Marta Llorca

Infant exposure of perfluorinated compounds: levels in breast milk and commercial baby food.

In this study, an analytical method to determine six perfluorinated compounds (PFCs) based on alkaline digestion and solid phase extraction (SPE) followed by liquid chromatography-quadrupole-linear ion trap mass spectrometry (LC-QqLIT-MS) was validated for the analysis of human breast milk, milk infant formulas and cereals baby food. The average recoveries of the different matrices were in general higher than 70% with a relative standard deviation (RSD) lower than 21% and method limits of detection (MLOD) ranging from 1.2 to 362 ng/L for the different compounds and matrices. The method was applied to investigate the occurrence of PFCs in 20 samples of human breast milk, and 5 samples of infant formulas and cereal baby food (3 brands of commercial milk infant formulas and 2 brands of cereals baby food). Breast milk samples were collected in 2008 from donors living in Barcelona city (Spain) on the 40 days postpartum. Perfluorooctanesulfonate (PFOS) and perfluoro-7-methyloctanoic acid (i,p-PFNA) were predominant being present in the 95% of breast milk samples. Perfluorooctanoic acid (PFOA) was quantified in 8 of the 20 breast milk samples at concentrations in the range of 21-907 ng/L. Commercial formulas and food were purchased also in 2009 from a retail store. The six PFCs were detected in all brands of milk infant formulas and cereals baby food analyzed, being perfluorodecanoic acid (PFDA), PFOS, PFOA and i,p-PFNA the compounds detected in higher concentrations (up to 1289 ng/kg). PFCs presence can be associated to possible migration from packaging and containers during production processes. Finally, based on estimated body weight and newborn intake, PFOS and PFOA daily intakes and risk indexes (RI) were estimated for the firsts 6 month of life. We found that ingestion rates of PFOS and PFOA, with exception of one breast milk sample did not exceed the tolerable daily intake (TDI) recommended by the EFSA. However, more research is needed in order to assess possible risk associated to PFCs contamination during early stages of life.

Development and validation of a pressurized liquid extraction liquid chromatography-tandem mass spectrometry method for perfluorinated compounds determination in fish

This paper describes the development and validation of an analytical methodology to determine eight perfluorinated compounds (PFCs) in edible fish using pressurized liquid extraction (PLE) with water and solid-phase extraction (SPE) with an ion-exchanger as extraction and pre-concentration procedures, followed by liquid chromatography-quadrupole-linear ion trap mass spectrometry (LC-QqLIT-MS). The rapidity and effectiveness of the proposed extraction procedure were compared with those most commonly used to isolate PFCs from fish (ion-pairing and alkaline digestion). The average recoveries of the different fish samples, spiked with the eight PFCs at three levels (the LOQ, 10 and 100 microg kg(-1) of each PFC), were always higher than 85% with relative standard deviation (RSD) lower than 17%. A good linearity was established for the eight PFCs in the range from 0.003-0.05 to 100 microg kg(-1), with r>0.9994. The limits of quantification (LOQs) were between 0.003 and 0.05 microg kg(-1), which are well below those previously reported for this type of samples. Compared with previous methods, sample preparation time and/or LOQs are reduced. The method demonstrated its successful application for the analysis of different parts of several fish species. Most of the samples tested positive, mainly for perfluoropentanoic acid (PFPA), perfluorobutane sulfonate (PFBS) and perfluorooctanoic acid (PFOA) but other of the eight studied PFCs were also present.

Emerging food contaminants: a review

Governments throughout the world are intensifying their efforts to improve food safety. These efforts come as a response to an increasing number of food-safety problems and increasing consumer concerns. In addition, the variety of toxic residues in food is continuously increasing as a consequence of industrial development, new agricultural practices, environmental pollution, and climate change. This paper reviews a selection of emerging contaminants in food, including the industrial organic pollutants perfluorinated compounds (PFCs), polybrominated diphenyl ethers (PBDEs), and nanomaterials; the pharmaceutical residues antibiotics and coccidiostats; and emerging groups of marine biotoxins. The main analytical approaches for their detection and quantification in food will be presented and discussed with special emphasis on biological techniques, when these are feasible. In the last section, a summary of recent publications reporting the concentrations of these compounds in food will be presented and discussed.

