Models chemical speciation

The computer programs FITEQL (12) and MICROQL (13) were used to model chemical speciation in this study. FITEQL uses a non-linear, least squares optimization technique to calculate equilibrium constants from chemical data. The program was used here to select... 

Much has been written concerning the use of computers to model chemical speciation occurring in equilibrium systems (see, e.g., Duffield and Williams 1986) and so only a brief summary of this topic is given here. 

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. 

Webb LM, Taylor DM, Williams DR. 1998. Computer modeling of the chemical speciation of lanthanide and actinide elements in the human gastrointestinal tract Mouth and stomach. Radiat Prot Dosim 79(l/4) 219-222. 

Twiss, M., Errecalde, O., Fortin, C., Campbell, P., Jumarie, C., Denizeau, F., Berkelaar, E., Hale, B., and van Rees, K., Coupling the use of computer chemical speciation models and culture techniques in laboratory investigations of trace metal toxicity, Chem Spec Bioavailab, 13 (1), 9-24, 2001. 

Zirino, A. and Yamamoto, S., A pH-dependent model for the chemical speciation of copper, zinc, cadmium, and lead in seawater, Limnol Oceanogr, 17 (5), 661-671, 1972. 

This paper discusses (1) soil and groundwater and (2) aquatic equilibrium and ranking models. The second category deals with the chemical speciation in soil and groundwater, and with the environmental rating of waste sites, in cases where detailed modeling is not desirable. 

Parker, D.R., W. A. Norvell and R. L. Chaney, 1995, GEOCHEM-PC, a chemical speciation program for IBM and compatible personal computers. In R. H. Loep-pert, A. P. Schwab and S. Goldberg (eds.), Chemical Equilibrium and Reaction Models. Soil Science Society of America Special Publication 42,253-269. 

Most measurements of silver concentrations in natural waters prior to the use of clean techniques are considered inaccurate. Until analytical capabilities that exceed the dissolved-particulate classification are developed, it will be necessary to rely on laboratory and theoretical modeling studies to fully understand chemical speciation of silver in natural waters (Andren et al. 1995). 

Table 5.12 MINTEQA2 model inputs for a chemical speciation calculation of soluble complexes in two acidic stream waters...

Development of chemical speciation schemes which can be directly related to measures of bioavailability - This would allow the determination of which active trace element species merit the most intensive research from the standpoint of environmental perturbation. Some studies have attempted to correlate metal fractions determined by a particular technique (operationally defined speciation) with those that are bioavailable (functionally defined speciation) (Larsen and Svensmark, 1991 Buckley, 1994 Deaver and Rodgers, 1996). However, any correlation is only empirical and more research is required to achieve an understanding of the mechanisms involved in bioavailability and to develop rational predictive models. 

Computer simulation is now used extensively as a tool to help to understand and predict the transport of radionuclides through environmental systems. Most models relate to waste disposal and are based on measured parameters such as water movements, salinity, suspended load and the radionuclide concentration in the solute, suspended particulate matter and bottom deposits. Comparatively few attempts appear to have been made to include chemical speciation into this type of model, presumably because of the added complexity involved. Some modellers have attempted to take into account the characteristics of the major chemical phases such as those present in different particles or coatings (e.g. Martinez-Aquirre et al., 1994). Others have noted the importance of including details of particular chemical species present in industrial waste releases when constructing models to predict dispersion (Abril and Fraga, 1996). 

Bioavailability of metals in soil and sediments is a topic that requires strengthening from a scientific point of view. Chemical speciation models for metals in soil and sediment are in the process of being developed. Media- and matrix-related differences in intrinsic sensitivity of species comprise a topic that deserves to be studied. 

Tipping, E., Lofts, S., and Lawlor, A.J. (1998) Modeling the chemical speciation of trace metals in the surface waters of the Humber system. Sci. Total Environ. 210/211, 63-77. 

Tipping, E., Woof, C., Kelly, M., Bradshaw, K., and Rowe, J.E. (1995b) Solid-solution distributions of radionuclides in acid soils applications of the WHAM chemical speciation model. Environ. Sci. Technol. 29, 1365-1372. 

Chemical speciation in soil solutions and other natural waters can be calculated routinely with a number of software products offered in a variety of computational media.27 30 Five examples of these products are listed in Table 2.5. They differ principally in the method of solving the chemical equilibrium problem numerically, or in the chemical species and equilibrium constants considered, or in the model used to estimate single-species activity coefficients. Irrespective of these differences, all the examples follow a similar algorithm ... 

Physico-chemical speciation refers to the various physical and chemical forms in which an element may exist in the system. In oceanic waters, it is difficult to determine chemical species directly. Whereas some individual species can be analysed, others can only be inferred from thermodynamic equilibrium models as exemplified by the speciation of carbonic acid in Figure 9. Often an element is fractionated into various forms that behave similarly under a given physical (e.g., filtration) or chemical (e.g., ion exchange) operation. The resulting partition of the element is highly dependent upon the procedure utilised, and so known as operationally defined. In the following discussion, speciation will be exemplified with respect to size distribution, complexation characteristics, redox behaviour and methylation reactions. 

Finally, models were calculated which predict the variations in chemical speciation of copper resulting from changes in the chemical parameters pH, carbonate alkalinity, concentration of dissolved organic matter, and concentration of total dissolved copper. 

The chemical speciation of copper in river water and model solutions was investigated by a titration technique in which cupric ion activities were measured at constant pH as the total copper concentration ([Cujoj]) was varied by incremental additions of CUSO4. pCu(-log cupric ion activity) was measured with a cupric ion-selective electrode (Orion 94-29) and pH with a glass electrode (Beckman 39301) both coupled to a single junction Ag/AgCl reference electrode (Orion 90-01) in a temperature controlled (25 + 0.5°C) water bath. Total copper concentrations in the titrated solutions were determined directly by atomic absorption spectrophotometry (Perkin Elmer 603) using a graphite furnace (Perkin Elmer 2200). Measurement of total copper concentrations is necessary because of adsorptive loss of copper from solution onto container and/or electrode surfaces. 

Chemical Speciation Models. Using the stability constants derived by us for copper complexes with hydroxo and carbonate ligands (Table I) and for natural organic ligands (Table II), the Newport and Neuse Rivers were modeled for copper speciation as a function of pH, total copper, carbonate alkalinity and total dissolved organic matter. Speciation models were calculated from the equation ... 

Figure 10. Chemical speciation model for dissolved copper in the Newport River at 25°C as a function of total copper concentration, (a) In situ pH 5.95, [Aik] = 0.05mM and I = 0.0005M (b) pH 7.00, [Aik] = 0.05mU and I = 0.005M and (c) pH 8.00, [Aik] = 0.55mM and I =...

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