RESUMO
The presence of contaminants of emerging concern in aquatic ecosystems represents an ever-increasing environmental problem. Aquatic biota is exposed to these contaminants, which can be absorbed and distributed to their organs. This study focused on the assessment, distribution, and ecological risk of 32 CECs in a Spanish river impacted by effluents from a wastewater treatment plant, analyzing the organs and plasma of common carp. Environmental concentrations in water and sediment were examined at sites upstream and downstream of the wastewater treatment plant. The two downstream sites showed 15 times higher total concentrations (12.4 µg L-1 and 30.1 µg L-1) than the two upstream sites (2.08 µg L-1 and 1.66 µg L-1). Half of the CECs were detected in fish organs, with amantadine having the highest concentrations in the kidney (158 ng g-1 w.w.) and liver (93 ng g-1 w.w.), followed by terbutryn, diazepam, and bisphenol F in the brain (50.2, 3.82 and 1.18 ng g-1 w.w.). The experimental bioaccumulation factors per organ were compared with the bioconcentration factors predicted by a physiologically based pharmacokinetic model, obtaining differences of one to two logarithmic units for most compounds. Risk quotients indicated a low risk for 38 % of the contaminants. However, caffeine and terbutryn showed an elevated risk for fish. The mixed risk quotient revealed a medium risk for most of the samples in the three environmental compartments: surface water, sediment, and fish.
Assuntos
Monitoramento Ambiental , Sedimentos Geológicos , Águas Residuárias , Poluentes Químicos da Água , Poluentes Químicos da Água/análise , Águas Residuárias/química , Animais , Sedimentos Geológicos/química , Medição de Risco , Carpas , Rios/química , Espanha , PeixesRESUMO
Pharmaceuticals and pesticides can be considered hazardous compounds for Mediterranean coastal wetland ecosystems. Although many of these compounds co-occur in environmental samples, only a few studies have been dedicated to assessing the ecotoxicological risks of complex contaminant mixtures. We evaluated the occurrence of 133 pharmaceuticals and pesticides in 12 sites in a protected Mediterranean wetland, the Albufera Natural Park (ANP), based on conventional grab sampling and polar organic chemical integrative samplers (POCIS). We assessed acute and chronic ecological risks posed by these contaminant mixtures using the multi-substance Potentially Affected Fraction (msPAF) approach and investigated the capacity of a constructed wetland to reduce chemical exposure and risks. This study shows that pharmaceuticals and pesticides are widespread contaminants in the ANP, with samples containing up to 75 different compounds. POCIS samplers were found to be useful for the determination of less predictable exposure profiles of pesticides occurring at the end of the rice cultivation cycle, while POCIS and grab samples provide an accurate method to determine (semi-)continuous pharmaceutical exposure. Acute risks were identified in one sample, while chronic risks were determined in most of the collected samples, with 5-25% of aquatic species being potentially affected. The compounds that contributed to the chronic risks were azoxystrobin, ibuprofen, furosemide, caffeine, and some insecticides (diazinon, imidacloprid, and acetamiprid). The evaluated constructed wetland reduced contaminant loads by 45-73% and reduced the faction of species affected from 25 to 6%. Our study highlights the need of addressing contaminant mixture effects in Mediterranean wetlands and supports the use of constructed wetlands to reduce contaminant loads and risks in areas with high anthropogenic pressure.
