Abstract
The association of molybdenum(VI) oxyanions with metal cations was investigated in solutions of low ionic strength, such as those prevailing in most natural waters. Potentiometric titrations were carried out for the systems containing molybdenum(VI) anions and divalent metal cations (M = Mg, Ca, Sr, Ba, Mn, Fe, Co, Ni, Cu, Zn, Cd, Hg and Pb). This selection includes the major cations and some other cations of high environmental relevance. The interaction of iron(III) with Mo(VI) anions was also studied. At neutral and basic pH values and for those systems where the solubility of the molybdate salt is high enough, ionic species pairs such as [M(MoO4)] predominate. At acidic pH values, [M(HMoO4)]+ and [M(Mo7O24)]4– are formed, the latter species are only relevant for total molybdenum concentrations higher than 1 mmol·L−1. These results provide the basis for molybdenum speciation in natural aquatic systems, on which the environmental fate, bioavailability and toxicity of the element depend.
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Cotton, F.A., Wilkinson, G., Murillo, C.A., Bochman, M.: Inorganic chemistry, 6th edn. Wiley, New York (1999)
Selinus, O. (ed.): Essentials of medical geology. Elsevier Academic Press, London (2005)
Mendel, R.R., Bittner, F.: Cell biology of molybdenum. Biochim. Biophys. Acta 1763, 621–635 (2006)
Kabata-Pendias, A., Mukherjee, A.B.: Trace elements from soil to human. Springer-Verlag, Berlin (2007)
The IUPAC Stability Constants Database: SC-Database and Mini-SCDatabase, version 2007
May, P.M., Murray, K.: JESS—a joint expert speciation system. Talanta 38, 1409–1417 (1991)
Murata, K., Ikeda, S.: Studies on polynuclear molybdates in the aqueous solution by laser Raman spectroscopy. Spectrochim. Acta A39, 787–794 (1983)
Petterson, L., Andersson, I., Ohman, L.-O.: Multicomponent polyanions. 31P NMR study of aqueous molybdophosphates. Acta Chem. Scand. A39, 53–58 (1985)
Cruywagen, 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 (2002)
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)
Bodek, I., Lyman, W.J., Reehl, W.F., Rosenblatt, D.H.: Environmental inorganic chemistry. Pergamon Press, New York (1988)
Greenwood, N.N., Earnshaw, A.: Chemistry of the elements, 2nd edn. Butterworth Heinemann Press, Oxford (1997)
Richens, D.T.: The chemistry of aqua ions. Wiley and Sons, New York (1997)
Schweitzer, G.K., Pesterfield, L.L.: The aqueous chemistry of the elements. Oxford University Press, Oxford (2010)
Holland, H.D., Turekian, K.K. (eds.): Treatise on geochemistry, Vol. 5: surface and groundwater, weathering, and soils, 2nd edn. Elsevier–Pergamon, Oxford (2003)
Kabata-Pendias, A., Pendias, H.: Trace elements in soils and plants, 3rd edn. CRC Press, Boca Raton (2001)
Muldrow, C., Hepler, L.: Heats of precipitation and formation of lead and calcium molybdates. J. Phys. Chem. 62, 982–984 (1958)
Felmy, A., Rai, D., Mason, M.: The solubility of CaMoO4(c) and an aqueous thermodynamic model for Ca2+– \( {\text{MoO}}_{4}^{{2 - }} \)-ion-interactions. J. Solution Chem. 21, 525–532 (1992)
Grobler, S., Suri, S.: Solubilities of the molybdates and tungstates of silver and copper(II) in water by ion-selective electrodes. J. Inorg. Nucl. Chem. 42, 51–53 (1980)
Vlek, P., Lindsay, W.: Thermodynamic stability and solubility of molybdenum minerals in soils. Soil Sci. Soc. Am. J. 41, 42–46 (1977)
Saito, A., Tomari, H., Choppin, G.: Spectrophotometric studies of metal cation interaction with nanomolybdomanganate(IV) anion, \( {\text{MnMo}}_{9} {\text{O}}_{{32}}^{{6 - }} \). Inorg. Chim. Acta 258, 145–153 (1997)
Polemio, M., Bufo, S., Paoletti, S.: Evaluaton of ionic strength and salinity of groundwaters: effect of the ionic composition. Geochim. Cosmochim. Acta 44, 809–814 (1980)
Schwarzenwach, G., Flaschka, H.: Complexometric titrations, 2nd edn. Methuen, London (1969)
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)
Ozeki, T., Kihara, H., Hikime, S.: Studies of Raman spectra and equilibria of isopolymolybdate ions in aqueous acidic solutions by factor analysis. Anal. Chem. 59, 945–950 (1987)
Torres, J., Pintos, V., Gonzatto, L., Domínguez, S., Kremer, C., Kremer, E.: Selenium chemical speciation in natural waters: Protonation and complexation behavior of selenite and selenate in the presence of environmentally relevant cations. Chem. Geol. 288, 32–38 (2011)
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We would like to thank Comisión Sectorial de Investigación Científica, CSIC (Programa de Apoyo a Grupos), and Agencia Nacional de Investigación e Innovación, ANII (Project FCE_1_2011_1_6491) from Uruguay, for financial support.
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Torres, J., Gonzatto, L., Peinado, G. et al. Interaction of Molybdenum(VI) Oxyanions with +2 Metal Cations. J Solution Chem 43, 1687–1700 (2014). https://doi.org/10.1007/s10953-014-0231-y
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DOI: https://doi.org/10.1007/s10953-014-0231-y