Miquel Vidal

Determination of Cd, Cu, Pb and Zn in environmental samples: microwave-assisted total digestion versus aqua regia and nitric acid extraction

Abstract We validated the determination of the content of Cd, Cu, Pb and Zn using two digestion protocols: a microwave-assisted total digestion and an aqua regia extraction procedure based on the International Organization for Standardisation (ISO) 11466 method. Our goal in validating these two protocols, along with a nitric acid digestion, is to propose a rapid, cheap and easily automated digestion method for monitoring heavy metal content in environmental samples. We applied the digestion protocols to samples with a wide range of organic matter such as sediments, soils, sludges and plant material. For samples with a low carbonate or organic matter contents, such as sediments and agricultural soils, aqua regia digestion in an aluminium block was revealed to be an optimum estimator for the total metal content. For samples with a high organic matter content, such as organic horizons of forest floor layers, plant material and organic soils, nitric acid digestion could substitute microwave (MW)-hydrofluoric acid (HF) digestion. Except in a few samples with high organic matter or low heavy metal content, the RSD values obtained after the application of the proposed digestion procedures were lower than 5%. Based on the obtained results, a decision flow chart for choosing the fit-for-purpose digestion procedure is suggested.

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.

Prediction of the impact of the Aznalcóllar toxic spill on the trace element contamination of agricultural soils

The interaction of several trace elements (Cd, Zn, Cu, Pb, As, Bi, and Tl) was studied by leaching experiments in agricultural soils affected by the Aznalcóllar toxic spill. The spill led to contamination by acid waste waters and sludge deposition. The levels of contamination recorded after the sludge was removed from soils showed that highly contaminated areas remained. A comparison of soils directly affected by sludge deposition and acid waste waters with soils contaminated only by acid waste waters demonstrated that Zn/As and Cd/As ratios were good indicators of the two contributions to the contamination. Soil samples were characterised and grouped according to their texture and carbonate content. The response of elements to single extractions with CaCl2 0.01 mol l-1, CaCl2 1 mol l-1, CH3COOH 0.43 mol l-1, and EDTA 0.05 mol l-1 enabled us to estimate their mobility in the soils. Cd and Zn were found to be the most mobile elements. Cu showed an intermediate mobility, especially in an acidic medium. Pb, As, Bi and Tl were found to be non-mobile elements. A comparison of referent, low and highly contaminated samples showed that the presence of sludge had an effect on desorption yields, in part due to the short-term after the contamination. Calculations of a relative scale of long-term mobility, between soils and trace elements, provided further conclusions derived from the use of single extractions.

Distribution of radiocaesium in organic soils

Abstract Radiocaesium added to organic soils remains plant-available far longer than might be predicted from the behaviour of the element in mineral soils. To investigate this, the distributions of radiocaesium added to a low-ash peat and a peaty podzol were studied using sequential extraction with ammonium acetate, sodium pyrophosphate, sodium hydroxide, and ammonium acetate after peroxidation. Comparisons were made with the distribution reported for mineral soils. Changes in distribution between soil phases with time were measured on a sequence of samples treated with radiocaesium over a period of 4 years. Extractions were performed on soils pretreated with HF to remove mineral matter, on soil fractions enriched or depleted in mineral matter isolated physically by means of wet sieving, and on soil fractions obtained by density separation with chloroform and ‘Nemagon’. These experiments showed that, even in a highly organic peat, the mineral components were important for the eventual fixation of radiocaesium. Oxidizable organic matter corresponding to humin also strongly retained caesium.

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.

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).

New best estimates for radionuclide solid-liquid distribution coefficients in soils. Part 1: radiostrontium and radiocaesium.

Best estimates for the solid-liquid distribution coefficients (K(d)) of radiostrontium and radiocaesium for various soil types, were derived from geometric means (GM) calculated from grouping soils by texture and organic matter content, and also using soil cofactors governing soil-radionuclide interaction. The K(d) (Sr) GM for Sand, Loam, Clay and Organic groups were similar, although the value for the Sand group was significantly lower. The Sr cofactor approach, based on the ratios of cation exchange capacity (CEC) to Ca and Mg concentrations in the soil solution, leads to K(d) (Sr) GM with a lower variability, from which best estimates could be proposed. The K(d) (Cs) GM for Sand and Organic groups differed, although similar values were obtained for Loam and Clay groups. Grouping the K(d) (Cs) according to the Radiocaesium Interception Potential (RIP) and the RIP divided by the K concentration in the soil solution also allows to suggest K(d) (Cs) best estimates with a lower variability.

New best estimates for radionuclide solid–liquid distribution coefficients in soils. Part 3: miscellany of radionuclides (Cd, Co, Ni, Zn, I, Se, Sb, Pu, Am, and others)

New best estimates for the solid-liquid distribution coefficient (K(d)) for a set of radionuclides are proposed, based on a selective data search and subsequent calculation of geometric means. The K(d) best estimates are calculated for soils grouped according to the texture and organic matter content. For a limited number of radionuclides this is extended to consider soil cofactors affecting soil-radionuclide interaction, such as pH, organic matter content, and radionuclide chemical speciation. Correlations between main soil properties and radionuclide K(d) are examined to complete the information derived from the best estimates with a rough prediction of K(d) based on soil parameters. Although there are still gaps for many radionuclides, new data from recent studies improve the calculation of K(d) best estimates for a number of radionuclides, such as selenium, antimony, and iodine.