Labile rhizosphere soil solution fraction for prediction of bioavailability of heavy metals and rare earth elements to plants

A labile rhizosphere soil solution fraction has been recommended to predict the bioavailability of heavy metals and rare earth elements to plants. This method used moist rhizosphere soil in combination with a mixture of 0.01 mol L(-1) of low-molecular-weight organic acids (LMWOAs) as extractant. The extracted soil solutions were fractionated into two colloidal fractions of <0.45 microm (F(3)) and <0.2 microm (F(2)), and one truly dissolved fraction including free metal ions and inorganic and organic complexes (fractionr(0.2 microm, LMWOAs) approximately r(0.45 microm, LMWOAs). In the case of rare earth elements the good correlation was obtained for both the wheat roots and shoots. Generally, the correlation coefficients obtained by LMWAOs were better than that obtained by the first step of BCR method. Therefore, LMWAOs and F(lrss) were strongly recommended to predict the bioavailability of metals in soil pools to plants.     

Sources of 137Cs fluvial export from a forest catchment evaluated by stable carbon and nitrogen isotopic characterization of organic matter

Fluvial export of particulate and dissolved ¹³⁷Cs was investigated to reveal its sources and transfer mechanisms in a broadleaved forest catchment using a continuous collection system. The finest size fraction (<75 µm), consisting of decomposed litter and surface mineral soil, was the dominant fraction in the particulate ¹³⁷Cs load, although the contribution of coarser size fractions increased during high water discharge in 2014. The dissolved ¹³⁷Cs originated from the decomposition of ¹³⁷Cs-contaminated litter. Temporal changes in ¹³⁷Cs distribution in the litter–mineral soil system indicated that the dissolved ¹³⁷Cs load will be moderated in several years, while particulate ¹³⁷Cs load has the potential to continue for a long time.

     

Pollution at and below Sites used for Mixing and Loading of Pesticides

Sites used for mixing and loading of pesticides in sprayers and for washing tractors and sprayers may be point sources of pesticides. Pollution may be caused by accidental spills during filling, disposal of excess spray solution, rinsing of sprayer and tractor or from leaking nozzles on the sprayer. Ground water sampled 2-4 m below sites used for mixing and loading has been analysed for 23 or 46 different pesticides and metabolites in two Danish counties (Storstrøm and Bornholm). Further, the surface pollution at sites used for mixing, loading and rinsing was determined by elution with water of soil sampled in the top 10 cm. In all ground water samples pesticide pollution was determined to be above the European drinking water level (0.1 µg L m 1 ). The highest concentrations and most pesticides were found below loading and mixing sites at machine pools, where the highest concentrations were the phenoxyacid herbicides dichlorprop (750 µg L m 1 ) and 2,4-D (800 µg L m 1 ). The herbicides bentazone, mecoprop and dinoseb were also found in relatively high concentrations (5-60 µg L m 1 ). The surface soil sampled at the top 0-10 cm at sites used for loading and washing sprayers at six farms was eluted with water. These analyses also showed that many different pesticides and relatively high concentrations could be leached out from the soil. Twenty-four different pesticides and metabolites were found, and though most concentrations were below 10 µg L m 1 about 10% of the water samples contained more than 50 µg L m 1 . The results demonstrate that sites used for mixing, loading and washing can be seriously contaminated with pesticides even in ground water 2-4 m below the sites. This implies that ground water, nearby wells and well borings are at risk of pollution and indicates the need for better farm practice.     

Chemical Characterization of Silage Effluents and their Influence on Soil Bound Heavy Metals

Abstract

Silage effluents, generated during silaging of various crops, are produced in high amounts in cattle breeding farms. Due to their acidity and high content of dissolved organic matter, they are causing disposal problems. On the other hand, their ability to mobilise soil bound trace elements (i.e. heavy metals) might be useful for the decontamination of polluted soils.

With an aim to perform metal leaching studies, silage effluents from various ensiled crops (maize, rape, grass, clover, sugar-beet leaves) were collected from Bavarian farms and analysed for their main inorganic and organic constituents. Important TOC sources (TOC concentrations from 13.9 to 53.6 gl^?1) are short chain aliphatic acids (concentrations between 235 and 638 mM·D1^?1; predominant compound: lactic acid), amino acids (ranging from 22.8 to 151 mM·D1^?1) and polypeptides (concentrations from 3.8 to 20.0 g·D1^?1).