Perfluorinated Compounds in Food: A Global Perspective

Perfluorinated compounds (PFCs) are resistant to breakdown and are turning up in unexpected places around the world, becoming emerging food contaminants. Although these chemicals have been used in countless products since the 1950s, they have been subject to little control until now. There is still an insufficient knowledge of their sources, occurrence, and hazards for food safety decision making. This article provides a comprehensive review of the food contamination levels and dietary intake risks posed by PFCs, as well as the specific methods developed for their determination. It is based on the evaluation of the published literature between 2004 and the beginning of 2010, with special emphasis on those reports of the last two years and in the examination of the growing body of studies on the exposure assessment and food occurrence of PFCs. The current state-of-the art and future perspectives in extraction, clean-up, detection, identification, confirmation, and quantification highlighting the advantages and limitations of each technique have been summarized. How much is known about the sources and pathways of food web and human exposure, which is needed to control and manage the release of these emerging toxic contaminants, has also been explained.

Hospital wastewater treatment by fungal bioreactor: removal efficiency for pharmaceuticals and endocrine disruptor compounds.

Hospital effluents contribute to the occurrence of emerging contaminants in the environment due to their high load of pharmaceutical active compounds (PhACs) and some endocrine disruptor compounds (EDCs). Nowadays, hospital wastewaters are co-treated with urban wastewater; however, the dilution factor and the inefficiency of wastewater treatment plants in the removal of PhACs and EDCs make inappropriate the co-treatment of both effluents. In this paper, a new alternative to pre-treat hospital wastewater concerning the removal of PhACs and EDCs is presented. The treatment was carried out in a batch fluidized bed bioreactor under sterile and non-sterile conditions with Trametes versicolor pellets. Results on non-sterile experiments pointed out that 46 out of the 51 detected PhACs and EDCs were partially to completely removed. The total initial PhAC amount into the bioreactor was 8185 μg in sterile treatment and 8426 μg in non-sterile treatment, and the overall load elimination was 83.2% and 53.3% in their respective treatments. In addition, the Microtox test showed reduction of wastewater toxicity after the treatment. Hence, the good efficiency of the fungal treatment regarding removal of the wide diversity of PhACs and EDCs detected in hospital effluents is demonstrated.

Analysis of perfluoroalkyl substances in waters from Germany and Spain.

Water has been identified as one of the main routes of human exposure to perfluoroalkyl substances (PFASs). This work assessed the presence of 21 PFASs along the whole water cycle using a new fast and cost effective analytical method based on an online sample enrichment followed by liquid chromatography coupled to tandem mass spectrometry (LC-MS/MS). The method was validated for different types of matrices (ultrapure water, tap water and treated wastewater). The quality parameters for the 21 selected compounds presented good limits of detection (LOD) and quantification (LOQ) ranging, in general, from 0.83-10 ng/L to 2.8-50 ng/L, respectively. The method was applied to assess the occurrence of PFASs in 148 water samples of different steps along the whole water cycle, including: mineral bottled water, tap water, river water and treated effluent wastewater, from Germany to Spain. In addition, in order to prove the good performance of the online analytical method, the analysis of PFASs was carried out in parallel using a method based on offline anionic solid phase extraction (SPE) followed by LC-MS/MS. Consistent results were obtained using both approaches. The more frequently found compounds were perfluoroalkyl acids, such as the perfluorobutanoic acid which was in the 54% of the tap water samples investigated with concentrations in the range between 2.4 and 27 ng/L, the perfluoroheptanoic acid (0.23-53 ng/L) and perfluorooctanoic acid (0.16-35 ng/L), and the sulphonate perfluorooctanesulfonate (0.04-258 ng/L) which was the second more frequent compound and also the compound found in with the higher concentration. It should be remarked that the 88% of the samples analyzed presented at least one of the compounds at quantifiable concentrations. In addition, PFASs including short chain compounds were proved to be prevalent in drinking water, and the 50% of the drinking water samples showed quantifiable concentrations of PFASs. It should be said that the great majority of the samples may not pose an immediate health risk to consumers, and just 6 of the drinking water samples presented concentrations of PFOS exceeding the Provisional Health Advisory (PHA) level established by the Office of Water from the USEPA for PFOS, which was set in 200 ng/L.

