International audience | The presence of contaminants of emerging concern in the aquatic environment directly impacts water-living organisms and can alter their living functions. These compounds are often metabolized and excreted, but they can also be accumulated and spread through the food chain. The metabolized contaminants can also lead to the formation of new compounds with unknown toxicity and bioaccumulation potential. In this work, we have studied the occurrence, bioconcentration, and biotransformation of CECs in glass eels (Anguilla anguilla) using UHPLC-HRMS. To select the target CECs, we first carried out an environmental risk assessment of the WWTP effluent that releases directly into the Adour estuary (Bayonne, Basque Country, France). The risk quotients of every detected contaminant were calculated and three ecotoxicologically relevant contaminants were chosen to perform the exposure experiment: propranolol, diazepam, and irbesartan. An experiment of 14 days consisting of 7 days of exposure and 7 days of depuration was carried out to measure the bioconcentration of the chosen compounds. The quantitative results of the concentrations in glass eel showed that diazepam and irbesartan reached BCF ≈10 on day 7, but both compounds were eliminated after 7 days of depuration. On the other hand, propranolol's concentration remains constant all along with the experiment, and its presence can be detected even in the non-exposed control group, which might suggest environmental contamination. Two additional suspect screening strategies were used to identify metabolization products of the target compounds and other xenobiotics already present in wild glass eels. Only one metabolite was identified, nordiazepam, a well-known diazepam metabolite, probably due to the low metabolic rate of glass eels at this stage. The xenobiotic screening confirmed the presence of more xenobiotics in wild glass eels, prominent among them, the pharmaceuticals exemestane, primidone, iloprost, and norethandrolone. ☆ This paper has been recommended for acceptance by. Eddy Y. Zeng. ☆☆ Contaminants of Emerging Concern in Glass Eel (Anguilla anguilla): Occurrence, Bioconcentration and Biotransformation.

The presence of contaminants of emerging concern in the aquatic environment directly impacts water-living organisms and can alter their living functions. These compounds are often metabolized and excreted, but they can also be accumulated and spread through the food chain. The metabolized contaminants can also lead to the formation of new compounds with unknown toxicity and bioaccumulation potential. In this work, we have studied the occurrence, bioconcentration, and biotransformation of CECs in glass eels (Anguilla anguilla) using UHPLC-HRMS. To select the target CECs, we first carried out an environmental risk assessment of the WWTP effluent that releases directly into the Adour estuary (Bayonne, Basque Country, France). The risk quotients of every detected contaminant were calculated and three ecotoxicologically relevant contaminants were chosen to perform the exposure experiment: propranolol, diazepam, and irbesartan. An experiment of 14 days consisting of 7 days of exposure and 7 days of depuration was carried out to measure the bioconcentration of the chosen compounds. The quantitative results of the concentrations in glass eel showed that diazepam and irbesartan reached BCF ≈10 on day 7, but both compounds were eliminated after 7 days of depuration. On the other hand, propranolol's concentration remains constant all along with the experiment, and its presence can be detected even in the non-exposed control group, which might suggest environmental contamination. Two additional suspect screening strategies were used to identify metabolization products of the target compounds and other xenobiotics already present in wild glass eels. Only one metabolite was identified, nordiazepam, a well-known diazepam metabolite, probably due to the low metabolic rate of glass eels at this stage. The xenobiotic screening confirmed the presence of more xenobiotics in wild glass eels, prominent among them, the pharmaceuticals exemestane, primidone, iloprost, and norethandrolone.

The flame retardants hexabromobenzene (HBB) and pentabromobenzene (PBB) have been extensively used and become ubiquitous pollutants in the aquatic environment and biota, but their potential toxic effects on wildlife remained unknown. In this study, by using zebrafish (Danio rerio) as a model, the bioconcentration and developmental neurotoxicity were investigated. Zebrafish embryos were exposed to HBB and PBB (0, 30, 100 and 300 μg/L) from 2 until 144 h post-fertilization (hpf). Chemical analysis showed bioconcentrations of both chemicals, while HBB is readily metabolized to PBB in zebrafish larvae. Embryonic exposure to both chemicals did not cause developmental toxicity, but induced locomotor behavioral anomalies in larvae. Molecular docking results indicated that both chemicals could bind to zebrafish acetylcholinesterase (AChE). Furthermore, HBB and PBB significantly inhibited AChE activities, accompanied by increased contents of acetylcholine and decreased choline in larvae. Downregulation of the genes associated with central nervous system (CNS) development (e.g., mbp, α1-tubulin, gfap, shha) as well as the corresponding proteins (e.g., Mbp, α1-Tubulin) was observed, but gap-43 was upregulated at both gene and protein levels. Together, our results indicate that both HBB and PBB exhibit developmental neurotoxicity by affecting various parameters related to CNS development and indications for future toxicological research and risk assessment of the novel brominated flame retardants.

While terrestrial organisms such as livestock are consumed regularly, studies of internal distribution and bioaccumulation of persistent organic pollutants (POPs) have been focused more on aquatic organisms. In this study, we have assessed the internal distribution and fate of legacy (PCDD/Fs and PCBs) and emerging POPs (HBCDs and PFASs), and TBBPA in 42 tissues of a Bos Taurus. PCDD/Fs, DL-PCBs, and HBCDs were found 3, 4, and 4-fold higher in the lipid-rich organs (subcutaneous fat, visceral fat, large intestine) compared to the remaining organs and muscles, owing to their hydrophobic properties. The TBBPA concentration in the excrement was 36-fold higher compared to the average tissues, suggesting a short internal half-life of TBBPA. Among PFASs, PFUnDA displayed 98% contribution from all ionic PFASs in the tissues due to its strong binding affinity, high exposure via feed and water, and increasing emergence of PFUnDA and its precursors in the Southeast Asian countries. While our study suggests that, at the moment, there is no significant health risks to the general Korean population, the future changes in environmental exposure as well as the internal dynamics and fate of various POPs species should be kept in mind when consuming various parts of livestock.

