Assessing sorption of fluoroquinolone antibiotics in soils from a Kd compilation based on pure organic and mineral components.

The presence of fluoroquinolone (FQ) antibiotics in soils may cause a threat to human health due to overexposure and the generation of antibiotic resistance genes. Understanding their sorption behavior in soils is important to predict subsequent FQ (bio) availability. Here, FQ sorption in pure soil organic (i.e., humic substances) and mineral (i.e., metal oxides; phyllosilicates) components is evaluated through a solid-liquid distribution coefficient (Kd (FQ)) dataset consisting of 243 entries originated from 80 different studies, to elucidate their respective contribution to the overall Kd (FQ) in bulk soils. First, different factors affecting FQ sorption and desorption in each of these soil phases are critically discussed. The strong role of pH in Kd (FQ), due to the simultaneous effect on both FQ speciation and surface charge changes, encouraged the derivation of normalized sorption coefficients for the cationic, zwitterionic and anionic FQ species in humic substances and in different phyllosilicates. Kd (FQ) in metal oxides revealed a key role of metal nature and material specific surface area due to complexation sorption mechanisms at neutral pH. Cumulative distribution functions (CDF) were applied to each dataset to establish a sorption affinity range for each phase and to derive best estimate Kd (FQ) values for those materials where normalized sorption coefficients to FQ species were unavailable. The data analysis conducted in the different soil phases set the basis for a Kd (FQ) prediction model, which combined the respective sorption affinity of each phase for FQ and phase abundance in soil to estimate Kd (FQ) in bulk soils. The model was subsequently validated with sorption data in well characterized soils compiled from the literature.

Construction and validation of parametric models to predict radium sorption in soils.

Elucidating the factors affecting the transfer of naturally occurring radionuclides (NOR) between environmental compartments is a key part of the assessment of ecosystem's exposure to naturally occurring radionuclide materials (NORM). For that, the sorption and desorption solid-liquid distribution coefficients (Kd) of radium (Ra) were quantified in a collection of 31 soil samples with contrasting edaphic properties under controlled conditions in laboratory batch experiments. Ra sorption was demonstrated to be moderate to high, with Kd (Ra) values ranging from 102 to 103 L kg-1. Ra sorbed was mostly irreversible, as evidenced by desorption percentages lower than 2 %. An exploratory analysis with partial least squares (PLS) regression identified the soil properties that correlated with Kd (Ra) and discarded those that were not relevant for describing Kd variability. A dataset of the sorption Kd (Ra) values and associated soil properties was built from our own data and from the literature after performing an in-depth review of similar Ra sorption studies. For the first time, Kd (Ra) parametric prediction models were constructed using univariate linear regression (ULR) and multivariate linear regression (MLR). Ra sorption in soils was mostly explained by the soil properties directly or indirectly related to the available exchange sites, such as the levels of water-soluble and exchangeable Ca and Mg as well as the pH of the contact solution. The most promising models explained around 80 % of the Kd (Ra) data variance, only needing Kd (Ca + Mg) or additional soil descriptors such as pH, Mn content, and the specific surface area. The validation of the proposed models confirmed that Kd (Ra) can be predicted with only a few soil properties that can be characterised in routine analysis. Thus, the proposed models could be used to estimate the interaction of Ra in soils in risk assessment.

Using a batch test to derive sorption data of fluoroquinolone antibiotics in humic acids.

Fluoroquinolone antibiotics (FQs) are of concern due to their disrupting effects on environmental bacterial communities. Evaluating FQ sorption by soil components is important to understand their interaction with soils and to address their environmental (bio)availability. However, data in soil organic components, especially humic acids, are scarce. Batch experiments following OECD guidelines are suitable for testing the sorption of pollutants in solid matrices. Here, we applied this methodology, with specific changes in the experimental setup, to derive sorption data and to identify the factors affecting sorption of four common FQs in seven humic acids with contrasting properties. The effect of shaking time, pH, calcium concentration in solution and dissolved organic carbon (DOC) content on the quantification of the solid-liquid distribution coefficient (Kd) of norfloxacin in three reference humic acids was evaluated. Sorption reversibility and sorption analogy of four FQs were additionally assessed in these three reference materials, whereas the effect of initial norfloxacin concentration was evaluated in the overall set of seven humic acids. Sorption was fast, strong, non-linear, irreversible and affected by changes in the pH and calcium levels in solution. The bell-shaped sorption trend at varying pH values confirmed the key role of FQ speciation in sorption and the high Kd values indicated a positive effect of soil organic matter components on FQ sorption in bulk soils at environmentally relevant pH values.•Relevant factors affecting sorption of pollutants in environmental matrices must be considered to derive Kd values with low variability and high representativeness.•In this article we modify the experimental conditions of standard batch tests to identify the factors that affect the sorption of FQs in humic acids.•The methodological approach followed can be extrapolated to the evaluation of other combinations of pollutant and environmental matrix.