Wastewater reuse in Mediterranean semi-arid areas: The impact of discharges of tertiary treated sewage on the load of polar micro pollutants in the Llobregat river (NE Spain).

The presence of sewage-borne micro contaminants in environmental waters is directly related to the discharge of treated effluents from wastewater treatment plants (WWTP) and the flow rate of the receiving river waters. Mediterranean rivers, in particular, are characterized by important fluctuations in the flow rates and heavy pollution pressures resulting from extensive urban, industrial and agricultural activities. This translates into contamination levels in these rivers often higher than those in other larger European basins. The present work provides an overview of the occurrence of five groups of organic contaminants (131 compounds) namely pharmaceuticals, illicit drugs, polar pesticides, estrogens, alkylphenols and related ethoxylates in WWTP tertiary treatment effluents. Data gathered during a period of water reuse carried out in the lower stretch of the Llobregat river (NE Spain), in the surroundings of the town of Barcelona as a consequence of the severe drought that took place along the years 2007-2008 are presented as illustrative example. In general, measured concentrations of the target compounds were in the low to mid ngL(-1) range. The total concentration of each compound class downstream to the discharge point was similar or slightly higher than that found upstream. Regarding the loads calculated for each compound, the relative contribution from the river upstream and the tertiary effluent were highly compound depending with no apparent trend. However, estimation of the overall bulk loads for each compound class determined in the Llobregat river showed the following rank order: pharmaceuticals>alkylphenols>pesticides>illicit drugs≫estrogens.

Assessment of perfluoroalkyl substances in food items at global scale

This study assessed the levels of 21 perfluoroalkyl substances (PFASs) in 283 food items (38 from Brazil, 35 from Saudi Arabia, 174 from Spain and 36 from Serbia) among the most widely consumed foodstuffs in these geographical areas. These countries were chosen as representatives of the diet in South America, Western Asia, Mediterranean countries and South-Eastern Europe. The analysis of foodstuffs was carried out by turbulent flow chromatography (TFC) combined with liquid chromatography with triple quadrupole mass spectrometry (LC-QqQ-MS) using electrospray ionization (ESI) in negative mode. The analytical method was validated for the analysis of different foodstuff classes (cereals, fish, fruit, milk, ready-to-eat foods, oil and meat). The analytical parameters of the method fulfill the requirements specified in the Commission Recommendation 2010/161/EU. Recovery rates were in the range between 70% and 120%. For all the selected matrices, the method limits of detection (MLOD) and the method limits of quantification (MLOQ) were in the range of 5 to 650 pg/g and 17 to 2000 pg/g, respectively. In general trends, the concentrations of PFASs were in the pg/g or pg/mL levels. The more frequently detected compounds were perfluorooctane sulfonic acid (PFOS), perfluorooctanoic acid (PFOA) and perfluorobutanoic acid (PFBA). The prevalence of the eight-carbon chain compounds in biota indicates the high stability and bioaccumulation potential of these compounds. But, at the same time, the high frequency of the shorter chain compounds is also an indication of the use of replacement compounds in the new fluorinated materials. When comparing the compounds profile and their relative abundances in the samples from diverse origin, differences were identified. However, in absolute amounts of total PFASs no large differences were found between the studied countries. Fish and seafood were identified as the major PFASs contributors to the diet in all the countries. The total sum of PFASs in fresh fish and seafood was in the range from the MLOQ to 28ng/g ww. According to the FAO-WHO diets composition, the daily intake (DI) of PFASs was calculated for various age and gender groups in the different diets. The total PFASs food intake was estimated to be between 2300 and 3800 ng /person per day for the different diets. Finally, the risk intake (RI) was calculated for selected relevant compounds. The results have indicated that by far in no case the tolerable daily intake (TDI) (150, 1500, 50,000, 1,000,000, 150, 1500 ng/kg body weight, for perfluorohexanesulfonate (PFHxS), fluorotelomer alcohol (FTOH), perfluorobutanesulfonic acid (PFBS), perfluorobutanoic acid (PFBA), PFOS and PFOA, respectively) was exceeded.

