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Arsenic sequestration by organic sulphur in peat

Nature Geoscience volume 5, pages 66–73 (2012)Cite this article

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Abstract

Wetlands cover more than 6% of the global ice-free land area, and have been recognized as important sinks for arsenic. Wetland soils and sediments are subject to frequent changes in redox conditions, driven by fluctuations in the water table and shifts in biological activity. Under oxic conditions, natural organic matter promotes arsenic release from metal-(hydr)oxides, thereby enhancing arsenic mobility. Under strongly reducing conditions, however, organic matter triggers the formation of arsenic-sequestering sulphides, leading to a reduction in arsenic mobility. Furthermore, the sorption of arsenic to natural organic matter is increasingly thought to suppress arsenic mobility, but the binding mechanisms have remained elusive. Here we use X-ray absorption spectroscopy to analyse the speciation of solid-phase arsenic in peat samples collected from a naturally arsenic-enriched peatland in Switzerland. We show that natural organic matter can completely sequester arsenic through the formation of covalent bonds between trivalent arsenic and organic sulphur groups, which have an average arsenic–sulphur bond distance of 2.26 Å. We suggest that by binding arsenic in this way, natural organic matter plays an active role in arsenic immobilization in sulphur-enriched, anoxic wetlands.

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Figure 1: Element distribution and geochemical conditions in four selected peat profiles from Gola di Lago, Switzerland.
Figure 2: Arsenic K-edge XAS data of selected peat samples and reference compounds.
Figure 3: Shell-fit results for two organic As compounds (I, II) and a peat sample (III) from profile B1 (179 cm).
Figure 4: Iron K-edge XAS data of selected peat samples and reference compounds.

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References

  1. Reddy, K. R. & DeLaune, R. D. Biogeochemistry of Wetlands: Science and Applications (CRC Press, 2008).

    Book  Google Scholar 

  2. Du Laing, G. et al. Presence and mobility of arsenic in estuarine wetland soils of the Scheldt estuary (Belgium). J. Environ. Monit. 11, 873–881 (2009).

    Article  Google Scholar 

  3. Bauer, M., Fulda, B. & Blodau, C. Groundwater derived arsenic in high carbonate wetland soils: Sources, sinks, and mobility. Sci. Total Environ. 401, 109–120 (2008).

    Article  Google Scholar 

  4. Rothwell, J. J. et al. Arsenic retention and release in ombrotrophic peatlands. Sci. Total Environ. 407, 1405–1417 (2009).

    Article  Google Scholar 

  5. Rothwell, J. J. et al. Storage and behavior of As, Sb, Pb, and Cu in ombrotrophic peat bogs under contrasting water table conditions. Environ. Sci. Technol. 44, 8497–8502 (2010).

    Article  Google Scholar 

  6. La Force, M. J., Hansel, C. M. & Fendorf, S. Arsenic speciation, seasonal transformations, and co-distribution with iron in a mine waste-influenced palustrine emergent wetland. Environ. Sci. Technol. 34, 3937–3943 (2000).

    Article  Google Scholar 

  7. McArthur, J. M. et al. Natural organic matter in sedimentary basins and its relation to arsenic in anoxic ground water: The example of West Bengal and its worldwide implications. Appl. Geochem. 19, 1255–1293 (2004).

    Article  Google Scholar 

  8. Nickson, R. T., McArthur, J. M., Ravenscroft, P., Burgess, W. G. & Ahmed, K. M. Mechanism of arsenic release to groundwater, Bangladesh and West Bengal. Appl. Geochem. 15, 403–413 (2000).

    Article  Google Scholar 

  9. Smedley, P. L. & Kinniburgh, D. G. A review of the source, behaviour and distribution of arsenic in natural waters. Appl. Geochem. 17, 517–568 (2002).

    Article  Google Scholar 

  10. Redman, A. D., Macalady, D. L. & Ahmann, D. Natural organic matter affects arsenic speciation and sorption onto hematite. Environ. Sci. Technol. 36, 2889–2896 (2002).