The release of heavy metals from two adsorbents (bentonite and peat) and from a polluted soil under the influence of silage effluents was studied in batch tests. The leaching efficiencies for the soil bound metals increase following the order: sugar-beet leaves < clover < maize < rape < grass. The extraction rates obtained with grass silage juice are: Cd 74.7%, Zn 55.7%, Cu 53.5%, Ni 38.9%, Cr 12.7% and Pb 8.9%. After neutralisation the leaching rates dropped, with the exception of copper.     

Separation and quantification of quantum dots and dissolved metal cations by size exclusion chromatography–ICP-MS

The prevalence of engineered metallic nanoparticles within electronic products has evoked a need to assess their occurrence and fate within environmental systems upon potential release of these nanoparticles. Quantum dots (QDs) are mixed-metal nanocrystals with the smallest of particle sizes (2–10 nm) that readily leach heavy metal cations in water, potentially creating a co-occurrence of nanoparticulate and dissolved metal pollutants. In this report, we develop a size exclusion chromatography–inductively coupled plasma–mass spectrometry method (SEC-ICP-MS) for the rapid separation and quantification of ~5-nm-sized CdSe/ZnS QDs and dissolved Cd²⁺ and Zn²⁺ cations in water. The SEC-ICP-MS method provided a wide chromatographic separation of CdSe/ZnS QDs and dissolved Cd²⁺ and Zn²⁺ cations only when using the smallest SEC column pore size available and an eluent composition that prevented loss of metals to column polymer surfaces by using a surfactant to ensure elution of QDs (ammonium lauryl sulfate) and a complexing ligand to ensure elution of metal cations (ethylenediaminetetraacetate). Detection limits were between 0.2 and 2 µg L^–1 for Cd²⁺ and Zn²⁺ among dissolved cation and QD phases, and ranges of linearity covered two to three orders of magnitude. Gold nanoparticles of sizes 5, 10, 20 and 50 nm were also effectively separated from dissolved Au³⁺ cations, illustrating the method applicability to a wide range of nanoparticle sizes and compositions. QD and dissolved metal concentrations measured by SEC-ICP-MS were comparable to those measured using the more conventional method of centrifuge ultrafiltration on split samples for dissolved and total metals. The applicability of the SEC-ICP-MS method to environmental systems was verified by measuring QDs and dissolved metals added to samples of natural waters. The method was also applied to monitoring CdSe/ZnS dissolution kinetics in an urban river water. The SEC-ICP-MS developed here may offer improved automation for characterising heterogeneous suspensions containing >1 µg L^–1 heavy metals.     

Association of uranium with colloidal and suspended particulate matter in Arabian sea near the west coast of Maharashtra (India)

The purpose of the present study is the association of natural uranium in seawater with colloidal and suspended-particulate matter was determined. The separation of suspended particulate material (>0.45 µm) and colloidal fraction (as dissolved fractions) in seawater were done by suction and ultra filtration techniques. Seawater samples were collected at 1 km away from the shore and subjected to sequential fractionation in nine stages ranging from 2.7 µm to 1.1 nm. Suspended particulate matter were separated in three different size groups namely >2.7 µm, <2.7–>0.45 µm and <0.45–>0.22 µm by suction filtration using cellulose acetate and nitrate membranes filters. To concentrate the solution with colloidal particles <0.22 µm–1.1 nm (0.5 k Nominal Molecular Weight cut-off Limit {NMWL}), the solution obtained from filtration through <0.22 µm was passed through stirred ultra-filtration cell. The pH and conductivity at different stages of fractionation (dissolved) showed minor variations. The concentration of uranium was measured in suspended and dissolved fractions by using a pulsed nitrogen laser at 337.1 nm. In order to evaluate the role of mineral colloids in various stages of filtration, concentration of calcium, magnesium, potassium were measured by using ion chromatography and atomic absorption spectrometry. The clay mineral at seawater pH (approximately 8) behave as negative ions and provides binding site for the positively charge species of uranium. Among the dissolved fraction, the maximum concentrations of colloidal uranium was observed about 4 times higher than that compared to average concentration of 6.93±3.10 ppb in other fractions. In the case of suspended particulate matter, the concentration of uranium was below detection limits (<1 ppb). The maximum concentration of Ca, Mg and K in the dissolved fraction were in the <1.1 nm fraction, while for suspended particulate matter, the concentration of Ca, Mg and K decreased with the decrease in size and it is highest in the fraction of 0.22 –0.45 µm.This revised version was published online in November 2005 with corrections to the Cover Date.     

