CHEMICAL PARTITIONING OF HEAVY METALS IN SOILS, CLAYS AND ROCKS AT HISTORICAL LEAD SMELTING SITES

J. E. MASKALL and I. THORNTON

Environmental Geochemistry Research Group, Centre for Environmental Technology, Royal School of Mines, Imperial College of Science, Technology and Medicine, London, U.K. E-mail: j.maskall@plymouth.ac.uk

(Received 25 June, 1996; accepted in nal form 5 October, 1997)

Abstract. The chemical partitioning of lead and zinc is described in contaminated soils and underlying strata at historical lead smelting sites. Sections of soil-rock cores from eight sites of age 200 to c.1900 yr were analysed using a sequential extraction procedure. Of the total amount of lead and zinc present in soils, only a small proportion is in a readily mobile form. However, this proportion increases signicantly as the pH falls below 5 and for lead reaches 37% in soils at Bole A. A high proportion of lead in soils appears to be associated with the carbonate and specically adsorbed phase. It is suggested that this is partly due to the formation of cerussite (PbCO3 ) in soils contaminated with calcareous slag wastes. Lead present in the residual phase in contaminated soils may be related to the presence of the element in silicate slag particles. Rapid migration of lead to a depth of 5.6 m in sandstone at Bole A was related to its high solubility in the acidic soils and rock at this site. Comparable migration at Bole C proceeds by a different mechanism, possibly with lead in association with Fe-Mn oxides and slag particles. In clay inll in fractured sandstone at Bole A, anthropogenic lead present at a depth of 4.4 m was extracted predominantly in the fraction representing Fe-Mn oxides. Keywords: contamination, lead, migration, partitioning, soil, zinc

1. Introduction The long term leaching and migration of contaminants from improperly disposed wastes can result in pollution of ground and surface waters. Data on the mobility and migration of heavy metals at historically contaminated sites is valuable for the assessment and management of contemporary pollution problems. The potential for release of contaminants from waste materials and their movement in soils can be assessed using a variety of leaching and extraction techniques (Quevauvillier et al., 1996). In this paper, the chemical partitioning of lead and zinc in contaminated soils and clays is assessed using a ve-step sequential extraction procedure. The soils and clays were taken from core samples collected from eight historical lead smelting sites in use between 200 and c.1900 yr ago. The sections of the soil-rock cores selected for this study comprised slag-contaminated soils and underlying
Present Address Department of Environmental Sciences, University of Plymouth, Drake

Circus, Plymouth, PL4 8AA, UK Water, Air, and Soil Pollution 108: 391409, 1998. 1998 Kluwer Academic Publishers. Printed in the Netherlands.

