Pyrethroid bioaccumulation in Mediterranen dolphins

Pyrethroids are organic pollutants with high hydrophobicity used as insecticides. Concern exists about aquatic organisms¿ exposure to their toxicity. They were believed to be converted to non-toxic metabolites in mammals, but our group has detected them in human breast milk and has proved their bioaccumulation in marine mammals and river fish. The present study investigates the occurrence of pyrethroid compounds in liver samples from striped dolphins (Stenella coeruleoalba)and common dolphins (Delphinus delphis) from southern Spain, as the first attempt to determine the occurrence and bioaccumulation and distribution of pyrethroids in marine mammal tissues from the Mediterranean Sea. Samples of dolphin tissue were collected from the Abloran Sea (south of Spain) between 2003 and 2010, including 37 liver samples from striped dolphin and different tissues¿blubber, muscle, liver, brain and kidneys¿from 11 common dolphins. The analytical method monitored 10 pyrethroids, including cypermethrin and detamethrin. For the sample preparation?lyophilized sample was spiked with internal standards, extracted by sonication and underwent a clean-up with alumina and C18 SPE cartridges. Extracts were analysed by GC-NCI-MS/MS. Method recoveries for the pyrethroids ranged 53-116?% and method LODs and LOQs were 0.02-0.46?ng/g and 0.08-1.54?ng/g, respectively. Pyrethroids were detected in 87?% of the striped dolphins and 100?% of the common dolphins, with total concentrations of nd-5,210?ng/g?lw and 69-2,036?ng/g?lw, respectively. These levels were higher than those reported found in dolphins from Brazil (7.0-68?ng/g?lw). Permethrin and tetramethrin were the main contributors to the pyrethroid profiles for all tissues. The samples of striped dolphins where used to observe that bioaccumulation of pyrethroids was unlike that of persistent organic pollutants (POPs), as pyrethroid levels were not correlated to the age of the specimens. Levels slightly increase from calves to juveniles, whereas juveniles present similar levels to adults. Metabolization of pyrethroids after achieving sexual maturity might account for this pattern. Because of the pyrethroids lipophilic behaviour, blubber was the most contaminated tissue and brain showed the lowest levels. Normalizing the data to the lipid content, the highest value was for muscle by far, suggesting a preference for that tissue. SETA

Degradation of selected agrochemicals by the white rot fungus Trametes versicolor

Use of agrochemicals is a worldwide practice that exerts an important effect on the environment; therefore the search of approaches for the elimination of such pollutants should be encouraged. The degradation of the insecticides imiprothrin (IP) and cypermethrin (CP), the insecticide/nematicide carbofuran (CBF) and the antibiotic of agricultural use oxytetracycline (OTC) were assayed with the white rot fungus Trametes versicolor. Experiments with fungal pellets demonstrated extensive degradation of the four tested agrochemicals, at rates that followed the pattern IP > OTC > CP > CBF. In vitro assays with laccase-mediator systems showed that this extracellular enzyme participates in the transformation of IP but not in the cases of CBF and OTC. On the other hand, in vivo studies with inhibitors of cytochrome P450 revealed that this intracellular system plays an important role in the degradation of IP, OTC and CBF, but not for CP. The compounds 3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropane carboxylic acid (DCCA) and 3-phenoxybenzoic acid (PBA) were detected as transformation products of CP, as a result of the breakdown of the molecule. Meanwhile, 3-hydroxycarbofuran was detected as a transformation product of CBF; this metabolite tended to accumulate during the process, nonetheless, the toxicity of the system was effectively reduced. Simultaneous degradation of CBF and OTC showed a reduction in toxicity; similarly, when successive additions of OTC were done during the slower degradation of CBF, the fungal pellets were able to degrade both compounds. The simultaneous degradation of the four compounds successfully took place with minimal inhibition of fungal activity and resulted in the reduction of the global toxicity, thus supporting the potential use of T. versicolor for the treatment of diverse agrochemicals

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.This research has been supported by the European Union 7th Framework Programme funding under Grant Agreement No. 603629-ENV-2013-6.2.1-Globaqua, by the Generalitat de Catalunya (Consolidated Research Groups 2017 SGR 1404 - Water and Soil Quality Unit) and by the Generalitat Valenciana (ANTROPOCEN@, PROMETEO/2018/155).Peer reviewe

First report of pyrethroid bioaccumulation in wild river fish: A case study in Iberian river basins (Spain)

