Aquatic Geochemistry

, Volume 19, Issue 2, pp 97–113 | Cite as

Hydrogen Cyanide Accumulation and Transformations in Non-polluted Salt Marsh Sediments

  • A. KamyshnyJr.
  • H. Oduro
  • Z. F. Mansaray
  • J. Farquhar
Original Paper
First Online:
Received:
Accepted:

Abstract

While cyanide is known to be produced by many organisms, including plants, bacteria, algae, fungi and some animals, it is generally thought that high levels of cyanide in aquatic systems require anthropogenic sources. Here, we report accumulation of relatively high levels of cyanide in non-polluted salt marsh sediments (up to 230 μmol kg−1). Concentrations of free cyanide up to 1.92 μmol L−1, which are toxic to aquatic life, were detected in the pore-waters. Concentration of total (free and complexed) cyanide in the pore-waters was up to 6.94 μmol L−1. Free cyanide, which is released to the marsh sediments, is attributed to processes associated with decomposition of cord grass, Spartina alterniflora, roots and possibly from other sources. This cyanide is rapidly complexed with iron and adsorbed on sedimentary organic matter. The ultimate cyanide sink is, however, associated with formation of thiocyanate by reaction with products of sulfide oxidation by Fe(III) minerals, especially polysulfides. The formation of thiocyanate by this pathway detoxifies two poisonous compounds, polysulfides and hydrogen cyanide, preventing release of free hydrogen cyanide from salt marsh sediments into overlying water or air.

Keywords

Hydrogen cyanide Metallo-cyanide complexes Thiocyanate Sulfide oxidation intermediates Inorganic polysulfides Sulfide 
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Notes

Acknowledgments

This work was supported by the Max Planck Society (T.G.F. and A.K.), Marie Curie Outgoing International Fellowship SULFUTOPES number POIF-GA-2008-219586 (to A.K.), NSF Geobiology and Low Temperature Geochemistry Program grant number: 0843814 (to A. K., JF and Z.F.M.) and the NASA Astrobiology Institute (J.F.). The authors would like to thank George W. Luther and Andrew Madison (University of Delaware) for assistance during sampling of Delaware Great Marsh. The authors are grateful to Donald E. Canfield and Daniel L. Eldridge for valuable comments on the manuscript. The revised manuscript benefited by the comments of two anonymous reviewers and the Associated Editor David J. Burdige.