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clays and rocks into which metals were known to have migrated. The cores have been analysed previously to establish the extents and rates of vertical migration of metals in a number of geological parent materials (Maskall et al., 1995, 1996). In addition, mineralogical analysis of slag wastes has been undertaken at seven of the sites (Gee et al., 1997). The data for the chemical partitioning of metals are discussed in relation to the mineralogy of the slag wastes and to the characteristics of metal migration. The sequential extraction technique used is based on that of Tessier et al. (1979) which has been adapted for multi-element analysis by ICP-AES (Li et al., 1995). Although this method was originally intended for analysis of aquatic sediments, it has also been successfully applied to the study of soils and dusts (Harrison et al., 1981; Hickey and Kittrick, 1984; Gibson and Farmer, 1986; Clevenger, 1990). However, the main limitation of this approach is that the geochemically dened phases are not perfectly differentiated; there is a certain amount of overlap between fractions and extraction efciency can vary with the type of soil under investigation (Valin and Morse, 1982; Kheboian and Bauer, 1987; Martin et al., 1987). Nevertheless, sequential extraction data do provide an indication of the relative bonding strength of metals in different solid phases and their usefulness can be enhanced when combined with data from other analytical techniques. Previous studies on contaminated soils have shown that the partitioning of metals depends strongly on their mineralogical and chemical form which in turn is inuenced by the source of contamination. Research by Li (1993) indicated that variations in the partitioning of lead between old mining and smelting sites in Derbyshire, U.K. was related to the form of lead present. The proportion of lead extractable by MgCl2 was higher at the smelting site and this was attributed to the presence of anglesite (PbSO4 ) and Pb-oxides in the emission particulates and slag wastes. In the old mining area however, the relatively low proportion of lead in the same step was attributed to the presence of lead as cerussite (PbCO 3 ), galena (PbS) and pyromorphite (Pb5 (PO4 )3 Cl) and the higher pH of the contaminated soils. A high proportion of lead at both the smelting and mining sites was extracted in the step representing the carbonate and specically adsorbed phase. In comparison, studies of metal partitioning in urban soils from Lancaster (Gibson and Farmer, 1984) and Glasgow (Gibson and Farmer, 1986) revealed a high proportion of lead to be present in the reducible fraction and as such was considered to be associated with Fe-Mn oxides. Precipitation of metals as carbonates and hydroxycarbonates has been identied as the dominant control on metal migration in several sedimentary rock types (Newman and Ross, 1985). Similar results have been reported for metal migration in glacial deposits (Gibb and Cartwright, 1982) and in a natural clay underlying a landll site (Yanful et al., 1988). In all these cases, the presence of carbonate species leads to elevated pH levels which encourage metal-carbonate precipitation reactions. Additional controls on metal migration identied in the eld include cation exchange and adsorption (Gibb and Cartwright, 1982; Newman and Ross,

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1985), adsorption by Mn oxides (Kobuty-Amacher et al., 1992) and adsorption to organic matter (Dorr and Munnich, 1991; Dumontet et al., 1990). In an experimental study of metal movement through soils, Korte et al. (1976) found that soil texture, surface area, free iron oxide concentration and pH were the most important factors for predicting movement.

2. Materials and Methods Sites of former lead smelting activity were identied from historical records and archaeological studies. Core sampling was undertaken at eight sites; two eighteenth century cupolas, four medieval boles and two Roman sites, and was concentrated in areas of slag contamination. Seven of the sites were located in Derbyshire, England whilst Roman A was located in Clwyd in North Wales. The variations of total metal concentrations in the soil-rock proles at these sites have already been published (Maskall et al., 1995, 1996). The core sections selected for this study comprised slag-contaminated soils and the underlying clays and rocks into which metals were known to have migrated. Details of the selected sections of core are given in Table I in terms of the site, depth, material present and the lead migration rate for the particular core. The core sections from Cupola A, Bole B, Bole D and Roman A were chosen in order to investigate the metal partitioning where migration had been attenuated by clay layers underlying contaminated soils. Conversely, core sections from Bole A and Bole C were selected as the contaminated soils were directly underlain by sandstone into which signicant migration of lead had occurred. Soils, clays and rocks were subsampled from the cores, air-dried at 30 C for 72 hr, disaggregated with a pestle and mortar, passed through a 2 mm sieve and milled to a size of < 180 m. Total metal concentrations were determined by digesting the milled material with a concentrated nitric/perchloric acid mixture and analysing by ICP-AES (Thompson and Walsh, 1983). The chemical partitioning of metals was assessed using a sequential extraction procedure based on that of Tessier et al. (1979) adapted for ICP-AES by Li et al. (1995). It was carried out progressively on an initial weight of 1.0 g of milled material using the following extractions: Step 1: 0.5 m magnesium chloride adjusted to pH 7.0 with 10% ammonia solution. Step 2: 1 m sodium acetate adjusted to pH 5.0 with acetic acid. Step 3: 0.04 m hydroxylamine hydrochloride in 25% acetic acid. Step 4: 30% hydrogen peroxide in 0.02 m nitric acid Step 5: 60% perchloric acid, 70% nitric acid and 35% hydrouoric acid. The method is intended to distinguish ve fractions representing the following phases; exchangeable (step 1), carbonate and specically adsorbed (step 2), iron and manganese oxide (step 3), organic and sulphide (step 4) and residual (step 5). However, the amount of metal extracted in each step does not necessarily cor-