Analysis of perfluorinated compounds in sewage sludge by pressurized solvent extraction followed by liquid chromatography-mass spectrometry.

Perfluorinated compounds (PFCs) are widely used in everyday life and one of the main recipients of these compounds is waste water treatment plants (WWTPs). Due to the structure and physicochemical properties of PFCs, these compounds could be redistributed from influent water to sludge. This work reports a new validated protocol for the analysis of 13 perfluorinated acids, 4 perfluorosulfonates and the perfluorooctanesulfonamide. The present work has been focused to develop a sensitive and robust method for the analysis of 18 PFCs in sewage sludge, based on pressurized solvent extraction (PSE) followed by solid phase extraction (SPE) clean-up, analytes separation by liquid chromatography and analysis in a hybrid quadrupole-linear ion trap mass spectrometer (LC-QLiT-MS/MS) working in single reaction monitoring (SRM) mode. The final methodology was validated using a blank sewage sludge fortified at different concentration levels. The method limits of detection were ranging in general from 15 to 79 ng/kg. These values were comparable to the decision limit (CCα) and the detection capability (CCβ), which were 17-1134 ng/kg and 18-1347 ng/kg, respectively. The percentage of recovery was from 79 to 111% in the most cases at different spiked levels. Finally, the repeatability of the method was in the range 4% (PFOS and PFOA) to 25% (RSD %). In order to evaluate the applicability of the method, 5 sludge samples were analyzed. The results showed that the 18 PFCs were present in all samples. However, the concentrations for most of them were below the limits of quantification. The compound present at higher concentrations was perfluorooctanesulfonate (PFOS), which was in concentrations from 53.0 to 121.1 μg/kg. The other PFCs were at concentrations between 0.3 and 30.3 μg/kg.

Solid-phase treatment with the fungus Trametes versicolor substantially reduces pharmaceutical concentrations and toxicity from sewage sludge

For safe biosolid-land-applying, sludge should be contaminant-free. However, it may contain important amounts of micropollutants, not removed in the wastewater-treatment-processes. An alternative treatment with the fungus Trametes versicolor was applied in sterile solid-phase systems consisting of sludge and a lignocellulosic substrate. Fungal colonization and activity were demonstrated during the process, according to monitoring of ergosterol, laccase activity and the naproxen-degradation test (ND24). Fourteen out of 43 analyzed pharmaceuticals were found in the raw sludge. After treatment, phenazone, bezafibrate, fenofibrate, cimetidine, clarithromycin, sulfamethazine and atenolol were completely removed, while removals between 42% and 80% were obtained for the remaining pharmaceuticals. Toxicological analyses (Daphnia magna, Vibrio fischeri and seed germination) showed an important reduction in sludge toxicity after treatment. Results suggest that a solid-phase treatment with T. versicolor may reduce the ecotoxicological impact of micropollutants present in sewage sludge. This is the first report of a fungal-approach for elimination of emerging pollutants from biosolids.