A new method based on selective fluorescent polymers (PSresin) for the analysis of 90Sr in presence of 210Pb in environmental samples.

90Sr is of major concern in emergency and environmental control plans. It is one of the main fission products in nuclear facilities and is a high-energy beta emitter that presents chemical properties similar to those of calcium. 90Sr is commonly detected using methods based on liquid scintillation counting (LSC) following a chemical separation to remove potential interferences. However, these methods generate mixed wastes (hazardous and radioactive). In recent years, an alternative strategy using PSresins has been developed. For 90Sr analysis with PSresins, 210Pb is the main interferent that should be considered, as it is also strongly retained in the PSresin. In this study, a procedure was developed involving a precipitation with iodates to separate lead from strontium before the PSresin separation. Moreover, the method developed was compared with well-established and routinely used methods based on LSC, revealing that the new method produced equivalent results in less time and with less waste generation.

Use of the modified BCR three-step sequential extraction procedure for the study of trace element dynamics in contaminated soils.

The modified BCR three-step sequential extraction procedure was used to examine the temporal dynamics of trace elements in soils contaminated by an accidental spill from an opencast mine in south-west Spain. Soils were mainly contaminated with pyritic sludge and acidic wastewater, whereas some soils were affected only by acidic wastewater. The distributions obtained for both some major (Ca, Fe and Mn) and trace elements (As, Cd, Cu, Pb and Zn) in the sludge and soil samples taken at different times after the accident, 1-3 months and 21 months, were compared. Sequential extractions were useful in identifying different sources of contamination, and in obtaining additional information on the solubility of secondary minerals formed by pyrite oxidation. Thus, the effectiveness of the BCR procedure has proved to be a useful tool for predicting short- and long-term mobility of trace elements, even in complex environmental scenarios.

Radionuclide sorption-desorption pattern in soils from Spain.

The pattern of radiostrontium and radiocesium sorption-desorption was examined in 30 Spanish soils by the quantification of the distribution coefficients (Kd) with batch tests, the evaluation of sorption reversibility with a single extraction, the estimation of sorption dynamics by the application of drying-wetting cycles, and the calculation of Kdadjusted values as an input for risk assessment models. The data obtained overlapped with those found in soils from other climatic areas, suggesting identical interaction mechanisms and allowing the extrapolation of parameterisations and prediction models among different scenarios.

Prediction of radionuclide aging in soils from the Chernobyl and Mediterranean areas.

The aging of soil-pollutant interaction, which may lead to an increase in pollutant fixation, is the main driving force in the natural attenuation of contaminated soils. Here a test was evaluated to predict the aging of radiostrontium and radiocesium in soils from the Chernobyl and Mediterranean areas. After contamination, soils were maintained at various temperatures for up to 12 mo, with or without drying-wetting (DW) cycles. Changes in the quantity of radionuclide reversibly sorbed over time were monitored using an extraction test (1 mol L(-1) NH(4)Cl; 10 mL g(-1); 16 h). The fixed fraction could not be predicted from soil properties controlling the sorption step. Aging was not as relevant for Sr as for Cs. The time elapsed since contamination was the main factor responsible for the slight (up to 1.3-fold) decreases in Sr extraction yields. The additional effect of DW cycles was negligible. Instead, all factors accelerated Cs aging due to the enhancement of Cs trapping by clay interlayer collapse, with up to 20-fold increases in Cs fixation. The DW cycles also caused secondary effects on the Cs-specific sorption pool, which were beneficial or detrimental depending on the soil type. Extraction yields from laboratory aged samples agreed with those from field samples taken a few years after the Chernobyl accident. These results confirm the prediction capacity of the laboratory test and its usefulness in risk assessment exercises and in the design of intervention actions, particularly because neither fixation nor aging were related to the soil properties, such as clay content.

Effect of ageing on the availability of heavy metals in soils amended with compost and biochar: evaluation of changes in soil and amendment properties.

Remediation strategies using soil amendments should consider the time dependence of metal availability to identify amendments that can sustainably reduce available pollutant concentrations over time. Drying-wetting cycles were applied on amendments, soils and soil + amendment mixtures, to mimic ageing at field level and investigate its effect on extractable Cd, Cu, Ni, Pb and Zn concentrations from three contaminated soils. The amendments investigated were municipal waste organic compost and biochars. The amendments, soils and mixtures were characterised by their physicochemical properties at different ageing times. The amendments were also characterised in terms of sorption capacity for Cd and Cu. The sorption capacity and the physicochemical properties of the amendments remained constant over the period examined. When mixed with the soils, amendments, especially the compost, immediately reduced the extractable metals in the soils with low pH and acid neutralisation capacity, due to the increase in pH and buffering capacity of the mixtures. The amendments had a relatively minor impact on the metal availability concentrations for the soil with substantially high acid neutralisation capacity. The most important changes in extractable metal concentrations were observed at the beginning of the experiments, ageing having a minor effect on metal concentrations when compared with the initial effect of amendments.