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TABLE I Samples selected for metal partitioning study Site Core(s) Material Depth (m) n Pb migration rate (cm y1 ) 0.11 1.48 0.79 0.31 0.720.77

Cupola A Cupola B Bole A Bole B Bole C

1 1+3 2 1 1+3

Bole D

Roman A Roman B

1 3

Soil Clay Soil Soil Sandstone Soil Clay Soil Clay Sandstone Soil Clay Sandstone Soil Clay Soil Clay Limestone

00.5 0.51.6 00.8 00.4 0.44.3 00.5 0.51.2 00.5 0.50.6 0.63.2 01.0 1.01.5 1.51.6 1.72.3 2.34.8 00.2 0.20.7 0.71.3

4 6 9 2 12 4 3 5 1 4 5 2 1 3 2 1 3 1

1.44

0.07 0.54

respond to that present in each geochemically dened phase in the test material. The geochemical phases at each extraction step are largely operationally dened and indicate relative rather than absolute chemical speciation. The main interpretations are based on the solubility of metals but are supplemented with additional mineralogical analyses where available. In this paper, the fractions are referred to in terms of the extraction step and the geochemical phase considered to be the predominant source of metal is added in parentheses e.g. step 1 (exchangeable).

3. Results and Discussion 3.1. ACCURACY OF THE

SEQUENTIAL EXTRACTION PROCEDURE

The overall accuracy of the sequential extraction procedure was assessed by analysis of reference materials from the National Institute of Standards and Technology (NIST). The sums of the concentrations from the ve steps were compared with the certied values for the total concentrations and the results, expressed in terms of

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TABLE II Recovery of metals from sequential extraction procedure (%) Sample NIST SRM 2710 NIST SRM 2711 Contaminated Soils Underlying Clays Underlying Rocks Element Pb Zn Pb Zn Pb Zn Pb Zn Pb Zn Mean 91 92 93 89 97 100 114 105 105 107 Range 8894 8793 9295 8790 84112 82121 92217 74168 84139 88141 SD 2 3 1 1 6 10 29 25 13 12 n 4 4 3 3 33 33 17 17 18 18

% recovery, are shown in Table II. The recovery rates are generally high (> 80%) and the mean rates lie within or very close to the target range of 90 110%. Mean recovery rates of metals in soils, clays and rocks were determined by comparing the sum of the analyses for the ve steps with the total metal concentration determined by digestion with nitric and perchloric acids. The results also fall generally within the target range (Table II). However, recovery rates for metals in underlying clays reached elevated levels in a limited number of samples where the total metal concentrations were very low. 3.2. G ENERAL
TRENDS IN METAL PARTITIONING

The concentrations of metals in the ve fractions in contaminated soils and underlying clays show that the amounts of metals that are extracted at each stage can vary widely (Table III). The proportions of lead and zinc extracted in step 1 (exchangeable) are generally low and on average range between 26% of the total metal. In comparison with results gained by Li (1993), the lead data for this study are more similar to those of the mining area than the smelting area (Table IV). This is because the soils in this study were invariably collected from the most contaminated part of the smelting sites and contained therefore a high proportion of calcareous slag wastes which tend to elevate the soil pH (Maskall et al., 1995, 1996). Indeed for both soils and clays, the proportions of metals extracted in step 1 (exchangeable) are signicantly and inversely related to pH (Figure 1) and similar relationships have been reported by Iyengar et al. (1981) and Li (1993). The one site which featured a high proportion (37%) of lead in soils in step 1 (exchangeable) was Bole A which had the lowest pH of all the sites with an average of 3.9.

