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Monitoring pesticides in the environment requires the use of sensitive analytical methods. However, existing methods are generally not suitable for analyzing small organisms, as they require large matrix masses. This study explores the development of a miniaturized extraction protocol for the monitoring of small organisms, based on only 30 mg of matrix. The miniaturized sample preparation was developed using fish and macroinvertebrate matrices. It allowed the characterization of 41 pesticides and transformation products (log P from -1.9 to 4.8) in small samples with LC-MS/MS, based on European guidelines (European Commission DG-SANTE, 2019). Quantification limits ranged from 3 to 460 ng g -1 dry weight (dw) for fish and from 0.1 to 356 ng g -1 dw for invertebrates, with most below 60 ng g -1 dw. Extraction rates ranged from 70% to 120% for 35 molecules in fish. Recoveries ranged from 70% to 120% for 37 molecules in macroinvertebrates. Inter-day precision was below 30% for 32 molecules at quantification limits. The method was successfully applied to 17 fish and 19 macroinvertebrates collected from two ponds of the French region of Dombes in November and May 2018, respectively. Both sample matrices were nearly always contaminated with benzamide, imidacloprid-desnitro, and prosulfocarb at respective concentrations of 42-237, 3, and 30-165 ng g -1 dw in fish, and 62-438, 2-6, and 15-29 ng g -1 dw in macroinvertebrates. Results show that this method is an effective tool for characterizing polar pesticides in small biotic samples., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

The synthesis and structure-activity relationship (SAR) of a series of pyridyl-isoxazole based agonists of S1P1 are discussed. Compound 5b provided potent in vitro activity with selectivity, had an acceptable pharmacokinetic profile, and demonstrated efficacy in a dose dependent manner when administered orally in a rodent model of arthritis., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

Fish are often exposed to various molecules like pesticides. Some of these compounds get biomagnified within aquatic food web, inducing health hazards of consumers. However, behaviors of many pesticides are still unknown. This work aims to study the uptake and the elimination of some of them in muscle tissue of edible fish (azoxystrobin, clomazone, diflufenican, dimethachlor, carbendazim, iprodion, isoproturon, mesosulfuron-methyl, metazachlor, napropamid, quizalofop, and thifensulfuron-methyl). Two freshwater fish species (Perca fluviatilis and Cyprinus carpio) were exposed to a mixture of these 13 pesticides, via multi-contaminated pellets, and then, eliminated. Compounds were measured in food, water and muscle tissue using multi-residues methods. Kinetics, biomagnification factors (BMFs) and half-lives (t1/2) were estimated and they did not show a large difference between the species. Muscular BMFs ranged from 2 × 10(-6) (mesosulfuron-methyl in perch) to 1 × 10(-3) (isoproturon and napropamid in perch) and t1/2 ranged from 0.8 (mesosulfuron-methyl in perch) to 40.3d (napropamid in carp). BMFs were also modeled as a function of Kow value. All BMF values were explained by the model, except for diflufenican which had a BMF lower than that expected by our modeling work, probably due to an efficient metabolism. Results led to the conclusion that none of these chemicals would probably be biomagnified within aquatic food webs., (Copyright © 2013 Elsevier Ltd. All rights reserved.)

Nitrogen and carbon stable isotope analyses are frequently used to assess contaminant biomagnification in animals in the wild. Previous studies, mainly on plant but also on animal tissues, have shown that chemical stress can lead to shifts in delta(15)N. In order to assess if an exposure to DDT at realistic concentration disrupted stable isotope signature in animals, delta(15)N and delta(13)C were studied in several tissues (liver, muscle, gill) of Perca fluviatilis fed with the same commercial diet uncontaminated or contaminated with DDT. We observed no DDT effect on the delta(15)N and delta(13)C of fish tissues. Our results show that stable isotopes can remain useful for field ecotoxicological studies despite food-chain contamination. However, correlations between the delta(13)C or delta(15)N values measured in the different organs were only found in DDT treated fish, suggesting some disruption of major biochemical compound metabolism in tissues.

In order to assess pollutant transfer in Camargue ponds from bordering agrosystems, a biomonitoring assay was conducted in irrigation and drainage channels of rice fields in the Rhone Delta (France). A filter-feeding bivalve, the Asian clam, Corbicula fluminea, was used as bioindicator and caged in upstream and downstream channels of an area of conventional rice fields. After 6 weeks incubation, many lipophilic biocides were identified in Corbicula tissues, including pesticides used in rice plantations (pretilachlor, oxadiazon), pesticides presumed in use in the Rhone basin [diuron and its metabolite 3,4 dichloroaniline (3,4-DCA)] and organochlorine pesticides (OCPs) banned for several decades. In addition, PCBs were highly bioaccumulated in Corbicula. Downstream bivalves had significantly lower concentrations of OCPs, PCB and 3,4-DCA. However, the exposure biomarkers (glutathione S-transferase, catalase and propionylcholinesterase) were not correlated with the decreased concentrations. The results of this experiment raise several questions concerning the potential role of immersed plants in a retention process.

A screening of relevant biomarkers was carried out in order to evaluate metabolic and cellular damages in European eels exposed to a non-point source contamination by persistent organic pollutants (POP) such as polycyclic aromatic hydrocarbons (PAH) and organochlorine compounds (OC) in a protected area, the Nature Reserve of Camargue (France). Investigations were focused on metabolic responses including detoxification mechanisms (biotransformation, antioxidant process), energy requirements and enzymatic membrane markers either involved in neuronal conduction (acetylcholinesterase, AChE) or in osmoregulation and energy metabolism (ATPases). The hepatic and muscular glycogen rates seemed to be suitable biomarkers as well as three hepatic activities involved in the protection against oxyradicals: catalase, glutathione peroxidase (SeGPx) and superoxide dismutases (SOD). The muscle and gill ATPases as well as the muscle and brain AChE showed more significant relevance in terms of biomarkers than the biotransformation enzymes: ethoxyresorufine-O-deethylase (EROD) and uridine diphospho-glucuronyl transferase (UDPGT). However, most of these enzymatic activities depend on numerous abiotic factors, which must be taken into account in such a biomarker assessment approach. Our study provides some conclusive elements to approve the use in situ of biomarkers developed from laboratory studies. It also raises a question regarding the location of contaminant impregnation in fish organ, in relation with age, development status or mode of contamination, and its influence on biomarker response. If the relevance of membrane indicators is confirmed, this study provides an original statement of the extent of the ecotoxicological threat for the aquatic species in a protected area, due to the occurrence of POP in the cell membranes.