Deriving parametric and probabilistic Kd values for fluoroquinolones in soils.

The evaluation of the sorption affinity of fluoroquinolone antibiotics (FQs) in soils, by means of the derivation of solid-liquid distribution coefficients (Kd), is a valuable information for assessing their environmental mobility. Aiming to develop Kd (FQ) prediction tools in soils, in the first stage of this study we constructed a Kd (FQ) sorption dataset using current literature data. Furthermore, additional sorption and desorption data for norfloxacin were obtained in seven different soils of contrasting properties. Sorption isotherms of norfloxacin were linear under the experimental conditions tested and desorption percentages increased for scenarios in which low sorption was noted. Sorption tests in the same soils were then extended to ciprofloxacin, enrofloxacin and ofloxacin and pooled in the dataset, revealing comparable Kd (FQ) values among the FQ tested after analyzing the overall dataset consisting in 312 entries of Kd (FQ). A partial least square (PLS) regression model was then developed to predict values of Kd (FQ) based on specific relevant soil properties (i.e., pH, cation exchange capacity and organic carbon and texture information), and, for the first time, FQ properties (fraction of cationic FQ species) affecting sorption. Additionally, probabilistic, Kd (FQ) best estimates in soils were derived through cumulative distribution functions (CDFs) for the overall and for partial datasets created by grouping Kd (FQ) values according to key soil properties affecting FQ sorption (i.e., pH, organic carbon content and texture information). This latter approach permitted to derive more representative Kd (FQ) best estimates for the soils to be assessed, and with a lower related variability than that derived from the overall dataset. Best estimates Kd (FQ) values were > 1000 L kg-1 for most acidic to neutral soils, suggesting strong sorption, although lower sorption and thus higher environmental mobility may be expected in scenarios with soils with alkaline pH, low OC and high sand contents. SYNOPSIS: This study aims to derive parametric and probabilistic Kd values for fluoroquinolone antibiotics in soils on the basis of a few relevant soil physicochemical properties.

Presence of novel and legacy flame retardants and other pollutants in an e-waste site in China and associated risks.

Electrical and Electronic Equipment (EEE) residues and their management have been widely identified as potential sources of plasticizers and flame retardants to the environment, especially in non-formal e-waste facilities. This study evaluates the distribution, partitioning and environmental and human impact of organophosphate esters (OPEs), legacy polychlorinated biphenyls (PCBs), polybromodiphenyl ethers (PBDEs) and organochlorine pesticides (OCPs) in the e-waste recycling area of Baihe Tang village, in the Qingyuan county, Guangdong province, China. A plastic debris lump accumulated in a small pond during years was identified as the main source of pollution with ∑pollutants of 8400 µg/g dw, being OPEs the main contaminants detected, followed by PBDEs. This lump produced the contamination of water, sediments, soils and hen eggs in the surrounding area at high concentrations. Plastic-water and water-sediment partitioning coefficients explained the migration of OPEs to the water body and accumulation in sediments, with a strong dependence according to the KOW. Triphenyl phosphate (TPhP), tricresyl phosphate (TCPs) and high chlorination degree PCBs produced a risk in soils and sediments, considering the lowest predicted no effect concentration, while the presence of PCBs and PBDEs in free range hen eggs exceeded the acceptable daily intake. OCPs were detected at low concentrations in all samples. The presence of organic contaminants in e-waste facilities worldwide is discussed to highlight the need for a strict control of EEE management to minimize environmental and human risks.

