Multiple sulfur isotope analysis of volatile organic sulfur compounds and their sulfonium precursors in coastal marine environments

Oduro, Harry; Kamyshny, Alexander; Guo, Weifu; Farquhar, James

doi:10.1016/j.marchem.2010.12.004

Cited by 32 publications

(51 citation statements)

References 85 publications

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“…In these three cases, the anomalous isotope effects have been attributed to differences in intersystem crossing (ISC) rates from an initially excited singlet state to a reactive (or dissociative) triplet state. Similar spin-orbit effects have been shown to cause anomalous LIF intensities in 37 ClO 2 vs. 35 ClO 2 for particular vibrational bands (45). A recent study by Muskatel et al (46) demonstrates a theoretical basis for similar isotope effects during the photolysis of N 2 .…”

Section: Results Of Photochemical Experimentsmentioning

confidence: 71%

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Vibronic origin of sulfur mass-independent isotope effect in photoexcitation of SO₂and the implications to the early earth’s atmosphere

Whitehill

Xie

et al. 2013

Proc. Natl. Acad. Sci. U.S.A.

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Signatures of mass-independent isotope fractionation (MIF) † Significant deviations from these mass-dependent scaling laws are referred to as mass-independent fractionation (MIF), and serve as important tracers in the earth and planetary sciences (see refs. 3-5).Early studies suggested that MIF could result only from nucleosynthetic processes (6), and the earliest measurements of oxygen MIF in calcium-aluminum inclusions of meteorites originally were interpreted to be nucleosynthetic in origin (7). It eventually was suggested (8) that chemical processes, such as tunneling or processes associated with predissociation, also might produce MIF. The first experimental evidence for a chemical origin of MIF came from ozone generated by an electric discharge or UV radiation (9, 10). The discovery of oxygen MIF in stratospheric ozone (11) soon triggered intense research into the physiochemical origin of MIF in the ozone system (see refs. 12-14). The possible chemical origins of MIF signatures still are poorly understood.For the sulfur isotope system ( 32 S, 33 S, 34 S, and 36 S), Farquhar et al. (15) made the remarkable discovery that mass-independent sulfur isotope fractionation (S-MIF) is prevalent in sedimentary rocks older than ca. 2.4 Ga but absent in rocks from subsequent periods. The disappearance of S-MIF at about 2.4 Ga (16, 17) signifies a fundamental change in the earth's surface sulfur cycles, and generally is linked to the suppression of both SO 2 photolysis and the formation of elemental sulfur aerosols by the rise of atmospheric oxygen levels (15,18,19). The Archean S-MIF is considered the most compelling evidence for an anoxic early atmosphere and constrains Archean oxygen levels to be less than 10−5 of present levels (19). This model of oxygen evolution, however, depends critically on the assumption that UV photolysis of SO 2 by ∼200 nm radiation is the ultimate source of the anomalous sulfur isotope signature (18). Constraining the source of the S-MIF requires a thorough understanding of the physiochemical origins of S-MIF during the photochemistry of SO 2 .SO 2 exhibits two strong absorption band systems in the UV region: one between 185 nm and 235 nm (C 1 B 2 ←X

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Section: Results Of Photochemical Experimentsmentioning

confidence: 71%

“…These were captured and analyzed for quadruple sulfur isotope ratios using techniques described in Oduro et al (37) and Ono et al (26).…”

Section: Methodsmentioning

confidence: 99%

Vibronic origin of sulfur mass-independent isotope effect in photoexcitation of SO₂and the implications to the early earth’s atmosphere

Whitehill

Xie

et al. 2013

Proc. Natl. Acad. Sci. U.S.A.

