An effective method for the simultaneous extraction of 173 contaminants of emerging concern in freshwater invasive species and its application.

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.

Estimation of legal and illegal drugs consumption in Valencia City (Spain): 10 years of monitoring.

Wastewater-based epidemiology (WBE) approach provides objective, quantitative, near real-time profiles of illicit drug consumption by monitoring the concentration of unchanged parent drugs or their metabolites entering the municipal sewage system. Valencia is the third most populous city in Spain (an important country for the use and transit of several of these drugs). Estimations of consumption over long periods of time will help get better understanding of spatial and temporal trends in the use of licit and illicit drugs. Accordingly, applying the "best practice" protocol, 16 drugs of abuse and metabolites were monitored in this study, and 8 were daily measured during one-two weeks between 2011 and 2020 at the inlet of three wastewater treatment plants of Valencia City. Analysis of the selected compounds was performed by liquid chromatography-triple quadrupole mass spectrometry, and the concentrations obtained were used to back-calculate the consumption data. Cannabis, tobacco, and cocaine were the most consumed drugs whereas opioids were less used. Cannabis and cocaine consumption are on average 2.7-23.4 and 1.1-2.3 g/day/1000inh, respectively, and their use tended to increase since 2018. Weekly profiles were characterized by higher consumption of cocaine, ecstasy, and heroin during weekends compared to weekdays. Similarly, during "Las Fallas" (main local festivity), increased use of cocaine and amphetamine-type stimulants, mainly MDMA, was measured. WBE proved to be an objective and useful methodology to get more insight on temporal drugs of abuse consumption, and the changes derived from local festivities.

Determination of organic pollutants in Anguilla anguilla by liquid chromatography coupled with tandem mass spectrometry (LC-MS/MS).

One of the aspects considered about the presence of contaminants in the aquatic ecosystems is their possible effect on critically endangered species, as the case of European eel, Anguilla anguilla. However, there is a lack of analytical methods to determine these contaminants due to the complexity of eel matrix (contains 5-20 % of lipids and 5-15 % of proteins). Thus, a multi-residue method using QuEChERS extraction a clean-up based on new specific sorbents (to eliminate lipids) and liquid chromatography tandem mass spectrometry (LC-MS/MS) was developed to determine a mix of 21 contaminants. Compared to the previously reported methods (Degani et al., 1986), which were developed for mussels, in this study, one of the proposed extraction methods were adapted to different fish tissues of higher complexity, such as liver and muscle of A. anguilla.•The effectivity of dispersive solid phase extraction (dSPE) using new specific Enhanced Matrix Removal (EMR-lipid) as clean-up for lipid removal was tested.•Clean extracts of matrices with high protein (5-15 %) and lipid (5-20 %) content were obtained ensuring robustness and durability of the analytical systems.•Emerging contaminants extractable by this procedure comprise four different families (pesticides, perfluoroalkyl substances (PFASs), pharmaceuticals and drugs of abuse). Then, it could be further applied to wide scope screening strategies.

Carbamazepine exposure in the sea anemones Anemonia sulcata and Actinia equina: Metabolite identification and physiological responses.

Pharmaceuticals and other emerging contaminants (EC) have been increasingly detected and measured in coastal waters and large effort has been devoted to knowing the effects these substances have in coastal ecosystems. Anthozoa class is underrepresented in ecotoxicology studies despite some of their species being endangered. Anemonia sulcata and Actinia equina are species widely distributed in the Mediterranean Sea. The objectives of this work have been to evaluate the ability of these species to accumulate carbamazepine (CBZ) from water, to determine the effects of this pharmaceutical on some physiological and biochemical endpoints and to characterize the degradation routes followed by this compound in Anthozoa tissues (biotransformation) and water. Sea anemones were exposed to 1 µg L-1 and 100 µg L-1 of CBZ in artificial sea water in a semi-static system for 8 days. At several times small portions of the tentacles and whole organisms were taken. Ion transport (measured as NKATPase activity), energetic metabolism (measured as glucose and lactate levels) and nitrogen excretion (measured as ammonia concentration in tissues) were determined. CBZ-exposed individuals of A. sulcata and A. equina were analyzed by ultra-high-performance liquid chromatography high-resolution mass spectrometry (UHPLC-HRMS) on a quadrupole-time-of-flight (QqTOF). The structures of nine metabolites have been tentatively identified using HRMS and HRMS/MS data with the aid of the free available Medline database. The current work constitutes the first study on the identification of Cnidarian metabolites of CBZ in species of the Anthozoa class.

Returning of Hippocampus hippocampus (Linnaeus, 1758) (Syngnathidae) in the Faro Lake - oriented Natural Reserve of Capo Peloro, Italy.

This study reports the returning of the seahorse in the Faro Lake and the most recent finding in a brackish coastal Mediterranean lagoon. After about 50 years from the first documented occurrence of Hippocampus hippocampus (Linnaeus, 1758) within the "Capo Peloro Lagoons", North East Sicily, two adult specimens were observed alive in 2015. During that time, until the present rediscovery, the species was not recorded in biological studies and censuses for the area. This paper increases the knowledge about both the threatened seahorse species and the Natural Oriented Reserve of Capo Peloro.