Examining sorption of perfluoroalkyl substances (PFAS) in biochars and other carbon-rich materials.

The use of carbon-rich sorbents to remove and/or immobilize perfluoroalkyl substances (PFAS) in contaminated environmental scenarios is attracting increasing interest. The identification of key sorbent properties responsible for PFAS sorption and the development of models that can predict the distribution coefficients (Kd) for PFAS sorption in these materials are crucial in the screening of candidate materials for environmental remediation. In this study, sorption kinetics, sorption isotherms, and the effects of pH, calcium concentration and dissolved organic carbon (DOC) content on PFAS sorption were evaluated in four representative carbon-rich materials: two biochars with contrasting properties, a compost, and charcoal fines rejected by the metallurgical industry. Subsequently, the sorption of seven PFAS with numbers of fluorinated carbons ranging from 4 to 11 was evaluated in a total of ten carbon-rich materials, including activated carbons, so as to build up a Kd prediction model. The sorption of PFAS increased with greater fluorinated chain length, suggesting that hydrophobic interactions play a major role in sorption and electrostatic interactions a minor one. These results were confirmed by a principal component analysis, which revealed that the CORG/O molar ratio and the specific surface area of the material were the two main sorbent properties affecting PFAS sorption. Furthermore, the DOC content in solution had a negative effect on PFAS sorption. Using this information, a simple Kd prediction model applicable to a wide range of materials and PFAS was developed, using only a few easily-derived physicochemical properties of sorbent (CORG/O molar ratio and SSA) and PFAS (number of CF2), and was externally validated with data gathered from the literature.

Examining samarium sorption in biochars and carbon-rich materials for water remediation: batch vs. continuous-flow methods.

Samarium (Sm) sorption from aqueous solutions was evaluated in biochars (derived from castor meal (CM), eucalyptus forest residues (CE), sugarcane bagasse (SB) and green pericarp of coconut (PC)) and in other carbon-rich materials (coal fines (CF); two commercial activated charcoals (GAC, NGAC)) by applying batch and continuous-flow sorption experiments. Batch experiments revealed great Kd values, in the range of 104-105 L kg-1, and high Sm sorption percentages (>97%, except for SB) in the range of environmental representative concentrations, using as-received materials, with no further treatments. Maximum sorption capacities were derived from sorption isotherms using the Langmuir model (from 1.2 to 37 mg g-1). Continuous-flow sorption experiments permitted to obtain maximum sorption capacities by mass balance and by fitting the experimental breakthrough curves to Thomas and Yan models. CF exhibited the greatest maximum sorption capacity (40 mg g-1) besting the commercial activated charcoals, while CM was established as the best biochar (7.2 mg g-1), with similar results to NGAC (12 mg g-1) but worse than GAC (36 mg g-1). The contribution of cation exchange in Sm sorption was confirmed to be significant for most materials based on the analyses of cations leached during continuous-flow sorption experiments. Maximum sorption capacities derived from Langmuir fitting correlated well with maximum sorption capacities obtained from continuous-flow experiments. Both methods were confirmed to be suitable to determine the maximum Sm sorption capacity of the materials and then to propose the most suitable materials that can act as alternative to commercial activated charcoals.

Plant uptake of perfluoroalkyl substances in freshwater environments (Dongzhulong and Xiaoqing Rivers, China).

This study provides new knowledge on the mobility, behavior, and partitioning of 17 perfluoroalkyl substances (PFASs) in the water-sediment-plant system along the Dongzhulong and Xiaoqing Rivers. The fate of PFASs in these rivers is also discussed. The study area is affected by the industrial production of perfluorooctanoic acid (PFOA). The ∑PFASs in water and sediments close to the industrial discharge were 84,000 ± 2000 ng/L and 2300 ± 200 ng/g dw, respectively, with the concentrations decreasing along the river due to dilution. PFOA was the dominant compound (74-97% of the ∑PFASs), although other PFASs were identified close to urban areas. Principal component analysis and solid-liquid distribution coefficients revealed that long-chain PFASs accumulated in the sediment whereas short-chain PFASs remained in the water all along the river. PFASs were taken up by plants and remobilized to different plant compartments according to shoot concentration factors (SCFs), root concentration factors (RCF), and transfer factors (TFs). Among the four plant species studied, floating plants absorbed high levels of PFASs, while rooted species translocated short-chain PFASs from the roots to the shoots. Therefore, floating species, due to their high uptake capacity and large proliferation rate, could eventually be used for phytoremediation.

