Environmental Pollution 125 (2003) 213225 www.elsevier.

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The solidsolution partitioning of heavy metals (Cu, Zn, Cd, Pb) in upland soils of England and Wales
E. Tippinga,*, J. Rieuwertsb,1, G. Panb,c,2, M.R. Ashmorec, S. Loftsa, M.T.R. Hillc,3, M.E. Faragob, I. Thorntonb
b a Centre for Ecology and Hydrology (Windermere), Ambleside, Cumbria LA22 0LP, UK Department of Environmental Science and Technology, Imperial College of Science, Technology and Medicine, Royal School of Mines, London SW7 2BP, UK c Department of Environmental Science, University of Bradford, Bradford BD7 1DP, UK

Received 3 July 2002; accepted 31 January 2003

Capsule: Solidsolution distributions of heavy metals can be described quantitively by multiple regression and mechanistic modelling.
Abstract Ninety-eight surface soils were sampled from the uplands of England and Wales, and analysed for loss-on-ignition (LOI), and total and dissolved base cations, Al, Fe, and trace heavy metals (Cu, Zn, Cd, Pb). The samples covered wide ranges of pH (3.48.3) and LOI (998%). Soil metal contents measured by extraction with 0.43 mol l1 HNO3 and 0.1 mol l1 EDTA were very similar, and generally lower than values obtained by extraction with a mixture of concentrated nitric and perchloric acids. Total heavy metal concentrations in soil solution depend positively upon soil metal content and [DOC], and negatively upon pH and LOI, values of r2 ranging from 0.39 (Cu) to 0.81 (Pb). Stronger correlations (r2=0.760.95) were obtained by multiple regression analysis involving free metal ion (Cu2+, Zn2+, Cd2+, Pb2+) concentrations calculated with the equilibrium speciation model WHAM/ Model VI. The free metal ion concentrations depend positively upon MHNO3 and negatively upon pH and LOI. The data were also analysed by using WHAM/Model VI to describe solidsolution interactions as well as solution speciation; this involved calibrating each soil sample by adjusting the content of active humic matter to match the observed soil pH. The calibrated model provided fair predictions of total heavy metal concentrations in soil solution, and predicted free metal ion concentrations were in reasonable agreement with the values obtained from solution-only speciation calculations. # 2003 Elsevier Science Ltd. All rights reserved.
Keywords: Chemical speciation; Heavy metals; Modelling; Soils; Uplands

1. Introduction Solidsolution partitioning exerts a major control on the transport and retention of heavy metals in soil water systems. Furthermore, for many soil biota, the
* Corresponding author. Tel.: +44-15394-42468; fax: +44-1539446914. E-mail address: et@ceh.ac.uk (E. Tipping). 1 Present address: Faculty of Environment, Trinity College, College Road, Carmarthen SA31 3EP, UK. 2 Present address: State Key Laboratory of Environmental Aquatic Chemistry, Chinese Academy of Sciences, Beijing 100085, China. 3 Present address: Maslen Environmental Ltd, Albion House, Vicar Lane, Bradford BD1 5AH, UK.

bioavailability of soil heavy metals depends upon concentrations and chemical forms in the soil solution (see e.g. Allen, 1993). In particular, free metal ion concentrations (Cu2+, Zn2+, etc.) provide the best guide to both partitioning and bioavailability. Therefore, quantitative, predictive, descriptions of the solidsolution interactions are needed. Two approaches to the problem can be identied. Firstly, empirical relationships have been derived, by multiple regression analysis, relating concentrations of either total dissolved metal or free metal ions to key soil variables such as total soil metal, pH and organic matter content (Jopony and Young, 1994; McBride et al., 1997; Sauve et al., 1997, 1998a,b, 2000). This approach has provided good descriptions of

0269-7491/03/$ - see front matter # 2003 Elsevier Science Ltd. All rights reserved. doi:10.1016/S0269-7491(03)00058-7

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metal chemistry, principally in metal-contaminated soils with relatively low levels of organic matter, i.e. with loss-on-ignition (LOI) values of 10% or less. However, there do not appear to have been applications to more organic-rich upland soils. A second approach is to use mechanistic models, that describe the interactions more comprehensively, taking into account competitive binding to both the solid soil materials and to solution ligands, including dissolved organic matter. For example, Benedetti et al. (1996) applied the NICADonnan model, which describes proton and metal binding to organic matter, to the upper, organic-rich horizons of a podzol and were able to account for solid-solution distributions of Cu and Cd. Another model that describes ion binding by organic matter is WHAM (Tipping, 1994). Tipping et al. (1995a) showed that WHAM could account for proton, aluminium, and base cation binding by organic-rich upland soils, while Tipping et al. (1995b) reported the successful prediction of solidsolution distributions of metallic radionuclides in the same soils. Tipping (2002) reported the application of WHAM to two soils in which Cd partitioning had been determined by Lee et al. (1996). For the more organic-rich soil, the solidsolution partitioning of Cd could be accounted for, but the involvement of mineral sorbents appeared necessary to explain the results with the other soil. One policy context in which such soilsolution partitioning is important is in the estimation of critical loads, i.e. the metal deposition at which metal accumulation in soils threatens soil microbes, plants, and higher organisms (de Vries and Bakker, 1998). Models of soilsolution partitioning are central to the critical load approach, both in modelling solution concentrations and free-ion activities, which may be more closely related to adverse biological eects, and in modelling the dynamics of metal inputs and outputs for dierent soils. However, the multiple regression partitioning models currently proposed for the calculation of critical loads are based primarily on data from mineral soils (e.g. de Vries and Bakker, 1998; Paces, 1998), and there is a need to establish eective models of soilsolution partitioning for the organic-rich soils which dominate large areas of the northern hemisphere. The work described here focuses on organic-rich soils from the uplands of England and Wales. These soils have accumulated heavy metals from atmospheric deposition, both long-distance and localised, and in some cases also from the weathering of soil mineral matter. Measurements were made of key soil parameters, including heavy metal contents, together with soil solution compositions. The resulting data set (98 samples) covers wide ranges of conditions, enabling speciation and regression analyses to be performed to identify the factors responsible for solidsolution partitioning, and to attempt to predict free metal ion concentrations.

