Voltammetric study of an FeS layer on a Hg electrode in supersaturated FeS chloride solution
D. Krznarić A and I. Ciglenečki A B
+ Author Affiliations
- Author Affiliations
A Center for Marine and Environmental Research, Institute Ruđer Bošković, Bijenička 54, 10000 Zagreb, Croatia.
B Corresponding author. Email: irena@irb.hr
Environmental Chemistry 12(2) 123-129 https://doi.org/10.1071/EN14016
Submitted: 17 January 2014 Accepted: 10 May 2014 Published: 5 September 2014
Environmental context. During the electrochemical analysis of natural waters, the Hg electrode could become the site for surface metal sulfide formation, such as FeS, which can have significant influence on the voltammetric determination of FeII. Reduction of FeII in such conditions can occur both on the bare Hg surface and on the FeS-modified Hg surface. Until recently, measurements of FeII have considered only the signal obtained from reduction on the bare Hg surface, and hence may have underdetermined the true FeII content of natural samples.
Abstract. Cyclic voltammetry at a Hg electrode was used for the study of an FeS layer formed on the electrode surface during scanning potential in a saturated FeS suspension containing FeS nanoparticles in chloride electrolyte. Newly presented results as a part of comprehensive study on FeS electrochemistry in model and natural samples confirm that the voltammetric peak at –1.1 V, which can often be recorded in anoxic waters containing Fe and sulfide species, represents reduction of Fe2+ on the Hg electrode surface modified by the FeS layer. Fe0 deposited on such a modified Hg surface is reoxidisable, often producing two oxidation peaks situated between –0.8 and –0.6 V (v. Ag/AgCl). These peaks represent two different Fe0 oxidation products, free Fe2+ and Fe2+ chloro complexes, FeCl+. By scanning the potential from –0.75 V in the positive direction, an oxidation exchange peak of Hg and FeS at ~–0.45 V occurs, which can be taken as a measure for FeS nanoparticles from bulk solution.
Additional keywords: modified Hg electrode, nanoparticles, voltammetry.
References
[1] W. Davison, J. Buffle, R. de Vitre, Direct polarographic determination of O2, FeII, MnII, S–II and related species in anoxic waters. Pure Appl. Chem. 1988, 60, 1535.| Direct polarographic determination of O2, FeII, MnII, S–II and related species in anoxic waters.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaL1cXmtFGms74%3D&md5=89db22ba925d472367b508b1c723ce91CAS |
[2] J. Buffle, R. R. De Vitre, D. Perret, G. G. Leppard, Combining field measurements for speciation in non perturbable waters, in Metal Speciation: Theory, Analysis, and Application (Eds J. R. Kramer, H. E. Allen) 1988, pp. 99–124 (Lewis Publishers Inc.: Chelsea, MI).
[3] R. R. de Vitre, J. Buffle, D. Perret, R. Baudat, A study of iron and manganese transformations at the O2/S–II transition layer in a eutrophic lake (Lake Bret, Switzerland): a multimethod approach. Geochim. Cosmochim. Acta 1988, 52, 1601.
| A study of iron and manganese transformations at the O2/S–II transition layer in a eutrophic lake (Lake Bret, Switzerland): a multimethod approach.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaL1cXksl2htrw%3D&md5=535fca35138d6b682e78a953e7a44e98CAS |
[4] S. M. Theberge, G. W. Luther, Determination of the electrochemical properties of a soluble aqueous FeS species present in sulfidic solutions. Aquat. Geochem. 1997, 3, 191.
| Determination of the electrochemical properties of a soluble aqueous FeS species present in sulfidic solutions.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaK1cXit1Kju7c%3D&md5=fcc5c512cd588e0b274571814352d827CAS |
[5] W. Davison, J. Buffle, R. de Vitre, Voltammetric characteization of a dissolved iron sulfide species by laboratory and field studies. Anal. Chim. Acta 1998, 377, 193.
