D.G. Kinniburgh

A review of the source, behaviour and distribution of arsenic in natural waters

The range of As concentrations found in natural waters is large, ranging from less than 0.5 μg l−1 to more than 5000 μg l−1. Typical concentrations in freshwater are less than 10 μg l−1 and frequently less than 1 μg l−1. Rarely, much higher concentrations are found, particularly in groundwater. In such areas, more than 10% of wells may be ‘affected’ (defined as those exceeding 50 μg l−1) and in the worst cases, this figure may exceed 90%. Well-known high-As groundwater areas have been found in Argentina, Chile, Mexico, China and Hungary, and more recently in West Bengal (India), Bangladesh and Vietnam. The scale of the problem in terms of population exposed to high As concentrations is greatest in the Bengal Basin with more than 40 million people drinking water containing ‘excessive’ As. These large-scale ‘natural’ As groundwater problem areas tend to be found in two types of environment: firstly, inland or closed basins in arid or semi-arid areas, and secondly, strongly reducing aquifers often derived from alluvium. Both environments tend to contain geologically young sediments and to be in flat, low-lying areas where groundwater flow is sluggish. Historically, these are poorly flushed aquifers and any As released from the sediments following burial has been able to accumulate in the groundwater. Arsenic-rich groundwaters are also found in geothermal areas and, on a more localised scale, in areas of mining activity and where oxidation of sulphide minerals has occurred. The As content of the aquifer materials in major problem aquifers does not appear to be exceptionally high, being normally in the range 1–20 mg kg−1. There appear to be two distinct ‘triggers’ that can lead to the release of As on a large scale. The first is the development of high pH (>8.5) conditions in semi-arid or arid environments usually as a result of the combined effects of mineral weathering and high evaporation rates. This pH change leads either to the desorption of adsorbed As (especially As(V) species) and a range of other anion-forming elements (V, B, F, Mo, Se and U) from mineral oxides, especially Fe oxides, or it prevents them from being adsorbed. The second trigger is the development of strongly reducing conditions at near-neutral pH values, leading to the desorption of As from mineral oxides and to the reductive dissolution of Fe and Mn oxides, also leading to As release. Iron (II) and As(III) are relatively abundant in these groundwaters and SO4 concentrations are small (typically 1 mg l−1 or less). Large concentrations of phosphate, bicarbonate, silicate and possibly organic matter can enhance the desorption of As because of competition for adsorption sites. A characteristic feature of high groundwater As areas is the large degree of spatial variability in As concentrations in the groundwaters. This means that it may be difficult, or impossible, to predict reliably the likely concentration of As in a particular well from the results of neighbouring wells and means that there is little alternative but to analyse each well. Arsenic-affected aquifers are restricted to certain environments and appear to be the exception rather than the rule. In most aquifers, the majority of wells are likely to be unaffected, even when, for example, they contain high concentrations of dissolved Fe.

Ion binding to natural organic matter : competition, heterogeneity, stoichiometry and thermodynamic consistency

Abstract The general principles of cation binding to humic materials are discussed. Important aspects that need to be included in general purpose speciation models are: the extreme binding heterogeneity of natural humic materials, the variable stoichiometry of binding (monodentate, bidentate and tridentate), the competition between specifically-bound ions, especially protons and metal ions, and electrostatic effects which give rise to ionic strength effects and the non-specific binding of counterions. The NICCA–Donnan model is a semi-empirical model that addresses these issues. It is similar to the previously published NICA–Donnan model except that it introduces an additional degree of scaling that ensures thermodynamic consistency and allows for variable stoichiometry of binding. It implicitly accounts for the large degree of chemical heterogeneity of humic particles. The NICCA (consistent NICA) model also recognizes that the affinity distributions are ion specific and are not fully correlated. The model requires no assumptions to be made about the geometry of the humic particles, but the Donnan submodel does allow for shrinking and swelling. Important model parameters such as the site density and median binding constants ( log K ) are not dependent on pH, metal ion concentration, ionic strength, etc. Data are analysed for H+, Ca2+, Cd2+, Cu2+, Pb2+ and Al3+ binding to a single purified peat humic acid. The NICCA–Donnan model captures the non-linearity of the observed isotherms even at very low free metal ion concentrations. After fitting the model to datasets containing only the proton and one metal ion, the model was able to predict Cd2+–Ca2+, Cu2+–Ca2+ and Pb2+–Al3+ competition reasonably well. It also gave satisfactory predictions of the H+/Mz+ molar exchange ratios. These ratios varied strongly with metal ion: Ca2+ (0.2–0.5); Cd2+ (0.5–1.0); Pb2+ (1.1–1.2); Cu2+ (1.2–1.7) and Al3+ (2.1–2.7), and also to a varying degree with pH and free metal ion concentration.