2. Methods 2.1. Sampling Samples of surface soil (05 cm) were collected from upland moorland sites at Dartmoor, the English Lake District, North Wales, the Peak District, and the Yorkshire Dales (Fig. 1). They were from the following soil types: brown earth, humic brown podzol, humic ranker, peat, peaty gley, podzol, stagnohumic gley, stagnopodzol. In each case, a block of intact soil, of approximate area 14 cm2, was encased in an air-tight container and placed immediately into cold storage in preparation for extraction of soil porewater. A separate quantity (100200 g) of soil was collected in preparation for analysis of total and extractable metals and soil properties. 2.2. Soil analyses Determinations were made of soil water content, by oven drying, and of LOI by ashing at 450  C. Total

Fig. 1. Location map. DM=Dartmoor, LD=Lake District, NW=North Wales, PD=Peak District, YD=Yorkshire Dales.

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soil metal contents were determined by digestion with a mixture of concentrated nitric and perchloric acids, followed by leaching of the residues with 5 mol l1 HCl, and analysis by ICPAES. Extractions with 0.43 mol l1 HNO3 were performed at a ratio of 1 g air dried soil (2 mm sieved) to 10 cm3 of extractant. After extraction for 2 h, the samples were centrifuged, 5 cm3 of the supernatant were removed to separate tubes and 0.5 cm3 of 5 mol l1 HCl was added prior to analysis by ICPAES. Extractions with 0.1 mol l1 Na2EDTA (ethylenedinitrolotetraacetate) were also made at a ratio of 1 g to 10 cm3. The supernatants after centrifugation were digested with concentrated nitric and perchloric acids, as for the total soil metal determinations, prior to ICPAES analysis, in order to remove the EDTA. 2.3. Soil solution extraction and analysis Blocks of eld moist soil, stored in air tight plastic boxes at 4  C since sampling, were brought into the laboratory. Drainage holes were punched into the base of each box. The lid of each box was removed in turn and high purity water was added gradually, in small aliquots, to the surface of the soil block. On the rst appearance of water drops in the saucer under the box, addition of water was stopped and further drainage allowed. When drainage had ceased, the contents of the saucer were added to the surface of the soil block. If no more drainage occurred, small amounts of water were again added to the surface. This process was repeated until the soil block could hold no more water, i.e. when the soil was at eld capacity. The lids of the boxes were then replaced and the boxes were wrapped in plastic wrapping lm and returned to storage at 4  C for a period of 1 week to allow equilibration of the soils with the added water. Before extraction of soil solution, the boxes of soil were brought to the laboratory and left for one or two days at room temperature. The wrapping lm was removed (but not the lid) and two soil solution RhizonTM samplers were inserted diagonally into the soil block through two diagonally opposite corner drainage holes at the base of the box, such that they extracted solution from the entire depth of the soil block. Once the samplers were in place, a 10-cm3 syringe was attached, with the syringe plunger fully inserted. The plunger was slowly withdrawn and held open (to counteract the resulting initial vacuum). The boxes were again wrapped in cling lm to prevent evaporation and left overnight for extraction to take place. Extracted solution, collected in the syringes overnight, was removed to centrifuge tubes for analysis. The soil solutions were analysed for pH with a combination glass/calomel electrode, and for DOC with a Dohrmann DC-190 TOC analyser. Metals were analysed by ICPMS after acidication with HNO3 (to 2%) and passage through a 0.2-mm lter.

2.4. Preliminary data manipulations Of the total of 116 samples collected, 17 of the data lines were incomplete. Except for EDTA extracts, if any data were missing for a sample the whole sample was rejected. In the case of EDTA extracts this was also done except for Cd, for which a relatively large proportion of samples gave values at the detection limit of the analytical method. In cases where duplicate determinations had been made, means were used. This led to a data set comprising 99 samples. However, one of these soils had a very high DOC concentration (> 700 mg l1), which was considered suspect. This sample was therefore rejected, giving a nal data set of 98 samples. The data are analysed in terms of relationships between dissolved metal concentrations (either total dissolved or free ions) and metal contents of the soil solids. Also involved are solid-phase contents of organic matter and concentrations of dissolved organic matter. The available measurements are of dissolved concentrations and total concentrations. Therefore it was necessary to modify the total concentrations in order to obtain values of solid-phase contents. The following assumptions were made; (a) Under the conditions of the experiments that yielded pore water, all the soil pore space was occupied by soil solution. (b) The soil samples in the experiments had the same bulk density (BD, g cm3) as in the eld, for which the following relationship connected BD to organic carbon (OC) content (% C); BD 1:38 0:29 ln OC n 19; r2 0:96 1 This equation was derived by A. Colgan and J.R. Hall (personal commununication) from data reported by McGrath and Loveland (1992). (c) Organic carbon was 58% of the LOI (Rowell, 1994). Then, the LOI values determined for the present samples were used to obtain BD, from which solid:solution ratios in the experiments were obtained. The dissolved metal and organic carbon concentrations were combined with the solid:solution ratios to calculate the fractions of the total soil contents in solution, and the amounts associated with the soil solids in the experiments were obtained by dierence. The modications were generally very small, average amounts in solution being < 1% for Cu, Zn, Cd, Pb and OC. The maximum percentages in solution in an individual sample were 4% for Cu, 19% for Zn, 9% for Cd, 0.7% for Pb and 0.5% for OC.

