Factors affecting the accumulation of perfluoroalkyl substances in human blood.

The aim of this study is to evaluate the presence of perfluoroalkyl substances (PFASs) in the blood of 46 residents from Barcelona and to study the factors that affect exposure. Compounds analysed included perfluorooctane sulfonate (PFOS), perfluorohexane sulfonate (PFHxS), perfluorobutane sulfonate (PFBS), perfluorooctanoate acid (PFOA) and perfluorononanoate acid (PFNA). Blood was liquid-liquid extracted and PFASs were determined by liquid chromatography coupled to tandem mass spectrometry. Good recoveries (between 97 ± 14 and 105 ± 13 %) were obtained and method detection limits were from 0.03 to 0.07 ng mL(-1). ΣPFASs ranged from 0.11 to 4.37 ng mL(-1). PFOS was the main compound detected at 0.09-3.35 ng mL(-1), followed by PFOA and PFHxS. PFBS and PFNA were seldom detected. Working conditions, smoking and gender did not cause any significant differences among ΣPFASs levels in the blood while age and parity produced decreased concentrations. On the other hand, laboratory working conditions produced significant higher PFOA levels compared to the general population. Compared to other studies, the PFASs levels in blood from Barcelona residents is low (mean ΣPFASs of 1.67 ± 0.88 ng mL(-1)) and with little variation among the studied population.

Bioaccumulation and effects of perfluorinated compounds (PFCs) in zebra mussels (Dreissena polymorpha).

Perfluorinated chemicals (PFCs) have been used for many years in numerous industrial products and are known to accumulate in organisms. A recent survey showed that tissue levels of PFCs in aquatic organisms varied among compounds and species being undetected in freshwater zebra mussels Dreissena polymorpha. Here we studied the bioaccumulation kinetics and effects of two major PFCs, perfluorooctane sulfonic acid compound (PFOS) and perfluorooctanoic acid (PFOA), in multixenobiotic transporter activity (MXR) and filtration and oxygen consumption rates in zebra mussel exposed to a range of concentrations of a PCF mixture (1-1,000 µg/L) during 10 days. Results indicate a low potential of the studied PFCs to bioaccumulate in zebra mussel tissues. PFCs altered mussel MXR transporter activity being inhibited at day 1 but not at day 10. Bioaccumulation kinetics of PFCs were inversely related with MXR transporter activity above 9 ng/g wet weight and unrelated at tissue concentration lower than 2 ng/g wet weight suggesting that at high tissue concentrations, these type of compounds may be effluxed out by MXR transporters and as a result have a low potential to be bioaccumulated in zebra mussels. Oxygen consumption rates but not filtering rates were increased in all exposure levels and periods indicating that at environmental relevant concentrations of 1 µg/L, the studied PFCs enhanced oxidative metabolism of mussels. Overall, the results obtained in this study confirm previous findings in the field indicating that an important fraction of PFC accumulated in mussel tissues is eliminated actively by MXR transporters or other processes that are metabolically costly.

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.

Development of a multi-residue method for the determination of organic micropollutants in water, sediment and mussels using gas chromatography-tandem mass spectrometry.

This study describes the development of a multiresidue method based on gas chromatography-electron ionization-tandem mass spectrometry (GC-EI-MS/MS) for the detection of sixteen polycyclic aromatic hydrocarbons (PAHs), five phthalate esters (PEs), seven polychlorinated biphenyls (PCBs), six polybrominated diphenyl ethers (PBDEs), six alkylphenols (APs), three organochlorined pesticides and their isomers or degradation products (OCPs) and bisphenol A in seawater, river water, wastewater treatment plant (WWTP) effluents, sediments and mussels. Solid phase extraction (SPE) was used for the extraction of target analytes in aqueous samples, and ultrasound assisted extraction for solid samples. GC-EI-MS/MS acquisition conditions in selected reaction monitoring (SRM) using two transitions per compound were optimized. In this way, quantification and unequivocal identification of organic micropollutants were performed in compliance with the Decision 2002/657/EC. Good linearity responses with coefficients of determination higher than 0.99 were obtained. Methodological detection limits (MDLs) in seawater ranged from 0.1 to 6 ng L(-1); in river water from 0.1 to 4.8 ng L(-1); in WWTP effluents from 1 to 75 ng L(-1); in sediments from 1 to 150 ng g(-1) and in mussels from 1 to 125 ng g(-1). MDLs and recovery yields were compared with other published methods and similarities or even improvements were achieved. The optimized method was applied to analyze five samples from each matrix collected in coastal areas, showing its potential use for marine pollution monitoring.

