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Plant uptake of trimethylantimony from contaminated soils


Antimony (Sb) is a hazardous pollutant that can be found at elevated concentrations in soils contaminated by mining activities or shooting ranges. While classified as a priority pollutant as well as a toxic pollutant by the US EPA, it has been much less studied than other relevant pollutants such as arsenic, lead or mercury. In soils, Sb occurs as inorganic trivalent Sb species, Sb(III), inorganic pentavalent Sb species, Sb(V), or trimethylantimony, TMSb. The latter organometallic species is a result of microbial biomethylation. In order to understand the transfer of the different antimony species into the food chain, it is important to study the first step, namely plant uptake from contaminated soil. In a review about alkylated antimony species, the author Filella states that Sb has been largely overlooked as an element of environmental concern and that the data on the physical and chemical properties of these organic compounds are fragmentary and old. Unfortunately investigations related to antimony speciation were limited by the availability of suitable extraction and analytical methods for antimony speciation analysis.

The new study:
The group of researchers introduce a new method that allows quantitative extraction of TMSb from different parts of plants using oxalic and ascorbic acid. The extraction method was combined with a HPLC-ICP-MS method for speciation analysis using ammonium tartarate as mobile phase under isocratic conditions.

The plant used for the investigations was ryegrass, grown in a growth chamber and exposed to the different Sb species via nutrient solutions, that were replaced every two days in order to reduce change of Sb speciation.  

After harvest, plant were separated into shoots and roots, washed and dried before grinding. Extraction of Sb species was performed using a newly developed method using oxalic and acetic acids in an ultrasonic bath for 30 min. This method recovered more than 70% of the total antimony. Speciation analysis was performed by using HPLC-ICP-MS using a reversed-phase column under isocratic conditions. This speciation method recovered the antimony species extracted quantitatively.

Figure: Lolium perenne (ryegrass)

Most of the antimony in the ryegrass was found in the roots and Sb concentration were 100 times higher for Sb(III)-exposed plants than for Sb(V)- or TMSb-exposed plants. In roots and shoots of the Sb(III)-exposed plants, Sb(III) contributed to about 45 and 26 % of the total Sb. The rest of the antimony present mostly consisted of Sb(V), except in the roots, where a very small part (~0.5%) was TMSb.

In plants exposed to Sb(V) only about 60% of the Sb in the roots was found to be Sb(V) while the rest was Sb(III). Interestingly, no Sb(III) was found in the shoots. Most importantly, TMSb was found in the shoots of Sb(V) exposed plants but not in the roots indicating fast transport from the roots and accumulation in the shoots.  

Remarkably, the roots of plants exposed to TMSb contained more than 75% of the Sb taken up as TMSb while the rest was exclusively Sb(V). This suggests that demethylation occurs at the roots or at their interface with the nutrient solution since no inorganic Sb was present in the nutrient solution and no degradation occurred during plant extraction. In the shoots a similar part of the total Sb was TMSb while the Sb(V) made up to only 15%. An unknown species occurred in the shoots with about 8% of the total Sb that probably could be DMSb or MMSb. The researchers were not able to identify this unknown species due to missing standards and the incompatibility of the mobile phase with ESI-MS for structure elucidation.

The authors are convinced that their method, while not without some interconversion problems for the inorganic species, will be useful for studying the soil-plant system with respect to antimony species.

The original study:

Adrien Mestrot, Ying Ji, Susan Tandy, Wolfgang Wilcke, A novel method to determine trimethylantimony concentrations in plant tissue, Environ. Chem. (2016). doi: 10.1071/EN16018

Used Instrumentation and materials:

Agilent 7700 X ICP-MS
Agilent HPLC Series 1200
Milestone Ethos 1600

Related Studies (newest first):

F. Cai, J. Ren, S. Tao, X. Wang, Uptake, translocation and transformation of antimony in rice (Oryza sativa L.) seedlings. Environ. Pollut., 209 (2016)  169-176. doi: 10.1016/j.envpol.2015.11.033

