Solid phase speciation of arsenic by sequential extraction in standard reference materials and industrially contaminated soil samples

Availability, mobility, (phyto)toxicity and potential risk of contaminants is strongly affected by the manner of appearance of elements, the so-called speciation. Operational fractionation methods like sequential extractions have been applied for a long time to determine the solid phase speciation of heavy metals since direct determination of specific chemical compounds can not always be easily achieved. The three-step sequential extraction scheme recommended by the BCR and two extraction schemes based on the phosphorus-like protocol proposed by Manful (1992, Occurrence and Ecochemical Behaviours of Arsenic in a Goldsmelter Impacted Area in Ghana, PhD dissertation, at the RUG) were applied to four standard reference materials (SRM) and to a batch of samples from industrially contaminated sites, heavily contaminated with arsenic and heavy metals. The SRM 2710 (Montana soil) was found to be the most useful reference material for metal (Mn, Cu, Zn, As, Cd and Pb) fractionation using the BCR sequential extraction procedure. Two sequential extraction schemes were developed and compared for arsenic with the aim to establish a better fractionation and recovery rate than the BCR-scheme for this element in the SRM samples. The major part of arsenic was released from the heavily contaminated samples after NaOH-extraction. Inferior extraction variability and recovery in the heavily contaminated samples compared to SRMs could be mainly contributed to subsample heterogeneity.     

Fractionation and speciation of arsenic in three tea gardens soil profiles and distribution of As in different parts of tea plant (Camellia sinensis L.)

The distribution pattern and fractionation of arsenic (As) in three soil profiles from tea (Camellia sinensis L.) gardens located in Karbi-Anglong (KA), Cachar (CA) and Karimganj (KG) districts in the state of Assam, India, were investigated depth-wise (0-10, 10-30, 30-60 and 60-100 cm). DTPA-extractable As was primarily restricted to surface horizons. Arsenic speciation study showed the presence of higher As(V) concentrations in the upper horizon and its gradual decrease with the increase in soil depths, following a decrease of Eh. As fractionation by sequential extraction in all the soil profiles showed that arsenic concentrations in the three most labile fractions (i.e., water-soluble, exchangeable and carbonate-bound fractions) were generally low. Most arsenic in soils was nominally associated with the organic and Fe-Mn oxide fractions, being extractable in oxidizing or reducing conditions. DTPA-extractable As (assumed to represent plant-available As) was found to be strongly correlated to the labile pool of As (i.e. the sum of the first three fractions). The statistical comparison of means (two-sample t-test) showed the presence of significant differences between the concentrations of As(III) and As(V) for different soil locations, depths and fractions. The risk assessment code (RAC) was found to be below the pollution level for all soils. The measurement of arsenic uptake by different parts of tea plants corroborated the hypothesis that roots act as a buffer and hold back contamination from the aerial parts.     

A test of sequential extractions for determining metal speciation in sewage sludge-amended soils

Sequential extraction procedures are widely used to estimate the quantity of trace metals bound to different solid fractions in contaminated soils. However, reliability of speciation of trace metals by these procedures remains largely unexamined. In the present study, the selectivity of each extraction step was tested by observing the effect of reversing the extraction order in the procedure. Two different sequential extraction methods and their reversed modes were used for metal fractionation in sewage sludge-amended soils. Significantly increased amounts of extractable metals (Cd, Cu, Pb and Zn) were evident in the sludge-amended soils compared to control soil by all extraction schemes; however, the amounts of metals extracted by each step were strongly dependent on the order of extraction, the type of reagents and the nature of the individual metals. Caution is advised in deducing the forms of soil metals from sequential extraction results from metal-contaminated soils.     

The impact of sequestration on the bioaccessibility of arsenic in long-term contaminated soils

Arsenic (As) contamination of soil poses a potential threat to human health, particularly for small children, through the incidental ingestion of soil from hand-to-mouth activity. In this study, we examined the relationship between As bioaccessibility using the simplified bioaccessibility extraction test (SBET) and the soil fractions that contribute to bioaccessible As in 12 long-term contaminated soils. Sequential fractionation of soils prior to As bioaccessibility assessment found that As was primarily associated with the specifically sorbed (3-26%), amorphous and poorly crystalline (12-82%), and the well crystalline (3-25%) oxyhydroxide Fe/Al phases with proportions varying depending on the mode of As input. Arsenic bioaccessibility in these soils ranged from less than 1% in the gossan soil to 48% in railway corridor soils. Soil fractions contributing to As bioaccessibility were found to be from the non-specifically (<1-11%), the specifically (<1-29%) sorbed and the amorphous and poorly-crystalline (30-93%) oxyhydroxide Fe/Al fractions. Significant correlations (p<0.05) were found between the As bioaccessible fraction and the amorphous and poorly-crystalline oxyhydroxide Fe/Al fractions indicating that this fraction is a key factor influencing As bioaccessibility in many anthropogenically contaminated soils.     