Multi-biochemical responses of benthic macroinvertebrate species as a complementary tool to diagnose the cause of community impairment in polluted rivers.

Biological indexes, based on benthic macroinvertebrate taxa, are currently used worldwide to measure river ecological quality. These indexes assign a global ecological status of the biotic community, but not necessarily may detect specific effects of water pollutants. Conversely a large set of biochemical markers measured in macroinvertebrate benthic species can detect sublethal effects and inform us about additional environmental factors that are impairing benthic communities. This is especially interesting in moderately polluted sites, where other stressors are already affecting communities but not too strongly to be detected by biotic indexes. Up to ten different markers belonging to distinct metabolic paths and 42 contaminants measured in sample collections of the caddis fly Hydropsyche exocellata were assessed across a polluted gradient in the industrialized Mediterranean River basins of Besós and Llobregat (NE, Spain). Twenty four sample collections were selected to include macroinvertebrate communities representing the five impairment degrees defined by the Spanish Environmental authorities using the biotic metrics. Results evidenced a clear deterioration of the ecological water quality parameters and benthic communities towards downstream reaches. Biochemical responses varied significantly across the studied samples and were able to differentiate samples within communities having a good and deteriorated ecological stage. Principal Component Analyses indicated that salinity was one of the major stresses affecting macroinvertebrate assemblages, whereas antioxidant and metabolizing enzymes responded differently and were closely related to high and presumably toxic levels of accumulated organic pollutants. Therefore these results indicate that the use of multiple -markers sensitive to water pollution may provide complementary information to diagnose environmental factors that are impairing macroinvertebrate communities.

Screening of perfluorinated chemicals (PFCs) in various aquatic organisms.

The aim of this study was to evaluate the occurrence of five perfluorinated chemicals (perfluorooctane sulfonic acid (PFOS), perfluorooctanoic acid (PFOA), perfluorononanoic acid (PFNA), perfluorohexane sulfonic acid (PFHxS), and perfluorobutane sulfonic acid) in aquatic organisms dwelling in either freshwater or marine ecosystems. Organisms selected were insect larvae, oysters, zebra mussels, sardines, and crabs, which are widespread in the environment and may represent potential bioindicators of exposure to PFCs. The study comprises the optimization of a solid-liquid extraction method and determination by high-performance liquid chromatography coupled to tandem mass spectrometry. Using spiked zebra mussels at 10 and 100 ng/g level, the method developed provided recoveries of 96% and 122%, and 82% to 116%, respectively, and a limit of detection between 0.07 and 0.22 ng/g ww. The method was highly sensitivity and robust to determine PFC compounds in a wide array of biological matrices, and no matrix interferents nor blank contamination was observed. Among organisms studied, none of the bivalves accumulated PFCs, and contrarily, insect larvae, followed by fish and crabs contained levels ranging from 0.23 to 144 ng/g ww of PFOS, from 0.14 to 4.3 ng/g ww of PFOA, and traces of PFNA and PFHxS. Assessment of the potential use of aquatic organisms for biomonitoring studies is further discussed.

Comparative toxicity of single and combined mixtures of selected pollutants among larval stages of the native freshwater mussels (Unio elongatulus) and the invasive zebra mussel (Dreissena polymorpha).

This study evaluated the impact of biocides (tributyltin, chlorthalonil and Irgarol 1051) and of pollutants (copper, inorganic and methyl mercury and 4-nonylphenol) occurring in Ebro River (NE Spain) on early developmental stages of native Spanish freshwater and invasive zebra mussels. Toxicity tests were conducted with embryos and glochidia of zebra mussel (Dreissena polymorpha) and the naiad species Unio elongatulus, respectively. Toxicity was quantified in terms of median effective concentration (EC50) impairing embryogenesis and glochidia viability in single and combined mixture exposures. Irgarol 1051 was not toxic at concentrations below 40x10(3)nM. Zebra mussel embryos were on average 50 fold more sensitive to the studied pollutants than glochidia. Tributyltin was the most toxic compound with EC50s for zebra mussel embryos and glochidia, respectively, of 1.24 and 47.93 nM, followed by chlorothalonil (3.65, 176.58 nM), methyl mercury (7.06, 156.4 nM), inorganic mercury (3.64, 518.28 nM), copper (19.73, 1358.55 nM) and 4-nonylphenol (33.99, 1221.48 nM). Combined toxicity of Ebro River pollutants (copper, inorganic and methyl mercury and 4-nonylphenol) was greater than additive in zebra mussel embryos and additive in glochidia. These results indicated that contaminant levels that affect zebra mussel embryos are not toxic to early life stages of the naiad mussel species U. elongatulus.

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.