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Kinetics of Thiocyanate Formation by Reaction of Cyanide with Tetrathionate

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Abstract

In aquatic systems a reaction between tetrathionate and cyanide results in the formation of thiocyanate. We have studied kinetics of the reactions of tetrathionate with free cyanide and two cyanide complexes, hexacyanoferrate(II) and hexacyanoferrate(III), at the environmentally relevant conditions. For the reaction between tetrathionate and free cyanide, the rate constant and the activation energy, but not the reaction order, strongly depend on pH. Our observations allow to propose the following pathways of thiocyanate formation by the reactions of free cyanide with tetrathionate: (1) tetrathionate reacts relatively slow with hydrogen cyanide at acidic and neutral conditions; and (2) tetrathionate reacts relatively fast with cyanide anion under highly alkaline conditions. Depending on environmental conditions, the half-lives of the reaction between free cyanide and tetrathionate will be in the ranges of hours to several years. Reactions of tetrathionate with hexacyanoferrate(II) and hexacyanoferrate(III) have no environmental significance as they are slower than the decomposition of tetrathionate. Strategy for improvement of analytical protocols for analysis of tetrathionate and cyanide is proposed based on the detected kinetics parameters.

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References

  • Avetisyan K, Buchshtav T, Kamyshny A (2019a) Kinetics and mechanism of polysulfides formation by a reaction between hydrogen sulfide and orthorhombic cyclooctasulfur. Geochim Cosmochim Acta 247:96–105

    Google Scholar 

  • Avetisyan K, Eckert W, Findlay AJ, Kamyshny A (2019b) Diurnal variations in sulfur transformations at the chemocline of a stratified freshwater lake. Biogeochemistry 146:83–100

    Google Scholar 

  • Breuer PL, Jeffrey MI (2004) The effect of ionic strength and buffer choice on the decomposition of tetrathionate in alkaline solutions. Hydrometallurgy 72:335–338

    Google Scholar 

  • Chambers LA, Trudinger PA (1979) Thiosulfate formation and associated isotope effects during sulfite reduction by Clostridium pasteurianum. Can J Microbiol 25:719–721

    Google Scholar 

  • Dash RR, Gaur A, Balomajumder C (2009) Cyanide in industrial wastewaters and its removal: a review on biotreatment. J Hazard Mater 163:1–11

    Google Scholar 

  • Davis RE (1958) Displacement reaction at the sulfur atom. II. The reaction of cyanide with tetrathionate. J Phys Chem 62:1599–1601

    Google Scholar 

  • Davis RE (1964) Nucleophilic displacement reactions at the sulfur-sulfur bond. Surv Prog Chem 2:189–238. https://doi.org/10.1016/B978-1-4832-0004-0.50010-8

    Article  Google Scholar 

  • Donato DB, Nichols O, Possingham H, Moore M, Ricci PF, Noller B (2007) A critical review of the effects of gold cyanide-bearing tailings solutions on wildlife. Environ Int 33:974–984

    Google Scholar 

  • Dowler MJ, Ingmanson DE (1979) Thiocyanate in Red Sea brine and its implications. Nature 279:51–52

    Google Scholar 

  • Dzombak DA, Ghosh RS, Young TC (2006) In: Dzombak DA, Ghosh RS, Wong-Chong GM (eds) Cyanide in water and soil: chemistry, risk, and management. CRC Press, Boca Raton, pp 57–92

    Google Scholar 

  • Findlay A (2016) Microbial impact on polysulfide dynamics in the environment. FEMS Microbiol Lett. 363:fnw103

  • Findlay A, Kamyshny A Jr (2017) Turnover rates of intermediate sulfur species (S 2−x , S0, S2O32−, S4O62−, SO32−) in freshwater and sediments. Front Microbiol 8:2551

    Google Scholar 

  • 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: chemistry, risk, and management. CRC Press, Boca Raton, pp 251–284