References

  1. Aller RC, Mackin JE, Cox RT Jr (1986) Diagenesis of Fe and S in Amazon inner shelf muds: apparent dominance of Fe reduction and implications of the genesis of ironstones. Cont Shelf Res 6:263–289CrossRefGoogle Scholar
  2. Boulegue J, Michard G (1977) Dissolution du soufre elementaire dans les solutions aqueuses diluees d`hydrogene sulfure. Comptes Rendus Acad Sci Paris 284C:713–716Google Scholar
  3. Canfield DE (1989) Reactive iron in marine sediments. Geochim Cosmochim Acta 53:619–632CrossRefGoogle Scholar
  4. Canfield DE, Raiswell R, Bottrell S (1992) The reactivity of sedimentary iron minerals toward sulfide. Am J Sci 292:659–683CrossRefGoogle Scholar
  5. Chakraborty S, Veeramani H (2006) Effect of HRT and recycle ratio on removal of cyanide, phenol, thiocyanate and ammonia in an anaerobic-anoxic-aerobic continuous system. Process Biochem 41:96–105CrossRefGoogle Scholar
  6. Chatwin TD, Zhang J, Gridley GM (1988) Natural mechanisms in soil to mitigate cyanide release. In: Proceedings of superfund ′88, the 9th National Conference, Hazardous Materials Control Research Institute, Washington, pp 467–473Google Scholar
  7. Cline JD (1969) Spectrophotometric determination of hydrogen sulfide in natural waters. Limnol Oceanogr 14:454–458CrossRefGoogle Scholar
  8. Davy AJ, Bishop GF (1991) Triglochin maritime (L.). J Ecol 79:531–555CrossRefGoogle Scholar
  9. Dzombak DA, Roy SB, Anderson TL, Kavanaugh MC, Deeb RA (2006a) in Cyanide in Water and Soil, eds Dzombak DA. Wong-Chong GM (CRC Press, Boca Raton, Florida), Ghosh RS, pp 209–224Google Scholar
  10. Dzombak DA, Ghosh RS, Young TC (2006b) In: Dzombak DA, Ghosh RS, Wong-Chong GM (eds) Cyanide in water and soil. CRC Press, Boca Raton, pp 57–92Google Scholar
  11. Ettlinger M, Eyjólfsson R (1972) Revision of the structure of the cyanogenic glucoside triglochinin. J Chem Soc Chem Comm 1972:572–573CrossRefGoogle Scholar
  12. Ferdelman TG, Church TM, Luther GW III (1991) Sulfur enrichment of humic substances in a Delaware salt marsh sediment core. Geochim Cosmochim Acta 55:979–988CrossRefGoogle Scholar
  13. Gensemer RW, DeForest DK, Stenhouse AJ, Higgins CJ, Cardwell RD (2006) In: Dzombak DA, Ghosh RS, Wong-Chong GM (eds) Cyanide in water and soil. CRC Press, Boca Raton, pp 251–284Google Scholar
  14. Ghosh RS, Meeussen JCL, Dzombak DA, Nakles DV (2006a) In: Dzombak DA, Ghosh RS, Wong-Chong GM (eds) Cyanide in water and soil. CRC Press, Boca Raton, pp 191–208Google Scholar
  15. Ghosh RS, Ebbs SD, Bushey JT, Neuhauser EF, Wong-Chong GM (2006b) In: Dzombak DA, Ghosh RS, Wong-Chong GM (eds) Cyanide in water and soil. CRC Press, Boca Raton, pp 225–236Google Scholar
  16. Kamyshny A Jr (2009) Improved cyanolysis protocol for detection of zero-valent sulfur in natural aquatic systems. Limnol Oceanogr Meth 7:442–448CrossRefGoogle Scholar
  17. Kamyshny Jr A, Oduro H, Farquhar J (2012) Quantification of free and metal-complexed cyanide by tetrathionate derivatization. Int J Environ Anal Chem, (in print), doi: 10.1080/03067319.2011.561339
  18. Kamyshny A Jr, Borkenstein CG, Ferdelman TG (2009) Protocol for quantitative detection of elemental sulfur and polysulfide zero-valent sulfur distribution in natural aquatic samples. Geostand Geoanal Res 33:415–435CrossRefGoogle Scholar
  19. Kamyshny A Jr, Zerkle AL, Mansaray Z, Ciglenečki I, Bura-Nakić E, Farquhar J, Ferdelman TG (2011) Biogeochemical sulfur cycle in water column of shallow stratified sea-water lake: speciation and quadruple sulfur isotope composition. Mar Chem 127:144–154CrossRefGoogle Scholar
  20. Karavaiko GI, Kondrat’eva TF, Savari EE, Grigor’eva NV, Avakyan ZA (2000) Microbial degradation of cyanide and thiocyanate. Microbiology 69:167–173CrossRefGoogle Scholar
  21. Keefe AD, Miller SL (1996) Was ferrocyanide a prebiotic reagent? Orig Life Evol Biosphere 26:111–129CrossRefGoogle Scholar
  22. Kelly DP, Chambers LA, Trudinger PA (1969) Cyanolysis and spectrophotometric estimation of trithionate in mixture with thiosulfate and tetrathionate. Anal Chem 41:898–901CrossRefGoogle Scholar
  23. Kim YM, Park D, Jeon CO, Lee DS, Park JM (2008) Effect of HRT on the biological pre-denitrification process for the simultaneous removal of toxic pollutants from cokes wastewater. Bioresour Technol 99:8824–8832CrossRefGoogle Scholar
  24. Knowles CJ (1976) Microorganisms and cyanide. Bacteriol Rev 40:652–680Google Scholar
  25. Kostka JE, Luther GW (1994) Partitioning and speciation of solid phase iron in saltmarsh sediments. Geochim Cosmochim Acta 58:1701–1710CrossRefGoogle Scholar
  26. Kostka JE, Luther GW (1995) Seasonal cycling of Fe in saltmarsh sediments. Biogeochemistry 29:159–181CrossRefGoogle Scholar
  27. Li Q, Jacob DJ, Bey I, Yantosca RM, Zhao Y, Kondo Y, Notholt J (2000) Atmospheric hydrogen cyanide (HCN): biomass burning source, ocean sink? Geophys Res Lett 27:357–360CrossRefGoogle Scholar
