Abstract
The standard thermodynamic properties at 25°C, 1 bar (ΔG of , ΔH of , S o, C oP , V o, ω) and the coefficients of the revised Helgeson–Kirkham–Flowers equations of state were evaluated for several aqueous complexes formed by dissolved metals and either arsenate or arsenite ions. The guidelines of Shock and Helgeson (Geochim Cosmochim Acta 52:2009–2036, 1988) and Sverjensky et al. (Geochim Cosmochim Acta 61:1359–1412, 1997) were followed and corroborated with alternative approaches, whenever possible. The SUPCRT92 computer code was used to generate the log K of the destruction reactions of these metal–arsenate and metal–arsenite aqueous complexes at pressures and temperatures required by the EQ3/6 software package, version 7.2b. Apart from the AlAsO o4 and FeAsO o4 complexes, our log K at 25°C, 1 bar are in fair agreement with those of Whiting (MS Thesis, Colorado School of Mines, Golden, CO, 1992). Moreover, the equilibrium constants evaluated in this study are in good to fair agreement with those determined experimentally for the Ca–dihydroarsenate and Ca–hydroarsenate complexes at 40°C (Mironov et al., Russ J Inorg Chem 40:1690, 1995) and for Fe(III)–hydroarsenate complex at 25°C (Raposo et al., J Sol Chem 35:79–94, 2006), whereas the disagreement with the log K measured for the Ca–arsenate complex at 40°C (Mironov et al., Russ J Inorg Chem 40:1690, 1995) might be due to uncertainties in this measured value. The implications of aqueous complexing between dissolved metals and arsenate/arsenite ions were investigated for seawater, high-temperature geothermal liquids and acid mine drainage and aqueous solutions deriving from mixing of acid mine waters and surface waters.
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Aiuppa A, Avino R, Brusca L, Caliro S, Chiodini G, D’Alessandro W, Favara R, Federico C, Ginevra W, Inguaggiato S, Longo M, Pecoraino G, Valenza M (2006) Mineral control of arsenic content in thermal waters from volcano-hosted hydrothermal systems: insights from island of Ischia and Phlegrean Fields (Campanian Volcanic Province, Italy). Chem Geol 229:313–330
Apollaro C, Marini L, De Rosa R (2006) Use of reaction path modeling to predict the chemistry of stream water and groundwater: a case study from the Fiume Grande valley (Calabria, Italy). Environ Geol (in press)
Baes CF, Mesmer RE (1976) The hydrolysis of cations. Wiley, New York
Bassett RL (1980) A critical evaluation of the thermodynamic data for boron ions, ion pairs, complexes, and polyanions in aqueous solution at 298.15 K and 1 bar. Geochim Cosmochim Acta 44:1151–1160
Bothe JV, Brown PW (1999) The stabilities of calcium arsenates at 23 ± 1°C. J Hazard Mater B 69:197–207
Brown PL, Sylva RN (1987) Unified theory of metal-ion-complex formation constants. J Chem Res S(4-5):(M)0110
Chiodini G, Cioni R, Guidi M, Marini L (1991) Chemical geothermometry and geobarometry in hydrothermal aqueous solutions: a theoretical investigation based on a mineral-solution equilibrium model. Geochim Cosmochim Acta 55:2709–2727
Cox JD, Wagman DD, Medvedev VA (1989) CODATA key values for thermodynamics. Hemisphere Publishing Corporation, New York, 271 pp
Cullen WR, Reimier KJ (1989) Arsenic speciation in the environment. Chem Rev 89:713–764
Cutter GA (1992) Kinetic controls on metalloid speciation in seawater. Mar Chem 40:65–80
Donahue R, Hendry MJ (2003) Geochemistry of arsenic in uranium mine mill tailings, Saskatchewan, Canada. Appl Geochem 18:1733–1750
Dzombak DA, Morel FMM (1990) Surface complexation modeling. Hydrous ferric oxide. Wiley, New York, 393 p
Ellis AJ (1970) Quantitative interpretation of chemical characteristics of hydrothermal systems. Geothermics, Spec Issue 2, 2(1):516–528
Ellis AJ (1977) Geothermal fluid chemistry and human health. Geothermics 6:175–182
Giggenbach WF (1984) Mass transfer in hydrothermal alterations systems. Geochim Cosmochim Acta 48:2693–2711
Giggenbach WF (1987) Redox processes governing the chemistry of fumarolic gas discharges from White Island, New Zeland. Appl Geochem 2:143–161
Giggenbach WF (1997) The origin and evolution of fluids in magmatic-hydrothermal systems. In: Barnes HL (ed) Geochemistry of hydrothermal ore deposits, 3d edn. Wiley, New York, pp 737–796