    Google Scholar 

  • Ghosh W, Dam B (2009) Biochemistry and molecular biology of lithotrophic sulfur-oxidation by taxonomically and ecologically diverse bacteria and archaea. FEMS Microbiol Rev 33:999–1043

    Google Scholar 

  • Gould WD, King M, Mohapatra BR, Cameron RA, Kapoor A, Koren DW (2012) A critical review on destruction of thiocyanate in mining effluents. Miner Eng 34:38–47

    Google Scholar 

  • Henneke E, Luther GW III, de Lange GJ, Hoefs J (1997) Sulphur speciation in anoxic hypersaline sediments from the eastern Mediterranean Sea. Geochim Cosmochim Acta 61:307–321

    Google Scholar 

  • Ishikawa F (1927) Chemical kinetics of the reaction between tetrathionate and cyanide. Z Physik Chem 130:73–81

    Google Scholar 

  • Kamyshny A (2009) Improved cyanolysis protocol for detection of zero-valent sulfur in natural aquatic systems. Limnol Oceanogr Methods 7:442–448

    Google Scholar 

  • 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 33:415–435

    Google Scholar 

  • Kamyshny A, Zerkle AL, Mansaray ZF, Ciglenečki I, Bura-Nakić E, Farquhar J, Ferdelman TG (2011) Biogeochemical sulfur cycling in the water column of a shallow stratified sea-water lake: speciation and quadruple sulfur isotope composition. Mar Chem 127:144–154

    Google Scholar 

  • Kamyshny A Jr, Oduro H, Farquhar J (2012) Quantification of free and metal-complexed cyanide by tetrathionate derivatization. Intern J Environ Anal Chem 92:1506–1517

    Google Scholar 

  • Kamyshny A, Oduro H, Mansaray ZF, Farquhar J (2013) Hydrogen cyanide accumulation and transformations in non-polluted salt marsh sediments. Aquat Geochem 19:97–113

    Google Scholar 

  • Karavaiko GI, Kondrat’eva EE, Savari EE, Grigor’eva NV, Avakyan ZA (2000) Microbial degradation of cyanide and thiocyanate. Microbiology 69:167–173

    Google Scholar 

  • Karchmer JK (1970) Analytical chemistry of sulfur and its compounds. Wiley, Hoboken

    Google Scholar 

  • Kelly DP (1989) Oxidation of sulphur compounds. In: Cole JA, Ferguson S (eds) The nitrogen and sulphur cycles: Society for General Microbiology Symposium 42. Cambridge University Press, pp 65–98

  • Kelly DP (1999) Thermodynamic aspects of energy conservation by chemolithotrophic sulfur bacteria in relation to the sulfur oxidation pathways. Arch Microbiol 171:219–229

    Google Scholar 

  • Kelly DP, Chambers LA, Trudinger PA (1969) Cyanolysis and spectrophotometric estimation of trithionate in mixture with thiosulfate and tetrathionate. Anal Chem 41:898–901

    Google Scholar 

  • Kelly DP, Shergill JK, Lu WP, Wood AP (1997) Oxidative metabolism of inorganic sulfur compounds by bacteria. Antonie van Leeuwenhoek 71:95–107. https://doi.org/10.1023/A:1000135707181

    Article  Google Scholar 

  • Koh T (1990) Analytical chemistry of polythionates and thiosulfate. Anal Sci 6:3–14

    Google Scholar 

  • Koh T, Okabe K (1994) Spectrophotometric determination of sulfide, sulfite, thiosulfate, trithionate and tetrathionate in mixtures. Analyst 119:2457–2461

    Google Scholar 

  • Koppenol WH (1980) Effect of a molecular dipole on the ionic strength dependence of a bimolecular rate constant. Biophys J 29:493–508

    Google Scholar 

  • Kurashova I, Kamyshny A Jr (2019) Kinetics of thiocyanate formation by reaction of cyanide and its iron complexes with thiosulfate. Aquat Geochem. https://doi.org/10.1007/s10498-019-09361-y

