Oxygen-18 study of the aqueous-phase oxidation of sulfur dioxide

Holt, Ben D.; Kumar, Romesh; Cunningham, P.T.

doi:10.1016/0004-6981(81)90186-4

Cited by 84 publications

(69 citation statements)

References 27 publications

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“…After 1945, drinking water was produced at a very low rate in order to contribute to the regional water supply. Between 1968 and1981, the technical production capacity of the water works was progressively increased from 30 000 to 124 000 m 3 day 1 . The highest production of ¾36 ð 10 6 m 3 year 1 was realized in the mid 1980s.…”

Section: Regional Settingmentioning

confidence: 99%

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Sulphur cycling in the drinking water catchment area of Torgau–Mockritz (Germany): insights from hydrochemical and stable isotope investigations

Knöller

Trettin

Strauch

2005

Hydrological Processes

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Abstract:The hydrochemical composition of groundwater and the isotopic composition of sulphur compounds in sediments (υ 34 S of sulphide, inorganic sulphate) and groundwater (υ 34 S, υ 18 O of dissolved sulphate) have been investigated to reveal the reasons for elevated concentrations of dissolved groundwater sulphate in the drinking water catchment area of Torgau-Mockritz (Germany).The three most important anthropogenic sources of sulphate identified in this study are historic atmospheric sulphate deposition, predominantly of anthropogenic origin, inorganic fertilization, and dissolution of gypsum from waste dumps. Owing to their overlapping isotopic range, no clear differentiation between the individual anthropogenic sources is possible. Sulphate from the oxidation of sedimentary sulphides, however, was recognized by its negative sulphur isotope signature (υ 34 S < 5‰). The mobilization of sulphate from different soil sulphur species is closely connected with variable isotopic fractionations, resulting in a wide isotopic variation range for the sulphate entering the saturated zone. Generally, sulphur and oxygen isotope ratios of the dissolved groundwater sulphate range from 19 to C37‰ (Vienna Cañon Diablo troilite) and from 2 to C19‰ (Vienna standard mean ocean water), respectively. Sulphate from the majority of groundwater samples can be assigned to anthropogenic sources. Sulphate from sulphide oxidation is especially present in samples from the upper sampling level and the groundwater surface. Sulphate concentrations above 700 mg l 1 are mostly caused by the oxidation of sulphide. Sulphate that occurs in low and moderate concentrations dominantly originates from anthropogenic sources. υ 34 S distribution patterns were used to locate the sources for the elevated sulphate concentrations in the raw water. It was shown that the sulphate is not mobilized in the immediate vicinity of the production wells. Rather, it originates in an area ¾1Ð5 km west of the intake. The main mobilization mechanism there is the oxidation of reduced sedimentary sulphur species.Beyond its local significance, this study presents a general example how changes in the sulphur cycle indicate major, anthropogenically induced alterations of the hydrochemical situation in catchment areas.

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Section: Regional Settingmentioning

confidence: 99%

“…However, different research papers that discuss the behaviour of the oxygen isotopes during the atmospheric oxidation of SO 2 (Holt et al, 1981(Holt et al, , 1982(Holt et al, , 1983McCarthy et al, 1998) suggest a similar range of the υ 18 O in recent and historic deposition.…”

Section: Isotopic Composition Of Atmospheric Sulphur Depositionmentioning

confidence: 99%

Sulphur cycling in the drinking water catchment area of Torgau–Mockritz (Germany): insights from hydrochemical and stable isotope investigations

Knöller

Trettin

Strauch

2005

Hydrological Processes

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“…(Matsuhisa et al, 1978), is a useful tool for estimating the relative importance of different sulfate formation pathways because each oxidant transfers its 17 O signature to the product (Table 1) through SO 2 oxidation (Savarino et al, 2000). SO 2 has 17 O = 0 ‰ due to the rapid isotopic exchange with abundant vapor water whose 17 O is near 0 ‰ (Holt et al, 1981). S(IV) oxidation by H 2 O 2 and O 3 leads to 17 O(SO 2− 4 ) = 0.7 and 6.5 ‰, respectively, on the basis of 17 O(H 2 O 2 ) = 1.4 ‰ (Savarino and Thiemens, 1999) and assuming 17 O(O 3 ) = 26 ‰ (Vicars and Savarino, 2014;Ishino et al, 2017 (Dubey et al, 1997;Luz and Barkan, 2005;Lee et al, 2002;Bao et al, 2000).…”

