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The numerical modeling of ZnII speciation amongst the environmental inorganic ligands Cl–, OH–, CO32–, SO42–, and PO43– requires reliable values for the relevant stability (formation) constants. This paper compiles and provides a critical review of these constants and related thermodynamic data. It recommends values of log10 βp,q,r° valid at Im = 0 mol·kg–1 and 25 °C (298.15 K), and reports the empirical reaction ion interaction coefficients, ∆ε, required to calculate log10 βp,q,r values at higher ionic strengths using the Brønsted–Guggenheim–Scatchard specific ion interaction theory (SIT). Values for the corresponding reaction enthalpies, ∆rH, are reported where available. There is scope for additional high-quality measurements for the Zn2+ + H+ + CO32– system and for the Zn2+ + OH– and Zn2+ + SO42– systems at I > 0. In acidic and weakly alkaline fresh water systems (pH < 8), in the absence of organic ligands (e.g., humic substances), ZnII speciation is dominated by Zn2+(aq). In this respect, ZnII contrasts with CuII and PbII (the subjects of earlier reviews in this series) for which carbonato- and hydroxido- complex formation become important at pH > 7. The speciation of ZnII is dominated by ZnCO3(aq) only at pH > 8.4. In seawater systems, the speciation at pH = 8.2 is dominated by Zn2+(aq) with ZnCl+, Zn(Cl)2(aq), ZnCO3(aq), and ZnSO4(aq) as minor species. This behaviour contrasts with that for CuII and PbII for which at the pH of seawater in equilibrium with the atmosphere at 25 °C (log10 {[H+]/c°} ≈ 8.2) the MCO3(aq) complex dominates over the MCln(2–n)+ species. The lower stability of the different complexes of ZnII compared with those of CuII, PbII, and CdII is also illustrated by the percentage of uncomplexed M2+ in seawater, which is ca. 55, 3, 2, and 3.3 % of [MII]T, respectively.

The numerical modeling of CdII speciation amongst the environmental inorganic ligands Cl–, OH–, CO32–, SO42–, and PO43– requires reliable values for the relevant stability (formation) constants. This paper compiles and provides a critical review of these constants and related thermodynamic data. It recommends values of log10 βp,q,r° valid at Im = 0 mol kg–1 and 25 °C (298.15 K), along with the equations and empirical reaction ion interaction coefficients, ∆ε , required to calculate log10 βp,q,r values at higher ionic strengths using the Brønsted–Guggenheim–Scatchard specific ion interaction theory (SIT). Values for the corresponding reaction enthalpies, ∆rH, are reported where available. Unfortunately, with the exception of the CdII-chlorido system and (at low ionic strengths) the CdII-sulfato system, the equilibrium reactions for the title systems are relatively poorly characterized. In weakly acidic fresh water systems (–log10 {[H+]/c°} < 6), in the absence of organic ligands (e.g., humic substances), CdII speciation is dominated by Cd2+(aq), with CdSO4(aq) as a minor species. In this respect, CdII is similar to CuII [2007PBa] and PbII [2009PBa]. However, in weakly alkaline fresh water solutions, 7.5 < –log10 {[H+]/c°} < 8.6, the speciation of CdII is still dominated by Cd2+(aq), whereas for CuII [2007PBa] and PbII [2009PBa] the carbonato- species MCO3(aq) dominates. In weakly acidic saline systems (–log10 {[H+]/cϒ} < 6; –log10 {[Cl–]/c°} < 2.0) the speciation is dominated by CdCln(2–n)+ complexes, (n = 1–3), with Cd2+(aq) as a minor species. This is qualitatively similar to the situation for CuII and PbII. However, in weakly alkaline saline solutions, including seawater, the chlorido- complexes still dominate the speciation of CdII because of the relatively low stability of CdCO3(aq). In contrast, the speciation of CuII [2007PBa] and PbII [2009PBa] in seawater is dominated by the respective species MCO3(aq). There is scope for additional high-quali

This document presents a critical evaluation of the equilibrium constants and reaction enthalpies for the complex formation reactions between aqueous Hg(II) and the common environmental inorganic ligands Cl-, OH-, CO32-, SO42-, and PO43-. The analysis used data from the IUPAC Stability Constants database, SC-Database, focusing particularly on values for 25 &DEG; C and perchlorate media. Specific ion interaction theory (SIT) was applied to reliable data available for the ionic strength range I-c &LE; 3.0 mol dm(-3). Recommended values of log(10) β(p,q,r)&DEG; and the associated reaction enthalpies, &UDelta;H-r(m)&DEG;, valid at I-m = 0 mol kg(-1) and 25 &DEG; C, were obtained by weighted linear regression using the SIT equations. Also reported are the equations and specific ion interaction coefficients required to calculate log(10) β(p,q,r) values at higher ionic strengths and other temperatures. A similar analysis is reported for the reactions of H+ with CO32- and PO43-. Diagrams are presented to show the calculated distribution of Hg(II) amongst these inorganic ligands in model natural waters. Under typical environmental conditions, Hg(II) speciation is dominated by the formation of HgCl2(aq), Hg(OH)Cl(aq), and Hg(OH)(2)(aq).