Chinese researchers have identified a previously unknown Sb species, trimethylmonothioantimony (TMMTSb). TMMTSb was readily formed when trimethylantimony (TMSb) reacted with sulphide.
Background: 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 sulphide. 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 in 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):
L. Ye, C.Y. Jing,
Environmental geochemistry of thioantimony: formation, structure and transformation as compared with thioarsenic, Environ. Sci.: Processes Impacts, 23 (2021) 1863-1872.
DOI: 10.1039/D1EM00261A 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 B. Planer-Friedrich, J. Forberg, R. Lohmayer, C.F. Kerl, F. Boeing, H. Kaasalainen, A. Stefánsson,
Relative abundance of thiolated species of As, Mo, W, and Sb in hot springs of Yellowstone National Park and Iceland. Environ. Sci. Technol. 54 (2020) 4295–4304.
DOI: 10.1021/acs.est.0c00668 Q.H. Guo,
B. Planer-Friedrich, L. Luo, M.L. Liu, G. Wu, Y.M. Li, Q. Zhao,
Speciation of antimony in representative sulfidic hot springs in the YST geothermal province (China) and its immobilization by spring sediments. Environ. Pollut. 266 (2020) 115221.
DOI: 10.1016/j.envpol.2020.115221 L. Ye, X.G. Meng, C.Y. Jing,
Influence of sulfur on the mobility of arsenic and antimony during oxic-anoxic cycles: Differences and competition. Geochim. Cosmochim. Acta 288 (2020) 51–67.
DOI: 10.1016/j.gca.2020.08.007 P.C. Loni, M. Wu, W. Wang, H. Wang, L. Ma, C. Liu, Y. Song, O.H. Tuovinen,
Mechanism of microbial dissolution and oxidation of antimony in stibnite under ambient conditions. J. Hazard. Mater. 385 (2020) 121561.
DOI: 10.1016/j.jhazmat.2019.121561 M.C. He, N.N. Wang, X.J. Long, C.J. Zhang, C.L. Ma, Q.Y. Zhong, A.H. Wang, Y. Wang, A. Pervaiz, J. Shan,
Antimony speciation in the environment: Recent advances in understanding the biogeochemical processes and ecological effects. J. Environ. Sci. (China) 75 (2019) 14–39.
DOI: 10.1016/j.jes.2018.05.023
L. Ye, S. Qiu, S., Li, X., Jiang, Y., Jing, C., 2018.
Antimony exposure and speciation in human biomarkers near an active mining area in Hunan, China. Sci. Total Environ., 640–641 (2018) 1–8.
DOI: 10.1016/j.scitotenv.2018.05.267 L. Yan, J. Song, T. Chan, C. Jing,
Insights into antimony adsorption on {001} TiO2: XAFS and DFT study. Environ. Sci. Technol. 51 (2017) 6335–6341.
DOI: 10.1021/acs.est.7b00807 H.L. Yang, M.C. He,
Speciation of antimony in soils and sediments by liquid chromatography-hydride generation-atomic fluorescence spectrometry. Anal. Lett., 48 (2015) 1941–1953.
DOI: 10.1080/00032719.2015.1004077 B. Planer-Friedrich, A.C. Scheinost,
Formation and structural characterization of thioantimony species and their natural occurrence in geothermal waters. Environ. Sci. Technol. 45 (2011) 6855–6863.
DOI: 10.1021/es201003k M. Filella, P.A. Williams,
Antimony biomethylation in culture media revisited in the light of solubility and chemical speciation considerations. Environ. Toxicol. 25 (2010) 431–439.
DOI: 10.1002/tox.20587 L. Duester, R.A. Diaz-Bone, J. Kösters,
A.V. Hirner, Methylated arsenic, antimony and tin species in soils. J. Environ. Monit. 7 (2005) 1186–1193.
DOI: 10.1039/b508206d S. Wehmeier,
J. Feldmann, Investigation into antimony mobility in sewage sludge fermentation. J. Environ. Monit 7 (2005) 1194–1199.
DOI: 10.1039/b509538g K. Michalke, E.B. Wickenheiser, M. Mehring,
A.V. Hirner, R. Hensel,
Production of volatile derivatives of metal(loid)s by microflora involved in anaerobic digestion of sewage sludge. Appl. Environ. Microbiol. 66 (2000) 2791–2796.
DOI: 10.1128/AEM.66.7.2791-2796.2000
J. Lintschinger, O. Schramel, A. Kettrup,
The analysis of antimony species by using ESI-MS and HPLC-ICP-MS. Fresenius. J. Anal. Chem. 361 (1998) 96–102.
DOI: 10.1007/s002160050841
A.V. Hirner, J. Feldmann,
E. Krupp, R. Grumping, R. Goguel,
W.R. Cullen,
Metal(loid)organic compounds in geothermal gases and waters. Org. Geochem. 29 (1998) 1765–1778.
DOI: 10.1016/S0146-6380(98)00153-3 R.O. Jenkins, P.J. Craig,
W. Goessler, D. Miller, N. Ostah, K.J. Irgolic,
Biomethylation of inorganic antimony compounds by an aerobic fungus: Scopulariopsis brevicaulis. Environ. Sci. Technol. 32 (1998) 882–885.
DOI: 10.1021/es970824p
M.O. Andreae, P.N. Froelich,
Arsenic, antimony, and germanium biogeochemistry in the Baltic sea. Tellus Ser. B-Chem. Phys. Meteorol. 36 (1984) 101–117.
DOI: 10.1111/j.1600-0889.1984.tb00232.x M.O. Andreae, J.F. Asmode, P. Foster, L. Vantdack,
Determination of antimony (III), antimony(V), and methylantimony species in natural-waters by atomic absorption spectrometry with hydride generation. Anal. Chem. 53 (1981) 1766–1771.
DOI: 10.1021/ac00235a012
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