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2.5. Chemical speciation calculations The main chemical speciation model used in the present work is WHAM/Model VI which has the same structure as WHAM (Tipping, 1994), but with Humic Ion-Binding Model V (Tipping & Hurley, 1992) replaced by the more advanced Model VI (Tipping, 1998). The original WHAM model was also used, for comparative purposes. Briey, Model VI consists of a discrete-site description of the cation-complexing properties of fulvic acid (FA) and humic acid (HA), combined with a sub-model for electrostatic eects on specic binding and a Donnan sub-model for counterion accumulation. Complexation reactions with inorganic ligands in solution are also accounted for. Model VI postulates a wider range of binding site strengths than Model V. Metals and protons bind at common sites, some of which are multidentate with respect to the metals. The model has been parameterised with large numbers of published data sets obtained from laboratory studies. Tipping et al. (2002) have published revised default parameter values describing the binding of Al and Fe(III) by fulvic and humic acids in Model VI. For the present study, we used Fe(III) data from Langford and Khan (1975) for FA, and Liu and Millero (1999) for HA, to derive new values of the key Model V parameter pKMHA, which quanties metalproton exchange (Tipping, 1994). The values of pKMHA are 0.0 and 0.4, respectively. The models are applied to eld samplessoil solutions and whole soils in the present workby xing all parameters at their default (average) values, and adjusting or optimising the concentrations of humic matter that are active in cation binding (see e.g. TipTable 1 Relationships between heavy metal soil measures (mol g1 dry soil) y log CuHNO3 log ZnHNO3 log CdHNO3 log PbHNO3 log CuEDTA log ZnEDTA log CdEDTA log PbEDTA log CuEDTA log ZnEDTA log CdEDTA log PbEDTA x log CuCA log ZnCA log CdCA log PbCA log CuCA log ZnCA log CdCA log PbCA log CuHNO3 log ZnHNO3 log CdHNO3 log PbHNO3 Slope 1.08 0.85 0.99 1.03 1.16 0.85 0.99 1.02 0.99 1.01 0.99 0.97 Intercept 0.12 1.33 0.40 0.05 0.51 1.51 0.37 0.03 0.17 0.03 0.10 0.09 r2 0.85 0.47 0.71 0.95 0.85 0.38 0.63 0.82 0.86 0.86 0.85 0.83

ping et al., 1995a; Dwane and Tipping, 1998; Bryan et al., 2002). The use of the model implies that binding by humic matter controls the accumulation and release of geochemically active metal, which we equate with metal that is extractable by 0.1 M HNO3see Section 3.1. It is assumed that the soil systems under study may contain aluminium and iron hydroxides, dissolution and precipitation of which control the solution activities of Al3+ and Fe3+, and thereby the extents of binding of Al and Fe(III) to humic matter. This is signicant in competition towards heavy metals. 2.6. Regression analysis These were performed using the statistical software within Microsoft Excel. The signicance of values of r2 was determined using F-tests. In multiple regressions, the signicance of each variable was assessed by t-tests, and their relative importance by the step-up procedure (Snedecor and Cochran, 1967).

3. Results 3.1. Summary of the observations Fig. 2 shows distributions of some of the variables over the 98 soil samples. The soils can be classied into three types on the basis of pH, 63 being acid (pH < 5), 11 intermediate (pH 57) and 24 alkaline (pH > 7). The variations in soil pH appear to be due mainly to variations in the supply of Ca from weathering, as shown by the large range in solution concentrations of Ca. The alkaline soils are principally from sites underlain by limestone. The soil contents of organic matter, as measured by LOI, varied from ca. 10 to 100%. Concentrations of DOC ranged from ca. 5 to 500 mg l1. The higher values are unlikely to be an accurate reection of true soil water concentrations, and certainly not of drainage water concentrations (see Section 4). Possible linear relationships among pH, LOI and [DOC] were sought. The strongest (r2=0.37) was a negative correlation of LOI with pH, which arises principally because the alkaline soils tend to have low LOI. Table 1 summarises the relationships between the different measures of the four heavy metals, denoted by MCA for digestion with nitric and perchloric acids, MHNO3 for extraction with 0.43 mol l1 nitric acid, and MEDTA for extraction with 0.1 mol l1 EDTA. For Cu, Cd and Pb, the three metal measures were very similar, the regression slopes being near to unity and the intercepts not signicantly dierent from zero. This also applied to ZnHNO3 and ZnEDTA, but neither was well correlated with ZnCA; the slopes and intercepts indicate that in general the soils contain appreciable amounts of Zn that require harsh conditions for their liberation. We

Subscripts indicate extractions of soil with HNO3, a mixture of concentrated nitric and perchloric acids (CA), and EDTA. No. of data=98 in all cases, except CdEDTA (97). All values of r2 are signicant (P<0.01). All slopes are signicant (P <0.01). Italic intercept values are signicant (P<0.05).

