Arsenic (As) occurs in a variety of different chemical forms, among them volatile (gaseous) species, usually referred to as arsine and methylarsines. Here we demonstrate that arsine and methylarsines are stable in air in concentrations at the μg/L gas level. We determined half-lives of approximately 8 h under daytime conditions (UV light) for all methylated arsines, while the same species were found to be considerably more stable in night-time (dark) conditions. Arsine (AsH₃) showed under both day and night-time conditions, considerably higher stabilities than methylated arsines. We show here that volatile As species seem stable enough to travel considerable distances in the atmosphere from a point source before converting into nonvolatile, oxidized compounds. Also, the degradation pathway leading to the conversion to nonvolatile compounds was investigated using computational chemistry. Arsine and methylarsines' reactions with the hydroxyl radical (•OH) as well as As-C and As-H bonds strengths in the species studied were modeled. Results showed that conversion could not be explained by H abstraction, nor by OH addition. Moreover, it was found that As-C and As-H bonds strengths are not the determining factor responsible for the decrease in stability with ascending methylation of the different volatile arsine species, as previously suggested.
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Sci Total Environ
April 2022
School of Civil and Environmental Engineering, Cornell University, Ithaca, NY 14853, USA. Electronic address:
Flooded soils are important environments for the biomethylation and subsequent volatilization of arsenic (As), a contaminant of global concern. Conversion of inorganic to methylated oxyarsenic species is thought to be the rate-limiting step in the production and emission of volatile (methyl)arsines. While methanogens and sulfate-reducing bacteria (SRB) have been identified as important regulators of methylated oxyarsenic concentrations in anaerobic soils, the effects of these microbial groups on biovolatilization remain unclear.
View Article and Find Full Text PDFSci Total Environ
February 2018
Chemische Analytik, BayCEER, University of Bayreuth, D-95440 Bayreuth, Germany.
To quantify arsenic (As) volatilisation by peatlands and to elucidate the environmental factors governing As volatilisation, a series of anoxic incubations with acidic fen soil collected in northeast Bavaria in Germany were performed at 15°C for 4months. Arsenic volatilisation summed to 2.32ng As in the control, which was 1.
View Article and Find Full Text PDFEnviron Sci Technol
May 2011
TESLA (Trace Element Speciation Laboratory), Chemistry Department, University of Aberdeen, Aberdeen, AB24 3UE, UK.
Arsenic (As) occurs in a variety of different chemical forms, among them volatile (gaseous) species, usually referred to as arsine and methylarsines. Here we demonstrate that arsine and methylarsines are stable in air in concentrations at the μg/L gas level. We determined half-lives of approximately 8 h under daytime conditions (UV light) for all methylated arsines, while the same species were found to be considerably more stable in night-time (dark) conditions.
View Article and Find Full Text PDFEnviron Sci Technol
March 2011
Institute of Biological and Environmental Sciences, University of Aberdeen, Cruickshank Building, St Machar Drive, Aberdeen AB24 3UU, United Kingdom.
The biogeochemical cycle of arsenic (As) has been extensively studied over the past decades because As is an environmentally ubiquitous, nonthreshold carcinogen, which is often elevated in drinking water and food. It has been known for over a century that micro-organisms can volatilize inorganic As salts to arsines (arsine AsH(3), mono-, di-, and trimethylarsines, MeAsH(2), Me(2)AsH, and TMAs, respectively), but this part of the As cycle, with the exception of geothermal environs, has been almost entirely neglected because of a lack of suited field measurement approaches. Here, a validated, robust, and low-level field-deployable method employing arsine chemotrapping was used to quantify and qualify arsines emanating from soil surfaces in the field.
View Article and Find Full Text PDFSpectrochim Acta Part B At Spectrosc
June 2008
Institute of Analytical Chemistry of the ASCR, v.v.i., Vídeòská 1083, 14220 Prague, Czech Republic.
An improvement of current method of selective hydride generation based on pre-reduction for differentiation of tri- and pentavalent arsenicals is described, applied for the oxidation state specific speciation analysis of inorganic, mono-, di- and trimethylated arsenicals with minimum sample pretreatment using atomic absorption spectrometry with the multiatomizer. The preconcentration and separation of arsine, methylarsine, dimethylarsine and trimethylarsine is then carried out by means of cryotrapping. Presented study shows that 2% (m/v) L-cysteine hydrochloride monohydrate (L-cys) currently used for off-line pre-reduction of pentavalent arsenicals can be substituted with 1% (m/v) thioglycolic acid (TGA).
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