A novel method to determine trimethylantimony concentrations in plant tissue
Adrien Mestrot A D , Ying Ji B , Susan Tandy B and Wolfgang Wilcke A C
+ Author Affiliations
- Author Affiliations
A University of Bern, Institute of Geography, Hallerstrasse 12, 3012 Bern, Switzerland.
B Eidgenössische Technische Hochschule (ETH) Zurich, Institute of Terrestrial Ecosystems, Universitätstrasse 16, 8092 Zurich, Switzerland.
C Karlsruhe Institute of Technology, Institute of Geography and Geoecology, Reinhard-Baumeister-Platz 1, 76131 Karlsruhe, Germany.
D Corresponding author. Email: adrien.mestrot@giub.unibe.ch
Environmental Chemistry 13(6) 919-926 https://doi.org/10.1071/EN16018
Submitted: 19 January 2016 Accepted: 5 July 2016 Published: 1 August 2016
Environmental context. Antimony enters the soil mostly through mining and shooting activities and can thereafter be taken up by plants. In the soil, antimony may undergo several transformations such as biomethylation, leading to the formation of trimethylantimony. Here, we measured for the first time the uptake and translocation of trimethylantimony in a plant using a new extraction and analysis method.
Abstract. Antimony (Sb) is a relevant pollutant that can be found in elevated concentrations in soils near Sb mines and at shooting ranges. In soils, Sb occurs as trivalent Sb, SbIII, pentavalent Sb, SbV, or trimethylantimony, TMSb ((CH3)3SbO), the latter being the result of microbial biomethylation. It is important to understand the transfer of Sb species from soil to plants to assess the role of Sb in the food chain. However, this research has historically been hampered by the lack of suitable extraction and analytical methods. In this study, we validated an efficient and reliable extraction technique using oxalic acid and ascorbic acid (72.6 ± 1.3 % of Sb extracted) as well as a high-pressure liquid chromatography–inductively coupled plasma mass spectrometry (HPLC-ICP-MS) speciation analysis method to assess the uptake of TMSb in ryegrass (Lolium perenne L.), a common pasture plant, in a hydroponics experiment. Our results show that TMSb and SbIII are not converted to other species during extraction and that TMSb is taken up by ryegrass roots and translocated to the shoots. Our study also points at specific methylation–demethylation mechanisms occurring in the plant. Moreover, an unknown Sb species was found in the shoots of TMSb-treated plants, highlighting the need for further research. These new extraction and speciation methods will enable researchers to study the soil–plant transfer of organo-Sb compounds in a reliable and consistent manner.
Additional keywords: antimony, biomethylation, extraction, speciation, HPLC-ICP-MS.
References
[1] United States Environmental Protection Agency Priority Pollutants and Toxic Pollutants Lists 2014. Available at http://water.epa.gov/scitech/methods/cwa/pollutants.cfm [Verified 6 October 2015].[2] US Geological Survey Mineral Commodity Summary 2015 (U.S. Geological Survey: Reston, VA).
[3] S. Ackermann, R. Gieré, M. Newville, J. Majzlan, Antimony sinks in the weathering crust of bullets from Swiss shooting ranges. Sci. Total Environ. 2009, 407, 1669.
| Antimony sinks in the weathering crust of bullets from Swiss shooting ranges.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD1MXht1GnsrY%3D&md5=cc87ab31f6bbf60a1cb4774c522e174eCAS | 19117594PubMed |
[4] 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. 2011, 159, 2427.
| Distribution, speciation and availability of antimony (Sb) in soils and terrestrial plants from an active Sb-mining area.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC3MXhtFeht7bF&md5=a00da04b3be0db7b2f8897c954668e65CAS | 21767897PubMed |
[5] 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. 2014, 497–498, 319.
| Antimony in the soil–water–plant system at the Su Suergiu abandoned mine (Sardinia, Italy): strategies to mitigate contamination.Crossref | GoogleScholarGoogle Scholar | 25137381PubMed |
[6] 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. 2015, 529, 213.