Modelling the sorption behaviour of perfluoroalkyl carboxylates and perfluoroalkane sulfonates in soils.

A simple parametric model was developed to predict the sorption of perfluoroalkyl substances (PFASs) in soils. Initially, sorption and desorption solid-liquid distribution coefficients (Kd and Kd,des respectively) of eight PFASs (five perfluoroalkyl carboxylates, PFCAs, and three perfluoroalkane sulfonates, PFSAs) in seven soils with organic carbon (OC) content ranging from 1.6 to 41% were quantified using batch experiments. The information obtained helped to fill the gaps in a literature-based database of Kd values of PFASs, which was lacking data on soils with high OC content. The overall dataset finally comprised 435 entries. Normalized sorption coefficients for the soil OC and mineral fraction contents (KOC and KMIN respectively) were deduced for each PFAS by correlating the corresponding Kd values obtained under a wide range of experimental conditions with the fraction of organic carbon (fOC) of the soils. Furthermore, the sorption mechanisms in each phase were shown to depend mainly on PFAS chain length. The dependence of KOC and KMIN values on PFAS chain length defined the basic equations to construct the model for predicting PFAS sorption, applicable to both PFCAs and PFSAs with chain lengths ranging from 3 to 11 fluorinated carbons. The validation of the proposed model confirmed its ability to predict the Kd of PFASs based only on the soil OC and silt+clay contents and PFAS chain length. Therefore, it can be used in the first stages of a risk assessment process aiming at estimating the potential mobility of PFASs in soils after a contamination event. SYNOPSIS: This study develops a new parametric model to predict the sorption of perfluoroalkyl substances (PFASs) in soils.

Deriving probabilistic soil distribution coefficients (Kd). Part 2: Reducing caesium Kd uncertainty by accounting for experimental approach and soil properties.

The solid-liquid distribution coefficient (Kd) is a key input parameter in radioecological models. However, its large variability hampers its usefulness in modelling transport processes as well as its accuracy in representing soil-radionuclide interactions. For the specific case of radiocaesium, the analyses of a Cs Kd soil dataset (769 entries) showed that values varied over a five order of magnitude range, and the resulting Cs Kd best estimate (calculated as a geometric mean = 2.5 × 103 L kg-1) lacked reliability and representativity. Grouping data and creation of partial datasets based on the experimental approach (short-term (< ~1 yr) vs. long-term experiments (> ~1 yr)) and soil factors affecting Cs interaction (i.e., the ratio of the radiocaesium interception potential (RIP) to the potassium content in soil solution (Kss); organic matter content (OM) and soil texture) succeeded in reducing variability a few orders of magnitude, with Cs Kd best estimates also differing by one-two orders of magnitude depending on the type of soil and experimental approach. The statistical comparison of the Cs Kd best estimates and related cumulative distribution functions of the partial datasets revealed a relevant effect of the sorption dynamics on Cs Kd values (with long-term values systematically higher than short-term ones), and that the RIP/Kss ratio was an excellent predictor of Cs Kd for short-term scenarios, whereas the RIP parameter could be predicted on the basis of texture information. The OM threshold to distinguish between OM threshold to distinguish between Mineral and Organic soils subclasses, regarding Cs interaction was determined to be 50% and 90% OM for short- and long-term scenarios, respectively. It was then recommended to select the Cs Kd input data depending on the soils and scenarios to be assessed (e.g., short- vs. long-term; OM %) to improve the reliability and decrease the uncertainty of the radioecological models.

Deriving probabilistic soil distribution coefficients (Kd). Part 3: Reducing variability of americium Kd best estimates using soil properties and chemical and geological material analogues.

