A.M. Tye

Predicting the activity of Cd2+ and Zn2+ in soil pore water from the radio-labile metal fraction

Abstract Cadmium and zinc were added at 3 and 300 mg kg −1 , respectively, to 23 soils and incubated at 16°C and 80% field capacity for 818 d. Following addition of metal, changes in the radio-labile concentrations of both elements were examined on seven separate sampling occasions over 818 d. At each sample time, soil pore water was extracted using Rhizon soil solution samplers, and concentrations of Cd, Zn, dissolved organic carbon, and major cations and anions were determined. The chemical speciation program WHAM 6 was used to determine free metal ion activity, (M 2+ ). Similar measurements were made on a set of historically contaminated soils from old mining areas, sewage sludge disposal facilities, and industrial sources. The two data sets were combined to give a range of values for p (Cd 2+ ) and p (Zn 2+ ) that covered 5 and 4 log 10 units, respectively. A pH-dependent Freundlich model was used to predict Zn 2+ and Cd 2+ ion activity in soil pore water. Total and radio-labile metal ion concentration in the solid phase was assumed to be adsorbed on the “whole soil,” humus, or free iron oxides to provide alternative model formats. The most successful models assumed that solubility was controlled by adsorption on soil humus. Inclusion of ionic strength as a model variable provided small improvements in model fit. Considering competition with Ca 2+ and between Zn 2+ and Cd 2+ produced no apparent improvement in model fit. Surprisingly, there was little difference between the use of total and labile adsorbed metal as a model determinant. However, this may have been due to a strong correlation between metal lability and pH in the data set used. Values of residual standard deviation for the parameterized models using labile metal adsorbed on humus were 0.26 and 0.28 for prediction of p (Cd 2+ ) and p (Zn 2+ ), respectively. Solubility control by pure Zn and Cd minerals was not indicated from saturation indices. However there may have been fixation of metals to non-radio-labile forms in CaCO 3 and Ca-phosphate compounds in the soils in the higher pH range. Independent validation of the Cd model was carried out using an unpublished data set that included measurements of isotopically exchangeable Cd. There was good agreement with the parameterized model.

Characterizing the availability of metals in contaminated soils. I. The solid phase: sequential extraction and isotopic dilution

The two approaches most commonly applied to characterizing the chemical form and ‘reactivity’ of metals in the soil solid phase are sequential extraction procedures (SEPs) and isotopic dilution (ID). The development and limitations of both approaches are described and their application to contaminated soils discussed. It may be argued that ID offers a better means of discriminating between ‘reactive’ and ‘inert’ forms of metal. However, the literature on SEPs is considerably larger, providing greater scope for comparative analysis of new data. Although ID methods are subject to operational constraints, the procedural dependency of SEPs is probably much greater. Thus greater effort has been expended to standardize and verify methodologies for SEPs. However, despite achieving a level of ‘political ratification’ at the procedural level, the use of SEPs within risk assessments for planning or development purposes is currently almost absent. The future for ID methods in this context may lie in site-specific risk assessments that include improved methods for the prediction of metal solubility and bioavailability.

Evaluating a free ion activity model applied to metal uptake by Lolium perenne L. grown in contaminated soils.

We investigated several formulations of the ‘free ion activity model’ (FIAM) as a means of describing plant uptake of soil Cd and Zn from contaminated soils. Lolium perenne was grown on a range of urban and metal-spiked agricultural soils selected to provide a wide range of Cd and Zn concentrations, pH values and other physico-chemical properties. Plants were grown under controlled conditions and above-ground biomass was harvested at regular intervals. Concentrations of Cd and Zn in the grass were compared with estimates of metal ‘capacity’ (total or radio-labile metal content in the soil) and ‘intensity’ (metal concentration in the soil solution or free divalent ion activity). The results suggested that ‘capacity’ terms alone were poor predictors of plant metal uptake (r2 values between 0.001 and 0.43), while metal ion ‘intensity’ provided quite reasonable predictions of the variation observed for several harvests of the grass (r2=0.60–0.87). Soil solution-to-plant transfer factors were highly pH-dependent which may suggest significant competition between trace metals and protons for sorption sites on roots. However, resolution of this question was confounded because of the strong co-variance between pH and p(M2+) in the soil pore water. Thus the influence of pH could not be separated from the effect of changing metal ion activity on uptake rate. Other possible effects on metal uptake such as dilution from increased biomass during growth and competition for uptake between different metal ions (Zn vs. Cd), or with Ca2+, appeared to play very minor roles in determining bioavailability. Several formulations of the FIAM failed to provide a consistently superior prediction of metal uptake when compared to purely empirical regression with pH and p(M2+) within the range of the data used to parameterise the models.

