Windermere Humic Aqueous Model Research Articles

Predicting Metal Uptake and Risk to the Human Food Chain from Leaf Vegetables Grown on Soils Amended by Long-Term Application of Sewage Sludge

The success of risk assessment of metal contaminated soils depends on how precisely one can predict the bio-availability of metals in soil and transfer to the human food chain. In the present investigation, we tested several formulations of the ‘free-ion activity model (FIAM)’ to predict uptake of Cd, Zn and Cu by perpetual spinach (Beta vulgaris, Cicla) grown on a range of soils amended with sewage sludge. The model was parameterised using data measured on samples of pore water extracted by centrifugation and with porous Rhizon samplers installed within the rhizosphere of the growing plants. Free ion activities (M2+) were estimated following speciation of solution data using version 6 of the ‘Windermere Humic Aqueous Model (WHAM-VI). For all three metals, the best formulation of the FIAM appeared to require only one hypothetical root sorption site without competition from protons. Values of (M2+) could also be predicted satisfactorily from a pH-dependent Freundlich relation. Thus, from a combined FIAM–Freundlich relation and population dietary information, it was possible to estimate risk (hazard quotients) to consumers from very simple soil measurements: extractable metal content (0.05 M EDTA (Zn and Cu) or 1 M CaCl2 (Cd)), soil humus content and pH. The role of increased soil organic matter content and soil pH, in reducing risk to consumers, is illustrated for Cd in a hypothetical soil at the current UK statutory Cd limit for sludge application to agricultural land.

Copper complexation by dissolved organic matter from surface water and wastewater effluent

Organic matter from wastewater treatment plants (wastewater organic matter, WWOM) has not been extensively studied with respect to complexation with copper, unlike natural organic matter (NOM). Acid–base and copper titrations were conducted on both types of organic matter. Experimental copper complexation data were compared to predictions from the Windermere Humic Aqueous Model (WHAM) Version VI. We found that NOM and WWOM have ligands with similar proton binding, but the copper binding of WWOM is not well predicted by WHAM especially at low copper concentrations because the concentrations of ligands that are most important at the low copper concentrations (below 10 −6 M) were found to be about 15 times higher in the WWOM. Consideration of sulfide present in the wastewater effluent does not fully explain this deviation. Due to the possibility that there exist nonhumics like biological macromolecules in WWOM, it may need to be considered as an alternative ligand to humics in toxicity and speciation predicting models like the biotic ligand model (BLM).

Soil‐solution speciation of CD as affected by soil characteristics in unpolluted and polluted soils

Total metal content by itself is insufficient as a measure to indicate actual environmental risk. Understanding the mobility of heavy metals in the soil and their speciation in the soil solution is of great importance for accurately assessing environmental risks posed by these metals. In a first explorative study, the effects of general soil characteristics on Cd mobility were evaluated and expressed in the form of empirical formulations. The most important factors influencing mobility of Cd proved to be pH and total soil content. This may indicate that current legislation expressing the requirement for soil sanitation in Flanders (Belgium) as a function of total soil content, organic matter, and clay does not successfully reflect actual risks. Current legal frameworks focusing on total content, therefore, should be amended with criteria that are indicative of metal mobility and availability and are based on physicochemical soil properties. In addition, soil-solution speciation was performed using two independent software packages (Visual Minteq 2.23 and Windermere Humic Aqueous model VI [WHAM VI]). Both programs largely were in agreement in concern to Cd speciation in all 29 soils under study. Depending on soil type, free ion and the organically complexed forms were the most abundant species. Additional inorganic soluble species were sulfates and chlorides. Minor species in solution were in the form of nitrates, hydroxides, and carbonates, the relative importance of which was deemed insignificant in comparison to the four major species.