| Mobility of antimony, arsenic and lead at a former antimony mine, Glendinning, Scotland.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC2MXms1yhsLc%3D&md5=23d7e2fdbd2447e8a96633be42edb5e9CAS | 26011617PubMed |
[7] S. Mitsunobu, T. Harada, Y. Takahashi, Comparison of antimony behavior with that of arsenic under various soil redox conditions. Environ. Sci. Technol. 2006, 40, 7270.
| Comparison of antimony behavior with that of arsenic under various soil redox conditions.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD28XhtVaqs7vI&md5=e036343c87933fd95348513a122be422CAS | 17180977PubMed |
[8] C. Wei, Z. Ge, W. Chu, R. Feng, Speciation of antimony and arsenic in the soils and plants in an old antimony mine. Environ. Exp. Bot. 2015, 109, 31.
| Speciation of antimony and arsenic in the soils and plants in an old antimony mine.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC2cXhsVyhsbzM&md5=27c5d8d503657c59556a2365a71742c3CAS |
[9] I. Corrales, J. Barceló, J. Bech, C. Poschenrieder, Antimony accumulation and toxicity tolerance mechanisms in Trifolium species. J. Geochem. Explor. 2014, 147, 167.
| Antimony accumulation and toxicity tolerance mechanisms in Trifolium species.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC2cXhtFygsbzP&md5=475bdfdf06647e2c99b05d05ebf7b0e8CAS |
[10] 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. 2014, 475, 83.
| Antimony uptake, translocation and speciation in rice plants exposed to antimonite and antimonate.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC2cXhs1ylsLo%3D&md5=a0bd330e03b4f9c667a325ab646111ceCAS | 24419289PubMed |
[11] X. Cui, Y. Wang, K. Hockmann, D. Zhou, Effect of iron plaque on antimony uptake by rice (Oryza sativa L.). Environ. Pollut. 2015, 204, 133.
| Effect of iron plaque on antimony uptake by rice (Oryza sativa L.).Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC2MXntlWmu7c%3D&md5=fc5e80a8c72c02fb42aaac39c7296725CAS | 25947970PubMed |
[12] F. Cai, J. Ren, S. Tao, X. Wang, Uptake, translocation and transformation of antimony in rice (Oryza sativa L.) seedlings. Environ. Pollut. 2016, 209, 169.
| Uptake, translocation and transformation of antimony in rice (Oryza sativa L.) seedlings.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC2MXitVSktrbI&md5=680410ba3058023e39a499d3fbd8edabCAS | 26686058PubMed |
[13] 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 2013, 371, 155.
| Effects of waterlogging on the solubility and redox state of Sb in a shooting range soil and its uptake by grasses: a tank experiment.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC3sXksVKqtr8%3D&md5=19f74c2b3221f6afefd849a23cfb4c95CAS |
[14] R. Kettler, K. Schenk, Indemnisations en Vertu de l’OTAS pour les Installations de Tir. Communication de l’OFEV Destinée aux Autorités D’Exécution. L’Environnement Pratique No. 0634 2006 (OFEV: Bern, Switzerland).
[15] M. Filella, Alkyl derivatives of antimony in the environment. Met. Ions Life Sci. 2010, 7, 267.
| Alkyl derivatives of antimony in the environment.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC3cXjvVegsr8%3D&md5=dae57a866f01d36b9ecd70bdaeaa1ec3CAS | 20877810PubMed |
[16] E. Dopp, A. D. Kligerman, R. A. Diaz-Bone, Organoarsenicals. Uptake, metabolism, and toxicity. Met. Ions Life Sci. 2010, 7, 231.
| Organoarsenicals. Uptake, metabolism, and toxicity.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC3cXjvVegsr4%3D&md5=94e0ecc8ce90c9e7b6b9dfc6a5cc9aa0CAS | 20877809PubMed |
[17] K. A. Graeme, C. V. Pollack, Heavy metal toxicity, part I: arsenic and mercury. J. Emerg. Med. 1998, 16, 45.