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Fig. 2. Distributions of soil chemical variables. The ordering is from lowest to highest, and is dierent for each variable.

assume that the HNO3 and EDTA extractions provide the best measures of geochemically active metal, i.e. metal that enters into interactions with the soil solids that control solution concentrations, while metal extracted with the concentrated acid mixture includes more recalcitrant forms. In the present work, we based our analysis on MHNO3, principally because we have used dilute HNO3 as an extractant in related work (Lawlor and Tipping, 2002; Tipping et al., 2003). The data for heavy metals (HNO3-extractable and dissolved concentrations) were examined for correlations with soil properties, by testing logarithmic relationships (except for pH). Only low values of r2 were obtained (data not shown). Metal extractable with HNO3 was weakly positively correlated (r240.13) with LOI for all four metals. Dissolved metal concentrations

were weakly positively correlated with DOC in all four cases (r240.23), and weakly negatively correlated with pH (r240.21). For Zn, Cd and Pb there were weak positive correlations with log%LOI (r240.11). Dissolved metals were positively correlated with HNO3extractable metal, giving r2 values of 0.13 (Cu), 0.28 (Zn), 0.30 (Cd) and 0.62 (Pb). 3.2. Multiple regression without speciation of the soil solution The most likely major variables explaining total solution metal concentrations (Msol) are loss-on-ignition, DOC concentration, pH, and the soil content of geochemically active total soil metal (MHNO3). The following regression equation was used:

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logMsol a log %LOI bpH c log MHNO3 d logDOC e 2

and Table 2 shows the results obtained. The geochemically active soil metal content was either the most or the second most important variable. For Cu and Pb, both of which are strongly bound by organic matter, DOC was important, whereas pH was more important for both Zn and Cd. Overall, LOI was the least important variable. Inclusion of HNO3-extractable Al and Fe in the multiple regressions had negligible eect on the regression coecients or r2 values. The regression model does not provide a suciently good prediction of dissolved metal concentrations for practical use, and so speciation of the soil solution was tried (Section 3.3). 3.3. Speciation of the soil solution A schematic picture of the assumed distribution of ions in soil is given in Fig. 3. The inorganic master species of the soil solution are protons, base cations (Na+, Mg2+, K+, Ca2+), anions (Cl, NO, SO2, 3 4 CO2), Al3+, Fe3+, Cu2+, Zn2+, Cd2+ and Pb2+. 3 (Since all the samples were from presumably oxic surface soil horizons, it was assumed that the iron was present exclusively in the ferric form.) The metals may form complexes with the anions, and they may undergo hydrolysis reactions, which are especially important for Al and Fe(III). In addition, they may interact with dissolved organic matter, represented by FA. The metals also undergo solidsolution partitioning. All of them can react with solid-phase organic matter, while Al may equilibrate with Al(OH)3 and Fe(III) with Fe(OH)3. Although the other metals are known to adsorb to oxide surfaces, such reactions are ignored here, because the soils are high in organic matter, which is assumed to dominate partitioning. Part of the soil solids is assumed to be inert with respect to metal binding; this fraction includes unreactive organic matter and mineral components.

Two approaches were taken to describe the partitioning reactions. Firstly the chemical speciation only of the soil solution was modelled, and multiple regression analyses were performed to try to establish relationships between solid and solution metal concentrations, and other soil variables (Section 3.4). This is basically the same approach that has been used by Sauve, McBride and co-workers (see references in Section 1), except that those workers made direct measurements of either the free metal aquo ion concentrations, or the concentrations of labile (assumed to represent inorganic) forms of the metal. The second approach was to include the soil solids in the speciation calculation, and to predict metal distributions in the whole system (Section 3.5). Applications of WHAM and WHAM/Model VI to speciate the samples of soil solution require as input data total concentrations of the signicant reactants. Ideally, these are H+, base cations, strong acid anions, Al, Fe(III) and humic substances, together with the heavy metals (Cu, Zn, Cd, Pb), and the partial pressure of CO2, or the total carbonate concentration. Concentrations of strong acid anions were not determined in the present work. Their concentrations were estimated by forcing a charge balance, assuming the anions to comprise Cl and SO4 at a ratio of 0.75:0.25 in terms of charge equivalents, typical for runo in the UK uplands (Patrick et al., 1995); however, the calculated free metal ion concentrations were insensitive to the Cl:SO4 ratio. This approximation does not introduce serious uncertainty, because the strong acid anions do not enter into signicant complexation reactions with the metals of interest, except that Cl complexation of Cd can account for up to 16% of the inorganic solution forms. Concentrations of humic substances were estimated from [DOC] by assuming that 65% of the DOC was due to FA, to describe ion-binding, while the remaining 35% was assumed inert. This division of DOC is based on modelling interactions with organic matter in surface

Table 2 Multiple regression parameters (Eq. 2) for total solution concentrations (Msol) of heavy metals a Cu Zn Cd Pb 0.30 0.54 0.61 0.47 b 0.03 0.18 0.20 0.20 c 0.38 0.60 0.78 0.89 d 0.51 0.39 0.28 0.79 e 4.50 1.11 0.31 1.23 r2 0.39 0.57 0.55 0.81 Fig. 3. Schematic picture of species distributions and interactions in the soilwater system. Charges are omitted for clarity, except for H+. Interactions shown by dotted arrows are considered by speciation with WHAM/Model VI in Section 3.5.