Grenthe I, Fuger J, Konings RJM, Lemire RJ, Muller AB, Nguyen-Trung C, Wanner H (1992) Chemical thermodynamics of uranium. Elsevier, Amsterdam, pp 715
Guidi M, Marini L, Scandiffio G, Cioni R (1990). Chemical geothermometry in hydrothermal aqueous solutions: the influence of ion complexing. Geothermics 19:415–441
Haas JR, Shock EL, Sassani DC (1995) Rare earth elements in hydrothermal systems: estimates of standard partial molal thermodynamic properties of aqueous complexes of the rare earth elements at high pressures and temperatures. Geochim Cosmochim Acta 59:4329–4350
Helgeson HC, Kirkham DH (1974) Theoretical prediction of the thermodynamic behavior of aqueous electrolytes at high pressures and temperatures: I. Summary of the thermodynamic/electrostatic properties of the solvent. Am J Sci 274:1089–1198
Helgeson HC, Kirkham DH, Flowers GC (1981) Theoretical prediction of the thermodynamic behavior of aqueous electrolytes at high pressures and temperatures: IV. Calculation of activity coefficients, osmotic coefficients and relative partial molal properties to 600°C and 5 kb. Am J Sci 281:1249–1516
Hogfeldt E (1982) Stability constants of metal-ion complexes. Part A: inorganic ligands. IUPAC Chem. Data Ser. no. 21. Pergamon, Oxford, p 310
Hummel W, Berner U, Curti E, Pearson FJ, Thoenen T (2002) Nagra/PSI chemical/01thermodynamic data base 01. Nagra technical report NTB 02-16, Nagra, Wettingen, Switzerland (see also http://www.upublish.com/books/hummel.htm
Jackson KJ, Helgeson HC (1985) Chemical and thermodynamic constraints on the hydrothermal transport and deposition of tin. I. Calculation of the solubility of cassiterite at high pressures and temperatures. Geochim Cosmochim Acta 49:1–22
Johnson JW, Oelkers EH, Helgeson HC (1992) SUPCRT 92: a software package for calculating the standard molal thermodynamic properties of minerals, gases, aqueous species, and reactions from 1 to 5000 bars and 0 to 1000°C. Comput Geosci 18:899–947
Langmuir D (1979) Techniques of estimating thermodynamic properties for some aqueous complexes of geochemical interest. In: Jenne EA (ed) Chemical modeling in aqueous systems: speciation, sorption, solubility, and kinetics. ACS Symp. Ser. 93, American Chemical Society, Washington, 353–387
Langmuir D, Mahoney J, MacDonald A, Rowson J (1999) Predicting arsenic concentrations in the porewaters of buried uranium mill tailings. Geochim Cosmochim Acta 63:3379–3394
Langmuir D, Mahoney J, Rowson J (2006) Solubility products of amorphous ferric arsenate and crystalline scorodite (FeAsO4 · 2H2O) and their application to arsenic behavior in buried mine tailings. Geochim Cosmochim Acta 70:2942–2956
Lemire RJ (1984) An assessment of the thermodynamic behavior of neptunium in water and model groundwaters from 25 to 150°C. AECL-7817, Atomic Energy of Canada Limited, Pinawa, Manitoba, pp 53
Lemire RJ, Tremaine PR (1980) Uranium and plutonium equilibria in aqueous solutions to 200°C. J Chem Eng Data 25:361–370
Loehr TM, Plane RA (1968) Raman spectra and structures of arsenious acid and arsenites in aqueous solutions. Inorg Chem 7:1708–1714
Lowenthal DH, Pilson MEQ, Byrne RH (1977) The determination of the apparent dissociation constants of arsenic acid in seawater. J Mar Res 35:653–669
Mahoney J, Langmuir D, Gosselin N, Rowson J (2005) Arsenic readily released to pore waters from buried mill tailings. Appl Geochem 20:947–959
Marsicano F, Hancock RD (1978) The linear free energy relation in the thermodynamics of complex formation, 2. Analysis of the formation constants of complexes of the large metal ions Ag+, Hg2+, and Cd2+ with ligands having “soft” and nitrogen-donor atoms. J Chem Soc Dalton 1978:228–234
Martell AE, Smith RM (1989) Critical stability constants: other organic ligands (2nd printing), vol 3. Plenum, New York, 3, 495 p
Mattigod SV, Sposito G (1979) Chemical modeling of trace metal equilibria in contaminated soil solutions using the computer program GEOCHEM. In: Jenne EA (ed) Chemical modeling in aqueous systems: speciation, sorption, solubility, and kinetics. American Chemical Society, Washington, pp 837–856
Mironov VE, Kiselev VP, Egizaryan MB, Golovnev NN, Pashkov GL (1995) Ion association in aqueous solutions of calcium arsenate. Russ J Inorg Chem 40:1690
Murphy WM, Shock EL (1999) Environmental aqueous geochemistry of actinides. In: Burns PC, Rinch R (eds) Uranium: mineralogy, geochemistry and the environment. Rev Mineral 38:221–253