The solid-liquid distribution coefficient (Kd) is a key input parameter in radioecological risk models. However, its large variability hampers its usefulness in modelling transport processes as well as its accuracy in representing soil-radionuclide interactions. To assist in the selection of Kd values and their cumulative distribution functions for study areas without site specific information, a critically reviewed dataset was developed, containing more than 5000 soil Kd entries for 83 elements and an additional 2000 entries of Kd data for 75 elements gathered from a selection of other geological materials. For the specific case of americium (Am), the dataset contained 109 entries for soils and 33 additional entries for sediment and subsoils. The analysis of the Am Kd soil dataset showed that values varied 4-orders of magnitude, and consequently the resulting Am Kd best estimate (geometric mean (GM): 4.6 × 103 L kg-1) lacked sufficient reliability. The objective of this study was to calculate cumulative distribution functions and statistically evaluate this dataset to determine if the Am Kd variability in soils could be reduced by considering various factors, including: 1) measurement methods, 2) key soil properties, 3) the use of chemical analogue data, and 4) the use of analogue data. Accounting for Am Kd experimental method (i.e., sorption vs. desorption; long-vs. short-term experiments) had little effect on reducing variability. However, accounting for key soil factors (i.e., organic matter content (OM), pH, soil texture) succeeded in reducing variability of Am Kd, especially when combining pH and OM. While previous data sets have used 20% OM content as a critical value to distinguish between mineral and organic soils, this study shows that this critical value should be reduced to 10% OM to minimize Am Kd variability. The inclusion in the dataset of Am Kd from other geological materials (e.g., gyttjas, tills, and subsoils) and Kd values from trivalent lanthanides (Ln (III)) and actinides (An (III)) (172 additional entries) did not statistically affect the Am Kd geometric means of the various pH and OM partial datasets. The larger composite dataset (> 310 entries), with both chemical analogues and geological material analogues to address data gaps, increased the statistical power for calculating Kd best estimates with lower variability, thereby enhancing their usefulness for radionuclide risk calculations.

Deriving probabilistic soil distribution coefficients (Kd). Part 1: General approach to decreasing and describing variability and example using uranium Kd values.

A general approach is presented to derive probabilistic radionuclide distribution coefficients (Kd) in soils from a Kd dataset. The main aim was to derive informed estimates with a low inherent uncertainty by restricting the Kd value data to subsets based on key soil factors and the experimental approach used to calculate the Kd value (e.g., sorption and desorption tests). As an example, the general approach was applied to uranium (U) Kd values that are part of a critically reviewed dataset containing more than 5000 soil Kd entries for 83 elements and an additional 2000 entries of Kd data for 75 elements gathered from a selection of other, non-soil, geological materials. The overall soil U Kd dataset included 196 values spanning a range of four orders of magnitude (1-67,000 L kg-1), with additional 50 entries for other geological materials. Whereas the effect of the experimental approach could be disregarded, major factors in decreasing U Kd variability were pH and organic matter content (OM). Limitation in the number of entries made it difficult to use texture information (sand, silt, clay) to further decrease U Kd variability. The integrated combination of pH + OM permitted some soil groups to have U Kd confidence intervals as narrow as two orders of magnitude. Specifically for U Kd, data in the Mineral (< 20% OM) and Organic (≥ 20% OM) partial datasets were significantly different. Analogue data from geological materials other than soils, such as subsoil, till and gyttja (a lacustrine mud having elevated organic matter (OM) contents), were also statistically evaluated to determine whether they could be used to fill U Kd data gaps. It was shown that U Kd from subsoils and tills, but not gyttjas, could be used to enhance soil U Kd datasets. Selection of probabilistic Kd values for risk modelling can be made more reliably and with less uncertainty by using appropriate geochemical data representative of the study site to narrow the wide range of potential Kd values.

Feasibility of using low-cost, byproduct materials as sorbents to remove heavy metals from aqueous solutions.

This work investigates the sorption of heavy metals by low-cost, byproducts such as charcoal fines (CF), waste green sand, and rice husk ash, in order to examine the feasibility of their use as alternative filter materials for metal-contaminated waters. The sorption of Cd, Cu, Pb, and Zn was investigated in batch experiments and sorption isotherms were constructed. The three byproducts showed high metal removal efficiencies (>95%, regardless of the metal concentration tested). The highest metal sorption distribution coefficients were obtained for CF, with maximum values within the 105-106 L kg-1 range for all the target metals. The sorption isotherms were satisfactorily fitted using the Freundlich equation and a linear model, the latter only being valid for initial metal concentrations lower than 0.4 mmol L-1. Sorption reversibility was very low, with desorption yields lower than 2% and desorption distribution coefficients often higher than 106 L kg-1. The values of the sorption and desorption parameters indicated that the use of these materials, especially CF, could constitute a low-cost alternative for the remediation of contaminated waters.