The assessment of point and diffuse metal pollution of soils from an urban geochemical survey of Sheffield, England

A model of soil variability as a continuous background process with superimposed point contamination was applied to 569 measurements of metal concentrations (Cr, Ni and Pb) in the topsoils of Sheffield, England. Robust estimators of the variogram were shown to be required to describe spatial variation of the metal concentrations at most sampled locations. This is diagnostic of the presence of a contaminant process. Values of the standardized kriging error from the cross-validation of each datum were used to identify spatial outliers for each metal. The ordinary kriged estimates of Cr, Ni and Pb were mapped after removing the outliers to estimate the background variation. Each of the 35 spatial outliers that occured in gardens have concentrations exceeding their Soil Guideline Value for residential land use with plant uptake, highlighting a potentially significant exposure pathway. The frequent observation of coal and furnace waste at these sites suggests that their dispersal, following domestic use and industrial processes, respectively, represents a significant point contaminant process. There was no evidence for spatial clustering of the point process. However, the spatial outliers of Cr and Ni showed a significant association with disturbed sites identified from historical land use maps, in part due to their prevalence in areas of historical steel manufacture. The magnitude of diffuse pollution for each metal in the urban soil was estimated by removing the spatial outliers and comparing robust measures of location with those from a survey of soils developed over the same parent materials in adjacent rural and peri-urban environments. The Winsorized mean Pb concentrations in urban topsoil (203 mg kg−1) were twice the value in the rural environment (101 mg kg−1), highlighting a very substantial diffuse Pb load to urban soils. The equivalent estimated diffuse components in urban soils for Cr and Ni were, respectively, 25% and 14% higher than the rural soils.

Urban geochemistry: research strategies to assist risk assessment and remediation of brownfield sites in urban areas.

Urban geochemical maps of Wolverhampton and Nottingham, based on multielement analysis of surface soils, have shown distribution patterns of “total” metals concentrations relating to past and present industrial and domestic land use and transport systems. Several methods have been used to estimate the solubility and potential bioavailability of metals, their mineral forms and potential risks to urban population groups. These include sequential chemical extraction, soil pore water extraction and analysis, mineralogical analysis by scanning electron microscopy, source apportionment by lead isotope analysis and the development of models to predict metal uptake by homegrown vegetables to provide an estimate of risk from metal consumption and exposure. The results from these research strategies have been integrated with a geographical information system (GIS) to provide data for future land-use planning.

Fractionation of lead in soil by isotopic dilution and sequential extraction

Environmental context The chemical reactivity of lead in soil is difficult to assess and depends on both soil conditions and the origins of the lead. This paper tests the combined application of lead isotopic techniques and chemical extraction against our understanding of lead fractionation in soils. Possibly against expectation, it appears that the ‘reactivity’ of lead can be high and yet there is tentative evidence that the original source of the metal affects its fractionation in soil, even after long contact times. Abstract ‘Reactivity’ or ‘lability’ of lead is difficult to measure using traditional methods. We investigated the use of isotopic dilution with 204Pb to determine metal reactivity in four soils historically contaminated with contrasting sources of Pb, including (i) petrol-derived Pb, (ii) Pb/Zn minespoil, (iii) long-term sewage sludge application and (iv) 19th century urban waste disposal; total soil Pb concentrations ranged from 217 to 13 600 mg kg–1. A post-spike equilibration period of 3 days and suspension in 5.0 × 10–4 M ethylenediaminetetraacetic acid provided reasonably robust conditions for measuring isotopically exchangeable Pb. However, in acidic organic soils a dilute Ca(NO3)2 electrolyte may be preferable to avoid mobilisation of ‘non-labile’ Pb. Results showed that the reactive pool of soil Pb can be a large proportion of the total soil lead content but varies with the original Pb source. A comparison of isotopic exchangeability with the results of a sequential extraction procedure showed that (isotopically) ‘non-labile’ Pb may be broadly equated with ‘residual’ Pb in organic soils. However, in mineral soils the ‘carbonate’ and ‘oxide-bound’ Pb fractions included non-labile forms of Pb. The individual isotopic signatures of labile and non-labile Pb pools suggested that, despite prolonged contact with soil, differences between the lability of the original contaminant and the native soil Pb may remain.

Kinetics of metal fixation in soils: Measurement and modeling by isotopic dilution

The bioavailability of metal contaminants in soils varies widely, depending on soil characteristics and the source of the contaminant. As a consequence, site-specific risk assessment requires accurate prediction of the bioavailable (or labile) fraction of soil metal. Moreover, metals in soil are subject to time-dependent processes, which affect their bioavailability and thereby complicate the prediction of future risk. The aim of the present study was to describe the development of simple, readily applicable models for the time-dependent changes in lability of Cd and Zn in soils. We present data showing the time-dependent behavior of radiolabile and soil solution concentrations of Cd and Zn during an incubation study over a period of 813 d in 23 diverse soils. The data are used to parameterize candidate models of metal fixation in soils designed to be readily applicable and therefore relevant to risk assessment. We conclude that the final extent of metal fixation increases with pH and generally is greater for Zn than for Cd; however, the rate of fixation is independent of pH and equivalent to a half-time to equilibrium of 29 and 89 d for Cd and Zn, respectively. It is possible that longer-term processes occur, especially for Zn, but these could not be detected in the present study.