© 2014 Elsevier Ltd. For the first time, this work described pyrethroid bioaccumulation in edible river fish samples. We analyzed 42 whole fish samples collected in 4 different Iberian rivers. All samples were positive to these insecticides. Levels of concentration ranged from 12 to 4938ngg-1 lipid weight (lw). Moreover, isomeric characterization was carried out. Our results remarked a general preference of cis isomers in bioaccumulation. Finally, the enantiomeric evaluation showed that there was an enantioselective bioaccumulation of some pyrethroids, depending on the studied species. Pyrethroid concentrations were compared with levels obtained for other common pollutants, such as flame retardants, personal care products, hormones and pharmaceuticals. The highest values corresponded to pyrethroid insecticides, even though, pyrethroid levels are safe for human consumption taken into account the current regulations.This research was funded by the Spanish Ministry of Science and Innovation through the project SCARCE (Consolider Ingenio 2010 CSD2009-00065). This work has also been partly funded by the Generalitat de Catalunya (Consolidated Research Groups 2014 SGR 418 — Water and Soil Quality Unit). Biotage is acknowledged for SPE cartridges

Estudi dels insecticides Piretroides en mostres biològiques i humanes

[cat] Aquesta tesi pretén donar una visió general del comportament dels piretroides en el medi ambient i, concretament en la biota salvatge. A més, com a conseqüència directa d’això, també avalua l’exposició humana a aquests insecticides. Els piretroides són uns insecticides emprats molt comunament. El seu ús avarca des d’usos agraris i ramaders fins a domèstics. També s’han emprat sovint en control de plagues i Salut Pública, com ara amb el control de mosquits vectors de malalties com la malària o el dengue. Per últim, l’ús dels piretroides sobre els humans tampoc no és estrany, ja que les fórmules més habituals de locions anti- polls i contra la sarna, entre d’altres, contenen piretroides com a principis actius. Aquests insecticides són sintètics o semi-sintètics. Deriven d’uns extractes naturals de flors de diferents espècies de Chrisantemum. Aquests extractes contenen piretrines que són ésters de l’àcid crisantèmic. Els piretroides, són, també, ésters d’aquest àcid que solen estar funcionalitzats. Segons si contenen un grup ciano en la posició alfa’ de l’àcid, es distingeixen els piretroides tipus I (que no contenen el grup ciano) i els de tipus II (que sí que el tenen). Aquestes molècules, són molècules amb 2 o 3 centres quirals, raó per la qual la isomeria d’aquests també és un tema important a tractar. Durant la tesi es va desenvolupar un mètode de determinació enantioselectiu per a 6 piretroides. Fins al inici de la tesi cap mètode quiral de la bibliografia era capaç de separar tots els enantiòmers d’un piretroide. El mètode desenvolupat demostrà l’eficàcia en separar els 4 isòmers de la tetrametrina. Per contra, amb la resta de piretroides del mètode (bifentrina, ciflutrina, cihalotrina, cipermetrina i peremetrina) només els isòmers cis es podien separar enantiomèricament, mentre que els trans no es podien discriminar. A més d’aquesta metodologia, es millorà la metodologia preexistent de quantificació de piretroides, la qual fou capaç, al final de la tesi, de determinar 19 piretroides i un pesticida organofosforat (clorpirifós) en una sola anàlisi. Un cop es tenia metodologia adecuada, es mostrejar fauna salvatge. Es dividí el tipus de fauna segons el medi que habiten les espècies, a saber, medi terrestre i medi aquàtic. Les espècies de medi terrestre que es van incloure en el estudi foren aus i grans mamífers de l’Antàrtida. De les aus es mostrejaren ous. Concretament, s’analitzaren ous infèrtils d’aus del Parc Natural de Doñana. El 96% de les mostres donaren positiu a la presència de piretroides. A més de l’anàlisi de piretroides s’analitzaren els delta15N i el delta14C, amb la finalitat de comprovar si els piretroides eren biomagnificables en la xarxa tròfica. Tot i que els resultats de isòtops estables no foren concloents, tot semblà indicar que l’exposició als piretroides venia donada per la dieta, tot i que no es biomagnificaven. En mostres de mamífers de l’Antàrtic no es trobaren nivells de piretroides detectables, la qual cosa indicà que aquests insecticides no es transporten llargues distàncies. Del medí aquàtic s’analitzaren peixos de riu i dofins. El 100% de les mostres presentà nivells quantificables de piretroides. Els peixos mostraren que l’exposició de piretroides ha d’estar relacionada amb quelcom més que no pas el medi físic ja que individus del mateix punt de presa de mostra presentaven perfils de piretroides diferents, és a dir, que la proporció d’un piretroide respecte d’un altre era diferent segon el individu analitzat. Això podia venir donat a una metabolització selectiva d’uns piretroides o a que l’exposició fos via dieta i els animals, que pertanyien a espècies diferents, tinguessin diferents hàbits alimenticis. Pel que fa a dofins, es va trobar que tant dofins brasilers com espanyols presentaven nivells de piretroides tot i que els primers solien presentar més nivells de cipermetrina i permetrina mentre que els segons de cipermetrina i tetrametrina. També es va demostrar la transferència materna com un possible problema toxicològic per als fetus i els lactants. Finalment, es va comprovar la distribució dels piretroides en diferents teixits i es va arribar a la conclusió que el teixit adipós és on més piretroides s’acumulen, tot i que, segurament gràcies a la unió amb diferents proteïnes, en teixits magres també s’hi trobaven nivells. Amb això es preferí per a mostrejos posteriors el fetge com a matriu a analitzar o, en cas de individus vius, el teixit adipós superficial. Respecte dels humans, es comprovà que la població general està exposada als piretroides a nivells relativament baixos. Els estudis es van fer en poblacions de Brasil, Colòmbia i Barcelona. Amb tot, donats els resultats, s’optà per aconsellar un millor control dels nivells de piretroides en llets maternes, sobretot de poblacions sobre-exposades, i una revisió dels valors de ingesta acceptables de piretroide en el cas de infants i lactants.[eng] The present Thesis is about pyrethroid insecticides. They are very used in agrarian, veterinarian and domestic environments. Besides, they are used in Public Health in order to control mosquito vectors of diseases such as malaria and dengue. They are chiral molecules, thus isomeric characteristics are important in their environmental behavior and toxicology. In this thesis, a new method for enantiomeric discrimination of 6 pyrethroids was developed. For the first time a method was able to separate all enantiomers of one pyrethorid, in this case, tetramethrin. Besides, the method was able to differentiate cis enantiomers of bifenthrin, cyfluthrin, cyhalothrin, cypermethrin and permethrin. Pyrethorids were evaluated in unfertile wild bird egg samples, Antarctic mammals, river fishes and dolphins. In 96% of bird eggs residues of pyrethroids were observed. In 100% of all the rest of matrices presented quantifiable levels of pyrethroids except for Antarctic mammal samples. First way of exposure to pyrethroids for these wild species seemed to be diet. However, no biomagnification was described. Long distance transport was discarded since Antarctic samples did not present levels of pyrethrids. Pyrethroids were mostly accumulated in lipid tissues, such as dolphin blubber. The best matrix to future monitoring was described as liver samples, even when for living individuals, superficial blubber sample could be used. Cis isomer of pyrethroids were more bioaccumulated than trans, except in the case of tetramethrin. In this last case, commercial mixtures, which are enhanced in trans isomer, could explain this observation. For the rest of pyrethroids, cis isomer was enhanced because of the preference of trans isomer in the isomer-selective metabolization of most of organisms. Regarding human exposure, breast milk samples from Brazil, Colombia and Spain were analyzed. All samples were positive in the pyrethroid determination analyses. Even when levels in general population seemed to be save, Acceptable Daily Intake values should be reconsidered for breastfed children

