TY - JOUR
T1 - Multiple sulfur isotope analysis of volatile organic sulfur compounds and their sulfonium precursors in coastal marine environments
AU - Oduro, Harry
AU - Kamyshny, Alexey
AU - Guo, Weifu
AU - Farquhar, James
N1 - Funding Information: The authors wish to thank George W. Luther, III and Andrew Madison (University of Delaware, College of Marine and Earth Studies) for aid in field sampling at the Delaware Great Marsh. We also thank Zahra Mansaray for help in lab support and assistance. This work was partially supported by NASA Astrobiology Institute–Carnegie Institution of Washington Team (to J.F.), NSF Geobiology and Low Temperature Geochemistry Program grant number 0843814 (to A.K.), and Marie Curie Outgoing International Fellowship SULFUTOPES number POIF-GA-2008-219586 (to A.K.).
PY - 2011/3/20
Y1 - 2011/3/20
N2 - Volatile methylated sulfur compounds emitted from terrestrial and aquatic ecosystems play a significant role in the global sulfur cycle, yet no satisfactory methods are available to trace their source and transformation in natural systems. Here we present a method for quantification and multiple sulfur isotopic analysis of a variety of volatile sulfur species as well as their natural precursors via hydrodesulfurization with a Raney nickel catalyst. The detection limit of this method for methanethiol (MT), dimethylsulfide (DMS), dimethyldisulfide (DMDS), and carbon disulfide (CS2) is 0.2mg of sulfur per sample. Average recovery of ~95% was attained for samples containing more than 1.3mg of these sulfur compounds. Triplicate to quadruplicate sulfur isotopic analyses of reduced standard materials yield average standard deviations of 0.3‰, 0.02‰, and 0.1‰, respectively, for δ34S, δ33S, and δ36S.The method developed here was used for determination of sulfur isotopic compositions of volatile organic sulfur compounds (VOSCs) and their precursor dimethylsulfoniopropionoate (DMSP) in sediment cores and a C4 plant Spartina alterniflora collected from the Delaware Great Marsh. Application of the method to these natural samples indicates that the S-isotope compositions of VOSCs and DMSP-S are similar to, but slightly 34S-depleted (~0.6-0.9), relative to porewater sulfide. These compounds are 34S-enriched (~1.7-2.0‰) relative to the compositions of the coexisting sulfide. Both suggest a relationship between source sulfide and these organic sulfur compounds.
AB - Volatile methylated sulfur compounds emitted from terrestrial and aquatic ecosystems play a significant role in the global sulfur cycle, yet no satisfactory methods are available to trace their source and transformation in natural systems. Here we present a method for quantification and multiple sulfur isotopic analysis of a variety of volatile sulfur species as well as their natural precursors via hydrodesulfurization with a Raney nickel catalyst. The detection limit of this method for methanethiol (MT), dimethylsulfide (DMS), dimethyldisulfide (DMDS), and carbon disulfide (CS2) is 0.2mg of sulfur per sample. Average recovery of ~95% was attained for samples containing more than 1.3mg of these sulfur compounds. Triplicate to quadruplicate sulfur isotopic analyses of reduced standard materials yield average standard deviations of 0.3‰, 0.02‰, and 0.1‰, respectively, for δ34S, δ33S, and δ36S.The method developed here was used for determination of sulfur isotopic compositions of volatile organic sulfur compounds (VOSCs) and their precursor dimethylsulfoniopropionoate (DMSP) in sediment cores and a C4 plant Spartina alterniflora collected from the Delaware Great Marsh. Application of the method to these natural samples indicates that the S-isotope compositions of VOSCs and DMSP-S are similar to, but slightly 34S-depleted (~0.6-0.9), relative to porewater sulfide. These compounds are 34S-enriched (~1.7-2.0‰) relative to the compositions of the coexisting sulfide. Both suggest a relationship between source sulfide and these organic sulfur compounds.
UR - http://www.scopus.com/inward/record.url?scp=79953316835&partnerID=8YFLogxK
U2 - https://doi.org/10.1016/j.marchem.2010.12.004
DO - https://doi.org/10.1016/j.marchem.2010.12.004
M3 - Article
SN - 0304-4203
VL - 124
SP - 78
EP - 89
JO - Marine Chemistry
JF - Marine Chemistry
IS - 1-4
ER -