Assuntos
Praguicidas , Poluentes Químicos da Água , Praguicidas/análise , Áreas Alagadas , Ecossistema , Monitoramento Ambiental/métodos , Compostos Orgânicos , Preparações Farmacêuticas , Poluentes Químicos da Água/análiseRESUMO
A robust and efficient extraction method was developed to detect a broad range of pollutants of emerging interest in three freshwater invasive species: American red crab (Prokambarus clarkii), Asian clam (Corbicula fluminea), and pumpkinseed fish (Lepomis gibbosus). One native species, "petxinot" clam (Anodonta cygnea), was also evaluated. Invasive species are often more resistant to contamination and could be used in biomonitoring studies to assess the effect of contaminants of emerging concern on aquatic ecosystems while preserving potentially threatened native species. So far, most extraction methods developed for this purpose have focused on analyzing fish and generally focus on a limited number of compounds, especially analyzing compounds from the same family. In this sense, we set out to optimize a method that would allow the simultaneous extraction of 87 PhACs, 11 flame retardants, 21 per- and poly-fluoroalkyl substances, and 54 pesticides. The optimized method is based on ultrasound-assisted solvent extraction. Two tests were performed during method development, one to choose the extraction solvent with the best recovery efficiencies and one to select the best clean-up. The analysis was performed by high-performance liquid chromatography coupled to high-resolution mass spectrometry. The method obtained recoveries between 40 and 120% and relative standard deviations of less than 25% for 85% of the analytes in the four validated matrices. Limits of quantification between 0.01 ng g-1 and 22 ng g-1 were obtained. Application of the method on real samples from the Albufera Natural Park of Valencia (Spain) confirmed the presence of contaminants of emerging concern in all samples, such as acetaminophen, hydrochlorothiazide, tramadol, PFOS, carbendazim, and fenthion. PFAS were the group of compounds with the highest mean concentrations. C. fluminea was the species with the highest detection frequency, and P. clarkii had the highest average concentrations, so its use is prioritized for biomonitoring studies.
Assuntos
Espécies Introduzidas , Espectrometria de Massas em Tandem , Animais , Espectrometria de Massas em Tandem/métodos , Ecossistema , Água Doce , Solventes/química , Extração em Fase Sólida/métodosRESUMO
A robust method was developed for the quantification of popular and highly occurrence contaminants of emerging concern from wastewater treatment plant effluents and is explained in detail. A homemade multi-layered and multi-sorbent solid phase extraction (SPE) cartridge was used to cover the wide range of polarities of the selected contaminants. A non-discriminant elution protocol was also applied. Liquid chromatography coupled to a high-resolution mass spectrometer (HRMS) Q-Exactive Orbitrap system was used for the separation and detection of the contaminants. A targeted data independent acquisition (DIA) mode with an inclusion list with the exact mass, retention time window and collision energy was tried for the first time obtaining good sensitivity, selectivity and high quality MS2 product ions.â¢116 compounds of a wide-scope of polarities and physic-chemical properties were validated using a surface water pool matrix.â¢SPE followed by LC-HRMS with a targeted DIA was used for the method validation at three concentration levels 5, 50, 500 µg l-1 in extract.â¢Good recoveries were obtained between 70 and 120% for the majority of the selected contaminants. Matrix effect, precision, and linearity were also evaluated and results proved the suitability for the method application.
RESUMO
Sustainable agriculture practices and integrated pest management for avoiding environmental pollution are necessary to maintain a high yield in vineyard areas. Pesticide residues in groundwater in a vineyard area of La Rioja (Spain) have been evaluated in previous years, and they could now have varied after farmers have adopted the different measures recommended. Accordingly, this research's objectives were (i) to evaluate the occurrence and seasonal distribution (spring, summer, and autumn samplings) of pesticides (36) plus their degradation products (DP) (11) in water and soil samples (23 + 15) in La Rioja (Northern Spain), and (ii) to compare the current water quality (2019) with that determined previously (2011). A multi-residue method based on solid phase extraction (for water samples) or solid liquid extraction (for soil samples) and high-performance liquid chromatography coupled to mass spectrometry (HPLC-MS) was used to determine and quantify pesticides. The results reveal the presence in waters of 30 compounds from those selected (15 fungicides + 2 DP, 7 insecticides + 1 DP, and 3 herbicides +2 DP), with 14 of them at concentrations > 0.1 µg L-1 (water quality threshold for human consumption). The highest number of compounds was detected in summer (waters) and spring (soils). The pesticides most frequently detected in water samples were the fungicides metalaxyl, tebuconazole, and boscalid, with the last one being the compound found in the highest number of soil samples. The comparison of water pollution in 2011 and 2019 indicates a significant decrease in the total concentration of herbicides, fungicides and insecticides in 95-100%, 76-90%, and 42-85% of samples in the three campaigns, respectively. The results indicate that an optimized and sustainable use of pesticides in intensive and high-yield agricultural areas could reduce environmental pollution.