Complexation of Ni, Cu, Zn, and Cd by DOC in some metal-impacted freshwater lakes: a comparison of approaches using electrochemical determination of free-metal-ion and labile complexes and a computer speciation model, WHAM V and VI

Complexation of Ni(II), Cu(II), Zn(II), and Cd(II) by dissolved organic carbon (DOC) in some freshwater lakes in Rouyn-Noranda, Québec, Canada, where they were impacted by effluents from a nearby copper smelter, was measured by kinetic and equilibrium methods using cathodic and anodic stripping voltammetry. The measured free-metal-ion and labile metal-complex concentrations were compared with the predictions made by a widely-used computer speciation model, the Windermere Humic Aqueous Model (WHAM): WHAM V and its improved version WHAM VI. If it is assumed that 65% of the DOC is “active”, i.e. behaving as isolated humic substances such as fulvic acid, both versions of WHAM are able to predict the labile and free-metal-ion concentrations of Ni, Zn, and Cd reasonably well; however, both underestimate the free-copper-ion concentration by one to two orders of magnitude. WHAM VI is generally better than or equal to WHAM V for successfully predicting most of the free-metal-ion concentrations. The modelled competition by Al(III) and Fe(III) in the lake surface waters showed that in most cases Cu(II) was most affected by this competition. WHAM VI predicts a larger effect from the Al(III) and Fe(III) competition than does WHAM V.

Mobility, bioavailability, and toxic effects of cadmium in soil samples

Total concentration is not a reliable indicator of metal mobility or bioavailability in soils. The physicochemical form determines the behavior of metals in soils and hence the toxicity toward terrestrial biota. The main objectives of this study were the application and comparison of three approaches for the evaluation of cadmium behavior in soil samples. The mobility and bioavailability of cadmium in five selected soil samples were evaluated using equilibrium speciation (Windermere humic aqueous model (WHAM)), extraction procedures (Milli-Q water, DMSO, and DTPA), and a number of bioassays (Microtox, growth inhibition test, contact toxicity test, and respiration). The mobility, represented by the water-extractable fraction, corresponded well with the amount of cadmium in the soil solution, calculated using the WHAM (r2=0.96, P<0.001). The results of the ecotoxicological evaluation, which represent the bioavailable fraction of cadmium, correlated well with DTPA extractability and also with the concentration of free cadmium ion, which is recognized as the most bioavailable metal form. The results of the WHAM as well as the results of extraction experiments showed a strong binding of cadmium to organic matter and a weak sorption of cadmium to clay minerals.

Evaluation of different approaches to quantify strong organic acidity and acid–base buffering of organic-rich surface waters in Sweden

The role of organic acids in buffering pH in surface waters has been studied using a small brownwater stream (26 mg L −1 TOC) draining a forested catchment in Northern Sweden. Under the conditions of elevated pressure of CO 2 stream field pH was changed between 3.5 and 6.1 during the acidification and alkalinization experiment. Acid–base characteristics of the natural organic matter were also determined using a high precision potentiometric method for a concentrated sample from the same stream. We compared the predictions from the Windermere Humic Aqueous Model ( WHAM Model V), a model derived from the potentiometric titration (diprotic/monoprotic acid model) and a previously derived triprotic acid model which only uses alkalinity and TOC as input variables. The predicted buffering characteristics of all three models are very similar in the pH range 4.5–7 which suggests that during routine analysis alkalinity and TOC are sufficient to give a good estimate of organic acid anion charge contribution in a large range of surface waters. A slightly adjusted version of WHAM V successfully describes the organic charge contribution in a large number of sampled surface water lakes, which were previously used to calibrate the triprotic model.

Laboratory measurements and modeling of metal-humic interactions under estuarine conditions

Equilibrium dialysis was used to measure Co- and Cu-binding by an isolated peat humic acid (PHA) in controlled laboratory experiments under simulated estuarine conditions: ionic strengths of 0.005 to 0.7 M in NaCl and mixed Na-Mg-Ca chloride solutions, with trace metal concentrations of ∼5 × 10−7 M, a PHA concentration of 10 mg/L, and at constant pH values of ∼7.8 (Co and Cu) and ∼4.6 (Cu only). Generally, Co- and Cu-humic binding decreased substantially with increasing ionic strength and, in the case of Cu, with decreasing pH. The presence of seawater concentrations of Ca and Mg had a relatively small effect on Co-humic binding and no measurable effect on that of Cu under the experimental conditions. The binding data were well-described by an equilibrium speciation code (the Windermere Humic Aqueous Model, WHAM) after optimising the fits by varying the metal-proton exchange constants for humic acid within justifiable limits (i.e., within 1 standard deviation of the mean exchange constants used in the WHAM database). The main factor producing the observed variations in metal-humic binding at constant pH was the electrostatic effect on the humic molecule. WHAM was used to predict Co- and Cu-humic binding in simulations of real estuaries. Co-humic binding is predicted to be relatively unimportant (generally <5% of total Co), whereas the Cu-humic complex is likely to be the dominant species throughout an estuary. The main factors producing changes in Co- and Cu-humic binding in the real-estuary simulations are the electrostatic effect on the humic molecule, ligand competition (mainly from carbonate species) for metals, and to a lesser extent Ca and Mg competition for humic binding sites. Variations in pH are significant only at the freshwater end of an estuary. WHAM simulations also indicated that competition effects between metals are more likely to occur in freshwaters than in seawater, due to enhanced electrostatic binding at low ionic strength.