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“…The DMS generated by the breakdown of the algal DMSP was sampled with an aqueous phase extraction to recover the DMS dissolved in the seawater and by purge and trap followed by the precipitation of DMS to recover gaseous DMS. In the aqueous phase extraction, DMS was extracted with carbon tetrachloride at −10°C and then reextracted with 30 mL of 5% (vol/ vol) HgCl 2 to precipitate the DMS into a white crystalline mercury complex (e.g., 3DMS-2Hg) (25,31). The precipitated DMS complexes were stored at 4°C in dark-brown Niskin bottles for later S-isotope analysis.…”

Section: Materials and Experimental Methodsmentioning

confidence: 99%

“…Purified algal DMSP samples and 3DMS-2Hg were reduced to Ag 2 S with a modified Raney nickel hydrodesulfurization method described by Oduro et al (25). Precipitated BaSO 4 was reduced to H 2 S by boiling in 25 mL of 5-N HCl and Thode solution [a mixture 320 mL of hydroiodic acid (HI), 524 mL of (hydrochloric acid [HCl], and 156 mL of hypophosphoric acid [H 2 PO 3 ])].…”

Section: Materials and Experimental Methodsmentioning

confidence: 99%

Sulfur isotope variability of oceanic DMSP generation and its contributions to marine biogenic sulfur emissions

Oduro

Alstyne

Farquhar

2012

Proc. Natl. Acad. Sci. U.S.A.

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Oceanic dimethylsulfoniopropionate (DMSP) is the precursor to dimethylsulfide (DMS), which plays a role in climate regulation through transformation to methanesulfonic acid (MSA) and nonseasalt sulfate (NSS-SO 4 2− ) aerosols. Here, we report measurements of the abundance and sulfur isotope compositions of DMSP from one phytoplankton species (Prorocentrum minimum) and five intertidal macroalgal species (Ulva lactuca, Ulva linza, Ulvaria obscura, Ulva prolifera, and Polysiphonia hendryi) in marine waters. We show that the sulfur isotope compositions (δ 34 S) of DMSP are depleted in 34 S relative to the source seawater sulfate by ∼1-3‰ and are correlated with the observed intracellular content of methionine, suggesting a link to metabolic pathways of methionine production. We suggest that this variability of δ 34 S is transferred to atmospheric geochemical products of DMSP degradation (DMS, MSA, and NSS-SO 4 2− ), carrying implications for the interpretation of variability in δ 34 S of MSA and NSS-SO 4 2− that links them to changes in growth conditions and populations of DMSP producers rather than to the contributions of DMS and non-DMS sources. COO − ] is a secondary metabolite that is produced and stored in large amounts by marine macroalgae (1) and microalgae (2). This β-sulfonium compound is widespread among marine taxa but is particularly abundant within specific groups of phytoplankton, zooplankton, macroalgae, halophytic plants, macroinvertebrates, and fishes (3-5). DMSP plays important ecophysiological functions in marine algae by acting as an antioxidant (6), a cryoprotectant, an osmolyte, and a precursor to an activated defense system (3). It is also an important carbon and sulfur source for marine bacterioplankton (7).The synthesis of DMSP by algae has been reviewed previously (3,8). It starts with the assimilation of seawater sulfate into the cytoplasm. The sulfate is subsequently transported into the chloroplasts, where it is reduced to sulfide in the presence of glutathionine and then transformed into cysteine. Cysteine is used to synthesize methionine, which is then transformed into DMSP via one of three pathways that differ among taxonomic groups of plants and algae (9-12). Thus, the biosynthesis of DMSP ultimately depends on the activity of the sulfate assimilation pathway; however, little is known about how DMSP synthesis differs among algae from diverse origins, except that the whole molecule is derived from sulfur amino acids.DMSP and its cleavage product dimethylsulfide [DMS; (CH 3 ) 2 S] have attracted much research interest because of their possible role in climate regulation (13,14). Since the introduction of the Charlson, Lovelock, Andreae, Warren (CLAW) hypothesis, which argues for feedback between biological DMS production, Earth's solar radiation, and the regulation of global climate (15), there has been an increasing emphasis by environmental scientists on determining the strength of the sea-to-air biogeochemical sources of DMS. This sea-to-air exchange of DMS is mediated through turbu...