Removal of Cd, Cu, Pb, and Zn from aqueous solutions by biochars.

Sorption and desorption of heavy metals (Cd, Cu, Pb, and Zn) was evaluated in biochars derived from sugarcane bagasse (SB), eucalyptus forest residues (CE), castor meal (CM), green coconut pericarp (PC), and water hyacinth (WH) as candidate materials for the treatment of contaminated waters and soils. Solid-liquid distribution coefficients depended strongly on the initial metal concentration, with K d,max values mostly within the range 10(3)-10(4) L kg(-1). For all biochars, up to 95 % removal of all the target metals from water was achieved. The WH biochar showed the highest K d,max values for all the metals, especially Cd and Zn, followed by CE (for Cd and Pb) and PC (for Cd, Pb, and Zn). Sorption data were fitted satisfactorily with Freundlich and linear models (in the latter case, for the low concentration range). The sorption appeared to be controlled by cationic exchange, together with specific surface complexation at low metal concentrations. The low desorption yields, generally less than 5 %, confirmed that the sorption process was largely irreversible and that the biochars could potentially be used in decontamination applications.

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.

Sorption behaviour of nonylphenol and nonylphenol monoethoxylate in soils.

Sorption behaviour of two alkylphenolic compounds (APCs), nonylphenol (NP) and nonylphenol monoethoxylate (NP1EO), was studied in five soils with contrasting characteristics. Sorption isotherms were obtained by equilibrating the soil samples with 0.01 mol L(-1) CaCl2 solutions containing different initial concentrations of NP or NP1EO. Linear fitting was generally appropriate for describing the sorption behaviour of NP and NP1EO in the soils, with the exception of two cases, for which the Freundlich model was more suitable for describing the sorption pattern of NP1EO. Solid-liquid distribution coefficients derived from sorption isotherms (Kd) varied from 24 to 1059 mL g(-1) for NP and from 51 to 740 mL g(-1) for NP1EO. For most soils, sorption Kd values were higher for NP than for NP1EO due to the higher hydrophobicity of NP. Sorption reversibility of NP and NP1EO was also tested from desorption isotherms. Desorption solid-liquid distribution coefficients (Kd,des), obtained from linear fitting, were between 130 and 1467 mL g(-1) for NP and between 24 and 1285 mL g(-1) for NP1EO. Kd,des values were higher than Kd values, which demonstrated that target compounds were irreversibly sorbed into soils, with the exception of the high desorption yield (45%) of NP1EO in the soil with the lowest content of organic matter. The fraction of soil organic carbon (FOC) was a key parameter that influenced the sorption of NP and NP1EO in soils, with logKOC values of 4.0 and 3.8, respectively.

Direct determination of resin and fatty acids in process waters of paper industries by liquid chromatography/mass spectrometry.

Liquid chromatography/mass spectrometry (LC/MS)-based methods were developed for the analysis of 10 resin acids and five fatty acids in process waters of paper industries. No fragmentation of target compounds was observed using atmospheric pressure chemical ionization (APCI) with negative ionization. The [M - H](-) ion permitted the individual quantification of fatty and aromatic resin acids, whereas the non-aromatic resin acids presented a single and common ion at m/z 301. Separation with two columns of different polarity permitted peak confirmation. The method that used a C(8) column with 2-propanol in the mobile phase allowed a certain separation and identification of the non-aromatic resin acids, whereas the method using a C(18) column provided detection limits 10-fold lower for fatty acids. Limits of detection were 0.10 ng for all compounds. Direct sample introduction was compared with liquid-liquid extraction, with similar recoveries (70-101%). Whereas slightly lower detection limits were obtained with liquid-liquid extraction, better reproducibility was observed for direct sample introduction. Resin and fatty acids were determined in process waters of several paper industries. Palmitic, dehydroabietic and non-aromatic resin acids were encountered in most water samples, at levels between 22 and 403 micro g l(-1). LC/MS with direct sample introduction was found to be a good alternative to traditional liquid-liquid extraction and gas chromatography for the analysis of such compounds since no derivatization was required and sample manipulation was minimal.

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.

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.

Quantitative assessment of the effects of agricultural practices designed to reduce 137Cs and 90Sr soil-plant transfer in meadows.