The solid-solution partitioning of heavy metals (Cu,Zn, Cd,Pb) in upland soils of England and Wales

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 (3.4-8.3) and LOI (9-98%). Soil metal contents measured by extraction with 0.43 mol l-1 HNO3 and 0.1 mol l-1 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=0.76-0.95) 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 solid-solution 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.     

Arsenic leachability and speciation in cement immobilized water treatment sludge

Arsenic leachability and speciation in cement immobilized water treatment sludge were investigated with leaching tests and X-ray absorption near edge structure (XANES) spectroscopy. The As leachability in the sludge determined with the toxicity characteristic leaching procedure (TCLP) and the waste extraction test (WET) was 283 and 7490 microgl(-1), respectively. Extractions with a lower liquid to solid ratio, under anaerobic conditions, and using citric acid buffer solution dramatically increased the leachate As concentration. XANES results showed that the As(III) composition was reduced from 51.1% of the total As content in the sludge to 16.3% in the cement treated sample with 28 days of cure. When the cement treated sample was cured for two years, the As(III) composition was decreased to 7.4%. The cement treatment reduced the As leachability. The leachate As(III) and total As concentrations were of the same order of magnitude in the samples cured for 28 days as for 2yr. However, consistently lower concentrations were detected in samples with longer cure time. The results of this study improve our understanding of arsenic speciation and leachability in the cement matrix after long cure times.     

Antimony availability in highly polluted soils and sediments - a comparison of single extractions

Forest/tilled soils and stream sediments from the highly polluted mining and smelting district of Príbram, Czech Republic, were subjected to single extraction procedures in order to determine the available contents of Sb and As. The results obtained from five widely-used 2-h single extraction tests were compared: deionised water, 0.01M CaCl(2), 1M NH(4)NO(3), 0.005M diethylentriaminpentaacetic acid (DTPA) and 0.1M Na(2)HPO(4). The ICP-MS determinations of Sb and As in the extracts were coupled with measurements of pH and Eh and geochemical modelling (PHREEQC-2) to determine their speciation in extracts and possible solubility-controlling phases. According to the speciation calculations, Sb in extracts was present mainly as Sb(V) with the exception of the DTPA extracts from highly organic and acidic forest soils, where Sb(III) species accounted for up to 34% of total Sb speciation. The highest extractabilities were observed for the 0.1M Na(2)HPO(4) solution (up to 9% of the total Sb and up to 34% of the total As concentration). The other extracting media yielded statistically the same results (p<0.05) with Sb extractabilities below 2% and As extractabilities below 8%. Thus, simple deionised water and 0.1M Na(2)HPO(4) extractions are preferred for quick estimates of easily-exchangeable and specifically-sorbed Sb, respectively.     

Arsenic release from flooded paddy soils is influenced by speciation, Eh, pH, and iron dissolution

Arsenic (As) is highly mobilized when paddy soil is flooded, causing increased uptake of As by rice. We investigated factors controlling soil-to-solution partitioning of As under anaerobic conditions. Changes in As and iron (Fe) speciation due to flooded incubation of two paddy soils (soils A and B) were investigated by HPLC/ICP-MS and XANES. The flooded incubation resulted in a decrease in Eh, a rise in pH, and an increase in the As(III) fraction in the soil solid phase up to 80% of the total As in the soils. The solution-to-soil ratio of As(III) and As(V) (R_L/S) increased with pH due to the flooded incubation. The R_L/S for As(III) was higher than that for As(V), indicating that As(III) was more readily released from soil to solution than was As(V). Despite the small differences in As concentrations between the two soils, the amount of As dissolved by anaerobic incubation was lower in soil A. With the development of anaerobic conditions, Fe(II) remained in the soil solid phase as the secondary mineral siderite, and a smaller amount of Fe was dissolved from soil A than from soil B. The dissolution of Fe minerals rather than redox reaction of As(V) to As(III) explained the different dissolution amounts of As in the two paddy soils. Anaerobic incubation for 30 d after the incomplete suppression of microbial activity caused a drop in Eh. However, this decline in Eh did not induce the transformation of As(V) to As(III) in either the soil solid or solution phases, and the dissolution of As was limited. Microbial activity was necessary for the reductive reaction of As(V) to As(III) even when Eh reached the condition necessary for the dominance of As(III). Ratios of released As to Fe from the soils were decreased with incubation time during both anaerobic incubation and abiotic dissolution by sodium ascorbate, suggesting that a larger amount of As was associated with an easily soluble fraction of Fe (hydr) oxide in amorphous phase and/or smaller particles.     