| Heavy metal toxicity, part I: arsenic and mercury.Crossref | GoogleScholarGoogle Scholar | 1:STN:280:DyaK1c7jt1WjsA%3D%3D&md5=b1ccc7ab7dca25b84f983d8a71f0b6e9CAS | 9472760PubMed |
[18] A. Pierart, M. Shahid, N. Sejalon-Delmas, C. Dumat, Antimony bioavailability: knowledge and research perspectives for sustainable agricultures. J. Hazard. Mater. 2015, 289, 219.
| Antimony bioavailability: knowledge and research perspectives for sustainable agricultures.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC2MXitlSguro%3D&md5=1c69a998609e11452057ebc2e097c2e7CAS | 25726907PubMed |
[19] R. Bentley, T. G. Chasteen, Microbial methylation of metalloids: arsenic, antimony, and bismuth. Microbiol. Mol. Biol. Rev. 2002, 66, 250.
| Microbial methylation of metalloids: arsenic, antimony, and bismuth.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD38XltFSltrs%3D&md5=0a8e66bce89038775c4595d2519fcc25CAS | 12040126PubMed |
[20] H. Yang, M. He, Adsorption of methylantimony and methylarsenic on soils, sediments, and mine tailings from antimony mine area. Microchem. J. 2015, 123, 158.
| Adsorption of methylantimony and methylarsenic on soils, sediments, and mine tailings from antimony mine area.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC2MXhtVOls73O&md5=b4c7a359702577c5dc6989e5b1a9c4b1CAS |
[21] 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 2009, 78, 820.
| 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.Crossref | GoogleScholarGoogle Scholar | 19269435PubMed |
[22] 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 1999, 124, 1243.
| An analytical method for the detection of methylantimony species in environmental matrices: methylantimony levels in some UK plant material.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaK1MXkvFKitrc%3D&md5=11634e5ee3e484a0b64bc6f32923a942CAS |
[23] R. Miravet, E. Bonilla, J. F. Lopez-Sanchez, R. Rubio, Antimony speciation in terrestrial plants. Comparative studies on extraction methods. J. Environ. Monit. 2005, 7, 1207.
| Antimony speciation in terrestrial plants. Comparative studies on extraction methods.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD2MXht1ers73F&md5=583d784667a4d2b6f4e7111b43d8fc80CAS | 16307073PubMed |
[24] 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. 2010, 29, 28.
| 1:CAS:528:DC%2BD1MXhsFOqu77P&md5=b93101f9b7f8ea9abdc939977db0b2f5CAS |
[25] 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 1998, 359, 245.
| Speciation of antimony(III), antimony(V) and trimethylstiboxide by ion chromatography with inductively coupled plasma atomic emission spectrometric and mass spectrometric detection.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaK1cXhvVGntbc%3D&md5=817609c7019b274717d43adb4431de1fCAS |
[26] M. J. Nash, J. E. Maskall, S. J. Hill, Developments with anion-exchange stationary phases for HPLC-ICP-MS analysis of antimony species. Analyst 2006, 131, 724.
| Developments with anion-exchange stationary phases for HPLC-ICP-MS analysis of antimony species.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD28XkvFOitbs%3D&md5=7f8e9552ed53d08fdca10e76fe94b67eCAS | 16732360PubMed |
[27] 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. 2002, 17, 1400.
| Optimization of an HPLC-HG-AFS method for screening SbV, SbIII, and Me3SbBr2 in water samples.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD38XnsVeisrg%3D&md5=bb866b6c85b07a31ce92fb1b16fa67a5CAS |
[28] A. H. Pétursdóttir, H. Gunnlaugsdottir, H. Joerundsdottir, A. Mestrot, E. M. Krupp, J. Feldmann, HPLC-HG-ICP-MS: a sensitive and selective method for inorganic arsenic in seafood. Anal. Bioanal. Chem. 2012, 404, 2185.
