Abstract
The association of tungsten(VI) and molybdenum(VI) oxyanions with metal cations was investigated under conditions simulating those prevailing in most natural waters. Potentiometric titrations were carried out for the systems containing tungsten(VI) or molybdenum(VI) anions and metal cations. The selection includes the major metal cations and some other ions of high environmental relevance. At neutral and basic pH values, in the presence of the most abundant metal cations, ionic pair species such as [Ca(WO4)] or [Ca(MoO4)] are formed to high extents. For the acidic pH range, polyoxoanion associations with cations are also found but are only relevant for tungsten(VI) in the conditions of the natural aquatic systems. The present results provide the basis for studying W(VI) and Mo(VI) speciation in natural aquatic systems, on which the environmental fate, bioavailability and toxicity of the elements depend.
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References
Koutsospyros, A., Braida, W., Christodoulatos, C., Dermatas, D., Strigu, L.N.: A review of tungsten: from environmental obscurity to scrutiny. J. Hazard. Mater. 136, 1–19 (2006)
Kletzin, A., Adams, M.W.W.: Tungsten in biological systems. FEMS Microbiol. Rev. 18, 5–63 (1996)
Strigul, N.: Does speciation matter for tungsten ecotoxicology? Ecotoxicol. Environ. Saf. 73, 1099–1113 (2010)
Mendel, R.R., Bittner, F.: Cell biology of molybdenum. Biochim. Biophys. Acta 1763, 621–635 (2006)
Vyskocil, A., Viau, C.: Assessment of molybdenum toxicity in humans. J. Appl. Toxicol. 19, 185–192 (1999)
Kabata-Pendias, A., Pendias, H.: Trace Elements in Soils and Plants, 3rd edn. CRC Press, Boca Raton (2011)
Strigul, N., Koutsospyros, A., Christodoulatos, C.: Tungsten speciation and toxicity: acute toxicity of mono-and poly-tungstates to fish. Ecotoxicol. Environ. Saf. 73, 164–171 (2010)
Strigul, N., Galdun, C., Vaccari, L., Ryan, T., Braida, W., Christodoulatos, C.: Influence of speciation on tungsten toxicity. Desalination 248, 869–879 (2009)
McGrath, S.P., Micó, C., Curdy, R., Zhao, F.J.: Predicting molybdenum toxicity to higher plants: influence of soil properties. Environ. Poll. 158, 3095–3102 (2010)
Bodek, I., Lyman, W.J., Feehl, W.F., Rosenblatt, D.H.: Environmental Inorganic Chemistry. Pergamon Press, New York (1988)
Alloway, B.J. (ed.): Environmental Pollution: Heavy Metals in Soils. Trace Metals and Metalloids in Soils and their Bioavailability, vol. 22, 3rd edn. Springer, New York (2013)
Clausen, J.L., Korte, N.: Environmental fate of tungsten from military use. Sci. Total Environ. 407, 2887–2893 (2009)
Hsu, S.C., Hsieh, H.L., Chen, C.P., Tseng, C.M., Huang, S.C., Huang, C.H., Huang, Y.T., Radashevsky, V., Lin, S.H.: Tungsten and other heavy metal contamination in aquatic environments receiving wastewater from semiconductor manufacturing. J. Hazard. Mater. 189, 193–202 (2011)
Yu, C., Xu, S., Gang, M., Chen, G., Zhou, L.: Molybdenum pollution and speciation in Nver River sediments impacted with Mo mining activities in western Liaoning, northeast China. Int. J. Environ. Res. 5, 205–212 (2011)
Seiler, R.L., Stollenwerk, K.G., Garbarino, J.R.: Factors controlling tungsten concentrations in ground water, Carson Desert, Nevada. Appl. Geochem. 20, 423–441 (2005)
