, Christine Geobiology, Vol. 16, Issue 5 https://doi.org/10.1111/gbi.12297	journal	June 2018
Biogeochemical sulfur cycling during Cretaceous oceanic anoxic events: A comparison of OAE1a and OAE2: CRETACEOUS OCEAN ANOXIA AND SULFUR Gomes, Maya L.; Hurtgen, Matthew T.; Sageman, Bradley B. Paleoceanography, Vol. 31, Issue 2 https://doi.org/10.1002/2015PA002869	journal	February 2016
Trace element chemistry of pyrite: A useful guide to the occurrence of sulfide base metal mineralization Ivor Roberts, F. Journal of Geochemical Exploration, Vol. 17, Issue 1 https://doi.org/10.1016/0375-6742(82)90019-X	journal	September 1982
Production and preservation of organic matter: The significance of iron: SIGNIFICANCE OF IRON Meyers, Stephen R. Paleoceanography, Vol. 22, Issue 4 https://doi.org/10.1029/2006PA001332	journal	November 2007
In situ determination of sulfur isotopes in sulfur-rich materials by laser ablation multiple-collector inductively coupled plasma mass spectrometry (LA-MC-ICP-MS) Mason, Paul R. D.; Košler, Jan; de Hoog, Jan C. M. J. Anal. At. Spectrom., Vol. 21, Issue 2 https://doi.org/10.1039/B510883G	journal	January 2006
Sulphur isotope geochemistry Thode, H. G.; Monster, J.; Dunford, H. B. Geochimica et Cosmochimica Acta, Vol. 25, Issue 3 https://doi.org/10.1016/0016-7037(61)90074-6	journal	November 1961
Pyrite formation in the water column and sediments of a meromictic lake Suits, Neil S.; Wilkin, Rick T. Geology, Vol. 26, Issue 12 https://doi.org/10.1130/0091-7613(1998)026<1099:PFITWC>2.3.CO;2	journal	January 1998
Analysis of sulfides in whole rock matrices by elemental analyzer–continuous flow isotope ratio mass spectrometry Studley, S. A.; Ripley, E. M.; Elswick, E. R. Chemical Geology, Vol. 192, Issue 1-2 https://doi.org/10.1016/S0009-2541(02)00162-6	journal	December 2002
Influence of sulfate reduction rates on the Phanerozoic sulfur isotope record Leavitt, W. D.; Halevy, I.; Bradley, A. S. Proceedings of the National Academy of Sciences, Vol. 110, Issue 28 https://doi.org/10.1073/pnas.1218874110	journal	June 2013
Marcasite in Black Shales--a Mineral Proxy for Oxygenated Bottom Waters and Intermittent Oxidation of Carbonaceous Muds Schieber, J. Journal of Sedimentary Research, Vol. 81, Issue 7 https://doi.org/10.2110/jsr.2011.41	journal	June 2011
Animal evolution, bioturbation, and the sulfate concentration of the oceans Canfield, D. E.; Farquhar, J. Proceedings of the National Academy of Sciences, Vol. 106, Issue 20 https://doi.org/10.1073/pnas.0902037106	journal	May 2009
Geochemical evidence for widespread euxinia in the Later Cambrian ocean Gill, Benjamin C.; Lyons, Timothy W.; Young, Seth A. Nature, Vol. 469, Issue 7328 https://doi.org/10.1038/nature09700	journal	January 2011

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