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Thiolation of trimethylantimony: A new cornerstone of the biogeochemistry of antimony


Antimony (Sb), a toxic metalloid, has received increasing attentions due to recent awareness of its rich chemistry. The element and its compounds are being considered as pollutants of priority interest both in the EU and the United States. The toxicity of antimony depends on its speciation: antimonite was reported to be more toxic than antimonate. Extensive research has been conducted on the different pathways of its environmental chemistry including redox transformations, thiolation and methylation reactions. Methylantimony species can be generated by different microbes especially sulfate-reducing bacteria. Thiolated Sb species such as trithioantimonate and tetrathioantimonate have been found in geothermal waters. Recently, monothioantimonate and dithioantimonate were identified in the incubated sediments. However, methylthioantimony species has not been reported.

The new study:
The purpose of this new study was to identify thiolated methylantimony species. Their existence is postulated as an analogue to methylarsenicals which are prone to be thiolated  by bacteria in presence of biogenic sulfide. For this reason, the researchers from China conducted microcosm incubations using the microbiota from hot spring sediments and paddy soil. Incubation experiments were conducted with Trimethylantimony (TMSb) at two concentration levels (10 and 100 µM) at 30°C with a PH = 6.8 in the dark anaerobically. Liquid samples were collected after 1, 2 and 5-day's incubation.

Solid phase extraction cartridges were used to preconcentrate the thiolated Sb species. TMMTSb was separated using HPLC-ICP-MS and further identified by Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS). Raman spectra demonstrated the Sb-S bonding structure. 1H and 13C NMR spectra indicated the presence of three identical methyl groups. Conclusively, the molecular formula was verified as SbS(CH3)3.

The authors concluded from the results, that the formation of TMMTSb in hot spring sediments and paddy soils was done by the help of sulfate-reducing bacteria belonging  to the class Clostridia. Since these bacteria are present in a variety of natural end engineered environments, the TMMTSb may play a considerable role to the biogeochemistry of Sb.

The original publication

Zhi-peng Yin, Li Ye, Wen Zhong, Chuan-yong Jing, Thiolation of trimethylantimony: Identification and structural characterization, J. Hazard. Mater., 423 (2022) 127259. DOI: 10.1016/j.jhazmat.2021.127259

Instrumentation used:

PerkinElmer Inc. - NexION 350 ICP-MS Spectrometer
PerkinElmer Inc. - Flexar LC

Related studies (newest first):

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S. Yamamura, C. Iida, Y. Kobayashi, M. Watanabe, S. Amachi, Production of two morphologically different antimony trioxides by a novel antimonate-reducing bacterium. Geobacter Sp. Svr. J. Hazard. Mater. 411 (2021) 125100. DOI: 10.1016/j.jhazmat.2021.125100

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last time modified: January 17, 2022


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