RESUMO
Currently, there are many contaminants of concern that need to be accurately determined to help assess their potential environmental hazard. Despite their increasing interest, yet few environmental occurrence data exist, likely because they are present at low levels and in very complex matrices. Therefore, multiresidue analytical methods for their determination need to be highly sensitive, selective, and robust. Particularly, due to the trace levels of these chemicals in the environment, an extensive extraction procedure is required before determination. This work details the development of a fast and cheap vortex-assisted matrix solid-phase dispersion-high performance liquid chromatography tandem-mass spectrometry (VA-MSPD-HPLC-MS/MS) method for multiresidue determination of 59 contaminants of emerging concern (CECs) including pharmaceuticals, personal care products, and booster biocides, in sediment. The validated method provided high sensitivity (0.42-36.8 ngg-1 dw quantification limits), wide and good linearity (r2 > 0.999), satisfactory accuracy (60-140%), and precision below 20% for most target analytes. In comparison with previous methods, relying on traditional techniques, the proposed method demonstrated to be more environmentally friendly, cheaper, simpler, and faster. The method was applied to monitor the occurrence of these compounds in sediments collected in Brazil, using only 2 g dw sediment samples, free-solid support, and 5 mL methanol as extraction solvent. The UV filter avobenzone, the UV stabilizer and antifreeze methylbenzotriazole, the preservative methylparaben, the fluoroquinolone antibiotic ciprofloxacin, and the biocides irgarol and 4,5-dichloro-2-octyl-4-isothiazolin-3-one were determined at concentrations in the range 1.44-69.7 ngg-1 dw.
Assuntos
Cosméticos , Desinfetantes , Brasil , Cromatografia Líquida de Alta Pressão , Cosméticos/análise , Análise Custo-Benefício , Desinfetantes/análise , Sedimentos Geológicos , Extração em Fase Sólida , Espectrometria de Massas em TandemRESUMO
The anodic oxidation (AO) of 30 pharmaceuticals including antibiotics, hormones, antihistaminics, anti-inflammatories, antidepressants, antihypertensives, and antiulcer agents, in solutions containing different supporting electrolytes media (0.05 M Na2SO4, 0.05 M NaCl, and 0.05 M Na2SO4 + 0.05 M NaCl) at natural pH was studied. A boron-doped diamond (BDD) electrode and a stainless-steel electrode were used as anode and cathode, respectively, and three current densities of 6, 20, and 40 mA cm-2 were applied. The results showed high mineralization rates, above 85%, in all the tested electrolytic media. 25 intermediaries produced during the electrooxidation were identified, depending on the supporting electrolyte together with the formation of carboxylic acids, NO3-, SO42- and NH4+ ions. The formation of intermediates in chloride medium produced an increase in absorbance. Finally, a real secondary effluent spiked with the 30 pharmaceuticals was treated by AO applying 6 mA cm-2 at natural pH and without addition of supporting electrolyte, reaching c.a. 90% mineralization after 300 min, with an energy consumption of 18.95 kW h m-3 equivalent to 2.90 USD m-3. A degradation scheme for the mixture of emerging contaminants in both electrolytic media is proposed. Thus, the application of anodic oxidation generates a high concentration of hydroxyl radicals that favors the mineralization of the pharmaceuticals present in the spiked secondary effluent sample.
Assuntos
Preparações Farmacêuticas , Poluentes Químicos da Água , Boro , Diamante , Eletrodos , Eletrólise , OxirreduçãoRESUMO
UV filters (UV-Fs) constitute a heterogeneous group of chemicals used as protection against the effects of UV radiation, widely used in all sort of goods and ubiquitous in the environment. The presence of these chemicals in fish is a matter of concern, because many UV-Fs display hormonal activity. In this study, muscle, gills, and liver from 11 Mugil liza individuals from the highly urbanized Guanabara Bay (Rio de Janeiro, Brazil) were analysed in order to detect eight UV-Fs and metabolites (4-dihydroxybenzophenone [BP1] (2-hydroxy-4-methoxybenzophenone [BP3], 4-methylbenzylidiene camphor [4MBC], ethylhexyl methoxycinnamate [EHMC], ethylhexyl dimethyl p-aminobenzoic acid [ODPABA], octocrylene [OC], 4-hydroxybenzophenone [4HB], and 4,4'-dihydroxybenzophenone [4DHB]) using liquid chromatography-tandem mass spectrometry (HPLC-MS/MS). Results showed that both target UV-Fs and metabolites were ubiquitous in the analysed tissues. Lower concentrations were observed in muscle and gills (3.07-31.6ngg-1 dry weight (dw)), whereas in liver significant amounts of metabolites (5.47-451ngg-1 dw) were present. With the concentrations determined in the fish, an estimation of the daily intake revealed that consumption of muscle in the diet represent from 0.3 to 15.2ng UV-Fs (kg body weight-1) d-1, higher than those reported in fish for selected persistent organic pollutants (POPs).