Neuberger CS, Helz GR (2005) Arsenic(III) carbonate complexing. Appl Geochem 20:1218–1225
Nriagu JO (1972a) Stability of vivianite and ion-pair formation in the system Fe3(PO4)2–H3PO4–H2O. Geochim Cosmochim Acta 36:459–470
Nriagu JO (1972b) Lead orthophosphates. I. Solubility and hydrolysis of secondary lead orthophosphate. Inorg Chem 11:2499–2503
Planer-Friedrich B, Lehr C, Matschullat J, Merkel BJ, Nordstrom DK, Sandstrom MW (2006) Speciation of volatile arsenic at geothermal features in Yellowstone National Park. Geochim Cosmochim Acta 70:2480–2491
Pokrovski G, Gout R, Schott J, Zotov A, Harrichoury J-C (1996) Thermodynamic properties and stoichiometry of As(III) hydroxide complexes at hydrothermal conditions. Geochim Cosmochim Acta 60:737–749
Pokrovski G, Zakirov I, Roux J, Testemale D, Hazemann J-L, Bychkov AY, Golikova GV (2002) Experimental study of arsenic speciation in vapor phase to 500°C: implications for As transport and fractionation in low-density crustal fluids and volcanic gases. Geochim Cosmochim Acta 66:3453–3480
Raposo JC, Olazábal MA, Madariaga JM (2006) Complexation and precipitation of arsenate and iron species in sodium perchlorate solutions at 25°C. J Sol Chem 35:79–94
Rard JA (1985) Chemistry and thermodynamics of europium and some of its simpler inorganic compounds and aqueous species. Chem Rev 85:555–582
Robins RG (1990) The stability and solubility of ferric arsenate-an update. In: Gaskell DR (ed) EPD Congress ’90, TMS annual meeting, pp 93–104
Ruaya JR, Seward TM (1987) The ion-pair constant and other thermodynamic properties of HCl up to 350°C. Geochim Cosmochim Acta 51:121–130
Sadiq M (1997) Arsenic chemistry in soils: an overview of thermodynamic predictions and field observations. Water Air Soil Pollut 93:117–136
Sassani DC, Shock EL (1998) Solubility and transport of platinum-group elements in supercritical fluids: summary and estimates of thermodynamic properties for ruthenium, rhodium, palladium, and platinum solids, aqueous ions, and complexes to 1000°C and 5 kbar. Geochim Cosmochim Acta 62:2643–2671
Schumm RH, Wagman DD, Bailey S, Evans WH, Parker VB (1973) Technical notes 270-1 to 270-8. National Bureau of Standards, USA
Sergeyeva EI, Khodakovsky IL (1969) Physicochemical conditions of formation of native arsenic in hydrothermal deposits. Geokhim 7:846–859
Shock EL, Helgeson HC (1988) Calculation of the thermodynamic and transport properties of aqueous species at high pressures and temperatures: correlation algorithms for ionic species and equation of state predictions to 5 kb and 1000°C. Geochim Cosmochim Acta 52:2009–2036
Shock EL, Helgeson HC (1990) Calculation of the thermodynamic and transport properties of aqueous species at high pressures and temperatures: standard partial molal properties of organic species. Geochim Cosmochim Acta 54:915–945
Shock EL, Koretsky CM (1993) Metal-organic complexes in geochemical processes: calculation of standard partial molal thermodynamic properties of aqueous acetate complexes at high pressures and temperatures. Geochim Cosmochim Acta 57:4899–4922
Shock EL, Koretsky CM (1995) Metal-organic complexes in geochemical processes: estimation of standard partial molal thermodynamic properties of aqueous complexes between metal cations and monovalent organic acid ligands at high pressures and temperatures. Geochim Cosmochim Acta 59:1497–1532
Shock EL, Helgeson HC, Sverjensky DA (1989) Calculation of the thermodynamic and transport properties of aqueous species at high pressures and temperatures: standard partial molal properties of inorganic neutral species. Geochim Cosmochim Acta 53:2157–2183
Shock EL, Oelkers EH, Johnson JW, Sverjensky DA, Helgeson HC (1992) Calculation of the thermodynamic properties of aqueous species at high pressures and temperatures: effective electrostatic radii, dissociation constants, and standard partial molal properties to 1000°C and 5 kb. J Chem Soc (Lond) Faraday Trans 88:803–826
Shock EL, Sassani DC, Willis M, Sverjensky DA (1997) Inorganic species in geologic fluids: correlations among standard molal thermodynamic properties of aqueous ions and hydroxide complexes. Geochim Cosmochim Acta 61:907–950