X. Cui, Y. Wang, K. Hockmann, D. Zhou, Effect of iron plaque on antimony uptake by rice (Oryza sativa L.). Environ. Pollut., 204 (2015) 133-140. doi: 10.1016/j.envpol.2015.04.019

C.Y. Wei, Z.F. Ge, W.S. Chu, R.W. Feng, Speciation of antimony and arsenic in the soils and plants in an old antimony mine. Environ. Exp. Bot., 109 (2015) 31-39. doi: 10.1016/j.envexpbot.2014.08.002

K. Macgregor, G. MacKinnon, J. G. Farmer, M. C. Graham, Mobility of antimony, arsenic and lead at a former antimony mine, Glendinning, Scotland. Sci. Total Environ., 529 (2015) 213-222. doi: 10.1016/j.scitotenv.2015.04.039

A. Pierart, M. Shahid, N. Sejalon-Delmas, C. Dumat, Antimony bioavailability: knowledge and research perspectives for sustainable agricultures. J. Hazard. Mater., 289 (2015) 219-234. doi: 10.1016/j.jhazmat.2015.02.011

H.L. Yang, M.C. He, Adsorption of methylantimony and methylarsenic on soils, sediments, and mine tailings from antimony mine area. Microchem. J., 123 (2015) 158-163. doi: 10.1016/j.microc.2015.06.005

R. Tisarum, Y. Chen, X. Dong, J. T. Lessl, L. Q. Ma, Uptake of antimonite and antimonate by arsenic hyperaccumulator Pteris vittata: effects of chemical analogs and transporter inhibitor. Environ. Pollut., 206 (2015) 49-55. doi: 10.1016/j.envpol2015.06.029

J. Ren, L. Q. Ma, H. Sun, F. Cai, J. Luo, Antimony uptake, translocation and speciation in rice plants exposed to antimonite and antimonate. Sci. Total Environ., 475 (2014) 83-89. doi: 10.1016/j.scitotenv.2013.12.103

I. Corrales, J. Barceló, J. Bech, C. Poschenrieder, Antimony accumulation and toxicity tolerance mechanisms in Trifolium species. J. Geochem. Explor., 147 (2014) 167-172. doi: 10.1016/j.gexplo.2014.07.002

R. Cidu, R. Biddau, E. Dore, A. Vacca, L. Marini, Antimony in the soil–water–plant system at the Su Suergiu abandoned mine (Sardinia, Italy): strategies to mitigate contamination. Sci. Total Environ.,497–498 (2014) 319-331.  doi: 10.1016/j.scitotenv.2014.07.117

X. Wan, S. Tandy, K. Hockmann, R. Schulin, Effects of waterlogging on the solubility and redox state of Sb in a shooting range soil and its uptake by grasses: a tank experiment. Plant Soil, 371 (2013) 155-166. doi: 10.1007/s11104-013-1684-2

Z.F. Ge, C.Y. Wei, Simultaneous analysis of SbIII, SbV and TMSb by high-performance liquid chromatography–inductively coupled plasma–mass spectrometry detection: application to antimony speciation in soil samples. J. Chromatogr. Sci., 51 (2013) 391-399. doi: 10.1093/chromsci/bms153

Y. Huang, Z. Chen, W. Liu, Influence of iron plaque and cultivars on antimony uptake by and translocation in rice (Oryza sativa L.) seedlings exposed to SbIII or SbV. Plant Soil, 352 (2012) 41-49. doi: 10.1007/s11104-011-0973-x  

G. Okkenhaug, Y. Zhu, L. Luo, M. Lei, X. Li, J. Mulder, Distribution, speciation and availability of antimony (Sb) in soils and terrestrial plants from an active Sb-mining area. Environ. Pollut., 159 (2011) 2427-2434. doi: 10.1016/j.envpol.2011.06.028

Monserrat Filella, Alkyl derivatives of antimony in the environment. Met. Ions Life Sci., 7 (2010) 267-301. doi: 10.1039/9781849730822-00267