Effect of Liquid Animal Manure Application on the Solubilization of Heavy Metals from Soil

Abstract

The effect of liquid animal manure on heavy metal solubilization in soil has been studied in the laboratory; three different types of experiments were carried out:

1) aerobic and anaerobic incubation of soil/manure mixtures

2) desorption of heavy metals from soil, as affected by manure liquid fraction

3) gel permeation chromatography of soil/manure aqueous extracts to identify components responsible for heavy metal solubilization.

Alf three different approaches showed that complexation involving high molecular weight dissolved organic matter from the soil/manure matrix is (together with pH) the most important driving force for heavy metal solubilization. As a consequence, chemical and microbial processes (e.g. nitrification) that influence dissolved organic matter concentrations in the soil solution, determine the degree of heavy metal solubilization in manured soil.     

The microenvironment of iron in (Ba,Ca)(Fe,Co)O3−δ catalyst system: A Mössbauer study

Undisturbed, non-fertilized woodland soil (“loamy sandy soil” type) from 1 m below surface was dry and wet sieved. Sieving fractions of <10–1000 μm were analyzed for total alpha-activity. Thorium and uranium contents were determined by alpha-spectrometry after radiochemical separation. Soluble and insoluble parts of thorium and uranium were determined in the sieved fractions indicating that the isotope distribution in soil correlates with the particle size distribution: The smaller the size fraction the higher the isotope content. Isotope ratios of²²⁸Th/²³²Th, and²³⁴U/²³⁸U are discussed.     

Membrane Filtration of Iron(III), Copper(II) and Lead(II) Ions as 1‐(2‐Pyridylazo) 2‐Naphtol (PAN) for Their Preconcentration and Atomic Absorption Determinations

A membrane filtration procedure for the preconcentration and atomic absorption spectrometric determination of Pb(II), Co(II) and Fe(III) ions in natural water samples has been established. Cellulose nitrate membrane filters (0.45 μm and 47 mm diameter) were used in all experiments. The procedure is based on chelate formation of the analyte metals with 1‐(2‐pyridylazo) 2‐naphtol (PAN) and on retention of the chelates on cellulose nitrate membrane filter. The cellulose nitrate membrane and analyte ions were completely dissolved by 500 μL of nitric acid at 85 °C on a hood and then metal determinations were performed by flame atomic absorption spectrometry. The method was applied to natural water samples for the determination of analyte ions with satisfactory results, e.g., recoveries > 95%, RSD's < 10%.     

Distribution of Heavy Metal Contents and Chemical Fractions in Anaerobically Digested Manure Slurry

Digested slurry samples from twenty-one large-scale anaerobic digestion plants together with intensive pig and dairy farms in Jiangsu Province of China were collected and analyzed for total and dissolved concentrations of Zn, Cu and As, as well as chemical characteristics. The results showed that total concentrations of Zn, Cu and As in digested pig slurries were concentrated to <10, <5 and 0.02–0.1 mg/l, respectively; while <2 and 10–30, <1, and 0.02–0.1 mg/l, respectively, in digested dairy slurries. Lowering the dietary supply of these elements to pig and dairy would be the most effective way to control heavy metal contents in digested manure slurries. Dissolved fractions of Zn, Cu and As accounted for 1–74%, 1–33% and 2–53% of the total concentrations, respectively, in digested pig slurries; and 18–65%, 12–58% and 3–68% in digested dairy slurries. The chemical fractions of heavy metals in digested slurries were not only dependent on the total concentrations of heavy metals in raw manures but also on conditions of digestion and storage. Oxidation pond systems could significantly cripple the total contents of heavy metals in digested slurries, and the removal effect was better in multi-oxidation-pond systems than that in primary-oxidation-pond systems. However, the chemical fractions of heavy metals in digested slurries changed in a complicated manner when stored in oxidation ponds, due to the suspended solid deposition, elements reduction, as well as variations of pH values and oxidation-reduction potential.     