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“…The glass wool in the aerosol trap was also collected. The organosulfur products were converted to silver sulfide using the Raney nickel hydrodesulfurization method of Oduro et al (2011). Multiple sulfur isotope ratios were measured as described in Sect.…”

Section: A R Whitehill Et Al: So 2 Photolysis As a Source For Sulfmentioning

confidence: 99%

SO<sub>2</sub> photolysis as a source for sulfur mass-independent isotope signatures in stratospehric aerosols

et al. 2015

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Abstract. Signatures of sulfur isotope mass-independent fractionation (S-MIF) have been observed in stratospheric sulfate aerosols deposited in polar ice. The S-MIF signatures are thought to be associated with stratospheric photochemistry following stratospheric volcanic eruptions, but the exact mechanism responsible for the production and preservation of these signatures is debated. In order to identify the origin and the mechanism of preservation for these signatures, a series of laboratory photochemical experiments were carried out to investigate the effect of temperature and added O 2 on the S-MIF produced by two absorption band systems of SO 2 : photolysis in the 190 to 220 nm region and photoexcitation in the 250 to 350 nm region. The SO 2 photolysis (SO 2 + hν → SO+O) experiments showed S-MIF signals with large 34 S/ 32 S fractionations, which increases with decreasing temperature. The overall S-MIF pattern observed for photolysis experiments, including high 34 S/ 32 S fractionations, positive mass-independent anomalies in 33 S, and negative anomalies in 36 S, is consistent with a major contribution from optical isotopologue screening effects and data for stratospheric sulfate aerosols. In contrast, SO 2 photoexcitation produced products with positive S-MIF anomalies in both 33 S and 36 S, which is different from stratospheric sulfate aerosols. SO 2 photolysis in the presence of O 2 produced SO 3 with S-MIF signals, suggesting the transfer of the S-MIF anomalies from SO to SO 3 by the SO + O 2 + M → SO 3 + M reaction. This is supported with energy calculations of stationary points on the SO 3 potential energy surfaces, which indicate that this reaction occurs slowly on a single adiabatic surface, but that it can occur more rapidly through intersystem crossing. Based on our experimental results, we estimate a termolecular rate constant on the order of 10 −37 cm 6 molecule −2 s −1 . This rate can explain the preservation of mass independent isotope signatures in stratospheric sulfate aerosols and provides a minor, but important, oxidation pathway for stratospheric SO 2 . The production and preservation of S-MIF signals requires a high SO 2 column density to allow for optical isotopologue screening effects to occur and to generate a large enough signature that it can be preserved. In addition, the SO 2 plume must reach an altitude of around 20 to 25 km, where SO 2 photolysis becomes a dominant process. These experiments are the first step towards understanding the origin of the sulfur isotope anomalies in stratospheric sulfate aerosols.

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Multiple sulfur isotope analysis of volatile organic sulfur compounds and their sulfonium precursors in coastal marine environments

Cited by 32 publications

References 85 publications

Vibronic origin of sulfur mass-independent isotope effect in photoexcitation of SO₂and the implications to the early earth’s atmosphere

Vibronic origin of sulfur mass-independent isotope effect in photoexcitation of SO₂and the implications to the early earth’s atmosphere

Sulfur isotope variability of oceanic DMSP generation and its contributions to marine biogenic sulfur emissions

SO<sub>2</sub> photolysis as a source for sulfur mass-independent isotope signatures in stratospehric aerosols

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Multiple sulfur isotope analysis of volatile organic sulfur compounds and their sulfonium precursors in coastal marine environments

Cited by 32 publications

References 85 publications

Vibronic origin of sulfur mass-independent isotope effect in photoexcitation of SO2and the implications to the early earth’s atmosphere

Vibronic origin of sulfur mass-independent isotope effect in photoexcitation of SO2and the implications to the early earth’s atmosphere

Sulfur isotope variability of oceanic DMSP generation and its contributions to marine biogenic sulfur emissions

SO&lt;sub&gt;2&lt;/sub&gt; photolysis as a source for sulfur mass-independent isotope signatures in stratospehric aerosols

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Vibronic origin of sulfur mass-independent isotope effect in photoexcitation of SO₂and the implications to the early earth’s atmosphere

Vibronic origin of sulfur mass-independent isotope effect in photoexcitation of SO₂and the implications to the early earth’s atmosphere

SO<sub>2</sub> photolysis as a source for sulfur mass-independent isotope signatures in stratospehric aerosols