Agricultural practices (ploughing and reseeding, addition of lime and fertiliser) were tested as a feasible remediation strategy to reduce 137Cs (RCs) and 90Sr (RSr) soil-plant transfer in natural meadows in areas affected by the Chernobyl fallout. Field experiments were carried out for 2 years at six sites, covering dry and wet meadows. Observed results at field scale showed that ploughing plus reseeding provoked the main reduction in RSr transfer, with no further reduction after liming, while ploughing + reseeding + K fertiliser led to the maximum decrease in RCs transfer at most sites. The direct effects of agricultural practices on the exchange complex and soil solution composition were quantified by subsequent soil analyses. At the doses applied, lime did not affect the Ca + Mg concentrations in the exchange complex and soil solution of the ploughed soils, thus suggesting that the decrease in RSr transfer on treated plots was mainly due to the changes in the plant species after reseeding. With respect to RCs, changes in the K+NH4+ concentrations in the exchange complex and soil solution were consistent with changes in soil-plant transfer. Finally, RSr and RCs soil-plant transfer in ploughed plots was well predicted from soil properties, such as the solid-liquid distribution coefficient, the ionic composition of the soil solution and the exchangeable cations, with Pearson correlation coefficients of 0.98 and 0.86, respectively, between calculated and experimental log transfer factors.

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.

Soil- and plant-based countermeasures to reduce 137Cs and 90Sr uptake by grasses in natural meadows: the REDUP project.

The effectiveness of a set of soil- and plant-based countermeasures to reduce 137Cs and 90Sr transfer to plants was tested in natural meadows in the area affected by Chernobyl fallout. Countermeasures comprised the use of agricultural practices (disking + ploughing, liming and NPK fertilisation), addition of soil amendments and reseeding with a selection of grass species. Disking + ploughing was the most effective treatment, whereas the K fertiliser doses applied were insufficient to produce a significant increase in K concentration in soil solution. The application of some agricultural practices was economically justifiable for scenarios with a high initial transfer, such as 137Cs-contaminated organic soils. The use of soil amendments did not lead to a further decrease in transfer. Laboratory experiments demonstrated that this was because of their low radionuclide sorption properties. Finally, experiments examining the effect of plant species on radionuclide transfer showed that both transfer and biomass can depend on the plant species, indicating that those with high radionuclide root uptake should be avoided when reseeding after ploughing.

Remediation of metal-contaminated soils with the addition of materials - part II: leaching tests to evaluate the efficiency of materials in the remediation of contaminated soils.

The effect of the addition of materials on the leaching pattern of As and metals (Cu, Zn, Ni, Pb, and Cd) in two contaminated soils was investigated. The examined materials included bentonites, silicates and industrial wastes, such as sugar foam, fly ashes and a material originated from the zeolitization of fly ash. Soil + material mixtures were prepared at 10% doses. Changes in the acid neutralization capacity, crystalline phases and contaminant leaching over a wide range of pHs were examined by using pH(stat) leaching tests. Sugar foam, the zeolitic material and MX-80 bentonite produced the greatest decrease in the leaching of pollutants due to an increase in the pH and/or the sorption capacity in the resulting mixture. This finding suggests that soil remediation may be a feasible option for the reuse of non-hazardous wastes.

The use of hard- and soft-modelling to predict radiostrontium solid-liquid distribution coefficients in soils.

The solid-liquid distribution coefficient (K(d)) is the parameter that governs the incorporation of contaminants in soils. Its estimation allows the prediction of the fate of contaminants in the short- and long-term after a contamination event. Here, the K(d) of radiostrontium (K(d)(Sr)), a radionuclide of significant environmental interest, was predicted by hard models, which are based on knowledge of the mechanisms governing its sorption, and by soft models based on Partial Least Squares (PLS), using a large data set with the main soil parameters. The two approaches were tested and compared for 30 soils in Spain. Correlations between the predicted and experimental values of K(d)(Sr) obtained using hard- and soft-modelling showed slopes close to 1 and regression coefficients higher than 0.95, which confirms that both approaches are able to obtain satisfactory estimates for K(d)(Sr) from soil parameters.

Comparison of mechanistic and PLS-based regression models to predict radiocaesium distribution coefficients in soils.

Radiocaesium sorption interaction descriptors were examined in 30 soil samples from Spain. Mechanistic and regression models were used to predict the solid-liquid distribution coefficients of radiocaesium (K(d)(Cs)) based on soil properties, and the obtained values were compared with the experimental ones, which were derived from batch experiments. The batch experiments used two contact solutions: one simulated the composition of the soil solution, and the other was the wash-off from the soil. Several mechanistic models of different complexity were tested based on the Radiocaesium Interception Potential (RIP), with satisfactory agreement between experimental and predicted values. A simplified model based on either the RIP, or the clay content and K status of the soil was proposed. Various multivariant regression models, which were constructed using the Partial Least Square Regression (PLS), were also evaluated. The RIP, clay content, and the K and NH(4)(+) contents were also identified by the regression models as the most relevant soil parameters to predict the K(d). As seen for the mechanistic models, the goodness of fit of the regression models was demonstrated by an excellent agreement between experimental and predicted values.