Speciation of scandium and gallium in soil

A method for the speciation of scandium and gallium in soil has been developed. The sequential extraction scheme of Tessier et al. for heavy metals was examined for the scandium and gallium separation. The regents proposed by Tessier were used for the extraction, and only for the residual fraction the HClO(4) was replaced with H(2)SO(4). The optimum conditions for leaching scandium and gallium from the soil were chosen for each fraction. Very sensitive, spectrophotometric methods based on the mixed complexes of Sc(III) and Ga(III) with Chrome Azurol S and benzyldodecyldimethylammonium bromide were applied for the scandium and gallium determination after their separation by solvent extraction. 100% mesityl oxide and a 0.5M solution of 2-thenoyltrifluoroacetone in xylene were chosen for the extraction of scandium and butyl acetate was selected for gallium. Soil samples from two different regions of Poland were the object of this research. The content of scandium and gallium found in the individual fractions of Upper Silesia soil (industrial region) was [in mugg(-1)] Sc: I, 1.52; II, 0.53; III, 7.78; IV, 1.79; V, 0.20; Ga: I, 24.7; III, 29.2; IV, 35.4; V, 6.9. In Podlasie soil (agricultural region), the content of both elements was clearly lower. The total content of scandium and gallium in the five soil fractions was in good correlation with the total content of these elements in the soils found after HF-H(2)SO(4) digestion. Analysis using the ICP-OES method gave comparable results.     

EDTA强化电动力学修复重金属复合污染土壤

在自制的电动力学装置中,研究多种重金属复合污染土壤的电动力学修复,通过在阴极添加络合剂EDTA来提高修复效率。实验结果表明,EDTA的引入提高了修复过程中的电流值,且EDTA与重金属的络合提高了污染物向电极液的迁移效率,从而强化了电动力学修复效果。在设定的浓度(0、0.01、0.02、0.05和0.1 mol/L)中,0.1 mol/L的EDTA具有最佳的修复效率。在此实验条件下,污染土壤中的总铜、总铅和总镉的去除率分别为90.2%、68.1%和95.1%。电动力学修复后,对土壤重金属进行化学形态分析,发现电动力学修复显著改变了土壤重金属存在形态,修复后土壤中的铜、铅、镉主要以较稳定的有机态和残余态形式存在,显著降低了对周边生物和环境的毒害。     

The ageing effect on the bioaccessibility and fractionation of arsenic in soils from China

Ingestion of contaminated soil has been recognized as an important exposure pathway of arsenic for humans, especially for children through outdoor hand-to-mouth activities. An improved sequential extraction procedure was employed in an attempt to reveal the relationship between bioaccessibility and fractionation of As in five soils from China. Arsenic bioaccessibility in acidic ( approximately pH 4.5) soils reached approximately stable levels after a sharp decline within one week of ageing. In contrast, As bioaccessibility in higher pH (>6.0) soils was found to be significantly higher and took two weeks of ageing to reach stable levels. The artificially added As was more labile than indigenous As. The main proportions of added As were found in the specifically sorbed and amorphous and poorly-crystalline hydrous Fe/Al oxide-bound fractions. Correlation analysis shows that the non-specifically and specifically sorbed As are likely to constitute the main proportion of bioaccessible soil As. The soil content of amorphous and crystalline Fe/Al oxides and soil pH appear to be the key factors controlling, not only the time needed to reach a steady state, but also the magnitude of the bioaccessibility of As added to the soils.     