Metal distribution and binding in balneological peats and their aqueous extracts

Binding of metals in typical bath peat samples (“Großes Gifhorner Moor”, Sassenburg/North Germany) and their aqueous extracts was characterized by means of a multi-method approach. For that purpose a sequential extraction procedure based on peat-filled chromatography columns was developed. Water-soluble metal and DOM (dissolved organic matter) fractions were subdivided by use of a stepwise increased pH gradient (pH 3.8–5), finally by the chelator EDTA and 0.1 mol L^–1 hydrochloric acid. Metal fractions very strongly bound to peat were assessed by an aqua regia extraction. Metal determinations required were performed by atomic spectrometry methods (AAS, ICP–OES, and TXRF). The metal and DOM concentrations in the peat extracts varied significantly, depending on the natural variety of the peat matter under study (e.g., Al: 25–674, Cd: 0.05–0.2, Cu: 5– 15.4, Fe: 77–1785, Mn: 21–505, Ni: 2–33, Pb: < 1, Zn: 9– 715 (μg L^–1); Na: 8–45, K: 1.3–14.9, Ca: 2–51, Mg: 1.1– 7.9 (mg L^–1); 26–73 mg L^–1 DOC). An increase of the pH increased the DOC (dissolved organic carbon) of the peat extracts, but hardly the concentration of heavy metals. The latter could only be re-mobilized by EDTA and dilute hydrochloric acid. Additional investigations of the peat extracts using tangential-flow ultrafiltration revealed that the heavy metals extracted at pH < 4 were predominantly dissociated. At higher pH (pH > 4.5) they were preferentially bound to macromolecular DOM. Moreover, using multistage ultrafiltration the size distribution of the DOM and their metal species was assessed.     

Determination of Heavy Metals in Bio-Collectors as Indicator of Environmental Pollution

The heavy metal levels in bio-collector ( Fabaceae Rabinia Pseudoacacia L. sprouts) samples collected from seven sites, which had the characteristic properties of the Sivas city, Turkey, in year 2000, have been determined by atomic absorption spectrometry (AAS), after the bio-collector sprouts were prepared for analysis by bio-collector-ultrasonic leaching method (BC-ULM). The results of the analyses were used to determine major sources and magnitude of heavy metal pollution. The mean concentration levels of Pb, Cu, Ni, Zn and Cd were found to be 6.8, 5.5, 6.7, 12.4 and 0.20 µg/g fresh bio-collector, respectively, for September 2000. The highest levels of the heavy metals at the sites affected by industrial emissions and heavy traffic were noted. The heavy metal levels in urban bio-collectors were several times higher than the background levels. After heavy metal pollution factors of each site were determined, their possible major pollutant sources were discussed.     

Essential oil and fractions isolated of Laurel to control adults and larvae of cattle ticks

Abstract

This study, was to evaluate the acaricidal effect of the essential oil (EO) and fractions (FR) obtained from Laurus nobilis leaves on Rhipicephalus (Boophilus) microplus. Eight fractions were obtained, however FR1: sabinene (37.83%), β-pinene (13.50%), 1,8-cineole (12.66%), α-pinene (12.56%) and FR8: α-terpineol (79.19%) were highlighted as to the larvicidal potential when submitted by Larval Packet Test. The EO was tested by the Adult Immersion Test, at concentrations of 200.00; 100.00 and 50.00?µL/mL caused mortality of engorged females, egg mass reduction and hatching inhibition. Two fractions are shown to be efficient in controlling larvae FR8 (LC₅₀?=?0.13?µL/mL, LC₉₉?=?0.51?µL/mL) and FR1 (LC₅₀?=?0.20?µL/mL, LC₉₉?=?0.56?µL/mL). The fractionation of EO was determinant to elucidate which compounds were responsible for the larvicidal potential. This study opens new perspectives to direct new bioassays with the compounds obtained in the fractionation, since they present high potential on cattle tick larvae.     

Properties and binding forms of cadmium and nickel in protein extracts from bean seeds (Phaseolus vulgaris L.)

A special ultrafiltration procedure in combination with photometry and atomic absorption spectrometry is described. This technique allows not only the determination of the qualitative distribution patterns of metals but also of the quantitative binding parameters of these metals to functional groups of organic compounds. The technique was applied to protein extracts of bean seeds (Phaseolus vulgaris L.). The results show that Cd and Ni have different binding mechanisms in these seeds. Both metals differ not only in their preferred binding behaviour to certain molecular size fractions but also in their potential binding sites and the binding properties. Whereas Cd in seeds from Cd-treated plants prefers binding partners with molecular weights >30 kD and <0.5 kD, Ni is preferably bound to compounds with molecular weights <5 kD. Cd exhibits a tendency to bind more selectively to sulfhydryl groups, but Ni more to non-specific binding sites. Sulfhydryl groups account for 71% of the total capacity for Cd whereas for Ni it is only 36%.     