Dependence of samarium-soil interaction on samarium concentration: Implications for environmental risk assessment.

The sorption and desorption behaviour of samarium (Sm), an emerging contaminant, was examined in soil samples at varying Sm concentrations. The obtained sorption and desorption parameters revealed that soil possessed a high Sm retention capacity (sorption was higher than 99% and desorption lower than 2%) at low Sm concentrations, whereas at high Sm concentrations, the sorption-desorption behaviour varied among the soil samples tested. The fractionation of the Sm sorbed in soils, obtained by sequential extractions, allowed to suggest the soil properties (pH and organic matter solubility) and phases (organic matter, carbonates and clay minerals) governing the Sm-soil interaction. The sorption models constructed in the present work along with the sorption behaviour of Sm explained in terms of soil main characteristics will allow properly assessing the Sm-soil interaction depending on the contamination scenario under study. Moreover, the sorption and desorption Kd values of radiosamarium in soils were strongly correlated with those of stable Sm at low concentrations (r = 0.98); indicating that the mobility of Sm radioisotopes and, thus, the risk of radioactive Sm contamination can be predicted using data from low concentrations of stable Sm.

Assessing the efficacy over time of the addition of industrial by-products to remediate contaminated soils at a pilot-plant scale.

The effect of the addition of industrial by-products (gypsum and calcite) on the leaching of As and metals (Cu, Zn, Ni, Pb and Cd) in a soil contaminated by pyritic minerals was monitored over a period of 6 months at a two-pit pilot plant. The contaminated soil was placed in one pit (non-remediated soil), whereas a mixture of the contaminated soil (80% w/w) with gypsum (10% w/w) and calcite (10% w/w) was placed in the other pit (remediated soil). Soil samples and leachates of the two pits were collected at different times. Moreover, the leaching pattern of major and trace elements in the soil samples was assessed at laboratory level through the application of the pHstat leaching test. Addition of the by-products led to an increase in initial soil pH from around 2.0 to 7.5, and it also provoked that the concentration of trace elements in soil extracts obtained from the pHstat leaching test decreased to values lower than quantification limits of inductively coupled plasma optical emission spectrometry and lower than the hazardous waste threshold for soil management. The trace element concentration in the pilot-plant leachates decreased over time in the non-remediated soil, probably due to the formation of more insoluble secondary minerals containing sulphur, but especially decreased in pit of the remediated soil, in agreement with laboratory data. The pH in the remediated soil remained constant over the 6-month period, and the X-ray diffraction analyses confirmed that the phases did not vary over time, thus indicating the efficacy of the addition of the by-products. This finding suggests that soil remediation may be a feasible option for the re-use of non-hazardous industrial by-products.

Sorption of perfluoroalkyl substances in sewage sludge.

The sorption behaviour of three perfluoroalkyl substances (PFASs) (perfluorooctanesulfonic acid (PFOS), perfluorooctanoic acid (PFOA) and perfluorobutanesulfonic acid (PFBS)) was studied in sewage sludge samples. Sorption isotherms were obtained by varying initial concentrations of PFOS, PFOA and PFBS. The maximum values of the sorption solid-liquid distribution coefficients (Kd,max) varied by almost two orders of magnitude among the target PFASs: 140-281 mL g(-1) for PFOS, 30-54 mL g(-1) for PFOA and 9-18 mL g(-1) for PFBS. Freundlich and linear fittings were appropriate for describing the sorption behaviour of PFASs in the sludge samples, and the derived KF and Kd,linear parameters correlated well. The hydrophobicity of the PFASs was the key parameter that influenced their sorption in sewage sludge. Sorption parameters and log(KOW) were correlated, and for PFOS (the most hydrophobic compound), pH and Ca + Mg status of the sludge controlled the variation in the sorption parameter values. Sorption reversibility was also tested from desorption isotherms, which were also linear. Desorption parameters were systematically higher than the corresponding sorption parameters (up to sixfold higher), thus indicating a significant degree of irreversible sorption, which decreased in the sequence PFOS > PFOA > PFBS.