Chemical speciation and extractability of Zn,Cu and Cd in two contrasting biosolids-amended clay soils

An incubation experiment was conducted to study the chemical speciation and extractability of three heavy metals in two contrasting biosolids-amended clay soils. One was a paddy soil of pH 7.8 and the other was a red soil of pH 4.7 collected from a fallow field. Anaerobically digested biosolids were mixed with each of the two soils at three rates: 20, 40 and 60 g kg(-1) soil (DM basis), and unamended controls were also prepared. The biosolids-amended and control soils were incubated at 70% of water holding capacity at 25 degrees C for 50 days. Separate subsamples were extracted with three single extractants and a three-step sequential extraction procedure representing acetic acid (HOAc)-soluble, reducible and oxidisable fractions to investigate the extractability and speciation of the heavy metals. As would be expected, there were good relationships between biosolids application rate and metal concentrations in the biosolids-amended soils. The three heavy metals had different extractabilities and chemical speciation in the two biosolids-amended soils. Ethylene diamine tetraacetic acid extracted more Cu, Zn and Cd than did the other two single extractants. The oxidisable fraction was the major fraction for Cu in both biosolids-amended soils and the HOAc-soluble and reducible fractions accounted for most of the Zn. In contrast, Cd was present mainly in the reducible fraction. The results are discussed in relation to the mobility and bioavailability of the metals in polluted soils.     

Evaluation of various chemical extraction methods to estimate plant-available arsenic in mine soils

Elevated levels of bioavailable As in mining soils, agricultural areas and human habitats may cause potential toxicity to human health, plants and microbe. Therefore, it is essential to determine proper soil chemical extraction method in order to estimate plant-available As in mining soils and protect agricultural and environmental ecosystems by evaluation of environmental risk and implementation of remediation measures. In this study, six single soil chemical extraction processes and four-step sequential chemical extraction protocol were used to determine the relative distribution of As in different chemical forms of soils and their correlations with total As in plants grown in mining areas and greenhouse experiments. The strongest relationship between As determined by single soil chemical extraction and As in plant biomass was found for sodium acetate and mixed acid extractant. The mean percent of total As extracted was: ammonium oxalate (41%)>hydroxylamine hydrochloride (32%)>mixed acid (16%)>phosphate (6%)>sodium acetate (1.2%)>water (0.13%). This trend suggests that most of the As in these soils is inside the soil mineral matrix and can only be released when iron oxides and other minerals are dissolved by the stronger chemical extractant. Single soil chemical extraction methods using sodium acetate and mixed acids, that extract As fractions complexed to soil particles or on the surface of mineral matrix of hydrous oxides of Fe, Mn and Al (exchangeable+sorbed forms) can be employed to estimate and predict the bioavailable As fraction for plant uptake in mining affected soils. In sequential chemical extraction methods, ammonium nitrate and hydroxylamine hydrochloride may be used to provide closer estimates of plant-available As in mining soils.     

Speciation distribution and mass balance of copper and zinc in urban rain, sediments, and road runoff

Heavy metal pollution in road runoff had caused widespread concern since the last century. However, there are little references on metal speciation in multiple environmental media (e.g., rain, road sediments, and road runoff). Our research targeted the investigation of metal speciation in rain, road sediments, and runoff; the analysis of speciation variation and mass balance of metals among rain, road sediments, and runoff; the selection of main factors by principal component analysis (PCA); and the establishment of equation to evaluate the impact of rain and road sediments to metals in road runoff. Sequential extraction procedure contains five steps for the chemical fractionation of metals. Flame atomic absorption spectrometry (Shimadzu, AA-6800) was used to determine metal speciation concentration, as well as the total and dissolved fractions. The dissolved fractions for both Cu and Zn were dominant in rain. The speciation distribution of Zn was different from that of Cu in road sediments, while speciation distribution of Zn is similar to that of Cu in runoff. The bound to carbonates for both Cu and Zn in road sediments were prone to be dissolved by rain. The levels of Cu and Zn in runoff were not obviously influenced by rain, but significantly influenced by road sediments. The masses for both Cu and Zn among rain, road sediments, and road runoff approximately meet the mass balance equation for all rainfall patterns. Five principal factors were selected for metal regression equation based on PCA, including rainfall, average rainfall intensity, antecedent dry periods, total suspended particles, and temperature. The established regression equations could be used to predict the effect of road runoff on receiving environments.     