| Voltammetric characteization of a dissolved iron sulfide species by laboratory and field studies.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaK1cXns1Kmurg%3D&md5=ba1a181fd7756f06664c5f8a32deb0f5CAS |
[6] D. Rickard, A. Oldroyd, A. Cramp, Voltammetric evidence for soluble FeS complexes in anoxic estuarine muds. Estuaries 1999, 22, 693.
| Voltammetric evidence for soluble FeS complexes in anoxic estuarine muds.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaK1MXntlCks74%3D&md5=596a0be29f3e441a210e15476fa01847CAS |
[7] G. W. Luther, B. Glazer, S. Ma, R. Trouwborst, B. R. Schultz, G. K. Druschel, C. Kraiya, Iron and sulfur chemistry in a stratified lake: evidence for iron-rich sulfide complexes. Aquat. Geochem. 2003, 9, 87.
| Iron and sulfur chemistry in a stratified lake: evidence for iron-rich sulfide complexes.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD2cXhvF2lsrY%3D&md5=13e6056b7ad08b247e7f0e93d10e2fb5CAS |
[8] G. W. Luther, T. F. Rozan, M. Taillefert, D. B. Nuzio, C. Di Meo, T. B. Shank, A. C. Lutz, S. C. Cary, Chemical speciation drives hydrothermal vent ecology. Nature 2001, 410, 813.
| Chemical speciation drives hydrothermal vent ecology.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD3MXjtVeks7s%3D&md5=a0619d39045246b2d6461319a7a9102eCAS | 11298448PubMed |
[9] E. Bura-Nakić, E. Viollier, D. Jezequel, I. Ciglenečki, Reduced sulfur species in anoxic water column of meromictic Pavin crater lake (Central Massif, France). Chem. Geol. 2009, 266, 311.
| Reduced sulfur species in anoxic water column of meromictic Pavin crater lake (Central Massif, France).Crossref | GoogleScholarGoogle Scholar |
[10] B. T. Glazer, G. W. Luther, S. K. Konovalov, G. E. Friederich, R. E. Trouwborst, A. S. Romanov, Documenting the suboxic zone of the Black Sea via high-resolution real-time redox profiling. Deep Sea Res. Part II Top. Stud. Oceanogr. 2006, 53, 1740.
| Documenting the suboxic zone of the Black Sea via high-resolution real-time redox profiling.Crossref | GoogleScholarGoogle Scholar |
[11] E. Bura-Nakić, D. Krznarić, D. Jurašin, G. R. Helz, I. Ciglenečki, Voltammetric characterization of metal sulfide particles and nanoparticles in model solutions and natural waters. Anal. Chim. Acta 2007, 594, 44.
| Voltammetric characterization of metal sulfide particles and nanoparticles in model solutions and natural waters.Crossref | GoogleScholarGoogle Scholar | 17560384PubMed |
[12] E. Bura-Nakić, V. Eric, I. Ciglenečki, Electrochemical and Colorimetric Measurements Show the Dominant Role of FeS in a Permanently Anoxic Lake. Environ. Sci. Technol. 2013, 47, 741.
| Electrochemical and Colorimetric Measurements Show the Dominant Role of FeS in a Permanently Anoxic Lake.Crossref | GoogleScholarGoogle Scholar | 23240551PubMed |
[13] D. Rickard, J. W. Morse, Acid volatile sulfide (AVS). Mar. Chem. 2005, 97, 141.
| Acid volatile sulfide (AVS).Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD2MXhtF2qurrI&md5=482dd109319cb0b57f2db1d30ea70bbeCAS |
[14] D. Rickard, The solubility of FeS. Geochim. Cosmochim. Acta 2006, 70, 5779.