Continuous sonoassisted digestion coupled to flow injection minicolumn separation for the determination of total and labile Cu and Fe in fresh waters by flame atomic absorption spectrometry

An automatic on-line system is developed for the trace determination of copper and iron species in fresh waters by flame atomic absorption spectrometry using only 5 and 2?mL of sample, for copper and iron determination, respectively. This system, which includes a home-made minicolumn of commercially available resin containing aminomethylphosphonic acid functional groups (Chelite P), comprises two operational modes. The first, used for the determination of the dissolved labile fraction (free copper and iron ions and their weak complexes) is based on the elution of this fraction from a minicolumn containing the chelating resin loaded in-situ with the sample. The second mode is used for the determination of total trace copper and iron concentrations. This last mode is based on the retention/preconcentration of total metals on the Chelite P resin after on-line sonoassisted digestion of water samples acidified with nitric acid (0.5?mol?L^?1 final concentration) to break down metal organic complexes present in fresh waters as river waters. The figures of merit for copper and iron determination in both fractions are given and the obtained values are discussed. The analytical method was characterized and the limit of detection and limit of quantification for the two metals were 0.5 and 1.6?µg?L^?1 for Cu and 2.3 and 6.1?µg?L^?1 for Fe, respectively. The repeatability, expressed as relative standard deviation, was in the range 1.0–2.1%. The speciation scheme was applied to the analysis of river surface water samples collected in Galicia (Northwest, Spain).     

Determination of trace amounts of cadmium,copper and nickel in environmental water and food samples using GO/MgO nanocomposite as a new sorbent

A solid phase extraction method based on graphene oxide (GO) modified with magnesium oxide (MgO) nanoparticles was developed for the preconcentration and determination of trace amounts of cadmium, copper and nickel ions. The adsorbed analytes were eluted by 4.0 mL of 0.1 M (EDTA) and injected to flame atomic absorption spectrometer. The factors influencing the complex formation and extraction of these heavy metals were optimized. Studies on potential interference by various anions and cations showed the method to be highly selective. The preconcentration factor was about 11 with relative standard deviation of <4.0 for 8 replication determination. The detection limits for the Cd, Cu, Ni were found to be 0.5, 3.4 and 25 µg L^?1, respectively. The method was successfully applied for the determination of cadmium, copper and nickel in tap water, well water, sea water, rice and macaroni samples with spike recoveries ranging 93–105 %.     

Inorganic arsenic speciation in various water samples with GFAAS using coprecipitation

A simple, economic and sensitive method for selective determination of As(III) and As(V) in water samples is described. The method is based on selective coprecipitation of As(III) with Ce(IV) hydroxide in presence of an ammonia/ammonium buffer at pH 9. The coprecipitant was collected on a 0.45 µm membrane filter, dissolved with 0.5 mL of conc. nitric acid and the solution was completed to 2 or 5 mL with distilled water. As(III) in the final solutions was determined by graphite furnace atomic absorption spectrometry (GFAAS). Under the working condition, As(V) was not coprecipitated. Total inorganic arsenic was determined after the reduction of As(V) to As(III) with NaI. The concentration of As(V) was calculated by the difference of the concentrations obtained by the above determinations. Both the determination of arsenic with GF-AAS in presence of cerium and the coprecipitation of arsenic with Ce(IV) hydroxide were optimised. The suitability of the method for determining inorganic arsenic species was checked by analysis of water samples spiked with 4–20 µg L^?1 each of As(III) and As(V). The preconcentration factor was found to be 75 with quantitative recovery (≥95%). The accuracy of the present method was controlled with a reference method based on TXRF. The relative error was under 5%. The relative standard deviations for the replicate analysis ( n?=?5) ranged from 4.3 to 8.0% for both As(III) and As(V) in the water samples. The limit of detection (3σ) for both As (III) and As(V) were 0.05 µg L^?1. The proposed method produced satisfactory results for the analysis of inorganic arsenic species in drinking water, wastewater and hot spring water samples.     