General purpose adsorption isotherms

The fitting of adsorption isotherm equations to experimental data is often an important aspect of data analysis. If the Langmuir and Freundlich isotherms are used, then consideration must be given to the proper weighting of the observations. Preferably nonlinear regression (nonlinear least squares) should be used since this enables these isotherms to be fitted directly and also enables other isotherms to be tested with little extra effort. Isotherms described here which are likely to show a wide range of applicability include the Toth, modified Dubinin-Radushkevich, and multisite Langmuir isotherms. These can also describe competitive adsorption (binary exchange) reactions and are well suited for heterogeneous exchangers such as soils and sediments. Specific examples discussed are the adsorption of P and K by soils, Na-Cu exchange by montmorillonite, and Zn adsorption by ferrihydrite.

Metal ion binding to humic substances: application of the non-ideal competitive adsorption model.

The application of a new model to describe metal ion binding by humic acids is discussed. Metal ion binding is always of a competitive nature since the proton is always present. Although of great practical importance, the combination of a chemically heterogeneous system with competitive binding poses difficult problems from both experimental and theoretical points of view. The new Non-Ideal Competitive Adsorption model (NICA model) used here is able to account for the non-ideal binding to heterogeneous ligands. A good description of the binding of H, Ca, Cd, and Cu to a purified peat humic acid is achieved over a wide range of free metal ion concentrations (-2 > log Me 2+ > -14) and pH (2 < pH < 10). The results show that binding of metal ions to humic acid is strongly influenced by the intrinsic chemical heterogeneity of the humic material itself as well as by ion-specific non-ideality. The results indicate that copper competes much more efficiently with protons bound to the phenolic type groups than calcium and cadmium.

Relating Ion Binding by Fulvic and Humic Acids to Chemical Composition and Molecular Size. 2. Metal Binding

Binding of Cu(II) and Pb(II) to a soil fulvic acid, humic acid, and two different size fractions of the humic acid was investigated with metal titration experiments at pH 4, 6, and 8. Proton and free metal ion activities in solution were monitored after each titration step using pH and ion selective electrodes (ISE), respectively. The amounts of base required to maintain constant pH conditions were recorded and used to calculate stoichiometric proton-to-metal ion exchange ratios. Despite clear differences in chemical composition and protonation behavior, the fulvic acid and all humic acid fractions exhibited very similar metal binding behavior. Binding of Cu(II) and Pb(II) generally increased with increasing pH and total metal concentration. At low to moderate metal ion concentrations, Cu(II) was bound more strongly to the humic substances than Pb(II). Only at high free metal concentrations, the amounts of metal ions sorbed were higher for Pb(II) than for Cu(II). The molar proton-to-metal ion exchange ratios ranged from 1.0 to 1.8 for Cu(II) and from 0.6 to 1.2 for Pb(II), suggesting that Cu(II) was bound as monodentate and bidentate complexes, while Pb(II) was bound predominantly as monodentate complexes. The metal ion binding data were quantitatively described with the consistent NICA-Donnan model. The best description of an entire multicomponent data set consisting of proton titration, Cu(II), and Pb(II) binding data was achieved when the entire data set was fitted simultaneously. To reduce the number of fitting parameters, results from size exclusion chromatography and solid state 13C NMR spectroscopy were used to estimate two of the NICA-Donnan model parameters. The values of the remaining NICA-Donnan parameters for the humic substances are within a narrow range, suggesting that generalized model parameters may be useful in geochemical modeling involving humic substances.

Metal ion binding by natural organic matter: from the model to the field.

With the newly developed NICCA-Donnan model, we estimate the activity of toxic metal ions from simple measurements like total metal concentration and organic matter content. The model evaluates Cu and Cd binding from three field systems, a mountain lake and two sandy soils, using model parameters calibrated for natural organic matter analogues with laboratory measurements. This is possible because the model includes site binding heterogeneity, electrostatic effects, competitive binding, and ion specific nonideality. The predictions derived closely matched the field observations when site binding densities are adjusted. The partition coefficients between soil and soil solution were also predicted for Cd and Cu under conditions where the organic matter controls the metal binding in both soil and soil solution. The model calculations show that in soil solutions 50% of the Cd and 99.99% of the Cu is bound to the dissolved organic matter. The model can be used to evaluate the effects of variations in the chemical conditions (e.g., acidification or total metal loading) on the free metal ion concentration in solution.

Arsenic and selenium

This chapter outlines the main effects of arsenic and selenium on human and animal health, their abundance and distribution in the environment, sampling and analysis, and the main factors controlling their speciation and cycling. Such information should help identify aquifers, water resources and soils at risk from high concentrations of arsenic and selenium, and areas of selenium deficiency. Human activity has had, and is likely to continue to have, a major role in releasing arsenic and selenium from the geosphere and in perturbing the natural distribution of these and other elements over the Earths surface.

