Speciation prediction

Equation 7 can be used to provide Insights about the nature of trace metal speciation in high complexatlon intensity systems. Using copper as an example, equation 8 provides speciation predictions in a system of inorganic ligands, L, and organic ligands, Lj. ... 

Preventive Measures. The intake uptake biokinetic model (lUBK) projects the impact of lead in the environment on blood lead. This model assumes conservatively high levels of intake and cannot account for chemical speciation, thus over-predictions of blood lead levels often occur. Nonetheless, because of the allegations of the impact of blood lead and neurobehavioral development, blood lead levels in children are being reduced adrninistratively to below 10 //g/dL. In order to do so, soil leads are being reduced to a level of between 500—1000 ppm where remediation is required. 

Prediction of the chemistry of plutonium in near-neutral aqueous media is highly dependent on understanding reactions that may be occurring in such media. One of the most important parameters is the stability and nature of complexes formed by plutonium in its four common oxidation states. Because Pu(III), Pu(IV), and Pu(VI) are readily hydrolysed, complexation reactions generally are studied in mildly to strongly acidic media. Data determined in acid media (and frequently at high concentrations of plutonium) then are used to predict the chemical speciation of plutonium at near-neutral pH and low concentrations of the metal ion. 

The distribution of metals between dissolved and particulate phases in aquatic systems is governed by a competition between precipitation and adsorption (and transport as particles) versus dissolution and formation of soluble complexes (and transport in the solution phase). A great deal is known about the thermodynamics of these reactions, and in many cases it is possible to explain or predict semi-quantita-tively the equilibrium speciation of a metal in an environmental system. Predictions of complete speciation of the metal are often limited by inadequate information on chemical composition, equilibrium constants, and reaction rates. 

The full appreciation of the overriding importance of metal speciation in evaluating the transport and effects of metals in an environment is a relatively recent event. As more information is gathered on the forms in which metals exist and are transported through various environmental compartments, it will become possible to predict more accurately the response of the biological communities exposed to the metals and hopefully avert or mitigate the adverse effects. 

Field and laboratory bioassay of chemosignals from related sympatric and allopatric species (overlapping and discrete distributions) are essential to an understanding of the relatedness or otherwise of functionally active compounds. The semiochemicals involved in speciation surely utilise the main and vomeronasal senses, but their relative contributions cannot be predicted at present. 

The interpretation of previous attempts at measuring the impact of metals on microbially mediated processes has been hindered by the use of a wide range of experimental conditions and measurements. Already, a shift from studies based on total metal concentration to those based on bioavailable metal concentrations has occurred. The next step will entail accurately predicting and measuring metal speciation patterns in order to identify microbial responses to metal speciation. Only then will it be possible to develop more effective methods to quantify and mitigate deleterious effects of metals on the myriad processes that microbes mediate in the environment. 

Trace element speciation in soil solution is affected by total metal concentrations in soils. Free Cu2+ activity increases with total Cu content in soils from Quebec and New York (Sauve et al., 1997). Total free Cu activity in soils could be predicted from total Cu content and soil pH ... 

Rubisov, D. H. Papangelakis, V. G. Sulfuric acid pressure leaching of laterites—prediction of metal solubilities and speciation analysis at temperature. EPD Congress 1999, Proceedings of Sessions and Symposia held at the TMS Annual Meeting, San Diego, Feb. 28-Mar. 4, 1999, 535-546. 

Garcia-Monco Carra et al. [296] have described a hybrid mercury film electrode for the voltammetric analysis of copper (and lead) in acidified seawater. Mercury plating conditions for preparing a consistently reproducible mercury film electrode on a glassy carbon substrate in acid media are evaluated. It is found that a hybrid electrode , i.e., one preplated with mercury and then replated with mercury in situ with the sample, gives very reproducible results in the analysis of copper in seawater. Consistently reproducible electrode performance allows for the calculation of a cell constant and prediction of the slopes of standard addition plots, useful parameters in the study of copper speciation in seawater. 

Sauve, S., Dumestre, A., McBride, M. and Hendershot, W. (1998). Derivation of soil quality criteria using predicted chemical speciation of Pb2+ and Cu2+, Environ. Toxicol. Chem., 17, 1481-1489. 

Luoma, S. N. (1995). Prediction of metal toxicity in nature from bioassays. In Metal Speciation and Bioavailability in Aquatic Systems, eds. Tessier, A. and Turner, D. R., Vol. 3, IUPAC Series on Analytical and Physical Chemistry of Environmental Systems. Series eds. Buffle J. and van Leeuwen H. P., John Wiley Sons, Ltd, Chichester, pp. 609-659. 

Model Studies. In model studies of adsorption, one deals with simple, well-defined systems, where usually a single well-characterized solid phase is used and the composition of the ionic medium is known, so that reactions competing with the adsorption may be predicted. It is not a trivial problem to compare the results from such model studies with those from field studies, or to use model results for the interpretation of field data. In field studies, a complex mixture of solid phases and dissolved components, whose composition is only poorly known, has to be considered competitive reactions of major ions and trace metal ions for adsorption may take place, and the speciation of the trace metal ions is often poorly understood. In order to relate field studies to model studies, distribution coefficients of elements between the dissolved and solid phases are useful. These distribution coefficients are of the following form ... 

In freshwater, Mn(II) oxidation is slightly slower than in 0.1M NaClO. The difference between the Mn(II) oxidation rate in freshwater and 0.1M NaCIO, is greatest at pH 8.5, at this pH the rate of Mn(II) oxidation is only 40% lower in the freshwater than in 0.1M NaClO. In the estuarine-water at pH 8.5 the rate of Mn(II) oxidation is 20 times slower than in 0.1M NaCIO,. The speciation calculations indicate why the model predicts the oxidation is slower than in natural waters (see, for example Table VII). 

At equilibrium, the reactant concentrations and products can be used to define a mass ratio called an equilibrium constant (A). This constant can then be used to predict the equilibrium concentrations of the reactants and products from the total amount of C or from either the equilibrium concentration of the products or the reactants. Although K is referred to as an equilibrium constant, it is a function of salinity, temperature, and pressure. With the appropriate value of K, calculations can be made to predict the equilibrium speciation of elements in seawater. The procedure for doing this is provided in the next section along with an expansion of K to multicomponent chemical systems. 

Equilibrium constants are also dependent on temperature and pressure. The temperature functionality can be predicted from a reaction s enthalpy and entropy changes. The effect of pressure can be significant when comparing speciation at the sea surface to that in the deep sea. Empirical equations are used to adapt equilibrium constants measured at 1 atm for high-pressure conditions. Equilibrium constants can be formulated from solute concentrations in units of molarity, molality, or even moles per kilogram of seawater. 

Although computer programs are now used to perform speciation calculations, examining how these calculations are performed provides important insights into the limitations of the model predictions. Thus, we will step through a small part of the calculation used to generate the results presented in Figure 5.4, which represents the iron... 

A full imderstanding of the speciation of dissolved iron requires consideration of ligands other than water and hydroxide. The most important ones are listed in Table 5.6 along with their concentration ranges in seawater and freshwater. For Fe(III) in seawater at pH > 4, the formation of complexes with hydroxide is most important, but at pH <4, sulfete, chloride, and fluoride pairing predominates (Figure 5.15b). To predict the equilibrimn speciation at low pH, these anions need to be added to the mass balance equation fiar Fe(III) (Eq. 5.20). Seawater with low pH tends to have low O2 concentrations. Under these conditions, most of the dissolved iron is present as Fe( II), which undergoes complexation with sulfide and carbonate. 

---