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Effect mass independent isotope fractionation of sulfur (δ33S and δ36S) during photolysis SO2 in experiments with broadband light source

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1. Title Title of document Effect mass independent isotope fractionation of sulfur (δ33S and δ36S) during photolysis SO2 in experiments with broadband light source
2. Creator Author's name, affiliation, country A. V. Ignatiev; Far East Geological Institute, Far Eastern Branch of the Russian Academy of Sciences ; Russian Federation
2. Creator Author's name, affiliation, country T. A. Velivetskaya; Far East Geological Institute, Far Eastern Branch of the Russian Academy of Sciences ; Russian Federation
2. Creator Author's name, affiliation, country V. V. Yakovenko; Far East Geological Institute, Far Eastern Branch of the Russian Academy of Sciences ; Russian Federation
3. Subject Discipline(s)
3. Subject Keyword(s) масс-независимое фракционирование; изотопы серы; ранняя атмосфера Земли; архей; фотохимия; диоксид серы
4. Description Abstract

This paper presents the results of experimental studies to examine the behavior of mass-independent isotope effects of sulfur Δ33S and Δ36S during photochemical processes initiated by broadband ultraviolet radiation. Experiments were performed in a flow photochemical reactor using a high pressure mercury lamp which is a source of radiation of a wide range with a maximum radiation intensity in the wavelength range 270−330 nm and weaker in the range 190−250 nm. We present measurements of the temperature and SO2 pressure dependence of the sulfur isotope ratios in the elemental sulfur products. Based on a comparative analysis of our isotope data with data from previous experimental studies with xenon and hydrogen lamps, it was shown that the character of the correlation dependences between the values of δ34S, Δ33S and Δ36S in elemental sulfur depends on the relative spectral distribution of the radiation intensity. Based on a comparison of our isotope data with data from previous experimental studies with xenon and hydrogen lamps, it was shown that the character of the correlation dependencies between the values of δ34S, Δ33S and Δ36S in elemental sulfur depends on the relative spectral distribution of the radiation intensity. The results of our experiments allow the possibility that photochemical processes in the range 250−330 nm could play a significant role in the production of an isotope sulfur anomaly in the Archean atmosphere. The conditions in which radiation in the 250−330 nm region prevail over the radiation in the 190−220 nm region are consistent with the assumption that the level of solar radiation reaching the Earth’s surface in Archean was several orders of magnitude larger in the wavelength range 200−300 nm compared with the current level of radiation in this range.

5. Publisher Organizing agency, location The Russian Academy of Sciences
6. Contributor Sponsor(s) Russian foundation for basic research (Array)
7. Date (DD-MM-YYYY) 16.07.2019
8. Type Status & genre Peer-reviewed Article
8. Type Type Research Article
9. Format File format
10. Identifier Uniform Resource Identifier https://journals.eco-vector.com/0016-7525/article/view/15321
10. Identifier Digital Object Identifier (DOI) 10.31857/S0016-7525647689-699
10. Identifier Digital Object Identifier (DOI) (PDF (Rus)) 10.31857/S0016-7525647689-699-11832
11. Source Title; vol., no. (year) Геохимия; Vol 64, No 7 (2019)
12. Language English=en ru
13. Relation Supp. Files Fig. 1. The spectral intensity of radiation of broadband light sources. The high-pressure DRSh-250 gas-discharge mercury lamp was used in this study in photochemical experiments. For comparison, the emission spectra of xenon and deuterium lamps used in photochemical experiments are shown (Whitehill, Ono, 2012; Ono et al., 2013; Whitehill et al., 2015). (92KB) doi: 10.31857/S0016-7525647689-699-12676
Fig. 2. A graph showing the change in the δ34S and Δ33S values ​​in the photochemical S0 product (elemental sulfur) as a function of temperature in SO2 photolysis experiments under the influence of the full spectral radiation of a Hg lamp, including a short-wave radiation line at a wavelength of 184.9 nm (squares). For comparison, the isotope data (star) from photochemical experiments with a Hg low-pressure lamp with resonant radiation lines at wavelengths of ~ 185 and 253 nm are given (Farquhar et al., 2001). The solid line represents the Archean trend ∆33S − δ34S, the dashed-dotted line shows the experimental trend. (61KB) doi: 10.31857/S0016-7525647689-699-12677
Fig. 3. Cross-sectional absorption cross-section for SO2, CO2, CH4 and H2O gases. The data are compiled from spectral atlas (Keller-Rudek et al., 2013). (80KB) doi: 10.31857/S0016-7525647689-699-12678
Fig. 4. Behavior of isotope effects depending on the pressure of SO2: (a) - for Δ33S; (b) - for δ34S. The data were obtained in experiments with a Hg lamp with a short-wave continuum boundary from 190 nm with a change in the pressure of SO2 in the range of 1–1013 mbar and a constant temperature. For comparison, the isotopic data of works are presented (Ono et al., 2013; Whithill, Ono, 2012; Masterson et al., 2011). (122KB) doi: 10.31857/S0016-7525647689-699-12679
Fig. 5. The isotope effects of ∆36S relative to ∆33S in the product of the photochemical reaction S0 (elemental sulfur), obtained in our photochemical experiments (squares), in comparison with the isotopic data of works (Ono et al., 2013) (diamonds) and (Whithill, Ono , 2012) (stars). The dashed line denotes isotope trends ∆36S – ∆33S, constructed: 1 - according to our data from Table. 2 at a temperature of ~ 30ºС (slope Δ36S / Δ33S = −1.7); 2 — according to the work (Ono et al., 2013) for experiments with the full Xe lamp spectrum at pSO2 = 0.25–0.972 mbar and pN2 ≈0.25 bar (slope ∆36S / ∆33S = −3.6); 3 - according to the work (Whithill, Ono, 2012) for experiments with Xe lamp with a filter that transmits radiation in the spectral range of 250–330 nm at pSO2 = 6.4–34.2 mbar (slope ∆36S / ∆33S = 0.64). For comparison, the Archean trend is shown, which is bounded by lines with a slope of ∆36S / ∆33S = −0.9 and −1.5. (85KB) doi: 10.31857/S0016-7525647689-699-12680
Fig. 6. Δ33S relative to δ34S in the photochemical product S0 (elemental sulfur) obtained in our experiments for an SO2 pressure in the range of 1–10 mbar (squares). For comparison, the isotope data from (Ono et al., 2013) (diamonds) are given. The dashed line denotes isotope trends ∆33S – δ34S from experimental data. The solid line represents the Archean trend with a slope of ∆33S / δ34S ~ 0.9. (79KB) doi: 10.31857/S0016-7525647689-699-12681
Fig. 7. Graph showing the change in δ34S and Δ33S values in the photochemical reaction S0 (elemental sulfur) as a function of temperature (7–200ºC) in experiments on photolysis of SO2 under the influence of Hg lamp radiation in the wavelength range> 190 nm with constant pressure SO2 ~ 1013 mbar. (60KB) doi: 10.31857/S0016-7525647689-699-12682
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15. Rights Copyright and permissions Copyright (c) 2019 Russian Academy of Sciences