Particle-phase concentrations and sources of legacy and novel flame retardants in outdoor and indoor environments across Spain.

Levels of particle-phase legacy polybrominated diphenyl ethers (PBDEs), and novel brominated and chlorinated flame retardants, such as decabromodiphenyl ethane (DBDPE) and Dechlorane Plus (DP), were measured in ambient outdoor air, indoor workplace air and indoor dust, in different locations across Spain. PBDE concentrations were generally higher in outdoor ambient air samples than in indoor air, ranging between 1.18 and 28.6 pg m-3, while DP was the main flame retardant (FR) in indoor air (2.90-42.6 pg m-3). A different behavior of legacy versus novel FRs was observed in all the environments and matrices considered, which seemed to indicate a progressive replacement of the former. Although the emission sources could not be fully identified, certain evidences suggested that high outdoor PBDE concentrations could be associated with old goods in landfills and recycling centers, while high indoor DP concentrations were linked to the presence of new electronic devices. A direct impact of land use on outdoor atmospheric DP concentrations was observed, with DP concentrations correlating with high density of buildings within a city. In addition, DP concentrations outdoors correlated with inorganic species with FR properties (e.g., Cr, Cu). Significant differences in the fraction of anti-DP to the total DP (Fanti ratio) were observed between indoor air (PM2.5) and dust (PM10), which could be related with: a) a dependence on particle size, suggesting a higher relative abundance of the anti-isomer in PM10 than in PM2.5, while similar concentrations were recorded for the syn-isomer; b) a higher deposition rate of the anti-isomer compared to the syn-isomer; and/or c) a more accentuated preferential degradation of the anti-isomer linked to artificial light or other agents coexisting in the air. The detectable presence of all the FR families analyzed in indoor air and dust points to the importance of monitoring these compounds in order to minimize human exposure.

Contaminants of emerging concern in freshwater fish from four Spanish Rivers.

This study investigated the occurrence of 135 contaminants of emerging concern (CECs) - pharmaceuticals, pesticides, a set of endocrine disrupting compounds (EDCs) (parabens, bisphenols, hormones, triazoles, organophosphorus flame retardants and triclosan), UV-filters, perfluoroalkyl substances (PFASs) and halogenated flame retardants (HFRs) - in 59 fish samples, collected in 2010 in 4 Spanish Rivers (Guadalquivir, Júcar, Ebro and Llobregat). Of the 135 CECs, 76 including 8 pharmaceuticals, 25 pesticides, 10 EDCs, 5 UV-filters, 15 PFASs and 13 HFRs were detected. Pharmaceuticals were the less frequently found and at lower concentrations. Pesticides, EDCs, UV-filters, PFASs and HFRs were detected more frequently (>50% of the samples). The maximum concentrations were 15 ng/g dry weight (dw) for pharmaceuticals (diclofenac), 840 ng/g dw for pesticides (chlorpyrifos), 224 ng/g dw for EDCs (bisphenol A), 242 ng/g dw for UV-filters (EHMC), 1738 ng/g dw for PFASs (PFHxA) and 64 ng/g dw for HFRs (Dec 602). The contaminants detected in fish are commonly detected also in sediments. In light of current knowledge, the risk assessment revealed that there was no risk for humans related to the exposure to CECs via freshwater fish consumption. However, results provide detailed information on the mixtures of CECs accumulated that would be very useful to identify their effects on aquatic biota.

Organic carbon content effects on bioavailability of pyrethroid insecticides and validation of solid phase extraction with Poly (2,6-diphenyl-p-phenylene oxide) Polymer by Daphnia magna toxicity tests.

Solid phase extraction with Poly (2,6-diphenyl-p-phenylene oxide) Polymer (Tenax) was used for determining the bioavailability of eleven pyrethroids in field collected sediments with different organic carbon content (OC). The bioavailable fraction of pyrethroids decreased with increasing OC in sediments; the percentages of desorption ranged from 10 to 20% for sediment with higher OC content (5.8%) and 15-40% for that with lower OC (2%). Generally pyrethroids showed low bioavailability and cyfluthrin resulted to be the most bioavailable among the studied pyrethroids. Acute toxicity tests with Daphnia magna were carried out on sediment spiked with three selected pyrethroids (λ-cyhalothrin, cypermethrin and deltamethrin) and served to validate the efficiency of Tenax as a method for assessing the bioavailability of pyrethroids. Toxicity test demonstrated that Tenax was able to remove the toxic bio-available fraction of pyrethroids in sediment. Extracts from Tenax beads after the desorption experiments and spiked sediment before desorption had an equivalent toxicity (LC50) to D. magna neonates at 48 and 72 h of exposure. These results indicate that Tenax beds can be used to predict bio-available and toxic fractions of pyrethroids sorbed to sediments to aquatic organisms like D. magna.