    Article  Google Scholar 

  • Kurashova I, Halevy I, Kamyshny A Jr (2018) Kinetics of decomposition of thiocyanate in natural aquatic systems. Environ Sci Technol 52:1234–1243. https://doi.org/10.1021/acs.est.7b04723

    Article  Google Scholar 

  • 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 27:357–360

    Google Scholar 

  • Liljeqvist M, Sundkvist J, Saleh A, Dopson M (2011) Low temperature removal of inorganic sulfur compounds from mining process waters. Biotechnol Bioeng 108:1251–1259

    Google Scholar 

  • Luther GW III, Church TM, Scudlark JR, Cosman M (1986) Inorganic and organic sulfur cycling in salt-marsh pore waters. Science 232:746–749

    Google Scholar 

  • Luthy RG, Bruce SG Jr (1979) Kinetics of reaction of cyanide and reduced sulfur species in aqueous solutions. Environ Sci Technol 13:1481–1487

    Google Scholar 

  • Oulego P, Laca A, Diaz M (2013) Kinetics and pathways of cyanide degradation at high temperatures and pressures. Environ Sci Technol 47:1542–1549

    Google Scholar 

  • Oulego P, Collado S, Laca A, Diaz M (2014) Simultaneous oxidation of cyanide and thiocyanate at high pressure and temperature. J Hazard Mater 280:570–578

    Google Scholar 

  • Podgorsek L, Imhoff JF (1999) Tetrathionate production by sulfur oxidizing bacteria and the role of tetrathionate in the sulfur cycle of Baltic Sea sediments. Aquat Microbial Ecol 17:255–265

    Google Scholar 

  • Rolia E, Chakrabarti CL (1982) Kinetics of decomposition of tetrathionate, trithionate and thiosulphate in alkaline media. Environ Sci Technol 16:852–857

    Google Scholar 

  • Rong L, Lim L, Takeuchi T (2005) Determination of iodide and thiocyanate in seawater by liquid chromatography with poly(ethylene glycol) stationary phase. Chromatographia 61:371–374

    Google Scholar 

  • Rowley WJ, Otto FD (1980) Ozonation of cyanide with emphasis on gold mill wastewaters. Can J Chem Eng 58(5):646–653

    Google Scholar 

  • Schippers A (2004) Biogeochemistry of metal sulfide oxidation in mining environments, sediments, and soils. In: Amend JP, Edwards KJ, Lyons TW (eds) Sulfur biogeochemistry—past and present. Special paper, vol 379. Geological Society of America, Boulder, pp 49–62

  • Schippers A, Jørgensen BB (2001) Oxidation of pyrite and iron sulfide by manganese dioxide in marine sediments. Geochim Cosmochim Acta 65:915–922

    Google Scholar 

  • Schippers A, Rohwerder T, Sand W (1999) Intermediary sulfur compounds in pyrite oxidation: implications for bioleaching and biodepyritization of coal. Appl Microbiol Biotechnol 52:104–110. https://doi.org/10.1007/S002530051495

    Article  Google Scholar 

  • Sekerka I, Lechner JF (1976) Potentiometric determination of low levels of simple and total cyanides. Water Res 10:479–483

    Google Scholar 

  • Smith A, Mudder T (2001) Chemistry and treatment of cyanidation wastes. Mining J. Books, London

    Google Scholar 

  • Sorokin DY (1996) Oxidation of sulfide and elemental sulfur to tetrathionate by chemoorganoheterotrophic bacteria. Microbiology 65:1–5

    Google Scholar 

  • Sorokin DY, Teske A, Robertson LA, Kuenen JG (1999) Anaerobic oxidation of thiosulfate to tetrathionate by obligately heterotrophic bacteria, belonging to the Pseudomonas stutzeri group. FEMS Microbiol Ecol 30:113–123

    Google Scholar 

  • Steudel R, Holdt G, Gobel T, Hazeu W (1987) Chromatographic-separation of higher polythionates SnO (2−)6 (n = 3…22) and their detection in cultures of thiobacillus-ferrooxidans—molecular composition of bacterial sulfur secretions. Angew Chem Inr Ed. Engl 26:151–153