Date pits waste as a solid phase extraction sorbent for the analysis of lead in wastewater and for use in manufacturing brick: An eco-friendly waste management approach

Lead (Pb(II)), an extremely hazardous heavy metal that has been shown to have detrimental effects on both the environment and humans, mostly gets into the ecosystem through industrial activities. In this work, a new solid-phase extraction (SPE) based on treated date pits bio-sorbent and iCAP Q inductively-coupled plasma mass spectrometry (iCAP Q ICP/MS) method has been optimized for the trace determination of Pb(II) in various industrial wastewater effluents. A cost-effective biomass material was prepared from date pits (DP), and chemically modified with H₂O₂ and successively used as SPE bio-sorbent for Pb(II) extraction. Extracting solutions for instance H₂SO₄, HNO₃ and HCl at various concentrations (1–5 mM) were optimized, and best extraction of Pb(II) was obtained by HCl (1 mM). The optimized SPE and iCAP Q ICP/MS method has offered excellent validation conditions in terms of coefficient of determination (CoD, R² > 0.999), detection limit (DL, 0.011 µg/L), quantification limit (QL, 0.034 µg/L), and run-to-run and day-to-day precision (RSD < 6 %). The optimized procedure was practically applied in the determination of Pb(II) in industrial wastewater comprising iron and steel, textile, printing and battery industries. Among the analyzed samples, the battery industry produced higher amounts of Pb(II) (18.55 µg/L) followed by iron and steel (14.65 µg/L), petroleum (12.38 µg/L) printing (5.78 µg/L) and textile (3.76 µg/L) industries. The recovery values were achieved between 95 % and 99 %. The obtained results have established the appropriateness of the offered technique as a new useful method for the routine examination of Pb(II) in industrial wastes. In addition, the current method could be expansively used in the proficient removal and identification of other heavy metals contaminants from similar matrices. Further, the metal ions saturated bio-sorbents were used in the preparations of bricks and it was found to be a successful approach for heavy metals and agricultural waste management.     

Trace elements in municipal solid waste incinerator fly ash

Municipal solid waste incineration (MSWI) significantly reduces volume and mass by as much as 80%, prolonging the life span of landfills. The concentration of heavy metals in the ash and their ability to leach into ground water is a serious concern when siting and designing MSWI ash landfills. Improved technology captures most heavy metals in the ash. The distribution of elements among the different ash particle sizes was determined by NAA. The bottom ash residue was separated into fractions ranging from 9.5 mm to 0.3 mm. The fly ash was separated into fractions from 250 m to 20 m. Landfills usually bury a mixture of both. The combined ash was separated into fractions over the entire range from >9.5 mm to <20 m. Thermal and epithermal neutron irradiations of size fractionated MSW bottom, fly and combined ash were performed to determine the distribution of various metals within the ash. Compared to normal soil, the ashes contained elevated amounts of numerous elements. Concentrations of the more enriched elements (Ag, Cd, Cr, Cu, Hg, Sb, Se, Sr and Zn) in fly ash were of particular interest as source markers.     

Evaluation of heavy metal bioavailability in soil amended with poultry manure using single and BCR sequential extractions

In the present study, three-step Community Bureau of Reference sequential extraction scheme (BCR-SES) and single extraction methods were performed to assess the mobility and availability of heavy metals (Cd, Cu, Pb, Fe and Zn) in an agricultural soil before and after amendment with poultry waste (PW).The PW samples were collected from poultry farms, situated in Hyderabad Sindh, Pakistan. The extractable heavy metals were measured by flame and electrothermal atomic absorption spectrometry. The validation of the method was carried out by analysis of a certified reference material of soil amended with sewage sludge (BCR-483). The single extractions using calcium chloride and EDTA, separately, while BCR-SESs were developed to evaluate the available heavy metals to plants and their environmental accessibility for control soil (CS), PW and soil amended with PW (SPW).The pH of the PW and SPW were found to be < 6.0, which may enhance the leaching of heavy metals to agricultural soil. The results from the partitioning study indicated that easily mobilised forms (acid exchangeable) of Cd were higher than other heavy metals. The oxidisable fractions of all heavy metals were dominant in PW and SPW as compared to found in CS samples. The EDTA- and CaCl₂-extractable heavy metals correspond to 5.0 to 10 and 0.5 to 3.0%, respectively of total contents in all three solid samples. Contamination factors revealed that the retention of Pb and Zn were higher compared with Cu, Cd and Fe in CS, PW and SPW samples.