Silva RJ, Bidoglio G, Rand MH, Robouch PB, Wanner H, Puigdomenech I (1995) Chemical thermodynamics of americium. Elsevier, Amsterdam, pp 374
Smedley PL, Kinniburgh DG (2002) A review of the source, behaviour and distribution of arsenic in natural waters. Appl Geochem 17:517–568
Smith RM, Martell AE (1976) Critical stability constants: inorganic complexes, vol 4. Plenum, New York, 4, 257 p
Stumm W, Morgan JJ (1981) Aquatic chemistry. An introduction emphasizing chemical equilibria in natural waters. Wiley, New York
Sverjensky DA (1987) Calculations of the thermodynamic properties of aqueous species and the solubilities of minerals in supercritical electrolyte solutions. In: Carmichael ISE, Eugster HP (eds) Thermodynamic modeling of geologic materials: minerals, fluids and melts, mineral. Soc. Amer., Rev. Mineral 17:177–209
Sverjensky DA, Fukushi K (2006) A predictive model (ETLM) for As(III) adsorption and surface speciation on oxides consistent with spectroscopic data. Geochim Cosmochim Acta 70:3778–3802
Sverjensky DA, Shock EL, Helgeson HC (1997) Prediction of the thermodynamic properties of aqueous metal complexes to 1000°C and 5 kb. Geochim Cosmochim Acta 61:1359–1412
Tanger JC, Helgeson HC (1988) Calculation of the thermodynamic and transport properties of aqueous species at high pressures and temperatures: revised equations of state for the standard partial molal properties of ions and electrolytes. Am J Sci 288:19–98
Tonkin JW, Balistrieri LS, Murray JW (2002) Modeling metal removal onto natural particles formed during mixing of acid rock drainage with ambient surface water. Environ Sci Technol 36:484–492
Tossell JA (2005) Calculation of the interaction of bicarbonate ion with arsenites in aqueous solution and with the surfaces of Al hydroxide minerals. In: O’Day PA, Vlassopoulos D, Meng X, Benning LG (eds) Advances in arsenic research: integration of experimental and observational studies and implications for mitigation. American Chemical Society symposium series, Washington, pp 118–130
Truesdell AH, Jones BF (1974) WATEQ, a computer program for calculating chemical equilbria of natural waters. USGS J Res 2:233–248
Vink BW (1996) Stability relations of antimony and arsenic compounds in the light of revised and extended Eh-pH diagrams. Chem Geol 130:21–30
Wagman DD, Evans WH, Parker VB, Schumm RH, Halow I, Bailey SM, Churney KL, Nuttall RL (1982) The NBS tables of chemical thermodynamic properties, selected values for inorganic and C1 and C2 organic substances in SI units. J Phys Chem Ref Data 11(Suppl 2):392
Whiting KS (1992) The thermodynamics and geochemistry of arsenic, with application to subsurface waters at the Sharon Steel Superfund Site at Midvale, Utah. MS Thesis, Colorado School of Mines, Golden, CO
Wolery TJ (1979) Calculation of chemical equilibrium between aqueous solutions and minerals: the EQ3/6 software package. Report UCRL-52658, Lawrence Livermore National Laboratory, Livermore
Wolery TJ (1992) EQ3NR, a computer program for geochemical aqueous speciation-solubility calculations: theoretical manual, user’s guide and related documentation (version 7.0). Report UCRL-MA-110662 PT III. Lawrence Livermore National Laboratory, Livermore
Wolery TJ, Daveler SA (1992) EQ6, A computer program for reaction path modeling of aqueous geochemical systems: Theoretical manual, user’s guide, and related documentation (version 7.0). Report UCRL-MA-110662 PT IV. Lawrence Livermore National Laboratory, Livermore
Zakaznova-Herzog VP, Seward TM, Suleimenov OM (2006) Arsenous acid ionisation in aqueous solutions from 25 to 300°C. Geochim Cosmochim Acta 70:1928–1938
Zotov AL, Kudrin AV, Levin KA, Shikina ND, Varyash LN (1994) Experimental studies of the solubility and complexing of selected ore elements (Au, Ag, Cu, Mo, As, Sb, Hg) in aqueous solutions. In: Shmulovich KI, Yardley BWD, Gonchar GG (eds) Fluids in the crust. Chapman Hall, London
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Marini, L., Accornero, M. Prediction of the thermodynamic properties of metal–arsenate and metal–arsenite aqueous complexes to high temperatures and pressures and some geological consequences. Environ Geol 52, 1343–1363 (2007). https://doi.org/10.1007/s00254-006-0578-5
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DOI: https://doi.org/10.1007/s00254-006-0578-5