Baseline geochemical conditions in the Chalk aquifer, Berkshire, U.K.: a basis for groundwater quality management

The Chalk aquifer is the most important British aquifer and is also important over much of northern Europe. Aquifer protection requires a sound knowledge of the baseline conditions and how these might vary, or have varied, with time. This detailed geochemical study of a representative area of Chalk in Berkshire, U.K., includes a consideration of several components: (1) the inputs from the atmosphere; (2) the interstitial water of the soil and the unsaturated zone; (3) the interstitial water in the confined and unconfined sections of the aquifer; and (4) the saturated, mainly fissure flow, along the hydraulic gradient which forms an important water supply of the Thames Valley region. Atmospheric inputs form an important source of some elements, but the dominant chemical characteristics of the Chalk groundwater are acquired during percolation through the soil and the upper unsaturated zone. During saturated flow downgradient the chemistry is modified mainly by incongruent reactions of the carbonate matrix and by redox reactions, and only to a minor extent by exchange reactions and mixing with residual saline connate water. The incongruent reaction of carbonate results in a marked increase in the Mg/Ca ratio and the Sr and 13C contents of the groundwater with increased residence time. Oxygen concentrations are reduced mainly by oxidation of Fe2+, and the onset of reducing conditions allows dissolved Fe2+ to increase and rapid denitrification to occur. The salinity profile through the confined Chalk confirms that residual connate water, up to one-fifth sea water concentration, still remains at depth, and this accounts for some salinity increase in the confined groundwater resulting from fissure water.pore water diffusional exchange. Timescales for groundwater movement have been established using tritium, radiocarbon, and indirectly using inert gas ratios and stable isotope ratios. On balance, it is concluded that all abstracted water is of Holocene age, although inert gas temperatures indicate cooler climatic conditions for recharge for some of the confined groundwater. The implications for development and aquifer protection are discussed, especially the prospect of natural in situ denitrification, problems of Fe solubility, and the recognition of groundwater of different maturities.

Analysis of proton binding by a peat humic acid using a simple electrostatic model

Detailed potentiometric titration data were collected for a purified peat humic acid (PPHA) over a range of pH (pH 3.5–10.5) and KNO3 background electrolyte concentrations (0.001–0.3 M). The data were analyzed following the master curve approach which includes both an electrostatic double layer model and a model for the intrinsic heterogeneity of the PPHA. Spherical and cylindrical double layer models gave equally good fits to the data. A salt dependence observed around pH 5 could not be completely removed by taking into account the electrostatic interactions. Hysteresis was observed to a much greater extent in the first titration cycle compared with the second cycle. This suggested that some slow and only partly reversible aggregation was occurring possibly as a result of the aggregation created during the purification of the humic acid. Titration curves for fully redispersed samples fitted the master curve approach (surface charge vs. surface pH) reasonably well but still displayed an ionic strength dependence at a pH of less than 5 which could not be accounted for using the simple electrostatic model. Heterogeneity analysis of the master curve showed that the affinity distribution had two peaks centred at log KHint ∼ 4 and log KHint ∼ 8 to 9. The total number of weak acid sites titrated between pH 3.5 and 10.5 was approximately 3.5 eq kg−1 but the total number of sites estimated from the isotherm analysis was 5.3–5.8 eq kgt1¯. Double Toth and double Langmuir-Freundlich isotherms fitted the data almost equally well but the implied distribution of sites between the more acidic “car☐ylic” sites and the weakly acidic “phenolic” sites varied with the isotherm chosen. An important source of uncertainty in the analysis was in estimating the charge on the humic acid at its initial pH of about pH 3.

Analysis of ion binding on humic substances and the determination of intrinsic affinity distributions

Abstract Humic substances are characterized by a variable electric potential and by a variety of binding sites leading to chemical heterogeneity. Binding of ions to these substances is influenced by both factors. A methodology based on acid—base titrations at several salt levels is presented that allows for the assessment of an appropriate electrostatic double-layer model and the intrinsic proton affinity distribution. The double-layer model is used for the conversion of pH to pHS for each data point, where HS is the proton concentration in the diffuse layer near the binding site. It is shown that with an appropriate double-layer model the proton binding curves at different salt levels converge into one “master curve” when plotted as a function of pHS. The intrinsic proton affinity distribution can then be derived from the “master curve” using the LOGA method. A rigorous analysis of metal binding to humic substances is complex and in practice is not feasible. Under two different (simplifying) assumptions, namely fully coupled and uncoupled binding, it is shown how intrinsic metal ion affinity distributions can be obtained. Model calculations show that apparent metal ion affinity distributions do not resemble the intrinsic metal ion affinity distribution.