All values of r2 are signicant (P<0.01). The variables all contribute signicantly (P <0.01) to the regressions, except log% LOI (P<0.025) and pH (not signicant) for Cu.

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and soil waters involving Al and H+ (Tipping et al., 1991, 2002), Cu (Dwane and Tipping, 1998; Vulkan et al., 2000; Bryan et al., 2002), and Cd (Tipping, 2002). Equilibrium with atmospheric CO2 was assumed, but very similar results were obtained if the pCO2 was set to 10 times the atmospheric value. Both Al and Fe(III) have to be taken into account, because they can compete signicantly with trace metals for binding by humic substances (Tipping et al., 2002). These two components were investigated by rst assuming that the measured concentrations in soil solution represented truly dissolved metal. This yielded ion activity products (IAP: aAl3+/a3 and aFe3+/a3 ), as H+ H+ shown for WHAM/Model VI in Fig. 4. The values of log IAP for Al range from ca. 5 at low pH to ca. 12 at pH $ 7, when calculated with either WHAM or WHAM/Model VI. The low-pH value is appreciably smaller than the solubility products (log Kso) for various forms of Al(OH)3, the lowest of which at the temperature of the experiments is ca. 8.0, for gibbsite (Palmer and Wesolowski, 1992). The value of 12 is greater than those in the range 89 reported for soil waters at pH > 5 (LaZerte, 1989). We interpret these results to indicate that, above pH $ 5, the soil solutions are oversaturated with respect to Al(OH)3, i.e. some of the Al in soil solution is present as colloidal suspended particulate matter, including Al(OH)3. Thus, activities of Al3+ are controlled either by solidsolution partitioning, combined with solution interactions, principally hydrolysis and binding by organic matter, or by equilibrium with Al(OH)3. We adopt a mid-range value of log Kso,25 of 8.5 for the Al(OH)3 solubility control. The IAP values for Fe(III) range from ca. 2 to 8 (Fig. 4). Values of log Kso,25 for Fe(OH)3 as high as 5 have been reported, for fresh precipitates, but aged material is appreciably less soluble, with log Kso,25 $ 2.5 (e.g. Baes & Mesmer, 1976). Therefore, it seems likely that virtually all the soil solutions are oversaturated with respect to Fe(OH)3,

and that much of the dissolved Fe(III) is due to colloidal Fe(OH)3. The low-pH results obtained with WHAM/Model VI (Fig. 4) suggest a solubility product of ca. 3 at 20  C, which corresponds to log Kso,25=2.7, if an enthalpy of reaction of 102 kJ mol1 (Liu and Millero, 1999) is applied. Fig. 5 compares free metal ion concentrations calculated with the two models. The ranges of variation are quite large, 6 log units for [Cu2+], 4 for [Zn2+], 2 for [Cd2+] and 8 for [Pb2+]. For nearly all the samples, and for each metal, agreement is within one order of magnitude. WHAM/Model VI tends to give higher values of [Zn2+] than WHAM, whereas the reverse is true for [Cu2+]. Results for [Cd2+] and [Pb2+] are in closer agreement. The dierences between the models in their predictions of free metal concentrations arise partly from their dierent assumptions, in particular the inclusion of low-abundance, high-anity binding sites in WHAM/Model VI, and partly because their parameter values are derived from dierent data sets (more data were available to parameterise Model VI). Fig. 6 compares free metal ion concentrations (WHAM/ Model VI) with total dissolved concentrations. It is seen that Cu and Pb are extensively complexed, Zn and Cd less so. These dierences reect the much stronger interactions of Cu and Pb with dissolved organic matter. (Hereinafter, the results refer only to speciation calculations performed with WHAM/Model VI.) 3.4. Multiple regression analysis based on speciated soil solution Multiple regression analysis was applied in order to derive relationships between solid-phase metal contents and the free metal ion concentrations, calculated as described earlier. Since the complexing eects of dissolved organic matter are accounted for by WHAM/ Model VI, the most likely determinants of solidsolu-

Fig. 4. Ion activity products for Al(OH)3 (lled circles) and Fe(OH)3 (open circles) as functions of pH, calculated for the soil solutions using WHAM/Model VI (see Section 3.3).

Fig. 5. Comparison of free metal ion concentrations calculated with WHAM and WHAM/Model VI. Dotted lines indicate one order of magnitude.

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Fig. 6. Comparison of free metal ion concentrations, calculated using WHAM/Model VI, with total dissolved metal concentrations. The 1:1 line is shown.

