Skip to main content

Advertisement

SpringerLink
Log in

Kinetics of Thiocyanate Formation by Reaction of Cyanide and Its Iron Complexes with Thiosulfate

  • Original Article
  • Published:
Aquatic Geochemistry Aims and scope Submit manuscript

Abstract

Reactions between cyanide and compounds, which contain S–S bonds, in aqueous media result in formation of thiocyanate. In this work, we studied the kinetics of reactions of thiosulfate with free cyanide and its complexes under environmental conditions. Rates of reactions between cyanide species and thiosulfate decrease in the following order: CN− > HCN > [Fe(CN)6]3− > [Fe(CN)6]4−. However, at neutral and slightly acidic pH range, reaction of thiosulfate with iron-cyanide complexes outcompetes its reaction with free cyanide, which exists in equilibrium with complexed cyanide. At environmentally relevant conditions, the characteristic time of reaction between free cyanide and thiosulfate was found to be tens of thousands of years, while for iron-cyanide complexes it was found to be hundreds to millions of years. Examples of application of kinetic parameters for calculation of rates of cyanide consumption in industrial (coke oven wastewater) and non-polluted natural aquatic system (Delaware Great Marsh) are provided.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5

Similar content being viewed by others

References

  • Bak F, Schuhmann A, Jansen K (1993) Determination of tetrathionate and thiosulfate in natural samples and microbial cultures by a new, fast and sensitive ion chromatographic technique. FEMS Microbiol Ecol 12:257–264. https://doi.org/10.1111/j.1574-6941.1993.tb00038.x

    Article  Google Scholar 

  • Bartlett PD, Davis REJ (1958) Reactions of elemental sulfur. II. The reaction of alkali cyanides with sulfur, and some single-sulfur transfer reactions. Am Chem Soc 80:2513

    Google Scholar 

  • Blonder B, Boyko V, Turchyn AV, Antler G, Sinichkin U, Knossow N, Klein R, Kamyshny A Jr (2017) Impact of aeolian dry deposition of reactive iron minerals on sulfur cycling in sediments of the Gulf of Aqaba. Front Microbiol 8:1131

    Google Scholar 

  • Chen KY, Morris JC (1972) Kinetics of oxidation of aqueous sulfide by O2. Environ Sci Technol 6(6):529–537

    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 (1962) Displacement reactions at the sulfur atom. III. The reaction of cyanide with thiosulfate. J Phys Chem 66:956

    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(7):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 AJ, Kamyshny A (2017) Turnover rates of intermediate sulfur species (S 2−x , S0, S2O3 2−, S4O6 2−, SO3 2−) in anoxic 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 

  • Ghosh RS, Dzombak DA, Luthy RG, Nakles DV (1999) Subsurface fate and transport of cyanide species at a manufactured-gas plant site. Water Environ Res 71:1205

    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 

  • Jaszczak E, Polkowska Ż, Narkowicz S, Namieśnik J (2017) Cyanides in the environment—analysis—problems and challenges. Environ Sci Pollut Res 24:15929–15948. https://doi.org/10.1007/s11356-017-9081-7

    Article  Google Scholar 

  • Jørgensen BB, Fossing H, Wirsen CO, Jannasch HW (1991) Sulfide oxidation in the anoxic Black Sea chemocline. Deep Sea Res 38(Suppl 2):S1083–S1103

    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, 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, 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 

  • Kamyshny A, Druschel G, Mansaray ZF, Farquhar J (2014) Multiple sulfur isotopes fractionation evidence of abiotic sulfur transformations in Yellowstone National Park geothermal springs. Geochem Trans 15:7

    Google Scholar 

  • Karavaiko GI, Kondrat’eva EE, Savari EE, Grigor’eva NV, Avakyan ZA (2000) Microbial degradation of cyanide and thiocyanate. Microbiology 69(2):167–173

    Google Scholar 

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

    Google Scholar 

  • Knossow N, Blonder B, Eckert W, Turchyn AV, Antler G, Kamyshny A Jr (2015) Annual sulfur cycle in a warm monomictic lake with sub-millimolar sulfate concentrations. Geochem Trans 16:7

    Google Scholar 

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

    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, 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 

  • 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. Biogeochem 14:57–88

    Google Scholar 

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

    Google Scholar 

  • Meeussen JCL, Keizer MG, De Haan FAM (1992) The chemical stability and decomposition rate of iron cyanide complexes in soil solutions. Environ Sci Technol 26(3):511–516