Section: Introductionmentioning

confidence: 99%

Isotopic constraints on heterogeneous sulfate production in Beijing haze

et al. 2018

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Abstract. Discerning mechanisms of sulfate formation during fine-particle pollution (referred to as haze hereafter) in Beijing is important for understanding the rapid evolution of haze and for developing cost-effective air pollution mitigation strategies. Here we present observations of the oxygen-17 excess of PM 2.5 sulfate ( 17 O(SO 2− 4 )) collected in Beijing haze from October 2014 to January 2015 to constrain possible sulfate formation pathways. Throughout the sampling campaign, the 12-hourly averaged PM 2.5 concentrations ranged from 16 to 323 µg m −3 with a mean of (141 ± 88 (1σ )) µg m −3 , with SO Our estimate suggested that in-cloud reactions dominated sulfate production on polluted days (PDs, PM 2.5 ≥ 75 µg m −3 ) of Case II in October 2014 due to the relatively high cloud liquid water content, with a fractional contribution of up to 68 %. During PDs of Cases I and III-V, heterogeneous sulfate production (P het ) was estimated to contribute 41-54 % to total sulfate formation with a mean of (48 ± 5) %. For the specific mechanisms of heterogeneous oxidation of SO 2 , chemical reaction kinetics calculations suggested S(IV) (= SO 2 q H 2 O + HSO − 3 + SO 2− 3 ) oxidation by H 2 O 2 in aerosol water accounted for 5-13 % of P het . The relative importance of heterogeneous sulfate production by other mechanisms was constrained by our observed 17 O(SO 2− 4 ). Heterogeneous sulfate production via S(IV) oxidation by O 3 was estimated to contribute 21-22 % of P het on average. Heterogeneous sulfate production pathways that result in zero-17 O(SO 2− 4 ), such as S(IV) oxidation by NO 2 in aerosol water and/or by O 2 via a radical chain mechanism, contributed the remaining 66-73 % of P het . The assumption about the thermodynamic state of aerosols (stable or metastable) was found to significantly influence the calculated aerosol pH (7.6 ± 0.1 or 4.7 ± 1.1, respectively), and thus influence the relative importance of heterogeneous sulfate production via S(IV) oxidation by NO 2 and by O 2 . Our local atmospheric conditions-based calculations suggest sulfate formation via NO 2 oxidation can be the dominant pathway in aerosols at high-pH conditions calculated assuming stable state while S(IV) oxidation by O 2 can be the dominant pathway providing that highly acidic aerosols (pH ≤ 3) exist. Our local atmospheric-conditions-based calculations illustrate the utility of 17 O(SO 2− 4 ) for quantifying sulfate forPublished by Copernicus Publications on behalf of the European Geosciences Union. 5516 P. He et al.: Isotopic constraints on heterogeneous sulfate production in Beijing haze mation pathways, but this estimate may be further improved with future regional modeling work.

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“…These studies are in reasonable agreement with concentration measurements, showing that anthropogenic, marine biota, volcanic injections and sea salt are the main sources influencing the sulfate budget. In a series of papers Kumar, 1984, 1988;Holt et al, 1981Holt et al, , 1982Holt et al, , 1983], Holt and collaborators showed that analysis of oxygen 18 isotope was suitable to discriminate between primary combustion sulfates (formed within point sources before emission into the atmosphere) and secondary sulfates (formed from gaseous sulfur compounds, principally SO2 by atmospheric conversion processes). However, single oxygen isotope ratio measurements alone (i.e., 180/160) can not distinguish between mass-dependent and mass-independent processes.…”

Section: Introductionmentioning

confidence: 99%

Laboratory oxygen isotopic study of sulfur (IV) oxidation: Origin of the mass‐independent oxygen isotopic anomaly in atmospheric sulfates and sulfate mineral deposits on Earth

Savarino¹,

Lee²,

Thiemens³

2000

J. Geophys. Res.

152

183

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Abstract. The oxygen isotopic composition (160, 170, and •80) of sulfate formed from different oxidative reactions has been investigated. In the aqueous phase, sulfur oxidation by H202, 03, and 02, catalyzed by Fe(m) and Mn(1I) were studied. In the gas phase we have investigated the only relevant reaction for the atmosphere: SO2 + OH and its chain termination reaction SO3 + H20. The results show that none of these reactions, gas or aqueous phase, produce a mass-independent oxygen isotopic composition in sulfate. Since H202 and 03 are known to possess a mass-independent isotopic signature, we have investigated the possible transfer of this anomaly to sulfate. It appears that both these oxidant species transfer their anomaly. Isotopic analysis shows that two oxygen atoms from H202 are found in the product H2SO4. This result is in accord with previous work. For 03 we found that only one of the original ozone oxygen transfers to the product sulfate. These isotopic results contradict the free radical reaction mechanism proposed by Penkett et al. [1979] but agree with the nonfree radical mechanism suggested by Erickson et al. [1977]. Therefore, it appears that only aqueous phase oxidation produces a mass-independent oxygen isotopic composition in sulfate. This finding is a response of the origin of the mass-independent oxygen isotopic composition of atmospheric and mineral deposits of sulfate on Earth [Bao et al., 2000; Lee, 1997]. Furthermore, this finding allows us to quantify the relative proportion of sulfate production by OH (gas phase formation) and by H202 and 03 (aqueous phase formation). The results can be used to test atmospheric chemical/transport models.

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Oxygen-18 study of the aqueous-phase oxidation of sulfur dioxide

Cited by 84 publications

References 27 publications

Sulphur cycling in the drinking water catchment area of Torgau–Mockritz (Germany): insights from hydrochemical and stable isotope investigations

Sulphur cycling in the drinking water catchment area of Torgau–Mockritz (Germany): insights from hydrochemical and stable isotope investigations

Isotopic constraints on heterogeneous sulfate production in Beijing haze

Laboratory oxygen isotopic study of sulfur (IV) oxidation: Origin of the mass‐independent oxygen isotopic anomaly in atmospheric sulfates and sulfate mineral deposits on Earth

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