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TABLE III Concentrations of metals in different fractions in slag contaminated soils (n=33) and underlying clays (n=17) (g g1 ) Slag Contaminated Soils Meana Meanb Range 1052 44 28219 238 11060 752 3551 292 7796 554 5 6 45 13 22 31 15 10 13 40 103960 0.6399 3689500 0.6977 3830600 25630 217400 14650 1341000 22560 Underlying Clays Meana Meanb Range 12 83 257 70 215 356 58 447 91 237 2 4 31 6 30 24 18 13 19 53 0.368 0.1409 41780 0.9449 21520 71770 2353 14650 5366 51300

Extraction Step 1 Step 2 Step 3 Step 4 Step 5 Pb Zn Pb Zn Pb Zn Pb Zn Pb Zn

a Expressed as a concentration (g g1 ). b Expressed as a proportion of the total concentration (%).

TABLE IV Mean proportions (%) of metals extracted in each fraction for a range of soils Extraction Cupola Aa (n=10) 21 8 29 12 21 27 25 11 4 42 Mining Areaa (n=11) 5 0.5 27 8 37 37 28 5.5 3 49 Glasgow Soilb (n=397) 2 3 11 7 51 17 19 29 17 43 Lancaster Soilc (n=4) 1 3 26 31 44 34 12 9 17 23

Step 1 Step 2 Step 3 Step 4 Step 5

Pb Zn Pb Zn Pb Zn Pb Zn Pb Zn

a Li (1993). b Gibson and Farmer (1986). c Gibson and Farmer (1984).

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Figure 1. All sites: variation of the proportion of lead extracted in step 1 with soil pH.

Higher proportions of lead are extracted in the second step (carbonate and specically adsorbed) which on average accounts for 45 and 31% of the total concentration in soils and clays respectively. The value for soils is particularly high and exceeds the corresponding gures from other studies of urban soils and soils contaminated by smelting and mining activities (Table IV). This may be due to the relatively high pH levels in soils at the study sites which have been elevated due to the release of calcium and carbonate compounds from the slag wastes (Maskall et al., 1995, 1996). The proportion of lead extracted in step 2 is signicantly related to pH (r = 0.73) and increases from approximately 20 to 80% over the pH range 4.0 7.2. Previous work has indicated that the importance of this fraction as a lead sink rises with increases in the pH and calcite contents of soils and dusts (Harrison et al., 1981; Gibson and Farmer, 1986). Soils from the study sites are highly contaminated and their lead content generally exceeds the theoretical maximum which can be adsorbed by the CEC. This suggests that some of the lead is present occluded in slag particles, specically adsorbed to soil constituents or precipitated. As the lead level in soils increases, the percentage of lead extractable in step 2 also increases ( r = 0.68). This provides further evidence that lead may be present in the specically adsorbed form or precipitated as carbonates in contaminated soils. Step 3 is operationally dened as the fraction bound to Fe-Mn oxides. However, it has been shown that in some carbonaceous soils, the second extraction step may not be effective in removing all the carbonate minerals into solution (Jouanneau