R. Miravet, E. Hernandez-Nataren, A. Sahuquillo, R. Rubio, J. F. Lopez-Sanchez, Speciation of antimony in environmental matrices by coupled techniques. TrAC, Trends Anal. Chem., 29 (2010) 28-39. doi: 10.1016/j.trac.2009.10.006

K. Müller, B. Daus, J. Mattusch, H. Staerk, R. Wennrich, Simultaneous determination of inorganic and organic antimony species by using anion-exchange phases for HPLC-ICP-MS and their application to plant extracts of Pteris vittata. Talanta, 78 (2009) 820-826. doi: 10.1016/j.talanta.2008.12.059

T. Kamiya, T. Fujiwara, Arabidopsis NIP1;1 transports antimonite and determines antimonite sensitivity. Plant Cell Physiol., 50 (2009) 1977-1981. doi: 10.1093/PCP/PCP130

A. Porquet, M. Filella, Structural evidence of the similarity of Sb(OH)3 and As(OH)3 with glycerol: implications for their uptake. Chem. Res. Toxicol., 20 (2007) 1269-1276. doi: 10.1021/tx700110m
S. Mitsunobu, T. Harada, Y. Takahashi, Comparison of antimony behavior with that of arsenic under various soil redox conditions. Environ. Sci. Technol. 40 (2006) 7270-7276. doi: 10.1021/es060694x

M. J. Nash, J. E. Maskall, S. J. Hill, Developments with anion-exchange stationary phases for HPLC-ICP-MS analysis of antimony species. Analyst, 131 (2006) 724-730. doi: 10.1039/b600155f

R. Miravet, E. Bonilla, J. F. Lopez-Sanchez, R. Rubio, Antimony speciation in terrestrial plants. Comparative studies on extraction methods. J. Environ. Monit., 7 (2005) 1207-1213. doi: 10.1039/b509115b

M. Potin-Gautier, F. Pannier, W. Quiroz, H. Pinochet, I. de Gregori, Antimony speciation analysis in sediment reference materials using high-performance liquid chromatography coupled to hydride generation atomic fluorescence spectrometry. Anal. Chim. Acta, 553 (2005) 214-222. doi: 10.1016/j.aca.2005.07.055

R. Miravet, J. F. López-Sánchez, R. Rubio, New considerations about the separation and quantification of antimony species by ion chromatography–hydride generation atomic fluorescence spectrometry. J. Chromatogr. A, 1052 (2004) 121-129. doi: 10.1016/j.chroma.2004.08.021

R. Bentley, T. G. Chasteen, Microbial methylation of metalloids: arsenic, antimony, and bismuth. Microbiol. Mol. Biol. Rev., 66 (2002) 250-271. doi: 10.1128/MMBR.66.2.250-271.2002

A. Sayago, R. Beltran, M. A. F. Recamales, J. L. Gomez-Ariza, Optimization of an HPLC-HG-AFS method for screening SbV, SbIII, and Me3SbBr2 in water samples. J. Anal. At. Spectrom., 17 (2002) 1400-1404. doi: 10.1039/b202065n

P. Craig, S. Forster, R. Jenkins, D. Miller, An analytical method for the detection of methylantimony species in environmental matrices: methylantimony levels in some UK plant material. Analyst, 124 (1999) 1243-1248. doi: 10.1039/A903787J

N. Ulrich, Speciation of antimony(III), antimony(V) and trimethylstiboxide by ion chromatography with inductively coupled plasma atomic emission spectrometric and mass spectrometric detection. Anal. Chim. Acta, 359 (1998) 245-253. doi: 10.1016/S0003-2670(97)00656-9

 Related EVISA Resources

Link Database: Antimony cycling in the environment
Link Database: Toxicity of antimony species

Related News

April 14, 2010: Antimony mine disaster
August 16, 2006: Toxic antimony species found in beverages stored in PET containers

last time modified: September 16, 2016

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