Kishida, K., Okamura, K., Ishibachi, J.: Tungsten enriched in submarine hydrothermal fluids. Earth Planet. Sci. Lett. 222, 819–827 (2004)
Johannesson, K.H., Berrylyons, W., Graham, E.Y., Welch, K.A.: Oxyanion concentrations in Eastern Sierra Nevada Rivers: boron, molybdenum, vanadium and tungsten. Aquat. Geochem. 6, 19–46 (2000)
Leybourne, M.I., Cameron, E.M.: Source, transport, and fate of rhenium, selenium, molybdenum, arsenic, and copper in groundwater associated with porphyry–Cu deposits, Atacama Desert, Chile. Chem. Geol. 2008(247), 208–228 (2008)
Stability Constants Database. IUPAC (2007)
May, P.M., Murray, K.: JESS—a joint expert speciation system. Talanta 38, 1409–1417 (1991)
Johannesson, K.H., Dave, H.B., Mohajerin, T.J., Datta, S.: Controls on tungsten concentrations in groundwater flow systems: the role of adsorption, aquifer sediment Fe(III) oxide/oxyhydroxide content and thiotungstate formation. Chem. Geol. 351, 76–94 (2013)
Murata, K., Ikeda, S.: Studies on polynuclear molybdates in the aqueous solution by laser Raman spectroscopy. Spectrochim. Acta A 39, 787–794 (1983)
Petterson, L., Andersson, I., Ohman, L.O.: Multicomponent polyanions. 31P NMR study of aqueous molybdophosphates. Acta Chem. Scand. A 39, 53–58 (1985)
Cruywagen, J.J., de Wet, H.: Equilibrium study of the adsorption of molybdenum(VI) on activated carbon. Polyhedron 7, 547–556 (1988)
Martire, D., Feliz, M., Capparelli, A.: Kinetic study of the molybdenum(VI)–l-histidine and molybdenum(VI)–imidazole systems. Polyhedron 8, 2225–2232 (1989)
Cruywagen, J.J.: Protonation, oligomerization and condensation reactions of vanadate(V), molybdate(VI) and tungstate(VI). Adv. Inorg. Chem. 49, 127–182 (2000)
Cruywagen, J.J., Draaijer, A.G., Heyns, J.B.B., Rohwer, E.A.: Molybdenum(VI), equilibria in different ionic media. Formation constants and thermodynamic quantities. Inorg. Chim. Acta 331, 322–329 (2001)
Farkas, E., Csoka, H.: Copper(II), nickel(II), zinc(II) and molybdenum(VI) complexes of desferroxamine B in aqueous solution. J. Inorg. Biochem. 65, 281–287 (1997)
Holm, R.H., Solomon, E.I., Majumdar, A., Tenderholt, A.: Comparative molecular chemistry of molybdenum and tungsten and its relation to hydroxylase and oxotransferase enzymes. Coord. Chem. Rev. 255, 993–1015 (2011)
Cruywagen, J.J., Van der Merwe, I.F.J.: Tungsten(VI) equilibria: a potentiometric and calorimetric investigation. J. Chem. Soc. Dalton Trans. 7, 1701–1705 (1987)
Van Put, J.W.: Crystallisation and processing of ammonium paratungstate (APT). Int. J. Refract. Metals Hard Mater. 13, 61–76 (1995)
Smith, B.J., Patrick, V.A.: Quantitative determination of sodium metatungstate speciation by NMR spectroscopy. Aust. J. Chem. 53, 965–970 (2000)
De Buysser, K., Van Driessche, I., Vermeir, P., Thuy, T.T., Schaubroeck, J., Hoste, S.: EXAFS analysis of blue luminescence in polyoxytungstate citrate gels. Phys. Stat. Sol. 245, 2483–2489 (2008)
Davantès, A., Costa, D., Lefèvre, G.: Infrared study of (poly)tungstate ions in solution and sorbed into layered double hydroxides: vibrational calculations and in situ analysis. J. Phys. Chem. 119, 12356–12364 (2015)
Cruywagen, J.J., Pienaar, A.T.: The adsorption of tungsten (VI) on activated carbon from 1.0 M Na(H)Cl solution. PoIyhedron 8, 71–76 (1989)