Concentrations and sources of legacy and novel flame retardants in outdoor and indoor environments

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. © 2018This work was partially funded by the Spanish Ministry of Economy, Industry and Competitiveness (MINEC) and the Agencia Estatal de Investigación (AEI) through project CGL2017-82093-ERC. The authors acknowledge the support from AGAUR SGR41 and SGR1404.Peer reviewe

Pyrethroid insecticides in wild bird eggs from a world heritage listed park: a case study in Doñana National Park (Spain)

Recent studies demonstrated that the common pyrethroid insecticides are present in aquatic biota tissues. In this study, 123 samples of unhatched eggs of 16 wild bird species collected from 2010 to 2012 in Doñana National and Natural Park were analysed to determine 13 pyrethroids. This study represents the first time that pyrethroids are detected in tissues of terrestrial biota, 93% of these samples being positive to those pollutants. Levels of total pyrethroids ranged from not detected to 324 ng g lw. The samples were characterized by stable isotope analysis. Species with diets based on anthropogenic food showed higher levels of pyrethroids and lower values of δN. Finally, we characterized the isomers of pyrethroids and discerned some isomeric- and enantiomeric-specific accumulations. In particular, tetramethrin and cyhalothrin showed an enantiomeric-selective accumulation of one enantiomer, highlighting the need to assess toxicological effects of each enantiomer separately to be able to make a correct risk assessment of pyrethroids in birds.This work was funded by the Spanish Ministry of Environment and Rural and Marine Affairs through the project IMPAR (Ref. 106/2010). This work has also been partly funded by the Generalitat de Catalunya (Consolidated Research Group “2014 SGR 418—Water and Soil Quality Unit”). Sampling of raptor eggs was funded by excellence project RNM-7307 of the Junta de Andalucía and CGL2011-28103 and CGL2015- 69445-P of the Spanish Ministry of Economy and Competitiveness. The authors also want to thank Renaud de Stephanis from the EBD-CSIC for the financial support with the stable isotope analysis