A. Rigol

Overview of the use of leaching/extraction tests for risk assessment of trace metals in contaminated soils and sediments

Abstract Comparison of the information obtained from the application of leaching/extraction procedures to contaminated soils and sediments is required to make the most appropriate choice for studying a given metal. In this article, the information obtained for Cd, Cr, Cu, Ni, Pb and Zn, when applying various single extraction and sequential extraction procedures, is critically assessed for contaminated samples with distinct origins and characteristics. The single-extraction procedures comprised the application of mild (CaCl 2 and NaNO 3 ) and acidic (CH 3 COOH) extractants and complexing agents (EDTA and DTPA). The original and modified BCR three-step sequential extraction procedures are also compared. Finally, useful criteria are proposed for the selection of leaching/extraction tests in certain scenarios.

Organic compounds in paper-mill process waters and effluents

Paper-mill effluents are characterized by the presence of color and suspended solids, bad smell, high concentration of nutrients that cause eutrophication of receiving waters, and high toxicity overall. This study attempts to give an overview of organic compounds that contribute to the toxicity of paper-mill waters and effluents, their levels, toxicological characterization and the methodologies used for their analysis. Families included are natural products, such as resin and fatty acids (wood extractives), additives used during paper-making, such as biocides, surfactants and phenolic compounds and by-products generated during bleaching, such as dioxins and furans. Several extraction methods, such as liquid-liquid extraction (LLE) or solid phase extraction (SPE) followed by gas chromatography-mass spectrometry (GC-MS) or liquid chromatography-mass spectrometry (LC-MS) with atmospheric pressure chemical ionization (APCI) or electrospray (ESP) are described and method performance is discussed for each family of compounds. This study contributes to the characterization of the organic fraction of paper-mill effluents and highlights elimination strategies.

An overview of the effect of organic matter on soil–radiocaesium interaction: implications in root uptake

This paper aims to give an overview of the effect of organic matter on soil-radiocaesium interaction and its implications on soil-to-plant transfer. Studies carried out after the Chernobyl accident have shown that high 137CS soil-to-plant transfer persists in organic soils over years. In most of these soils, the specific sites in clays control radiocaesium adsorption, organic compounds having an indirect effect. Only in organic soils with more than 95% of organic matter content and negligible clay content does adsorption occur mostly on non-specific sites. After a contamination event, two main factors account for the high transfer: the low solid-liquid distribution coefficient, which is due to the low clay content and high NH4+ concentration in the soil solution, and the low K+ availability, which enhances root uptake. The estimation of the reversibly adsorbed fraction, by means of desorption protocols, agrees with the former conclusions, since it cannot be correlated with the organic matter content and shows the lack of specificity of the adsorption in the organic phase. Moreover, the time-dependent pattern of the exchangeable fraction is related to soil-plant transfer dynamics.

Viability of organic wastes and biochars as amendments for the remediation of heavy metal-contaminated soils.

Composts derived from municipal (MOW and MSW) and domestic wastes (DOM), wastes from the olive oil industry (OWH and OP), green waste (GW), and biochars (BF and BS) were investigated to test their viability for remediating metal-contaminated soils. In addition to common analyses, the characterisation included structural analyses (FTIR and (13)C NMR), determination of the acid neutralisation capacity (ANC) and the construction of sorption isotherms for target metals (Pb, Zn, Cd, Ni and Cu). MOW and GW had the highest ANC values (4280 and 7100 meq kg(-1), respectively), and MOW, GW, DOM, BF and BS exhibited the highest solid-liquid distribution coefficients (Kd) with maximum values in the 10(4) L kg(-1) range. Sorption isotherms were fitted using linear and Freundlich models for better comparison of the sorption capacities of the materials. Based on their basic pH, high ANC and high sorption capacity, MOW, GW and biochars are the most promising materials.

New best estimates for radionuclide solid–liquid distribution coefficients in soils. Part 2. Naturally occurring radionuclides

Predicting the transfer of radionuclides in the environment for normal release, accidental, disposal or remediation scenarios in order to assess exposure requires the availability of an important number of generic parameter values. One of the key parameters in environmental assessment is the solid liquid distribution coefficient, K(d), which is used to predict radionuclide-soil interaction and subsequent radionuclide transport in the soil column. This article presents a review of K(d) values for uranium, radium, lead, polonium and thorium based on an extensive literature survey, including recent publications. The K(d) estimates were presented per soil groups defined by their texture and organic matter content (Sand, Loam, Clay and Organic), although the texture class seemed not to significantly affect K(d). Where relevant, other K(d) classification systems are proposed and correlations with soil parameters are highlighted. The K(d) values obtained in this compilation are compared with earlier review data.

Determination of toxic compounds in paper-recycling process waters by gas chromatography–mass spectrometry and liquid chromatography–mass spectrometry

Three analytical methods were developed for the determination of toxic compounds in recirculating waters of a paper-recycling industry. Three main groups of compounds were considered: (i) wood extractives originated from the raw material; (ii) biocides added during the production process and (iii) surfactants and other adjuvants present in the formulates of these biocides. Wood extractives considered in this study included fatty and resin acids. They were analysed by liquid-liquid extraction using methyl tert.-butyl ether, followed by gas chromatography-mass spectrometry for previous formation of the respective trimethylsilyl esters. Water samples were also extracted with Oasis HLB (copolymer [poly(divinylbenzene-co-N-vinylpyrrolidone]) solid-phase extraction cartridges of 60 mg and analysed by liquid chromatography-electrospray mass spectrometry for the determination of additives and biocides. Using these two approaches levels up to 15 mg/l for total resin and fatty acids, 5 mg/l for alkylbenzene sulfonates and 2-(thiocyanomethylthio)benzotiazol, 100 microg/l for bisphenol A and 2,2-dibromo-3-nitrilepropionamide, and 300 microg/l for nonylphenol ethoxycarboxylate were detected in process waters at different production treatment stages. These levels are of relevance since poor water quality affects the paper-recycling process, the primary water treatment process and eventually, the environmental water quality.