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et al., 1983). Metals extracted in step 3 therefore may contain a proportion of the carbonate forms in addition to those bound to Fe-Mn oxides, particularly in slag contaminated soils which have been shown to have higher carbonate content (Maskall et al., 1995). Nevertheless, step 3 (Fe-Mn oxides) accounts for 22% of the lead in soils which is low compared to soils from mining and urban areas (Table IV) and probably reects the dominant role of step 2 for this element in this study. A higher proportion of lead is extracted from the clays (30%). Step 3 represents the second most signicant sink for zinc after the step 5 (residual) and accounts for 31% of the element in soils and 24% in the clays. This fraction has also been found to hold large amounts of zinc in soils contaminated by copper smelting emissions (Kuo et al., 1983; Hickey and Kittrick, 1984). In soils, the percentage of zinc extracted in step 3 increases signicantly with pH (r = 0.69) which probably reects the enhanced scavenging of metals by Fe-Mn oxides at higher pH levels. Step 4 is operationally dened as the organic and sulphide fraction but it has been shown that the primary sulphide minerals, including PbS, can not be totally dissolved by this step (Forstner, 1985). Although the term organic/sulphide is used in the text, it should be regarded as the organic fraction with partial dissolution of the primary sulphide phase (Kim and Fergusson, 1991). However, sulphide minerals were not identied as a dominant lead bearing phase in slags at the study sites by Gee et al. (1997). Step 4 (organic and sulphide) accounts for relatively small proportions of metals in soils and clays (Table III). In contaminated soils, the percentage of metal extracted in this fraction increase with the CEC for both lead (r = 0.79) and zinc (r = 0.48). Step 5 (residual) accounts for a relatively high proportion of zinc in soils (40%) which reects results gained by Li (1993) for both smelting and mining areas in Derbyshire. The particularly high proportion of zinc present in clays (53%) in this step may represent residual zinc from within clay minerals as found by Iyengar et al (1981). In comparison, the proportions of lead extracted in soils (13%) and clays (19%) are low. The percentage of lead extracted in step 5 increases signicantly with the total lead concentration (r = 0.59). This may reect the presence of lead occluded in slag particles in highly contaminated soils and this is discussed further in Section 3.3. 3.3. M ETAL
PARTITIONING IN RELATION TO MINERALOGY

Mineralogical analysis of slag wastes and contaminated soils from seven of the study sites was undertaken by Gee et al. (1997) using a combination of Scanning Electron Microscopy and X-Ray Diffraction. In large slag fragments ( > 2 mm), lead was found to occur in several forms including lead oxide (PbO), pyromorphite (Pb5 (PO4 )3 Cl), cerrusite (PbCO3 ), hydrocerrusite (Pb3 (CO3 )2 (OH)2 ), galena (PbS), anglesite (PbSO4 ) and leadhillite (Pb4 SO4 (CO3 )2 (OH)2 ). In addition, lead was identied as a component of a number of silicate phases, some of which were glassy in nature. In contaminated soils, silicate slag particles (< 2 mm) were still

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recognisable but were more weathered than the larger fragments. In these particles, the lead phases had generally weathered to cerussite or hydrocerrusite but galena occasionally occurred, usually trapped within silicate material. It was suggested that this precipitation of lead mainly as cerrusite is related to the release of calcium and carbonate compounds from the slag wastes and the consequent elevation of pH in the contaminated soils (Gee et al., 1997). In addition, signicant amounts of glassy lead silicate material were found in soils, particularly at a sites with relatively high pH. The high proportion of lead extracted in step 2 (carbonate and specically adsorbed) at the study sites is further evidence of the widespread presence of cerrusite in soils indicated by Gee et al. (1997). Furthermore, the observation that the percentage of lead extracted in step 2 increases with the total lead content of the soils suggests that the formation of cerrusite is favoured in the most highly contaminated soils. These soils also tend to have the highest pH levels and would favour therefore the formation of cerrusite on thermodynamic grounds as the mineral is usually stable at a pH above 6.0 (Brookins, 1988). Lead in a glassy silicate form in soils would be expected to be extracted in step 5 (residual). In this step, we again observe that the percentage of lead extracted increases with the total lead concentration of the soils. This may indicate the presence of lead bearing silicates in the most highly contaminated (slag rich) soils but further work would be required to conrm this. 3.4. M ETAL
PARTITIONING IN RELATION TO METAL MIGRATION