    Google Scholar 

  • Mishra L, Paul KK, Jena S (2018) Characterization of coke oven wastewater. Earth Envirol Sci 167:012011

    Google Scholar 

  • Oluwole ASA, Onabolu AO, Cotgreave IA, Rosling H, Persson A, Link H (2003) Influence of endemic ataxic polyneuropathy and its relation to exposure to cyanide in a Nigerian community. J Neurol Neurosurg Psychiatry 74:1417–1422

    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 

  • Pal P, Kumar R (2014) Treatment of coke wastewater: a critical review for developing sustainable management strategies. Sep Purif Rev 43:89–123

    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 

  • 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

    Google Scholar 

  • Schippers A, Jørgensen BB (2002) Biogeochemistry of pyrite and iron sulfide oxidation in marine sediments. Geochim Cosmochim Acta 66:85–92

    Google Scholar 

  • Sehmel GA (1989) Cyanide and antimony thermodynamic database for the aqueous species and solids for the EPA-MINTEQ geochemical code, PNL-6835. Pacific Northwest Laboratory, Richland

    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 

  • Souren AWMG (2000) Living with cyanide. Geochem News 105:16–26

    Google Scholar 

  • Steudel R (1996) Mechanisms of the formation of elemental sulfur from aqueous sulfide in chemical and microbiological desulfurization processes. Ind Eng Chem Res 35:1417–1423

    Google Scholar 

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

    Google Scholar 

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

    Google Scholar 

  • Sӧrbo B (1957) A colorimetric method for the determination of thiosulfate. Biochim Biophys Acta 23:412

    Google Scholar 

  • Takasaki Y, Satoh H, Onuki M, Mino T, Ito K, Miki O (2007) Behavior of nitrite oxidizers in the nitrification/denitrification process for the treatment of simulated coke-oven wastewater. J Water Environ Technol 5:29–36

    Google Scholar 

  • Taube H (1943) Disappearance of thiosulfate in solutions of maleic acid; catalysis of cis-trans isomerization. Am Chem J 65:526–531

    Google Scholar 

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

    Google Scholar 

  • Urban PJZ (1961) Colorimetry of sulphur anions. I. An improved colorimetric method for the determination of thiosulphate. Anal Chem 179:415

    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, Dzombak DA, Gjosh RS (2006a) In: Dzombak DA, Ghosh RS, Wong-Chong GM (eds) Cyanide in water and soil: chemistry, risk, and management. CRC Press, Boca Raton, pp 1–14

    Google Scholar 

  • 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: chemistry, risk, and management. CRC Press, Boca Raton, pp 25–40

    Google Scholar 

  • Yin N, Yang G, Zhong Z, Xing W (2011) Separation of ammonium salts from coking wastewater with nanofiltration combined with diafiltration. Desalination 268:233–237

    Google Scholar 

  • Young TC, Zhao X, Theis TL (2006) In: Dzombak DA, Ghosh RS, Wong-Chong GM (eds) Cyanide in water and soil: chemistry, risk, and management. CRC Press, Boca Raton, pp 171–190

    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 T, Jørgensen BB, Teske A, Thamdrup B (2001) Influence of water column dynamics on sulfide oxidation and other major biogeochemical processes in the chemocline of the stratified Mariager Fjord (Denmark). Mar Chem 74:29–51

    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 

Download references

Acknowledgements

This work was supported by the Marie Curie Actions CIG PCIG10-GA-2011-303740 (ThioCyAnOx) Grant. We are grateful to Ido Ben Laish for help with establishing experimental protocols for analyses of cyanide and sulfur species. The authors would like to thank Valeria Boyko for assistance with experiments.

Author information

Authors and Affiliations

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

    Irina Kurashova & Alexey Kamyshny Jr.

Authors
  1. Irina Kurashova
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Alexey Kamyshny Jr.
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Alexey Kamyshny Jr..

Additional information

Publisher's Note

Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Kurashova, I., Kamyshny, A. Kinetics of Thiocyanate Formation by Reaction of Cyanide and Its Iron Complexes with Thiosulfate. Aquat Geochem 25, 219–236 (2019). https://doi.org/10.1007/s10498-019-09361-y

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10498-019-09361-y

Keywords

Search

Navigation