Reactions which relate to environmental mobility of arsenic and antimony.  II.  Oxidation of trimethylarsine and trimethylstibine

Parris, George E.; Brinckman, F. E.

doi:10.1021/es60122a010

Cited by 77 publications

(48 citation statements)

References 16 publications

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“…If these oxidized products can be metabolized by microorganisms, then the remobilization of antimony in biological systems can occur. The kinetics of this oxidation appear to be slower than those proposed by the only other antimony oxidation investigations in the literature (187,188).…”

Section: Microbial Methylation Of Antimonymentioning

confidence: 57%

Microbial Methylation of Metalloids: Arsenic, Antimony, and Bismuth

Bentley

Chasteen

2002

Microbiol Mol Biol Rev

517

316

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A significant 19th century public health problem was that the inhabitants of many houses containing wallpaper decorated with green arsenical pigments experienced illness and death. The problem was caused by certain fungi that grew in the presence of inorganic arsenic to form a toxic, garlic-odored gas. The garlic odor was actually put to use in a very delicate microbiological test for arsenic. In 1933, the gas was shown to be trimethylarsine. It was not until 1971 that arsenic methylation by bacteria was demonstrated. Further research in biomethylation has been facilitated by the development of delicate techniques for the determination of arsenic species. As described in this review, many microorganisms (bacteria, fungi, and yeasts) and animals are now known to biomethylate arsenic, forming both volatile (e.g., methylarsines) and nonvolatile (e.g., methylarsonic acid and dimethylarsinic acid) compounds. The enzymatic mechanisms for this biomethylation are discussed. The microbial conversion of sodium arsenate to trimethylarsine proceeds by alternate reduction and methylation steps, with S-adenosylmethionine as the usual methyl donor. Thiols have important roles in the reductions. In anaerobic bacteria, methylcobalamin may be the donor. The other metalloid elements of the periodic table group 15, antimony and bismuth, also undergo biomethylation to some extent. Trimethylstibine formation by microorganisms is now well established, but this process apparently does not occur in animals. Formation of trimethylbismuth by microorganisms has been reported in a few cases. Microbial methylation plays important roles in the biogeochemical cycling of these metalloid elements and possibly in their detoxification. The wheel has come full circle, and public health considerations are again important

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Section: Microbial Methylation Of Antimonymentioning

confidence: 57%

Microbial Methylation of Metalloids: Arsenic, Antimony, and Bismuth

Bentley

Chasteen

2002

Microbiol Mol Biol Rev

517

316

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“…Sb is often thought of as behaving similarly to As, although this generalization is not always with justification (Casiot et al, 2007;Wilson et al, 2010). Dimethylarsinic acid is very soluble in water, in contrast with dialkylstibinic acid, which is polymeric and relatively insoluble (Parris and Brinckman, 1976).…”

Section: Introductionmentioning

confidence: 99%

Speciation of antimony and arsenic in the soils and plants in an old antimony mine

Wei

Chu

et al. 2015

Environmental and Experimental Botany

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a b s t r a c tThe speciation changes of antimony (Sb) in soil-plant system are largely unknown as compared with those of arsenic (As). In this study, indigenous plants and associated soils were sampled at the Xikuangshan Sb mine (XKS), China. The Sb in the soils (441-1472 mg/kg) were far greater than As (32-354 mg/kg), and the Sb and As availabilities in the soils, were 5.5% and 3.9% in average, respectively. HPLC-ICP-MS revealed the presence of four species of Sb in the soils and plants, including Sb III , Sb V , TMSb and UnkSb (unknown). The use of XANES revealed that the UnkSb consisted of inorganic Sb in the form of Sb V . Inorganic Sb were prevalent in the soil and plant samples at the eight sites, whereas TMSb was observed in only a few of the rhizosphere soils, and, in plants at a few of the sites, primarily in the leaves and to a lesser extent in the stems. Arsenic was detected in the soils primarily as inorganic forms, while, DMA was detected in high proportions in all of the plant tissues at all of the sites. The methylation of Sb was far less than that of As in the indigenous plants at XKS. The results suggest that As and Sb differ in transformation characteristics in the soil-plant system in XKS.

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“…We have earlier reported on the formation and chemistry of Me3As(V) and Me3Sb(V) species in protic solvents (27). In view of the oxidation of Me3As (Fig.…”

Section: Resultsmentioning

confidence: 96%

“…This process is held as unlikely inasmuch as the observed 117Sn-or 119Sn-proton spin coupling for Me3Sn+ or Me2Sn2+ ions requires a stable CH3-Sn bond. In addition, little or no hydrolysis of the methyl-metal bond itself (to produce CH4 for example) is seen for any of these ions (27,33). The same NMR sample solutions were also examined by laser-Raman spectrometry which is a method particularly suited for optical spectrometry in aqueous media.…”

Section: Resultsmentioning

confidence: 99%

“…We have quantified the rates of several processes which can compete with the ultimate vaporization of biogenic Me3As into the atmosphere (17,27). These values are summarized in Figure 7, where it can be seen that neither rates of oxidation by 02 in aqueous solution (k < 10-2 M-1 sec-1) nor methylation (quaternization) by Mel (k = 3 x 10-3 M-1 sec-1) significantly dominate.…”

Section: Tranport Of Methylarsenicals From Aqueous Mediamentioning

confidence: 99%

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Questions concerning environmental mobility of arsenic: needs for a chemical data base and means for speciation of trace organoarsenicals.

Brinckman¹,

Parris²,

Blair³

et al. 1977

Environ Health Perspect

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Biomethylation of metals, including arsenic, apparently occurs as a global process. Health control strategies therefore depend on accurate analysis of arsenic's environmental mobility. Determining to what extent biotransformations occur and how resultant organometal(loids) are sequestered in food chains requires sophistication beyond present-day total element determinations. Rather, active molecular forms of arsenic must be speciated for each environmental compartment, and it is necessary to quantify the dynamics of arsenic's mobility. Thus, new chemical facts are needed yielding rates of methylation or demethylation of arsenic; partition coefficients of organoarsenicals between air, water, and organic phases; and arsenic redox chemistry in polar media. NBS research in this context is reviewed with examples of recent results emphasizing speciation methodology. Topic areas discussed are: the nature of aquated methylarsenic species (NMR and laser-Raman spectroscopy); transport of methylarsenicals from aqueous media (gas chromatography-graphite furnace AA detection applied to metabolic Me3As formation); and speciation of involatile organoarsenicals in aqueous media (demonstration of HPLC utilizing element-specific AA detection and appraisal of electrochemical detectors). IntroductionBiotransformations of metalloids such as arsenic have been known for years, but only in recent times has the ubiquitous biomethylation of arsenic (1) and a number of other elements, including heavy metals (2-4), become apparent as a general environmental process (5). Clearly, anthropogenic inputs in inorganic materials can and do enhance such transformations, resulting in transport of volatile or lipidsoluble pollutants. Moreover, there is evidence (6) that even higher organisms, specifically man, can invoke elimination processes which involve formation of methylarsenic compounds. Consequently,

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Reactions which relate to environmental mobility of arsenic and antimony. II. Oxidation of trimethylarsine and trimethylstibine

Cited by 77 publications

References 16 publications

Microbial Methylation of Metalloids: Arsenic, Antimony, and Bismuth

Microbial Methylation of Metalloids: Arsenic, Antimony, and Bismuth

Speciation of antimony and arsenic in the soils and plants in an old antimony mine

Questions concerning environmental mobility of arsenic: needs for a chemical data base and means for speciation of trace organoarsenicals.

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