| The solubility of FeS.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD28Xht1WmtbzE&md5=f8c7762ce7a3a6661103b9f1c37dfad9CAS |
[15] W. Davison, N. Phillips, B. J. Tabner, Soluble iron sulfide species in natural waters: reappraisal of their stoichiometry and stability constants. Aquat. Sci. 1999, 61, 23.
| Soluble iron sulfide species in natural waters: reappraisal of their stoichiometry and stability constants.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaK1MXisVCnt7w%3D&md5=14b269a1bec8e5bb5f48bca598fd7712CAS |
[16] E. Bura-Nakić, D. Krznarić, G. R. Helz, I. Ciglenečki, Characterization of iron sulfide species in model solutions by cyclic voltammetry. Revisiting an old problem. Electroanalysis 2011, 23, 1376.
| Characterization of iron sulfide species in model solutions by cyclic voltammetry. Revisiting an old problem.Crossref | GoogleScholarGoogle Scholar |
[17] G. R. Helz, I. Ciglenečki, D. Krznarić, E. Bura-Nakić, Voltammetry of sulfide nanoparticles and the FeS(aq) problem. in Aquatic Redox Chemistry (Eds P. G. Tratnyek, T. J. Grundl, S. B. Haderlein), 2011, pp. 265–282 (American Chemical Society: Washington, DC).
[18] I. Milanović, D. Krznarić, E. Bura-Nakić, I. Ciglenečki, Deposition and dissolution of metal sulfide layers at the Hg electrode surface in seawater electrolyte conditions. Environ. Chem. 2014, 11, 167.
| Deposition and dissolution of metal sulfide layers at the Hg electrode surface in seawater electrolyte conditions.Crossref | GoogleScholarGoogle Scholar |
[19] E. Bura-Nakić, M. Marguš, I. Milanović, D. Jurašin, I. Ciglenečki, The development of electrochemical methods for determining nanoparticles in the environment. Part II. Chronoamperometric study of FeS. Environ. Chem. 2014, 11, 187.
| The development of electrochemical methods for determining nanoparticles in the environment. Part II. Chronoamperometric study of FeS.Crossref | GoogleScholarGoogle Scholar |
[20] E. Itabashi, Investigation of iron group MII/M(Hg) systems in noncomplexing perchlorate solutions containing sulfide ions at a mercury electrode. J. Electroanal. Chem. 1979, 101, 113.
| Investigation of iron group MII/M(Hg) systems in noncomplexing perchlorate solutions containing sulfide ions at a mercury electrode.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaE1MXltlWitbo%3D&md5=18e42ae08611d5097dc98b8202033251CAS |
[21] E. Itabashi, Influence of sulfide and cyanide ions on the electrochemical behavior of the FeII–Fe(Hg) system in thiocyanate solutions at mercury electrodes. J. Electroanal. Chem. 1981, 117, 295.
| Influence of sulfide and cyanide ions on the electrochemical behavior of the FeII–Fe(Hg) system in thiocyanate solutions at mercury electrodes.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaL3MXpt1GrtQ%3D%3D&md5=35cbee637f7d6c1278dcd1fa5775f3e2CAS |
[22] K. Winkler, S. Kalinowski, T. Krogulec, A study of the deposition of iron on mercury and glassy carbon electrodes. J. Electroanal. Chem. 1988, 252, 303.
| A study of the deposition of iron on mercury and glassy carbon electrodes.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaL1cXmtl2ht74%3D&md5=b2bf489a83d0e42decb894b2de9d5ee6CAS |
[23] K. Winkler, T. Krogulec, The study of electrode processes of FeII–thiosulphate complexes on mercury electrodes. J. Electroanal. Chem. 1995, 386, 127.
| The study of electrode processes of FeII–thiosulphate complexes on mercury electrodes.Crossref | GoogleScholarGoogle Scholar |
[24] K. Winkler, T. Krogulec, Z. Galus, Formation of FeS and its effect on the FeII/Fe system in thiocyanate solution at mercury electrodes. Electrochim. Acta 1985, 30, 1055.