Wesolowski, D., Drummond, S.E., Mesmer, R.E., Ohmoto, H.: Hydrolysis equilibria of tungsten(V1) in aqueous sodium chloride solutions to 300 °C. Inorg. Chem. 23, 1120–1132 (1984)
Aveston, J.: Hydrolysis of tungsten(VI): ultracentrifugation, acidity measurements, and Raman spectra of polytungstates. Inorg. Chem. 3, 981–986 (1964)
Rozantsev, G.M., Sazonova, O.I.: Thermodynamic parameters of interconversions of isopolyanions in solutions of tungsten(VI). Russ. J. Coord. Chem. 31, 552–558 (2005)
Pyrzynska, K.: Determination of molybdenum in environmental samples. Anal. Chim. Acta 590, 40–48 (2007)
Bednar, A.J., Jones, W.T., Boyd, R.E., Ringelberg, D.B., Larson, S.L.: Geochemical parameters influencing tungsten mobility in soils. J. Environ. Qual. 37, 229–233 (2008)
Gustafsson, J.P.: Modelling molybdate and tungstate adsorption to ferrihydrite. Chem. Geol. 200, 105–115 (2003)
Torres, J., Gonzatto, L., Peinado, G., Kremer, C., Kremer, E.: Interaction of molybdenum(VI) oxyanions with +2 metal cations. J. Solution Chem. 43, 1687–1700 (2014)
Gans, P., O’Sullivan, B.: Glee, a new computer program for glass electrode calibration. Talanta 51, 33–37 (2000)
Gans, P., Sabatini, A., Vacca, A.: Investigation of equilibria in solution. Determination of equilibrium constants with the HYPERQUAD suite of programs. Talanta 43, 1739–1753 (1996)
Alderighi, L., Gans, P., Ienco, A., Peters, D., Sabatini, A., Vacca, A.: Hyperquad simulation and speciation (HySS): a utility program for the investigation of equilibria involving soluble and partially soluble species. Coord. Chem. Rev. 184, 311–318 (1999)
Torres, J., Pintos, V., Gonzatto, L., Domínguez, S., Kremer, C., Kremer, E.: Selenium chemical speciation in natural waters. Chem. Geol. 288, 32–38 (2011)
Bretti, C., Crea, F., De Stefano, C., Foti, C., Materazzi, S., Vianelli, G.: Thermodynamic properties of dopamine in aqueous solution. Acid–base properties, distribution, and activity coefficients in NaCl aqueous solutions at different ionic strengths and temperatures. J. Chem. Eng. Data 58, 2835–2847 (2013)
Bretti, C., De Stefano, C., Millero, F.J., Sammartano, S.G.: Modeling of protonation constants of linear aliphatic dicarboxylates containing –S–groups in aqueous chloride salt solutions, at different ionic strengths, using the SIT and Pitzer equations and empirical relationships. J. Solution Chem. 37, 763–784 (2008)
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Appendix
According to the SIT model [46–48]:
where K i is the measured protonation constant, \( K_{i}^{0} \) is the corresponding infinite dilution value, Δz 2 is the squared charge difference of reactants and products, DH is the Debye-Hückel term, i.e. Eq. A.2, I is the ionic strength on the molal scale, and Δε is the sum of the specific interaction coefficients of reactants and products.
In turn, the Debye-Hückel term, DH, is calculated as follows:
where
A = 0.505 kg1/2·mol−1/2 at 20.0 °C.
B = 1.5 kg1/2·mol−1/2.
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Torres, J., Tissot, F., Santos, P. et al. Interactions of W(VI) and Mo(VI) Oxyanions with Metal Cations in Natural Waters. J Solution Chem 45, 1598–1611 (2016). https://doi.org/10.1007/s10953-016-0522-6
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DOI: https://doi.org/10.1007/s10953-016-0522-6