As the proportion of metals that are extracted in step 1 (exchangeable) in the contaminated soils is generally low, it would be expected that the amounts of metal available for downwards migration would be limited. Indeed, previous work has indicated that the amounts of lead and zinc that had migrated and had been retained by the underlying strata were low compared to the amounts present in the soils (Maskall et al., 1995, 1996). Furthermore, previous work also indicated that for sites with similar geology, metal mobility tended to increase at lower soil pH (Maskall et al., 1995). This is supported by the observation that at lower soil pH levels the proportion of lead in step 1 (exchangeable) increases. However, the partitioning data also reveal that at lower pH levels the proportion of metals extracted in step 2 (carbonate and specically adsorbed) decreases. In the contaminated soils at the study sites therefore, metal mobility increases under conditions of low pH apparently via the dissolution of metal species held in the major reservoir classed as carbonate and specically adsorbed leading to an increase in metals in the exchangeable fraction. The underlying clays selected for this study are moderately contaminated and represent material in which the migration of metals has occurred but has been limited by the process of attenuation. Taking the clays as a group (excluding one outlier), the partitioning data show that as the total lead concentration increases, the percentage of lead extracted increases signicantly in step 2 (r = 0.86) and step 3 (r

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Figure 2. Cupola A: variation of lead concentrations in steps 15 with depth.

= 0.64) only. Similar results are found for zinc and suggest that specic adsorption, precipitation and adsorption to Fe-Mn oxides are important mechanisms for the attenuation of metals in clays although further work is required to conrm this. Yanful et al. (1988) report that the mobility of metals in a clay liner under a landll site was limited by precipitation as carbonates under conditions of high pH. The variation of metal partitioning with depth in a soil-clay prole at Cupola A is shown in Figures 25. The clay has limited the movement of lead to a few centimetres below the soil-clay interface whilst zinc has penetrated to a depth of 1.6 m. The greater mobility of zinc may be related to the higher proportion of the

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Figure 3. Cupola A: variation of the proportion of lead in steps 1-5 with depth.

element extracted in step 1 (exchangeable) compared to lead (Figures 3 and 5). High proportions of lead (41%) and zinc (35%) are extracted in step 4 (organic and sulphide) in the clay. The metals may be adsorbed onto organic matter which is present at a relatively high concentration (LOI = 29%). This is supported by the observation that in all the clays the percentage of lead extracted in step 4 is signicantly related to the organic matter content (r = 0.52). Rapid migration of lead to a depth of several metres was recorded in Crawshaw Sandstone at Bole A, an area where underlying clay layers were absent (Maskall et al., 1995). The variation of lead partitioning with depth in Core 2 is presented

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Figure 4. Cupola A: variation of zinc concentrations in steps 15 with depth.

in Figures 6 and 7. The low pH of the soils at this site results in a large proportion (37%) of lead extracted in step 1 (exchangeable). Lead appears to be migrating predominantly in the exchangeable form which remains the commonest lead species to a depth of nearly 4 m, perhaps maintained by the acid nature of the sandstone. This core from Bole A was studied by Whitehead et al. (1997) using lead isotope tracing and estimates were made of the proportions of lead in the sandstone originating from (i) the anthropogenic slag contamination at the surface and (ii) the natural background. It was found that for lead in contaminated sandstone at a depth of 1.4 2.3 m, 88% was of anthropogenic origin and for lead in contaminated fracture clay

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Figure 5. Cupola A: variation of the proportion of zinc in steps 1-5 with depth.

inll at 4.5 m, 98% was of anthropogenic origin. Table V shows the lead partitioning data for two of the contaminated sandstone samples used in the isotope study, a similar fracture clay inll sample from the same core and an uncontaminated sand from Cupola A. The data conrm that in the contaminated sandstone, a high proportion of the anthropogenic lead is present in step 1 (exchangeable). In the fracture clay inll however, a disproportionately high concentration of anthropogenic lead is extracted in step 3 suggesting that Fe-Mn oxides are important in attenuation of the element in subsurface clays. Results from Bole A support the suggestion that rapid and signicant metal migration is facilitated by a high metal solubility in soils which in this case is due to the relatively low soil pH.