Sorption behaviour of perfluoroalkyl substances in soils

The sorption behaviour of three perfluoroalkyl substances (PFASs), perfluorooctane sulfonic acid (PFOS), perfluorooctanoic acid (PFOA) and perfluorobutane sulfonic acid (PFBS), was studied in six soils with contrasting characteristics, especially in the organic carbon content. Sorption isotherms were obtained by equilibrating the soil samples with 0.01 mol L(-1) CaCl2 solutions spiked with increasing concentrations of the target PFAS. The sorption reversibility of PFASs was also tested for some of the samples. Liquid chromatography coupled to tandem mass spectrometry was used to quantify the target PFASs in the solutions. Both the Freundlich and linear models were appropriate to describe the sorption behaviour of PFASs in soils, and enabled us to derive solid-liquid distribution coefficients (Kd) for each compound in each soil. Kd values increased from 19 to 295 mL g(-1) for PFOS, from 2.2 to 38 mL g(-1) for PFOA and from 0.4 to 6.8 mL g(-1) for PFBS, and were positively correlated with the organic carbon content of the soil. KOC values obtained from the correlations were 710, 96 and 17 mL g(-1) for PFOS, PFOA and PFBS, respectively. Whereas Kd values decreased in the sequence PFOS>PFOA>PFBS, desorption yields were lower than 13% for PFOS, from 24 to 58% for PFOA, and from 32 to 60% for PFBS. This shows that the physicochemical characteristics of PFASs, basically their hydrophobicity, controlled their sorption behaviour in soils, with PFOS being the most irreversibly sorbed PFAS.

pHstatvs. single extraction tests to evaluate heavy metals and arsenic leachability in environmental samples.

Here we compared the pH(stat) test, which examines the leachability of major elements (Ca, Mg, Al, Fe, and Mn), dissolved organic carbon, and trace elements (Cd, Zn, Cu, Pb, and As) in a wide pH range, with single extraction tests based on the use of mild extractants (calcium chloride, acetic acid or EDTA). For this purpose, we examined samples from a variety of environmental conditions (sludges, mineral soils, organic soils, and soils with particulate and/or soluble contamination). Extraction yields obtained with CaCl(2) (0.01 mol L(-1)) and CH(3)COOH (0.43 mol L(-1)) correlated well with those from the pH(stat) at the same pH (r=0.98 and 0.95, respectively), while the use of EDTA (0.05 mol L(-1)) led to systematically higher extraction yields than those quantified with the pH(stat) at the same pH. However, the pH(stat) test had three distinct advantages: (1) it revealed the relationship between the solubility of the main soil phases and pH; (2) it showed the variation in pollutant leachability due to changes in pH; and (3) it better predicted the maximum contaminant availability. Thus we propose that the pH(stat) is the best laboratory tests to evaluate the contaminant leachability over a wide range of sample types (soil, sludge, and sediment).

Comparison of gas chromatography–mass spectrometry and liquid chromatography–mass spectrometry for the determination of fatty and resin acids in paper mill process waters

A comparative study of the performance of liquid chromatography (LC)-atmospheric pressure chemical ionisation (APCI)-mass spectrometry (MS) and gas chromatography (GC)-mass spectrometry techniques for the determination of resin and fatty acids from paper mill process waters was carried out. These compounds are responsible for the high toxicity of paper mill effluents and little research has been carried out regarding their analysis using mass spectrometric techniques. To prove the usability of GC and LC-MS, 16 treated and untreated water samples of recycle, kraft and pulp paper mills were analysed and good agreement was observed as regards to compounds detected and corresponding concentrations. This paper also reports the limits of detection, recoveries, reproducibility, linearity and precision using the two methods. GC-MS presented better selectivity and lower detection limits (below 0.2 microg/l), but derivatization of the extracts and the short life of derivatives (12-24 h) made the technique tedious and prone to high variations. Although LC-APCI-MS presented coelution of the non-aromatic resin acids, it also showed good sensitivity (limits of detection <3 microg/l) and permitted the detection of resin and fatty acids at microg/l level. In addition, since samples could be directly injected to the chromatographic system, LC-APCI-MS was proven as a powerful technique for quick and unequivocal quality control during papermaking.

Comparison of leaching tests for the study of trace metals remobilisation in soils and sediments

Several leaching tests were applied and compared to study metal remobilisation on various unpolluted and contaminated soils and on several contaminated sediments. The trace elements considered were Cd, Cr, Cu, Ni, Pb and Zn, and leaching tests consisted of the application of reagents with contrasting characteristics and strengths in order to assess the information provided. An extraction with aqua regia permitted the estimation of the pseudo-total metal content in the sample. Mild extractants such as H2O, CaCl2 and NaNO3 showed low and similar leaching capacities. Acid (CH3COOH) and complexing (EDTA) agents were more effective in remobilising trace metals from soils and sediments. Cd and Zn showed similar extraction characteristics under both extractant solutions, whereas Cu and Pb were more sensitive to complexation, and Ni and Cr to acidification processes. Sequential chemical extractions provided additional information on the association of the trace elements with the different soil and sediment phases. Cd and Zn showed the highest mobility, Pb was associated to reducible solid phases, Cu and Ni to oxidisable phases, and Cr remained mostly in the residual fraction. The results obtained in this paper provided valuable information for choosing a leaching test, which is an instrument of environmental analysis for the estimation of trace metal mobility.