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.

Leaching of heavy metals and alkylphenolic compounds from fresh and dried sewage sludge.

Reusing sewage sludge as a soil fertiliser has become a common alternative to disposal. Although this practice has a few benefits, it may contribute to the medium- and long-term contamination of the trophic chain because sewage sludge may contain heavy metals and organic contaminants. As the leaching of contaminants may depend on the sludge pre-treatment, the leaching of heavy metals (Cu, Ni, Pb, Zn and Cr) and alkylphenolic compounds (APCs) (octylphenol (OP), nonylphenol (NP), nonylphenol-mono-ethoxylate (NP1EO)) was investigated in five fresh and 40 °C dried sewage sludge samples from north-eastern Spain. FT-IR analyses and full-scan GC-MS chromatograms showed that sludge drying changed the nature of organic compounds leading to changes in their solubility. Moreover, sludge drying led to a higher relative contribution of dissolved organic carbon than the particulate organic carbon in the leachates. Leaching of Pb, Zn and Cr was below 5 % in both fresh and dried sludge samples, whereas Cu and Ni leached at rates up to 12 and 43 %, respectively, in some of the dried sludge samples. The leaching yields of OP, NP and NP1EO ranged from 1.3 to 35 % for fresh samples, but they decreased from 0.8 to 3.4 % in dried samples. The decrease in the leachability of APCs observed in dried sludge samples might be attributed to the fact that these compounds are associated with particulate organic matter, with significantly lower concentration or even absent in dried sludge than in fresh sludge samples. Therefore, it is recommended to dry the sludge before its disposal.

New quality-control materials for the determination of alkylphenols and alkylphenol ethoxylates in sewage sludge.

The determination of alkylphenols in sewage sludge is still hindered by the complexity of the matrix and of the analytes, some of which are a mixture of isomers. Most of the methods published in the literature have not been validated, due to the lack of reference materials for the determination of alkylphenols in sludge. Given this situation, the objectives of the present study were to develop a new quality-control material for determining octylphenol, nonylphenol and nonylphenol monoethoxylate in sludge. The material was prepared from an anaerobically digested sewage sludge, which was thermally dried, sieved, homogenized and bottled after checking for the bulk homogeneity of the processed material. Together with the sewage sludge, an extract was also prepared, in order to provide a quality-control material for allowing laboratories to test the measuring step. The homogeneity and 1-year stability of the two materials were evaluated. Statistical analysis proved that the materials were homogeneous and stable for at least 1 year stored at different temperatures. These materials are intended to assist in the quality control of the determination of alkylphenols and alkylphenol ethoxylates in sewage sludge.

Determination of alkylphenols and alkylphenol ethoxylates in sewage sludge: effect of sample pre-treatment.

A complete characterization of sewage sludge collected from five biological waste water treatment plants was done to determine physico-chemical parameters, heavy metals and alkylphenols, making special emphasis on sampling, homogenization, and sample pre-treatment. Ultrasonic extraction followed by gas chromatrography coupled with mass spectrometry was used to evaluate the effect of sample pre-treatment (untreated sample, freeze-drying, drying at 40 degrees C or drying at 100 degrees C) on the concentration of octylphenol (OP), nonylphenol (NP) and nonylphenol ethoxylates (NP1EO, NP2EO). Untreated samples and samples dried at 100 degrees C gave concentration levels up to 62% and 89% lower, respectively, than freeze-dried samples. In 50% of cases, freeze-dried samples led to significantly higher concentrations than those obtained by drying at 40 degrees C. Thus, freeze-drying is the recommended sample pre-treatment to prevent possible losses of OP, NP, and NP1EO. Using this methodology, concentrations detected were from 3.2 to 199 mg kg(-1) being NP followed by NP1EO found in highest concentration. The total concentration of NP and NP1EO exceeded the limit of 50 mg kg(-1) proposed by the draft European directive on sewage sludge in three out of five samples studied. Contrarily, heavy metals were below the legislated values.