Assuntos
Smegmamorpha , Protetores Solares/análise , Poluentes Químicos da Água/análise , Animais , Baías , Brasil , Monitoramento Ambiental , Brânquias/química , Fígado/química , Músculos/química , Espectrometria de Massas em Tandem , Raios UltravioletaRESUMO
Pyrethroids (PYR) and UV filters (UVF) were investigated in tissues of paired mother-fetus dolphins from Brazilian coast in order to investigate the possibility of maternal transfer of these emerging contaminants. Comparison of PYR and UVF concentrations in maternal and fetal blubber revealed Franciscana transferred efficiently both contaminants to fetuses (F/M > 1) and Guiana dolphin transferred efficiently PYR to fetuses (F/M > 1) different than UVF (F/M < 1). PYR and UVF concentrations in fetuses were the highest-ever reported in biota (up to 6640 and 11,530 ng/g lw, respectively). Muscle was the organ with the highest PYR and UVF concentrations (p < 0.001), suggesting that these two classes of emerging contaminants may have more affinity for proteins than for lipids. The high PYR and UVF concentrations found in fetuses demonstrate these compounds are efficiently transferred through placenta. This study is the first to report maternal transfer of pyrethroids and UV filters in marine mammals.
Assuntos
Golfinhos/metabolismo , Inseticidas/farmacocinética , Troca Materno-Fetal , Piretrinas/farmacocinética , Protetores Solares/farmacocinética , Poluentes Químicos da Água/farmacocinética , Tecido Adiposo/metabolismo , Animais , Brasil , Golfinhos/embriologia , Feminino , Inseticidas/análise , Exposição Materna , Placenta/metabolismo , Gravidez , Piretrinas/análise , Protetores Solares/análise , Distribuição Tecidual , Poluentes Químicos da Água/análiseRESUMO
Four previously unreported metabolism products of sulfaquinoxaline (SQX), a widely used veterinary medicine, were isolated and analyzed using liquid chromatography coupled to high-resolution Orbitrap mass spectrometry. Metabolites were structurally elucidated, and a fragmentation pathway was proposed. The combination of high-resolution MS(2) spectra, linear ion trap MS(2), in-source collision-induced dissociation (CID) fragmentation, and photolysis were used to analyze SQX and its metabolites. All metabolism products identified showed a similar fragmentation pattern to that of the original drug. Differential product ions were produced at m/z 162 and 253 which contain the radical moiety with more 16 Da units than sulfaquinoxaline. This occurs by a hydroxyl attachment to the quinoxaline moiety. With the exception of two low-intensity compounds, all the mass errors were below 5.0 ppm. The distribution of these metabolites in some animal species are also presented and discussed.
Assuntos
Sulfaquinoxalina/química , Animais , Biotransformação , Bovinos , Cromatografia Líquida de Alta Pressão , Radical Hidroxila/química , Hidroxilação , Indicadores e Reagentes , Fígado/química , Espectrometria de Massas , Aves Domésticas , Ovinos , Sulfaquinoxalina/metabolismo , Distribuição TecidualRESUMO
Most current bioexposure assessments for UV filters focus on contaminants concentrations in fish from river and lake. To date there is not information available on the occurrence of UV filters in marine mammals. This is the first study to investigate the presence of sunscreen agents in tissue liver of Franciscana dolphin (Pontoporia blainvillei), a species under special measures for conservation. Fifty six liver tissue samples were taken from dead individuals accidentally caught or found stranded along the Brazilian coastal area (six states). The extensively used octocrylene (2-ethylhexyl-2-cyano-3,3-diphenyl-2-propenoate, OCT) was frequently found in the samples investigated (21 out of 56) at concentrations in the range 89-782 ng·g(-1) lipid weight. São Paulo was found to be the most polluted area (70% frequency of detection). Nevertheless, the highest concentration was observed in the dolphins from Rio Grande do Sul (42% frequency of detection within that area). These findings constitute the first data reported on the occurrence of UV filters in marine mammals worldwide.