    Article  Google Scholar 

  11. Wang, S. & Mulligan, C. N. Effect of natural organic matter on arsenic release from soils and sediments into groundwater. Environ. Geochem. Health 28, 197–214 (2006).

    Article  Google Scholar 

  12. Bauer, M. & Blodau, C. Mobilization of arsenic by dissolved organic matter from iron oxides, soils and sediments. Sci. Total Environ. 354, 179–190 (2006).

    Article  Google Scholar 

  13. Bauer, M. & Blodau, C. Arsenic distribution in the dissolved, colloidal and particulate size fraction of experimental solutions rich in dissolved organic matter and ferric iron. Geochim. Cosmochim. Acta 73, 529–542 (2009).

    Article  Google Scholar 

  14. Kirk, M. F. et al. Bacterial sulfate reduction limits natural arsenic contamination in groundwater. Geology 32, 953–956 (2004).

    Article  Google Scholar 

  15. González A, Z. I., Krachler, M., Cheburkin, A. K. & Shotyk, W. Spatial distribution of natural enrichments of arsenic, selenium, and uranium in a minerotrophic peatland, Gola di Lago, Canton Ticino, Switzerland. Environ. Sci. Technol. 40, 6568–6574 (2006).

    Article  Google Scholar 

  16. Anawar, H. M. et al. Geochemical occurrence of arsenic in groundwater of Bangladesh: Sources and mobilization processes. J. Geochem. Explor. 77, 109–131 (2003).

    Article  Google Scholar 

  17. Yamazaki, C. et al. Vertical distribution of arsenic in Ganges delta sediments in Deuli Village, Bangladesh. Soil Sci. Plant Nutr. 49, 567–574 (2003).

    Article  Google Scholar 

  18. Buschmann, J. et al. Arsenite and arsenate binding to dissolved humic acids: Influence of pH, type of humic acid, and aluminum. Environ. Sci. Technol. 40, 6015–6020 (2006).

    Article  Google Scholar 

  19. Wang, S. & Mulligan, C. N. Enhanced mobilization of arsenic and heavy metals from mine tailings by humic acid. Chemosphere 74, 274–279 (2009).

    Article  Google Scholar 

  20. Thanabalasingam, P. & Pickering, W. F. Arsenic sorption by humic acids. Environ. Pollut. 12, 233–246 (1986).

    Article  Google Scholar 

  21. Liu, G. & Cai, Y. Complexation of arsenite with dissolved organic matter: Conditional distribution coefficients and apparent stability constants. Chemosphere 81, 890–896 (2010).

    Article  Google Scholar 

  22. Schmoeger, M. E. V., Oven, M. & Grill, E. Detoxification of arsenic by phytochelatins in plants. Plant Physiol. 122, 793–801 (2000).

    Article  Google Scholar 

  23. Zhao, F. J., Ma, J. F., Meharg, A. A. & McGrath, S. P. Arsenic uptake and metabolism in plants. New Phytol. 181, 777–794 (2009).

    Article  Google Scholar 

  24. Teixeira, M. C. & Ciminelli, V. S. T. Development of a biosorbent for arsenite: Structural modeling based on X-ray spectroscopy. Environ. Sci. Technol. 39, 895–900 (2005).

    Article  Google Scholar 

  25. Xia, K. et al. XANES studies of oxidation states of sulfur in aquatic and soil humic substances. Soil Sci. Soc. Am. J. 62, 1240–1246 (1998).

    Article  Google Scholar 

  26. Vairavamurthy, M. A. et al. Characterization of sulfur-containing functional groups in sedimentary humic substances by X-ray absorption near-edge structure spectroscopy. Energ. Fuel 11, 546–553 (1997).

    Article  Google Scholar 

  27. Zoller, H. & Kleiber, H. Vegetationsgeschichtliche Untersuchungen in der montanen und subalpinen Stufe der Tessintäler. Verh. Naturf. Ges. Basel 81, 90–154 (1971).

    Google Scholar 

  28. Franz, L. & Romer, R. L. Caledonian high-pressure metamorphism in the Strona-Ceneri zone (Southern Alps of Southern Switzerland and Northern Italy). Swiss J. Geosci. 100, 457–467 (2007).