Biotic ligand model of the acute toxicity of metals. 1. Technical Basis

The biotic ligand model (BLM) of acute metal toxicity to aquatic organisms is based on the idea that mortality occurs when the metal-biotic ligand complex reaches a critical concentration. For fish, the biotic ligand is either known or suspected to be the sodium or calcium channel proteins in the gill surface that regulate the ionic composition of the blood. For other organisms, it is hypothesized that a biotic ligand exists and that mortality can be modeled in a similar way. The biotic ligand interacts with the metal cations in solution. The amount of metal that binds is determined by a competition for metal ions between the biotic ligand and the other aqueous ligands, particularly dissolved organic matter (DOM), and the competition for the biotic ligand between the toxic metal ion and the other metal cations in solution, for example, calcium. The model is a generalization of the free ion activity model that relates toxicity to the concentration of the divalent metal cation. The difference is the presence of competitive binding at the biotic ligand, which models the protective effects of other metal cations, and the direct influence of pH. The model is implemented using the Windermere humic aqueous model (WHAM) model of metal-DOM complexation. It is applied to copper and silver using gill complexation constants reported by R. Playle and coworkers. Initial application is made to the fathead minnow data set reported by R. Erickson and a water effects ratio data set by J. Diamond. The use of the BLM for determining total maximum daily loadings (TMDLs) and for regional risk assessments is discussed within a probabilistic framework. At first glance, it appears that a large amount of data are required for a successful application. However, the use of lognormal probability distributions reduces the required data to a manageable amount.

Competition of Ca(II) and Mg(II) with Ni(II) for Binding by a Well-Characterized Fulvic Acid in Model Solutions

Competition of Ca(II) and Mg(II) with Ni(II) ions for binding sites of a well-characterized fulvic acid (FA) in model solutions at constant pH and ionic strength was investigated. The Competing Ligand Exchange Method with Chelex-100 and dimethyl glyoxime as the competing ligands was employed to measure the rate of free Ni 2+ ion release using graphite furnace atomic absorption spectrometry and adsorptive cathodic stripping voltammetry, respectively. The Windermere Humic Aqueous Model was used to predict the effect of competition of Ca(II) and Mg(II) on the binding of Ni(II) by the FA. The results show that the presence of high concentrations of Ca(II) and Mg(II) in model solutions has considerable effects on the binding of Ni(II) by the FA. Since the concentrations of Ca(II) and Mg(II) used are 4 orders of magnitude higher than those of Ni(II), Ca(II) and Mg(II) can outcompete Ni(II) for sites where electrostatic interactions dominate, resulting in Ni(II) forming weak Ni(II)-FA complexes that are labile. The significance is that in freshwaters containing humic substances and trace quantities of nickel and major cations, Ca 2+ and Mg 2+ , the competition of Ca 2+ and Mg 2+ with Ni 2+ for binding sites of humic substances produces weak Ni(II)-humate complexes that are labile, releasing free Ni 2+ ions.

Modeling Aluminum and Organic Matter Solubility in the Forest Floor Using WHAM

Several studies suggest that solution concentrations of Al in organic surface soils are controlled by complexation with organic matter. We applied the mechanistic Windermere humic aqueous model (WHAM) to describe the solubility of Al and organic matter as observed in a batch equilibrium study with a forest floor Oe horizon. WHAM is unique in that it considers interactions of soil organic matter with protons and metals. We also compared WHAM with a previously proposed linear regression model that describes Al solubility. A range of soil Al contents was established by adding different amounts of Al in batch prior to titration with acid or base. The soil Al content was described by the bound Al ratio (BAR), defined as the equivalent ratio of organically bound Al and carboxyl groups. The bound Al ratio and pH ranged from 0.1 to 3, and from 1.7 to 6.3, respectively. Solutions were undersaturated with respect to Al(OH)3, except at BAR ≥ 2 and pH ≥ 4.5. Aluminum solubility increased with increasing BAR. Organic matter solubility was greatest at low BAR and high pH. WHAM reproduced the observed pH and Al concentrations, using parameters derived from experimental data. At BAR &lt; 0.7, pH–pAl relationships were approximately linear. At BAR ≥ 0.7, there was a nonlinear increase in ΔpAl/ΔpH with pH. WHAM simulated the changing slope of the pH–pAl curves satisfactorily and reproduced observed trends in dissolved organic C (DOC) concentrations. This supports the hypotheses and assumptions concerning mechanisms for binding Al to soil organic matter in a forest floor, as embodied in WHAM.