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TABLE V Partitioning of lead in sandstones and fracture clay inll (g g1 ) Site Depth (m) Material Step 1 Step 2 Step 3 Step 4 Step 5 Total Lead Anthropogenic Leada Bole A 1.4 Contaminated Sandstone 41.4 14.4 10.6 0.4 13.5 80.3 70.7 Bole A 2.0 Contaminated Sandstone 52.8 12.0 6.0 0.2 12.0 83.0 73.0 Bole A 4.4 Fracture Inll Clay 30.0 84.0 222.0 9.4 30.0 375.4 370.4 Cupola A 1.3 Uncontaminated Sand 0.3 3.6 2.4 2.4 4.5 13.2 0

a Calculated using isotope ratios from Whitehead et al. (1997).

Considerable movement of lead and zinc have also been recorded in Namurian Sandstone in Core 3 at Bole C to a depth of over 4 m (Maskall et al., 1996). However, at this site, migration does not appear to have occurred by the same mechanism as at Bole A. A very low proportion of lead was found in step 1 (exchangeable); 0.5% in the slag contaminated soil and 0.2% on average in the sandstone with similar levels for zinc (Figures 8 and 9). This is probably related to the high pH (6.9) of the contaminated soil which is also fairly rich in organic matter. 46% of the lead in the contaminated sandstone is extracted in step 3 (FeMn oxide) and 34% in step 5 (residual). Most of the zinc is extracted in step 5 (residual) and the mean concentration (292 g g1 ) is too high to be entirely due to the natural background. Metal contamination at this site appears to be due to the downwards movement into the fractured sandstone of lead-rich iron and manganese oxides along with particles of slag containing lead and zinc although further work is required to conrm this.

4. Conclusions Of the total amounts of lead and zinc in contaminated soils and underlying clays taken from historical lead smelting sites, only relatively small proportions were extracted in a readily mobile form. However, these proportions increase with lowered soil pH and at Bole A, where mean pH is 3.9, 37% of lead present in soils was extracted in step 1 (exchangeable). A large proportion of lead in soils (mean = 45%) was extracted in step 2 (carbonate and specically adsorbed) and this proportion increases as the soils become more contaminated. This is partly related to

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Figure 6. Bole A: variation of lead concentrations in steps 15 with depth.

the presence of cerrusite (PbCO3 ) which forms as a weathering product in soils in the presence of calcium and carbonate compounds leached from the slag wastes. The proportion of lead extracted in step 5 (residual) also rises with contamination in soils and it is suggested that this is due to the increased presence of lead occluded in silicate slag particles. In the contaminated soils, metal mobility is enhanced under conditions of low pH apparently via the dissolution of metal species present in step 2 (carbonate and specically adsorbed) leading to an increase in the fraction representing exchangeable metal. At Bole A, the high mobility of lead in soils is linked to the rapid migration of the metal to a depth of 5.6 m. A high proportion of

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Figure 7. Bole A: variation of the proportion of lead in steps 1-5 with depth.

the anthropogenic lead in the contaminated sandstone at this site was present in a readily soluble form. Comparable migration at Bole C appears to have proceeded by another mechanism where metals are present in much less soluble forms. The processes controlling attenuation in the underlying clays remain unclear although there is some evidence that in a shallow clay at Cupola A, metals are associated with organic matter. In clay inll in fractured sandstone at Bole A, anthropogenic lead which has migrated to a depth of 4.4 m is found predominantly in the fraction representing Fe-Mn oxides.

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Figure 8. Bole C: variation of lead concentrations in steps 15 with depth.

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Figure 9. Bole C: variation of the proportion of lead in steps 1-5 with depth.

Acknowledgements This work is funded by the International Lead Zinc Research Organisation and The BOC Foundation for the Environment. The authors are grateful to Dr. Xiangdong Li and to postgraduate research students Keith Whitehead and Clare Gee for their contributions.

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