Fig. 7. Comparison of free metal ion concentrations predicted by multiple regression with values calculated from WHAM/Model VI speciation of the soil solutions. Dotted lines indicate one order of magnitude.

tion distributions were taken to be MHNO3, LOI and pH, suggesting the following regression equation: log M2 a log %LOI b pH c log MHNO3 d 3 The regressions using these variables explained much of the variation in the free metal ion concentrations, with values of r2 in the range 0.760.95 (Table 3). For all four metals the values of r2 are appreciably greater than those for the prediction of total dissolved concentrations (Table 2). In all cases pH was the most important variable, followed by MHNO3 and LOI. The relative importance of the soil variables is due in part to their degrees of variation. Thus, the range of pH is ca. 5 (log) units, that of log MHNO3 23 units, and that of log% LOI only 1 unit. Inclusion of soil Al and Fe contents in the regressions had hardly any eect, increases in r2 being < 0.01. Fig. 7 compares free metal ion concentrations computed by speciating the soil solutions with values predicted by the four-parameter multiple regression model. The data were also analysed in terms of partition coecients, KD, dened by KD MHNO3 M2 4

Values of KD dened in this way would be useful in predictive calculations, for example, in the dynamic modelling of soils subjected to varying inputs of metals, and undergoing changes in pH. The following regression equation was applied: log KD a log% LOI b pH c 5

The results of multiple regression analyses with two variables, pH and LOI, are shown in Table 4. In all cases, pH was the more signicant variable. The values of r2 are quite high, suggesting that the regression equations would indeed provide useful predictions of KD. Furthermore, the fact that the r2 values are comparable with those using Eq. (3)cf. Table 3 implies that the KD values are not strongly dependent on the value of MHNO3 over the range of 23 orders of magnitude in MHNO3 in our soils. Fig. 8 compares values of KD obtained from solution speciation with the predictions of the regression equations. Note that the KD values for Cu and Pb are higher than those for Zn and Cd, reecting their greater anities for organic matter.

Table 3 Multiple regression parameters [Eq. (3)] for free metal ion concentrations computed with WHAM/Model VI a Cu Zn Cd Pb 0.40 0.61 0.69 0.53 b 1.15 0.36 0.42 1.14 c 0.54 0.73 0.97 0.87 d 1.34 1.19 2.63 3.51 r2 0.94 0.76 0.76 0.95

Table 4 Multiple regression parameters [Eq. (5)] for log KD [dened by Eq. (4)] computed with WHAM/Model VI a Cu Zn Cd Pb 0.48 0.90 0.71 0.60 b 1.16 0.39 0.43 1.13 c 4.69 3.49 2.93 4.36 r2 0.93 0.69 0.73 0.94

All values of r2 are signicant (P<0.01). The variables all contribute signicantly (P<0.01) to the regressions, except LOI for Cu (P<0.025).

All values of r2 are signicant (P <0.01). The variables both contribute signicantly (P <0.01) to the regressions.

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Fig. 8. Comparison of KD values predicted by multiple regression with values calculated from WHAM/Model VI speciation of the soil solutions. Dotted lines indicateone order of magnitude.

3.5. Modelling solidsolution distributions with WHAM/ Model VI The purpose here is to represent the ion-binding components of the soil solid phase by humic substances, and to use WHAM/Model VI to predict solidsolution distributions of metal ions. The modelling requires all signicant ions to be taken into account. Thus we are attempting to describe simultaneously the distributions in the soilwater systems of H+, base cations, Al, Fe(III), and trace heavy metals (see Section 3.3 and Fig. 3). As input data, we have total soil contents of metals, DOC concentrations, and estimated solution concentrations of acid anions (Section 3.3). Solubility control by Al(OH)3 and Fe(OH)3 was assumed, as described in Section 3.3. The soil version of WHAM/ Model VI operates by computing pH, forcing the system to be in charge balance. It was therefore applied by adjusting the soil content of active humic substances in order to make the calculated pH the same as the observed value, for each soil sample. The ratio of HA to

FA was taken to be 84:16, as determined in previous work (Tipping et al., 1995a). Note that this procedure does not involve the optimisation of metal soilsolution distributions, and therefore the models are being used purely predictively with regard to those distributions. Model success or failure can be judged by comparing the predictions either with total dissolved metal concentrations or with free metal ion concentrations computed just from the solution compositions. Application of WHAM/Model VI to the data was successful for 93 of the 98 data sets; in the remaining ve, the required total concentration of humic substances exceeded the total organic content of the soil, suggesting either model failure or analytical error. Ignoring those ve results, the average ratio, RHS (g g1), of active humic substances to LOI ranged from 0.09 to 0.86. Essentially, the tting exercise has determined the content of active HS in each soil. If these values are plotted against %LOI (Fig. 9) it is seen that, at low values of LOI the active HS content increases approximately linearly with %LOI, whereas at %LOI values greater than about 40% the active soil content is approximately constant, with an average value of 0.17 g g1. This value is in agreement with values found in previous studies, where WHAM was applied to the results of batch titration experiments with organic soils (Tipping et al., 1995a; Lofts et al., 2001). Predicted total solution concentrations of heavy metals are compared with observed values in Fig. 10. The results show considerable scatter, but the predicted values are generally within an order of magnitude of the observations. The average ratios of predicted to observed total metal for Cu and Zn are close to unity (1.4 and 0.7, respectively), whereas for Cd and Pb the model predictions are generally too high (average ratios of 2.8 and 8.9, respectively). In the case of Cu, the predictions are poorly correlated with the observations (r2=0.34, for log data). Better correlations are obtained

Fig. 9. Soil contents of active humic substances obtained in the calibration of WHAM/Model VI (Section 3.5).

Fig. 10. Comparison of total solution metal concentrations, predicted by whole-soil modelling using WHAM/Model VI, with observations. Dotted lines indicateone order of magnitude.