| Formation of FeS and its effect on the FeII/Fe system in thiocyanate solution at mercury electrodes.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaL2MXltFaisLo%3D&md5=c6c7d6c43dd30c39fa68df4cad10211aCAS |
[25] N. Batina, I. Ciglenečki, B. Ćosović, Determinatin of elemental sulfur, sulfide, and their mixtures in electrolyte solutions by a.c. voltammetry. Anal. Chim. Acta 1992, 267, 157.
| Determinatin of elemental sulfur, sulfide, and their mixtures in electrolyte solutions by a.c. voltammetry.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaK38XlvFyjtLY%3D&md5=22c0d3104587fa932b4d52d2fc4c4303CAS |
[26] I. Ciglenečki, B. Ćosović, Electrochemical determination of thiosulfate in seawater in the presence of elemental sulfur and sulfide. Electroanalysis 1997, 9, 775.
| Electrochemical determination of thiosulfate in seawater in the presence of elemental sulfur and sulfide.Crossref | GoogleScholarGoogle Scholar |
[27] D. Krznarić, I. Ciglenečki, Electrochemical processes of sulfide in NaCl electrolyte solutions on mercury electrode. Electroanalysis 2005, 17, 1317.
| Electrochemical processes of sulfide in NaCl electrolyte solutions on mercury electrode.Crossref | GoogleScholarGoogle Scholar |
[28] I. Pižeta, G. Billon, J. C. Fischer, M. Wartel, Solid microelectrodes for in situ voltammetric measurements. Electroanalysis 2003, 15, 1389.
| Solid microelectrodes for in situ voltammetric measurements.Crossref | GoogleScholarGoogle Scholar |
[29] F. G. Bǎnicǎ, N. Spătaru, T. Spătaru, Catalytic hydrogen evolution in the presence of sulfide and cobalt ions. A study by cathodic stripping voltammetry on the hanging mercury drop electrode. Electroanalysis 1997, 9, 1341.
| Catalytic hydrogen evolution in the presence of sulfide and cobalt ions. A study by cathodic stripping voltammetry on the hanging mercury drop electrode.Crossref | GoogleScholarGoogle Scholar |
[30] N. Spătaru, F. G. Bǎnicǎ, Catalytic hydrogen evolution in cathodic stripping voltammetry on a mercury electrode in the presence of cobalt(II) ion and phenylthiourea or thiourea. Analyst (Lond.) 2001, 126, 1907.
| Catalytic hydrogen evolution in cathodic stripping voltammetry on a mercury electrode in the presence of cobalt(II) ion and phenylthiourea or thiourea.Crossref | GoogleScholarGoogle Scholar |
[31] F. G. Bǎnicǎ, M. Galik, I. Svancara, K. Vytras, Electrochemical investigation of metal sulfides at mercury electrodes using thiourea as a source of sulfide ion. Electroanalysis 2009, 21, 332.
| Electrochemical investigation of metal sulfides at mercury electrodes using thiourea as a source of sulfide ion.Crossref | GoogleScholarGoogle Scholar |
[32] E. Bura-Nakić, A. Róka, I. Ciglenečki, G. Inzelt, Electrochemical quartz crystal microbalance study of FeS particles attached to Au surface. Electroanalysis 2009, 21, 1699.
| Electrochemical quartz crystal microbalance study of FeS particles attached to Au surface.Crossref | GoogleScholarGoogle Scholar |
[33] M. Marguš, I. Ciglenečki, N. Batina, The development of electrochemical methods for determining nanoparticles in the environment. Part I. Voltammetry and in-situ ES-STM study of FeS in sodium chloride solutions. Environ. Chem. 2014, 11, 181.
| The development of electrochemical methods for determining nanoparticles in the environment. Part I. Voltammetry and in-situ ES-STM study of FeS in sodium chloride solutions.Crossref | GoogleScholarGoogle Scholar |