Testing a humic speciation model by titration of copper-amended natural waters

Experiments were carried out in which samples of natural waters that had been acidified and amended with copper nitrate were titrated with base, and the activity of Cu 2+ was monitored with an ion-specific electrode. The results could be explained in terms of the interactions of Cu 2+ with inorganic and organic ligands, as calculated using the Windermere Humic Aqueous Model (WHAM). Optimised fits were obtained by adjusting the concentration of “active” fulvic acid. The active fulvic acid represented about 80% of the total concentration of dissolved organic matter for upland pools and lakes, and about 40% for lowland rivers.

Modelling the chemical speciation of trace metals in the surface waters of the Humber system

Calculations have been performed to estimate the chemical speciation at equilibrium of six divalent trace metals (Co, Ni, Cu, Zn, Cd, Pb) in riverine, estuarine and marine surface waters of the Humber system. The Windermere Humic Aqueous Model (WHAM) was used to compute distributions of dissolved metals. In the rivers, the free aquo ion (M 2+) is a major part of dissolved Co, Ni, Zn and Cd, but accounts for less than 1% of Cu and Pb. The main complexes are formed with carbonate ligands and dissolved natural organic matter, represented by fulvic acid. In the low-salinity region of the estuary and in seawater, complexation with fulvic acid is less significant, although most of the Cu is still in this form, while the speciation of Cd is dominated by chloride complexes. Adsorption of metals by suspended particulate matter was calculated with a simple model involving the concentrations of the free aquo ions (M z +) and H +, together with a constant for each metal estimated from laboratory adsorption data. Calculated adsorbed concentrations were used to predict the partition coefficient ( K D) for each metal under different circumstances. The values can vary by an order of magnitude or more, depending upon solution conditions. Typical values for rivers, low-salinity water and seawater are within one order of magnitude of observations. However, there is a general tendency to underestimate K D, possible reasons being (1) neglect of electrostatic enhancement of adsorption at low ionic strengths; and (2) analytical overestimation of particulate metal in equilibrium with the solution phase. There is a strong case for the development of a more sophisticated adsorption model.

Solid-Solution Distributions of Radionuclides in Acid Soils: Application of the WHAM Chemical Speciation Model

The Windermere Humic Aqueous Model (WHAM) is tested with the data from laboratory experiments on three acid soils from the British Uplands. The model is reasonably successful at blind-predicting values of K D (solid-solution distribution coefficients) of Co, Sr, and Am on the basis of their interactions with soil humic matter. The competitive effects of aluminum are calculated to exert a strong influence on trace element binding. Organic matter interactions only explain the data for Cs in the case of the most organic-rich soil; the K D values are substantially underestimated in the other cases, presumably reflecting the presence in the soils of minerals bearing sites with high specificity toward Cs + . Calculations for soils in situ show the importance of binding by dissolved organic matter in determining the K D values for strongly complexed radionuclides such as Th and Am

WHAMC—A chemical equilibrium model and computer code for waters, sediments, and soils incorporating a discrete site/electrostatic model of ion-binding by humic substances

WHAM (Windermere Humic Aqueous Model) is designed to calculate equilibrium chemical speciation in surface and ground waters, sediments, and soils. The model is suitable especially for problems where the chemical speciation is dominated by organic matter (humic substances). WHAM combines Humic Ion-Binding Model V with a simple inorganic speciation code for aqueous solutions. Precipitation of aluminum and iron oxides, cation-exchange on an idealized clay mineral, and adsorption-desorption reactions of fulvic acid also are taken into account. The importance of ion accumulation in the diffuse layers surrounding the humic molecules is emphasized. Model calculations are performed with a BASIC computer code running on a Personal Computer.