    Article  Google Scholar 

  29. Pfeifer, H-R. et al. Natural arsenic-contamination of surface and ground waters in Southern Switzerland (Ticino). Bull. Appl. Geol. 7, 81–103 (2002).

    Google Scholar 

  30. O’Day, P. A., Vlassopoulos, D., Root, R. & Rivera, N. The influence of sulfur and iron on dissolved arsenic concentrations in the shallow subsurface under changing redox conditions. Proc. Natl Acad. Sci. USA 101, 13703–13708 (2004).

    Article  Google Scholar 

  31. Shi, W., Dong, J., Scott, R. A., Ksenzenko, M. Y. & Rosen, B. P. The role of arsenic-thiol interactions in metalloregulation of the a r s operon. J. Biol. Chem. 271, 9291–9297 (1996).

    Article  Google Scholar 

  32. Aizenshtat, Z., Krein, E. B., Vairavamurthy, M. A. & Goldstein, T. P. in Geochemical Transformations of Sedimentary Sulfur (eds Vairavamurthy, M. A. & Schoonen, M. A. A.) Ch. 2, 16–37 (Amer. Chemical. Soc., 1995).

    Book  Google Scholar 

  33. Helz, G. R. & Tossell, J. A. Thermodynamic model for arsenic speciation in sulfidic waters: A novel use of ab initio computations. Geochim. Cosmochim. Acta 72, 4457–4468 (2008).

    Article  Google Scholar 

  34. Helz, G. R. et al. Oligomerization in As(III) sulfide solutions: Theoretical constraints and spectroscopic evidence. Geochim. Cosmochim. Acta 59, 4591–4604 (1995).

    Article  Google Scholar 

  35. Funke, H., Scheinost, A. C. & Chukalina, M. Wavelet analysis of extended x-ray absorption fine structure data. Phys. Rev. B 71, 1–7 (2005).

    Article  Google Scholar 

  36. Renock, D. & Becker, U. A first principles study of the oxidation energetics and kinetics of realgar. Geochim. Cosmochim. Acta 74, 4266–4284 (2010).

    Article  Google Scholar 

  37. Van Schaik, J. W. J., Persson, I., Kleja, D. B. & Gustafsson, J. P. EXAFS study on the reactions between iron and fulvic acid in acid aqueous solutions. Environ. Sci. Technol. 42, 2367–2373 (2008).

    Article  Google Scholar 

  38. Cherry, J. A., Shaikh, A. U., Tallman, D. E. & Nicholson, R. V. Arsenic species as an indicator of redox conditions in groundwater. J. Hydrol. 43, 373–392 (1979).

    Article  Google Scholar 

  39. Lowers, H. A. et al. Arsenic incorporation into authigenic pyrite, Bengal Basin sediment, Bangladesh. Geochim. Cosmochim. Acta 71, 2699–2717 (2007).

    Article  Google Scholar 

  40. Farquhar, M. L., Charnock, J. M., Livens, F. R. & Vaughan, D. J. Mechanisms of arsenic uptake from aqueous solution by interaction with goethite, lepidocrocite, mackinawite, and pyrite: An X-ray absorption spectroscopy study. Environ. Sci. Technol. 36, 1757–1762 (2002).

    Article  Google Scholar 

  41. Zhang, H. & Selim, H. M. Reaction and transport of arsenic in soils: Equilibrium and kinetic modeling. Adv. Agron. 98, 45–115 (2008).

    Article  Google Scholar 

  42. Smith, E., Naidu, R. & Alston, A. M. Arsenic in the soil environment: A review. Adv. Agron. 64, 149–195 (1998).

    Article  Google Scholar 

  43. Cloy, J. M., Farmer, J. G., Graham, M. C. & Mackenzie, A. B. Retention of As and Sb in ombrotrophic peat bogs: Records of As, Sb, and Pb deposition at four Scottish sites. Environ. Sci. Technol. 43, 1756–1762 (2009).