| HPLC-HG-ICP-MS: a sensitive and selective method for inorganic arsenic in seafood.Crossref | GoogleScholarGoogle Scholar | 22926131PubMed |
[29] K. Marschner, S. Musil, J. Dëdina, Achieving 100 % efficient post-column hydride generation for As speciation analysis by atomic fluorescence spectrometry. Anal. Chem. 2016, 88, 4041.
| Achieving 100 % efficient post-column hydride generation for As speciation analysis by atomic fluorescence spectrometry.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC28Xjs1Wjs7s%3D&md5=99f9f79767da2a506024eca58fae7f58CAS | 26938848PubMed |
[30] 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 2005, 553, 214.
| Antimony speciation analysis in sediment reference materials using high-performance liquid chromatography coupled to hydride generation atomic fluorescence spectrometry.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD2MXhtFKmtb7M&md5=dabb6d9d5a9b693c678f1bf52d89625dCAS |
[31] Z. Ge, C. 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. 2013, 51, 391.
| 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.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC3sXlsVGksrk%3D&md5=e6498b43ca67c69e32f771327b23f87aCAS | 23019249PubMed |
[32] D. D. Link, P. J. Walter, H. M. Kingston, Development and validation of the new IPA microwave-assisted beach method 3051A. Environ. Sci. Technol. 1998, 32, 3628.
| Development and validation of the new IPA microwave-assisted beach method 3051A.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaK1cXmtVelt7s%3D&md5=6c974cb12f2f927174b4de1b96a035bdCAS |
[33] 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 2004, 1052, 121.
| New considerations about the separation and quantification of antimony species by ion chromatography–hydride generation atomic fluorescence spectrometry.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD2cXotV2hsbw%3D&md5=c33594bf22fa51107238b3aa5839804eCAS | 15527128PubMed |
[34] E. H. Larsen, S. Sturup, Carbon-enhanced inductively coupled plasma mass spectrometric detection of arsenic and selenium and its application to arsenic speciation. J. Anal. At. Spectrom. 1994, 9, 1099.
| Carbon-enhanced inductively coupled plasma mass spectrometric detection of arsenic and selenium and its application to arsenic speciation.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaK2MXhvFGitbc%3D&md5=56c526696d2dd8fe5e1a35dbe8053991CAS |
[35] 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 2012, 352, 41.
| Influence of iron plaque and cultivars on antimony uptake by and translocation in rice (Oryza sativa L.) seedlings exposed to SbIII or SbV.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC38Xjs1Omu7w%3D&md5=551ae40c2de7b93b93b5756c2554dd5fCAS |
[36] 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. 2007, 20, 1269.
| Structural evidence of the similarity of Sb(OH)3 and As(OH)3 with glycerol: implications for their uptake.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD2sXpsVelu74%3D&md5=fca02d59a2146142a4788a66a284739cCAS | 17713961PubMed |
[37] T. Kamiya, T. Fujiwara, Arabidopsis NIP1;1 transports antimonite and determines antimonite sensitivity. Plant Cell Physiol. 2009, 50, 1977.
| Arabidopsis NIP1;1 transports antimonite and determines antimonite sensitivity.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD1MXhsVajur%2FK&md5=4cce849d0a4626560d7dd007ebf882cfCAS | 19783540PubMed |
[38] 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. 2015, 206, 49.
| Uptake of antimonite and antimonate by arsenic hyperaccumulator Pteris vittata: effects of chemical analogs and transporter inhibitor.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC2MXhtV2ls7bJ&md5=53b5c9252848dcf6ecbd4f76592c8810CAS | 26142750PubMed |
[39] C. Lomax, W. Liu, L. Wu, K. Xue, J. Xiong, J. Zhou, S. P. McGrath, A. A. Meharg, A. J. Miller, F. Zhao, Methylated arsenic species in plants originate from soil microorganisms. New Phytol. 2012, 193, 665.
| Methylated arsenic species in plants originate from soil microorganisms.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC38XitVejsbk%3D&md5=d8b94c897558e9a671274af3ed088104CAS | 22098145PubMed |