Remediation of metal-contaminated soils with the addition of materials--part I: characterization and viability studies for the selection of non-hazardous waste materials and silicates.

Contamination episodes in soils require interventions to attenuate their impact. These actions are often based on the addition of materials to increase contaminant retention in the soil and to dilute the contaminant concentration. Here, non-hazardous wastes (such as sugar foam, fly ash and a material produced by the zeolitization of fly ash) and silicates (including bentonites) were tested and fully characterized in the laboratory to select suitable materials for remediating metal-contaminated soils. Data from X-ray fluorescence (XRF), N(2) adsorption/desorption isotherms, X-ray diffraction (XRD) and scanning electron microscopy/energy-dispersive X-ray spectroscopy (SEM-EDX) analyses revealed the chemical composition, specific surface area and the phases appearing in the materials. A pH titration test allowed the calculation of their acid neutralization capacity (ANC). The metal sorption and desorption capacities of the waste materials and silicates were also estimated. Sugar foam, fly ash and the zeolitic material were the best candidate materials. Sugar foam was selected because of its high ANC (17000 meq kg(-1)), and the others were selected because of their larger distribution coefficients and lower sorption reversibilities than those predicted in the contaminated soils.

Diffusion experiments for estimating radiocesium and radiostrontium sorption in unsaturated soils from Spain: comparison with batch sorption data.

As sorption data obtained from batch tests are often used to estimate pollutant transport in unsaturated soils, comparison between sorption data obtained in the two conditions is required to ensure a correct risk assessment. With this aim, radiostrontium and radiocesium apparent diffusion coefficients (D(a)) were quantified in nine unsaturated soils, and the derived distribution coefficients (K(d)) were compared with K(d) data from batch experiments. The D(a)(Sr) and the D(a)(Cs) ranged from 1.8x10(-11) to 1.5x10(-10) m(2) s(-1), and from 1.0x10(-13) to 5.9x10(-11) m(2) s(-1), respectively. The D(a)(Sr) varied according to both soil packing parameters and properties governing Sr interaction. For Cs, the soil sorption properties explained the variation on D(a)(Cs). The K(d) values derived from D(a) (from 0.014 to 1.8 L kg(-1) for Sr; from 0.55 to 942 L kg(-1) for Cs) were lower than from batch tests (from 1 to 97 L kg(-1) for Sr; from 10 to 14,600 L kg(-1) for Cs), thus indicating that batch data may not accurately describe radionuclide transport in unsaturated soils. However, the two sets of data correlated well, thus suggesting that radionuclide transport can be estimated from batch tests, which are faster than diffusion experiments.

Comparison of laboratory methodologies for evaluating radiostrontium diffusion in soils: planar-source versus half-cell methods.

A planar-source method, initially designed to obtain diffusion coefficients in compacted clay, is adapted here to determine the apparent diffusion coefficient (D(a)) of radiostrontium in soils representative of the Spanish territory. Experiments were carried out by varying the moisture content (F(moist)), and bulk dry density (ρ(bulk)) of the soil samples, in order to study the influence of these soil packing parameters on D(a) values. The moisture in the soil samples was established as the percentage of occupancy of each soil's field capacity (OFC). For a similar OFC, D(a) values in the examined soils ranged by approximately one order of magnitude (e.g. from 6.2 × 10(-)(11) to 6.5 × 10(-)(12)m(2)s(-)(1), at 100% of OFC; from 3.0 × 10(-)(11) to 3.8 × 10(-)(12)m(2)s(-)(1), at 60% of OFC). For a given soil, D(a) values increased when water content was increased. F(moist), and tortuosity (τ) explained D(a) variability, with R(2) values usually over 0.9. However, no good simple or multiple regressions between the soil packing parameters and D(a) were obtained with the whole dataset of all soils, which indicated that soil sorption capacity affects the diffusion of reactive radionuclides in soils. The inclusion of calculated K(d) values in the multiple regressions improved the correlations in all cases. Finally, D(a) values were compared with those obtained by the application of a half-cell method. The values of D(a) obtained by the planar-source methods were systematically lower than the half-cell ones, with a good correlation between the D(a) derived from both methods (R(2)=0.98).