    Article  Google Scholar 

  44. Ahmed, F., Bibi, M. H., Ishiga, H., Fukushima, T. & Maruoka, T. Geochemical study of arsenic and other trace elements in groundwater and sediments of the Old Brahmaputra river plain, Bangladesh. Environ. Earth Sci. 60, 1303–1316 (2010).

    Article  Google Scholar 

  45. Guo, H., Zhang, B. & Zhang, Y. Control of organic and iron colloids on arsenic partition and transport in high arsenic groundwaters in the Hetao basin, Inner Mongolia. Appl. Geochem. 26, 360–370 (2011).

    Article  Google Scholar 

  46. Braun-Blanquet, J. Plant Sociology: The Study of Plant Communities (McGraw-Hill, 1932).

    Google Scholar 

  47. Hansen, K., Reckleben, C., Diehl, I. & Klaer, H. A compact 7-cell Si-drift detector module for high-count rate X-ray spectroscopy. Nucl. Instrum. Methods Phys. Res. A 589, 250–258 (2008).

    Article  Google Scholar 

  48. Ravel, B. & Newville, M. Athena, Artemis, Hephaestus: Data analysis for X-ray absorption spectroscopy using Ifeffit. J. Synchrot. Radiat. 12, 537–541 (2005).

    Article  Google Scholar 

  49. Webb, S. M. SIXPack: A graphical user interface for XAS analysis using IFEFFIT. Phys. Scr. T115, 1011–1014 (2005).

    Article  Google Scholar 

  50. Ankudinov, A. L., Ravel, B., Rehr, J. J. & Conradson, S. D. Real-space multiple-scattering calculation and interpretation of X-ray-absorption near-edge structure. Phys. Rev. B 58, 7565–7576 (1998).

    Article  Google Scholar 

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Acknowledgements

We thank K. Barmettler for his support in the soil chemistry laboratory, M. Hoffmann, F. Maurer and K. Barmettler for field assistance, as well as S. Hassold and M. Maurer for mapping the vegetation at the field site. We acknowledge the ESRF for provision of synchrotron radiation facilities, and we would like to thank M. Chorro for assistance in using beamline BM29. Portions of this research were carried out at the light source DORIS III at DESY, a member of the Helmholtz Association (HGF). We are grateful to E. Welter for assistance in using beamline C (Hasylab). Portions of this research were also carried out at the SSRL, a Directorate of SLAC National Accelerator Laboratory and an Office of Science User Facility operated for the US Department of Energy Office of Science by Stanford University. We would like to thank J. Rogers for his support in using beamline 4-1. The authors furthermore acknowledge the support by the Electron Microscopy Center, ETH Zurich (EMEZ, Switzerland), in particular K. Kunze for performing the SEM–EDX analyses. Thanks to A. Massanek (TU Bergakademie Freiberg, Germany) and P. Brack (ETH Zurich) for their assistance in providing mineral reference compounds. We are also indebted to P. Poggiati and M. Sulmoni from the Department of Environment (Ticino, Switzerland) who granted the sampling permission for Gola di Lago. Financial support by the ETH Zurich (research grant 2708-2) is also gratefully acknowledged.

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  1. Institute of Biogeochemistry and Pollutant Dynamics, Soil Chemistry Group, ETH Zurich, 8092 Zurich, Switzerland

    Peggy Langner, Christian Mikutta & Ruben Kretzschmar

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  1. Peggy Langner
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Contributions

P.L. and C.M. performed the work in the field and at the synchrotron radiation facilities. P.L. analysed the samples in the laboratory, evaluated the results, and wrote the manuscript as part of her PhD thesis. C.M. conducted the shell-fit and wavelet-transform analyses. C.M. and R.K. initiated and supervised the project. All authors discussed the results and contributed to the manuscript.

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Correspondence to Christian Mikutta.

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Langner, P., Mikutta, C. & Kretzschmar, R. Arsenic sequestration by organic sulphur in peat. Nature Geosci 5, 66–73 (2012). https://doi.org/10.1038/ngeo1329

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