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for the other three metals, values of r2 being 0.63 for Zn, 0.54 for Cd and 0.83 for Pb. This trend in r2 follows the range of total solution concentrations, which is only about a factor of 30 for Cu, a factor of ca. 100 for Zn and Cd, and a factor of ca. 1000 for Pb. The plots in Fig. 11 show that the whole-soil model applications provide estimates of free metal ion concentrations that correlate well with the estimates made by speciating only the soil solution. The values of r2 for log-transformed data are 0.89, 0.81, 0.71 and 0.94 for Cu, Zn, Cd and Pb, respectively. We nd that concentrations of Cu2+ tend to be underestimated, by an average factor of 2.2, and those of Zn2+ by a factor of 3.7, while concentrations of Cd2+ and Pb2+ are overestimated by factors of 1.1 and 3.7. 3.6. Comparison with the results of Sauve and colleagues As mentioned in Section 1, Sauve and colleagues have analysed metal chemistry data for contaminated mineral soils by multiple regression, using measured free metal ion concentration as the key variable to be explained. It is of interest to explore how well their equations account for the data presented in this paper, and also to examine whether our equations can account for their observations. For copper, the following equation was obtained by McBride et al. (1997): pCu 1:28 1:37 pH 1:95 log CuT 1:95 log OM n 68; r2 0:80 6 Here, pCu is the negative logarithm of the Cu2+ activity, CuT is the total soil copper, in mg kg1, and OM is the organic matter content of the soil in gC kg1. An

additional equation for copper was derived by Sauve et al. (1998a): pCu 3:42 1:4 pH 1:7 log CuT 7 n 66; r2 0:85 Table 5 shows that Eq. (6) predicts our data poorly, all the values of Cu2+ activity (aCu2+) being two-to-three orders of magnitude too small, although the correlation between predicted and observed values was good. Eq. (7) is much more successful, predicting aCu2+ values on average only ve times too small, and with a high correlation. Sauve et al. (2000) reported the following equation for Cd: pCd 5:14 0:61 pH 0:79 log CdT 8 n 64; r2 0:70 and this gave predictions that were, on average, within a factor of two of the values of aCd2+ obtained in the present study, although the correlation was relatively low (r2=0.60). Finally, Sauve et al. (1998a) produced this regression for Pb: pPb 6:78 0:62 pH 0:84 log PbT 9 n 84; r2 0:64 which predicted aPb2+ values for our data that were, on average, 2.5 times the observations, with a high correlation (r2=0.92). When our regression Eq. (3), with the coecients given in Table 3, was applied to the data of Sauve et al. (1997) for Cu, and Sauve et al. (2000) for Cd, the metal activities were of the right magnitude, on average, but the correlations were low, with r2 $ 0.5 (Table 5). In both cases, the predicted values tended to be too high when metal activities were low. The pub lished data sets of Sauve and colleagues for Cu and Cd
Table 5 Comparisons of multiple regression equation predictions. Eqs. (6)(9) were used to predict the results of the present study. Eq. (3), derived in the present study, was used to predict the results of Sauve et al. (1997, 2000) Data set Present Cu Present Cu Present Cd Present Pb Cu, Sauve et al. (1997) Cd, Sauve et al. (2000) n 98 98 98 98 68 61 Eq. 6 7 8 9 3 3 Mean 0.003a 0.2a 1.6a 2.5a 0.7b 4.0b r2 0.83 0.87 0.60 0.92 0.50 0.54

Fig. 11. Comparison of free metal ion concentrations, predicted by whole-soil modelling using WHAM/Model VI, with values obtained from speciation calculations for the soil solution only. Dotted lines indicateone order of magnitude.

n=no. of data points. a apred/aWHAMVI is the ratio of the activity predicted with the specied equation (see text) to the activity estimated by speciation of the soil solution with WHAM/Model VI. b apred/aobs is the ratio of the activity predicted with Eq. (3) to the activity determined experimentally.

E. Tipping et al. / Environmental Pollution 125 (2003) 213225

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can be combined with the data reported in the present study to generate the following regression equations: log aCu 5:35 1:17 pH 1:09 log MCu 0:52 log %LOI n 165; r 0:87;
2

10

log aCd 0:22 0:45 pH 0:77 log MCd 0:21 log %LOI n 158; r 0:69:
2

11

4. Discussion The present data set covers wide ranges of soil conditions in terms of pH, base cations and organic matter, although it does not include LOI levels lower than 10%. The geographical spread of sampling sites means that most situations in the uplands of England and Wales are represented. Although acid soils are the most common, there are appreciable numbers of samples with high pH, the metal chemistries of which appear to be governed by the same processes that operate in the acid samples. The main inadequacy of the present data is that they do not include measurements of either free metal ions or other labile forms of the metals. For logistical reasons, and with the available resources, this would have been dicult to achieve for four metals in so many samples. Therefore, we have used speciation modelling, and the analysis depends very much on the ability of the models to provide accurate estimates of free metal ion concentrations. As mentioned in Section 3.3, there is published evidence that the models have such capabilities, but model-testing is far from complete, and the calculated values should therefore be regarded with appropriate caution. The fact that the calculated free metal ion concentrations lead to a coherent analysis of the partitioning data adds indirect support to the speciation modelling approach. The advantage of having a large, representative data set is that it provides a good test of the ability of modelling approaches to provide general predictions, that could be used to map actual and potential toxic eects (see below). Logistical constraints and resource limitations mean, however, that only one solidsolution partitioning state is observed for each metal in each soil. This means that the eect on partitioning of, for example, pH is seen only by comparing soil samples of different pH, rather than arranging for a single sample to experience a range of pH. Therefore, useful complementary information could be obtained from more detailed study of a sub-set of samples, for example by acid-base titrations (Tipping et al., 1995a,b; Lofts et al., 2001). Work on this aspect of soil metal chemistry is currently in progress in our laboratories.