Soil–plant interactions and the uptake of Pb at abandoned mining sites in the Rookhope catchment of the N. Pennines, UK : a Pb isotope study

This paper examines Pb concentrations and sources in soil, grass and heather from the Rookhope catchment in the North Pennines, UK, an area of historical Pb and Zn mining and smelting. Currently, the area has extensive livestock and sports shooting industries. Risk assessment, using the source-pathway-receptor paradigm, requires the quantification of source terms and an understanding of the many factors determining the concentration of Pb in plants. A paired soil and vegetation (grass and heather) geochemical survey was undertaken. Results showed no direct correlation between soil (total or EDTA extractable Pb) and vegetation Pb concentration. However, regression modelling based on the Free-Ion Activity Model (FIAM) suggested that the underlying mechanism determining grass Pb concentration across the catchment was largely through root uptake. Spatial patterns of (206/207)Pb isotopes suggested greater aerosol deposition of Pb on high moorland and prevailing wind facing slopes. This was evident in the isotopic ratios of the heather plants. Pb isotope analysis showed that new growth heather tips typically had (206/207)Pb values of ~1.14, whilst grass shoots typically had values ~1.16 and bulk soil and peat ~1.18. However, the (206/207)Pb ratio in the top few cm of peat was ~1.16 suggesting that grass was accessing Pb from a historical/recent pool of Pb in soil/peat profiles and consisting of both Pennine ore Pb and long-range Pb deposition. Isotope Dilution assays on the peat showed a lability of between 40 and 60%. A simple source apportionment model applied to samples where the isotope ratios was not within the range of the local Pennine Pb, suggested that grass samples contained up to 31% of non-Pennine Pb. This suggests that the historical/recent reservoir of non-Pennine Pb accessed by roots continues to be a persistent contaminant source despite the principal petrol Pb source being phased out over a decade ago.

Kinetics of zinc and cadmium release in freshly contaminated soils

The kinetics of metal release from the solid phase to solution was measured on two sets of 14 freshly contaminated soils with diverse properties. From measurements of metal concentrations in extracted soil pore water, the amount accumulated from the soil by diffusive gradients in thin-film (DGT) devices, and the distribution coefficient for labile metal, Kdl, estimated by isotopic exchange, we calculated the response time, Tc, of the soil-solution system to the removal of metal by DGT and the rate constant for release from the solid phase, k(-1). Resupply was so fast for Zn that Tc (and k(-1)) could be measured only in three of the soils, with either a silty or a sandy loam texture and low to intermediate pH (4.84-5.66). In only six clay soils was resupply of Cd too fast to measure. The generally slower release rates of Cd compared to Zn may reflect the 100-fold lower concentration of Cd, which allowed a greater proportion of it to occupy stronger binding sites with slower release rates. The rate constants derived indicate that supply from the solid phase to solution will not limit uptake of Cd or Zn by plants in clay soils, but it could be a factor in sandy or silty soils with a low pH. These findings suggest that risk assessment of clay soils could be undertaken using measurements of metals in soil solution. However, devices such as DGT, which respond to the kinetics of supply, are necessary to assess available metal in low pH, sandy, and silty soils.

Microscopic and chemical studies of metal particulates in tree bark and attic dust: evidence for historical atmospheric smelter emissions, Humberside, UK

Tree barks and attic dusts were examined as historical archives of smelter emissions, with the aim of elucidating the pathways of pollution associated with a plume of Sn and Pb contamination in top soils, found close to the former Capper Pass smelter, Humberside, UK. Samples were collected from three villages within the area of the contamination plume. Scanning electron microscopy (SEM) and bulk chemical analyses were used to assess particle type, number and deposition patterns. SEM analysis of dusts and bark revealed that Sn and Pb particles were present in samples from all three villages along with copper, zinc and iron particles. These were almost entirely <10 microm in diameter and occurred mostly as oxides, frequently forming clusters of sub-micron crystals. Samples further from the smelter contained considerably fewer particles. We present images of smelter derived Sn particles. Chemical assays of the barks and attic dusts demonstrated that concentrations of Sn, Pb, Cu, As, Sb and Cd diminished with increasing distance from the source. Strong positive correlations were found between Sn and Pb, As, Sb and Cd in the attic dusts. Enrichment factors (EF) were calculated for these trace elements based on topsoil element concentrations obtained from the soil survey of the study area. Decreases in these trace element concentrations and EF values with distance away from the smelter are consistent with trends found in the soil survey for Sn and Pb and are typical of deposition patterns around smelter stacks. The study demonstrates that tree bark and attic dusts can be effective archives of metal particulates deposited from large static emission sources.