Cadmium in soil solutions from a transect of soils away from a fertiliser bin

The effects of high inputs of phosphate fertiliser on Cd concentrations were studied in soil solutions extracted from topsoils. Soils were sampled along a transect at distances of 1-100 m away from a fertiliser bin. The transect was sampled four times during 1 year. Soil solutions were analysed for Cd, pH, major cations and anions, and other heavy metals (As, Cr, Cu, Pb). For one of the transect samplings, soil total Cd, Cr, Cu, Pb and P were also measured. Cd speciation in the soil solutions was calculated by the GEO-CHEM-PC computer program. Chemical composition varied substantially along the transect, and also between samplings, indicative of seasonal effects and the influence of a fresh application of superphosphate fertiliser during the year. Application of fertiliser decreased soil solution pH and increased the levels of heavy metals in soil solution. Generally, soil total Cd, Cr, Cu, Pb, and P decreased with increasing distance from the fertiliser bin. Correlations between P and the four heavy metals were: P and Cd (R2 = 0.978), P and Cr (R2 = 0.712), P and Pb (R2 = 0.538), P and Cu (R2 = 0.267). Less than 1% of the total Cd in the soil samples was found in the soil solution. The free metal ion Cd2+ accounted for 55-90% of solution Cd. Of the complexed species of Cd, the chloride and sulphate complexes were usually the most important, even when nitrate and phosphate concentrations were relatively high. The presence of As, Cr, Cu and Pb had no effect on Cd speciation.     

Thallium in fractions of soil formed on floodplain terraces

Two soils formed on the floodplain terrace of a rivulet flowing through the zinc-lead ore exploration area polluted with thallium and one soil from a floodplain terrace of the reference area were investigated in terms of thallium distribution between soil fractions. Such type of soil is formed on river floodplain terraces next to the main river channel and its composition records the history of river pollution. A sequential extraction of soil according to the BCR protocol was performed with an additional initial stage of extraction with water. Apart from labile thallium, thallium entrapped in the residual parent matter was also determined. Thallium was determined by flow-injection differential-pulse anodic stripping voltammetry. In all three cases, the major fraction is thallium entrapped in parent matter. Top soil from the polluted area contains 49.3% thallium entrapped in the residual parent matter, the bottom soil contains 41% while the reference soil contains 80% in this fraction. The major part of labile thallium is located in the reducible fraction (27.7% of total thallium in the top soil, 27% in the bottom soil and 12.4% of the reference soil). Second in terms of significance is the fraction of oxidizable thallium. The top soil contains 12% of total thallium concentration, the bottom soil contains 19% of total concentration, while the reference soil contains 4.1% of total concentration. The acid soluble/exchangeable fraction of thallium has almost the same significance as the oxidizable fraction. The top soil contains 10.4% of the total concentration, while the bottom soil contains 12% of the total concentration. Water soluble thallium concentration is very small. Comparison of the top and the bottom soil show that thallium has not been transported from the river channel onto the floodplain terrace over a long period.     

Retention and distribution of heavy metals in mangrove soils receiving wastewater

The distribution and chemical fractionation of heavy metals retained in mangrove soils receiving wastewater were examined by soil column leaching experiments. The columns, filled with mangrove soils collected from two swamps in Hong Kong and the People's Republic of China, were irrigated three times a week for 150 days with synthetic wastewater containing 4 mg l(-1) Cu, 20 mg l(-1) Zn, 20 mg l(-1) Mn and 0.4 mg l(-1) Cd. Soil columns leached with artificial seawater (without any heavy metals) were used as the control. At the end of the leaching experiments, soil samples from each column were divided into five layers according to its depth viz. 0-1, 1-3, 3-5, 5-10 and > 10 cm, and analyzed for total and extractable heavy metal content. The fractionation of heavy metals in the surface soil samples (0-1 cm) was investigated by the sequential extraction technique. In both types of mangrove soils, the surface layer (0-1 cm) of the columns receiving wastewater had significantly higher concentrations of total Cu, Cd, Mn and Zn than the control. Concentrations declined significantly with soil depth. The proportion of exchangeable heavy metals in soils receiving wastewater was significantly higher than that found in the control, about 30% of the total heavy metals accumulated in the soil masses of the treated columns were extracted by ammonium acetate at pH 4. The sequential extraction results show that in native mangrove soils (the soils without any treatment), the major portion of Cu, Zn, Mn and Cd was associated with the residual and precipitated fractions with very low concentrations in more labile phases. However, in mangrove soils receiving wastewater, a significantly higher percentage of Mn, Zn and Cd was found in the water-soluble and exchangeable fractions. Copper appeared to be more strongly adsorbed in mangrove soils than the other heavy metals. In general, heavy metal accumulation in the surface mangrove soils collected in Hong Kong was higher than those in the PRC, although the metals in the latter soil type were more strongly bound. These findings suggest that whether the heavy metal retained in managrove soils becomes a secondary source or a permanent sink would depend on the kinds of heavy metals and also the types of mangrove soils.     