The measured concentrations of DOC include some high values (> 100 mg l1), which far exceed the concentrations (130 mg l1) that are observed either in the porewaters of upland organic soils, collected by suction lysimeters (Hughes et al., 1994; Adamson et al., 2001) or in upland UK surface waters (see e.g. Tipping et al., 1988; Scott et al., 1998; Monteith and Evans, 2000). Therefore it seems unlikely that the soil solutions sampled in the present work are representative of soil water in situ. For example, it may be that the disturbance of soil structure caused by sampling leads to the solubilisation of entrapped dissolved organic matter, or to peptisation of colloidal forms. This uncertainty is important if soil solution composition is used to determine soil metal budgets, since metal associated with apparently soluble, but practically immobile, DOC would cause the overestimation of metal leaching losses. With regard to metal bioavailability, the uncertainty would be signicant if total solution concentrations were considered, but inconsequential if free metal ion concentrations were used. It can be concluded from the results of multiple regression analysis involving total solution metal concentrations that metal distributions are determined mainly by sites on organic matter, at which metal ions and protons compete for binding (cf. Fig. 3). Although signicant correlations can be obtained from such a regression analysis, considerably higher values of r2 are achieved when the soil solution is speciated (by model calculation). The improvements arise because metal binding by organic matter cannot be represented satisfactorily by combinations of linear terms, as is required by multiple regression analysis for unspeciated soil solutions. The results provide strong evidence for the key role of the free metal ion concentration in determining solidsolution partitioning. The comparisons of our regression equations and data with those of Sauve and colleagues (Section 3.6), and the modelling of combined data sets, attest to the robustness of the multiple regression approach. The regression equations are easy to use, and require relatively little input data, but should not be used outside the ranges of input data used to derive them. They are well suited to the estimation of metal partitioning from basic soil characteristics, with limited information about soil solution composition, and for large numbers of examples, as might be required in mapping exercises. The prediction of metal solidsolution partitioning with WHAM/Model VI can be considered reasonably successful (Section 3.5, Figs. 10 and 11), and given the consistency of under- or over-prediction of free metal ion concentrations (Fig. 11), the model could be optimised straightforwardly by making adjustments (which would be modest) of equilibrium constants for metal binding. Calibration of the model by estimation of the active content of humic matter is also required, and the

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results in Fig. 9 could be used to derive average humic contents, dependent upon LOI. WHAM/Model VI as presently applied to soils requires the system to be charge balanced, and therefore needs information, or assumptions, about total soil composition, if it is to be used to estimate metal speciation in a given soil. On the other hand, the ability of the model to speciate the entire soil means that it can be used to estimate how soil solution composition, notably pH and free metal ion concentrations, would depend upon, for example, changing inputs of acidifying pollutants. Thus, WHAM/Model VI is potentially a powerful tool in describing and predicting temporal changes in soil chemistry, within a consistent framework. One reason for carrying out the present work was to contribute to the evaluation of critical loads approaches in the environmental risk assessment of heavy metals transported by long-range (transboundary) atmospheric processes. The critical load is derived from a critical limit, above which the metals are judged to have deleterious eects. In the case of soils, the critical limit for a given metal may be expressed, for example, by the total soil metal content, the total solution metal concentration, or the free metal ion concentration. Calculation of the critical load requires an understanding of metal behaviour, including solidsolution partitioning, following atmospheric deposition, in order to calculate the deposition (critical load) at which the critical limit would be exceeded if the system were at steady-state (de Vries and Bakker, 1998). The multiple regression models, combined with the application of WHAM/Model VI to compute solution speciation, would be suitable for use in the calculation of steady state metal concentrations, given information about metal inputs (including deposition and weathering), removal processes (e.g. the harvesting of plants), soil properties, soil pH, and the DOC concentration in drainage water. In this way, calculations could be performed to determine the critical load per se, and also, combined with soil inventory data, to assess whether current solution concentrations and/or free ion activities exceed critical limits. An objection to steady-state modelling is that soil systems can take long periods to reach steady state (see e.g. Paces, 1998). Dynamic modelling may therefore be more appropriate, at least to explore the time scales involved, and again the models described here are potentially applicable. Information, or assumptions, about temporal changes in metal inputs to the system would be required, and account should also be taken of changes in soil conditions, notably in acidication status. The use of the multiple regression equations would require input data describing variations in soil pH, whereas WHAM/Model VI could be used to simulate acidication processes and metal behaviour simultaneously.

Acknowledgements We are grateful to B.M. Simon (CEH Windermere) for performing DOC determinations, to Barry Cole (Imperial College) for assistance with metal analyses, and to L. Baldwin (CEH Windermere) for secretarial assistance. This work was supported by the Environmental Diagnostics Programme of the UK Natural Environment Research Council, and by the Department of the Environment, Transport and the Regions (now the Department for Environment, Food and Rural Aairs), the Scottish Executive, the National Assembly of Wales and the Department of the Environment (in Northern Ireland) under contract EPG 1/3/144.

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