    Google Scholar 

  • Stumm W, Morgan JJ (1996) Aquatic chemistry, 3rd edn. Wiley, New York

    Google Scholar 

  • Sulonen MLK, Kokko ME, Lakaniemi A, Puhakka JA (2015) Electricity generation from tetrathionate in microbial fuel cells by acidophiles. J Hazard Mater 284:182–189

    Google Scholar 

  • Sulonen MLK, Kokko ME, Lakaniemi A, Puhakka JA (2016) Long-term stability of bioelectricity generation coupled with tetrathionate disproportionation. Bioresour Technol 216:876–882

    Google Scholar 

  • Suzuki I (1999) Oxidation of inorganic sulfur compounds: chemical and enzymatic reactions. Can J Microbiol 45:97–105

    Google Scholar 

  • Szekers L (1974) Analytical chemistry of sulphur acids. Talanta 21(1):1–44

    Google Scholar 

  • Takano B, Watanuki K (1988) Quenching and liquid chromatographic determination of polythionates in natural water. Talanta 35:847–854

    Google Scholar 

  • Takano B, Zheng Q, Ohsawa S (2000) A telemetering system for monitoring aqueous polythionates in an active crater lake. J Volcanol Geoth Res 97:397–406

    Google Scholar 

  • Upadhyay SK (2006) Chemical kinetics and reaction dynamics. Springer, New York

    Google Scholar 

  • Van den Ende FP, van Gemerden H (1993) Sulfide oxidation under oxygen limitation by a Thiobacillus thioparus isolated from a marine microbial mat. FEMS Microbiol Ecol 13:69–78

    Google Scholar 

  • Varga D, Horváth A (2007) Kinetics and mechanism of the decomposition of tetrathionate ion in alkaline medium. Inorg Chem 46:7654–7661

    Google Scholar 

  • Watts MP, Gan HM, Peng LY, Lê Cao K-A, Moreau JW (2017) In situ stimulation of thiocyanate biodegradation through phosphate amendment in gold mine tailings water. Environ Sci Technol 51:13353–13362

    Google Scholar 

  • Wong-Chong GM, Ghosh RS, Bushey JT, Ebbs SD, Neuhauser EF (2006) In: Dzombak DA, Ghosh RS, Wong-Chong GM (eds) Cyanide in water and soil: chemistry, risk, and management. CRC Press, Boca Raton, pp 25–40

    Google Scholar 

  • Xu Y, Schoonen MAA, Nordstrom DK, Cunningham KM, Ball JW (2000) Sulfur geochemistry of hydrothermal waters in Yellowstone National Park, Wyoming, USA, II: formation and decomposition of thiosulfate and polythionates in Cinder Pool. J Volcanol Geotherm Res 97:407–423

    Google Scholar 

  • Yu X, Zhou P, Xishi Z, Liu Y (2005) Cyanide removal y Chinese vegetation—quantification of the Michaelis-Menten kinetics. Environ Sci Pollut Res 12:221–222

    Google Scholar 

  • Zopfi J, Ferdelman TG, Fossing H (2004) Distribution and fate of sulfur intermediates—sulfite, tetrathionate, thiosulfate, and elemental sulfur—in marine sediments. Geol Soc Am Spec Pap 379:97–116

    Google Scholar 

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Acknowledgements

This work was funded by the Marie Curie Actions CIG PCIG10-GA-2011-303740 (ThioCyAnOx) Grant.

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  1. The Department of Geological and Environmental Sciences, Ben-Gurion University of the Negev, Beer Sheva, Israel

    Irina Kurashova & Alexey Kamyshny Jr.

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  1. Irina Kurashova
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  2. Alexey Kamyshny Jr.
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Correspondence to Alexey Kamyshny Jr..

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Kurashova, I., Kamyshny, A. Kinetics of Thiocyanate Formation by Reaction of Cyanide with Tetrathionate. Aquat Geochem 27, 63–77 (2021). https://doi.org/10.1007/s10498-020-09385-9

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