  28. Lord CJ III, Church TM (1983) The geochemistry of salt marshes: sedimentary ion diffusion, sulfate reduction, and pyritization. Geochim Cosmochim Acta 47:1381–1391CrossRefGoogle Scholar
  29. Luther GW III, Church TM, Scudlark JR, Cosman M (1986) Inorganic and organic sulfur cycling in salt-marsh pore waters. Science 232:746–749CrossRefGoogle Scholar
  30. Luther GW III, Ferdelman TG, Kostka JE, Tsamakis EJ, Church TM (1991) Temporal and spatial variability of reduced sulfur species (FeS2, S2O3 2−) and porewater parameters in salt marsh sediments. Biogeochemistry 14:57–88CrossRefGoogle Scholar
  31. Luthy RG, Bruce SG Jr (1979) Kinetics of reaction of cyanide and reduced sulfur species in aqueous solutions. Environ Sci Technol 13:1481–1487CrossRefGoogle Scholar
  32. Majak W, McDiarmid RE, Hall JW, Van Ryswyk AL (1980) Seasonal variation in the cyanide potential of arrowgrass (Triglochin maritima). Can J Plant Sci 60:1235–1241CrossRefGoogle Scholar
  33. Meeussen JCL, Keizer MG, de Haan FAM (1992) Chemical stability and decomposition rate of iron cyanide complexes in soil solutions. Environ Sci Technol 26:511–516CrossRefGoogle Scholar
  34. Rong L, Lim LW, Takeuchi T (2005) Determination of iodide and thiocyanate in seawater by liquid chromatography with poly(ethylene glycol) stationary phase. Chromatographia 61:371–374CrossRefGoogle Scholar
  35. Sahariah BP, Saswati C (2011) Kinetic analysis of phenol, thiocyanate and ammonia-nitrogen removals in an anaerobic-anoxic-aerobic moving bed bioreactor system. J Hazard Mater 190:260–267CrossRefGoogle Scholar
  36. Seeberg-Elverfeldt J, Schlüter M, Feseker T, Kölling M (2005) Rhizon sampling of porewaters near the sediment-water interface of aquatic systems. Limnol Oceanogr Methods 3:361–371CrossRefGoogle Scholar
  37. Sekerka I, Lechner JF (1976) Potentiometric determination of low levels of simple and total cyanides. Water Res 10:479–483CrossRefGoogle Scholar
  38. Shieh WK, Richards DJ (1988) Anoxic/oxic activated sludge treatment kinetics of cyanides and phenols. J Environ Eng-ASCE 114:639–654CrossRefGoogle Scholar
  39. Stratford J, Dias AEXO, Knowles CJ (1994) The utilization of thiocyanate as a nitrogen source by a heterotrophic bacterium: the degradative pathway involves formation of ammonia and tetrathionate. Microbiology 140:2657–2662CrossRefGoogle Scholar
  40. Szekeres L (1974) Analytical chemistry of sulfur acids. Talanta 21:1–44CrossRefGoogle Scholar
  41. Wild SR, Rudd T, Neller A (1994) Fate and effects of cyanide during wastewater treatment processes. Sci Total Environ 156:93–107CrossRefGoogle Scholar
  42. Wong-Chong GM, Dzombak DA, Gjosh RS (2006a) In: Dzombak DA, Ghosh RS, Wong-Chong GM (eds) Cyanide in water and soil. CRC Press, Boca Raton, pp 1–14Google Scholar
  43. Wong-Chong GM, Ghosh RS, Bushey JT, Ebbs SD, Neuhauser EF (2006b) In: Dzombak DA, Ghosh RS, Wong-Chong GM (eds) Cyanide in water and soil. CRC Press, Boca Raton, pp 25–40Google Scholar
  44. Wood AP, Kelly DP, McDonald IR, Jordan SL, Morgan TD, Khan S, Murrell JC, Borodina E (1998) A novel pink-pigmented facultative methylotroph, Methylobacterium thiocyanatum sp. nov., capable of growth on thiocyanate or cyanate as sole nitrogen sources. Arch Microbiol 169:148–158CrossRefGoogle Scholar
  45. Yao W, Millero FJ (1993) The rate of sulfide oxidation by δMnO2 in seawater. Geochim Cosmochim Acta 57:3359–3365CrossRefGoogle Scholar
  46. Yao W, Millero FJ (1996) Oxidation of hydrogen sulfide by hydrous Fe(III) oxides in seawater. Mar Chem 52:1–16CrossRefGoogle Scholar
  47. Young TC, Zhao X, Theis TL (2006) In: Dzombak DA, Ghosh RS, Wong-Chong GM (eds) Cyanide in water and soil. CRC Press, Boca Raton, pp 171–190Google Scholar
  48. Yu X, Zhou P, Xishi Z, Liu Y (2005) Cyanide removal y Chinese vegetation—quantification of the Michaelis-Menten kinetics. Environ Sci Pollut Res 12:221–226CrossRefGoogle Scholar
  49. Zopfi J, Böttcher ME, Jørgensen BB (2008) Biogeochemistry of sulfur and iron in Thioploca-colonized surface sediments in the upwelling area off central Chile. Geochim Cosmochim Acta 72:827–843CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media Dordrecht 2012

Authors and Affiliations

  • A. KamyshnyJr.
    • 1
    • 2
    • 3
  • H. Oduro
    • 1
    • 4
  • Z. F. Mansaray
    • 1
  • J. Farquhar
    • 1
  1. 1.Department of Geology and Earth Systems Science Interdisciplinary CenterUniversity of MarylandCollege ParkUSA
  2. 2.Department of BiogeochemistryMax Planck Institute for Marine MicrobiologyBremenGermany
  3. 3.Department of Geological and Environmental Sciences, Faculty of Natural SciencesBen-Gurion University of the NegevBeer ShevaIsrael
  4. 4.Department of Earth, Atmospheric, and Planetary Sciences (EAPS)Massachusetts Institute of TechnologyCambridgeUSA

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