Comparison between fractionation and bioavailability of trace elements in rhizosphere and bulk soils

Rhizosphere is a microbiosphere and has quite different chemical, physical and biological properties from bulk soils. A greenhouse experiment was performed to compare the difference of fractionation and bioavailability of trace elements Cr, Ni, Zn, Cu, Pb and Cd between rhizosphere soil and bulk soil. In the meantime, the influence of air-drying on the fractionation and bioavailability was also investigated by using wet soil sample as a control. Soils in a homemade rhizobox were divided into four zones: rhizosphere, near rhizosphere, near bulk soil and bulk soil zones, which was designated as S1, S2, S3 and S4. Elemental speciations were fractionated to water soluble, exchangeable and carbonate bound (B1), Fe-Mn oxide bound (B2), and organic and sulfide bound (B3) by a sequential extraction procedure. Speciation differences were observed for elements Cr, Ni, Zn, Cu, Pb and Cd between the rhizosphere and bulk soils, and between the air-dried and wet soils as well. The concentrations of all six heavy metals in fraction B1 followed the order of S2 > S3 > S1 > S4 and for B2, the order was S2 > S3 S4 > S1. For B3, the order was S1 > S3 S4 > S2, while for Cd the order was S2 > S3 approximately/= S4 > S1. The air-drying increased elemental concentration in fractions B1 and B2 by 20-50% and decreased in fraction B3 by about 20-100%. Correlation analysis also indicated that the bioavailability correlation coefficient of fraction B1 in rhizosphere wet soil to plants was better than that between either air-dried or nonrhizosphere soils. Therefore, application of rhizosphere wet soils should be recommended in the future study on the speciation analysis of trace elements in soils and bioavailability.     

Speciation of zinc in contaminated soils

The chemical speciation of zinc in soil solutions is critical to the understanding of its bioavailability and potential toxic effects. We studied the speciation of Zn in soil solution extracts from 66 contaminated soils representative of a wide range of field conditions in both North America and Europe. Within this dataset, we evaluated the links among the dissolved concentrations of zinc and the speciation of Zn(2+), soil solution pH, total soil Zn, dissolved organic matter (DOM), soil organic matter (SOM) and the concentrations of different inorganic anions. The solid-liquid partitioning coefficient (K(d)) for Zn ranged from 17 to 13,100Lkg(-1) soil. The fraction of dissolved Zn bound to DOM varied from 60% to 98% and the soil solution free Zn(2+) varied from 40% to 60% of the labile Zn. Multiple regression equations to predict free Zn(2+), dissolved Zn and the solid-liquid partitioning of Zn are given for potential use in environmental fate modeling and risk assessment. The multiple regressions also highlight some of the most important soil properties controlling the solubility and chemical speciation of zinc in contaminated soils.     

Influence of ozonation on extractability of Pb and Zn from contaminated soils

The effect of soil ozonation on Pb and Zn extraction with EDTA, bioavailability (Ruby's Physiologically Based Extraction Test, PBET) and mobility (Toxicity Characteristic Leaching Procedure, TCLP) of Pb was studied on contaminated soils taken from 7 different locations in the Mezica Valley, Slovenia. EDTA extraction (40 mmol kg(-1)) removed from 27.4+/-1.5% to 64.8+/-1.5% of Pb, and from 1.9+/-0.2% to 22.4+/-2.0% of Zn from tested soils, and significantly reduced soil Pb bioavailability (PBET) and mobility (TCLP). Pretreatment of tested soils with ozone before EDTA extraction enhanced EDTA extractability of Pb for 11.0 to 28.9%, but had no effect on the extractability of Zn. In most of the soils, ozonation had no statistically significant effect on bioavailability and mobility of Pb, residual after EDTA extraction. Using linear regression analysis we found a significant increase (p<0.01) in EDTA extractability of Pb after soil ozonation in soils with a higher initial Pb content. EDTA extractability of Pb after soil ozonation was also significantly higher for soils with a lower Pb extractability when treated with EDTA alone. We found no correlation between soil organic matter content and the percentage of the Pb fraction bound to soil organic matter (where from 25.6+/-1.3% to 73.2+/-0.6% of Pb reside in tested soils) and Pb extractability with EDTA after soil ozonation.