Warming and acidification are expected impacts of climate change to the marine environment. Besides, organisms that live in coastal areas, such as bivalves, can also be exposed to anthropogenic pollutants like pharmaceuticals (PhACs) and endocrine disrupting compounds (EDCs). In this study, the effects of warming and acidification on the bioconcentration, metabolization and depuration of five PhACs (sotalol, sulfamethoxazole, venlafaxine, carbamazepine and citalopram) and two EDCs (methylparaben and triclosan) were investigated in the mussel species (Mytilus galloprovincialis), under controlled conditions. Mussels were exposed to warming and acidification, as well as to the mixture of contaminants up to 15.7 μg L−1 during 20 days; followed by 20 days of depuration. All contaminants bioconcentrated in mussels with levels ranging from 1.8 μg kg−1 dry weight (dw) for methylparaben to 12889.4 μg kg−1 dw for citalopram. Warming increased the bioconcentration factor (BCF) of sulfamethoxazole and sotalol, whereas acidification increased the BCF of sulfamethoxazole, sotalol and methylparaben. In contrast, acidification decreased triclosan levels, while both stressors decreased venlafaxine and citalopram BCFs. Warming and acidification facilitated the elimination of some of the tested compounds (i.e. sotalol from 50% in control to 60% and 68% of elimination in acidification and warming respectively). However, acidification decreased mussels' capacity to metabolize contaminants (i.e. venlafaxine). This work provides a first insight in the understanding of aquatic organisms' response to emerging contaminants pollution under warming and acidification scenarios.

Uptake and translocation of imidacloprid (IMI), thiamethoxam (THX) and difenoconazole (DFZ) in rice plants (Oryza sativa L.) were investigated with a soil-treated experiment at two application rates: field rate (FR) and 10*FR under laboratory conditions. The dissipation of the three compounds in soil followed the first-order kinetics and DFZ showed greater half-lives than IMI and THX. Detection of the three compounds in rice tissues indicated that rice plants could take up and accumulate these pesticides. The concentrations of IMI and THX detected in leaves (IMI, 10.0 and 410 mg/kg dw; THX, 23.0 and 265 mg/kg dw) were much greater than those in roots (IMI, 1.37 and 69.3 mg/kg dw; THX, 3.19 and 30.6 mg/kg dw), which differed from DFZ. The DFZ concentrations in roots (15.6 and 79.1 mg/kg dw) were much greater than those in leaves (0.23 and 3.4 mg/kg dw). The bioconcentration factor (BCF), representing the capability of rice to accumulate contaminants from soil into plant tissues, ranged from 1.9 to 224.3 for IMI, from 2.0 to 72.3 for THX, and from 0.4 to 3.2 for DFZ at different treated concentrations. Much higher BCFs were found for IMI and THX at 10*FR treatment than those at FR treatment, however, the BCFs of DFZ at both treatments were similar. The translocation factors (TFs), evaluating the capability of rice to translocate contaminants from the roots to the aboveground parts, ranged from 0.02 to 0.2 for stems and from 0.02 to 9.0 for leaves. The tested compounds were poorly translocated from roots to stems, with a TF below 1. However, IMI and THX were well translocated from roots to leaves. Clothianidin (CLO), the main metabolite of THX, was detected at the concentrations from 0.02 to 0.5 mg kg−1 in soil and from 0.07 to 7.0 mg kg−1 in plants. Concentrations of CLO in leaves were almost 14 times greater than those in roots at 10*FR treatment.

Microplastics (MPs) have been shown to act as sorbent phases and thus carriers of organic chemicals in the aquatic environment. Therefore, concerns exist that MP ingestion increases the uptake and accumulation of organic chemicals by aquatic organisms. However, it is unclear if this pathway is relevant compared to other exposure pathways. Here we compared the bioconcentration capacity of two hydrophobic organic chemicals (i.e., chlorpyrifos and hexachlorobenzene) in a freshwater fish (Danio rerio) when exposed to chemicals through water only and in combination with contaminated polyethylene MPs. Additionally, a suite of biomarker analyses (acetylcholine esterase, glutathione S-transferase, alkaline phosphatase, catalase) was carried out to test whether MPs can enhance the toxic stress caused by chemicals. Two 14-day semi-static experiments (one for each chemical) were carried out with adult fish. Each experiment consisted of (1) a control treatment (no chemicals, no MPs); (2) a treatment in which fish were exposed to chlorpyrifos or hexachlorobenzene only through water; (3) a treatment in which fish were exposed to the chemicals through water and contaminated polyethylene MPs (100 mg MP/L). Two additional treatments were included for the biomarker analysis. These contained MPs at two different concentrations (5 and 100 mg MP/L) but no chemicals. The presence of contaminated MPs in contaminated water did not enhance but rather decreased the bioconcentration of both chemicals in fish compared to the treatment that contained contaminated water in absence of MPs. This was more pronounced for hexachlorobenzene, which is more hydrophobic than chlorpyrifos. Enzyme activity levels in fish were only significantly altered in the presence of MPs for alkaline phosphatase. This study indicates that MP presence in freshwater ecosystems is not expected to increase the risks associated with chemical bioconcentration in aquatic organisms and that other exposure pathways (i.e., uptake via respiration, skin permeability) may be of higher importance.

In recent years, reports of plastic debris in the gastrointestinal (GI) tract of fish have been well documented in the scientific literature. This, in turn, increased concerns regarding human health exposure to microplastics through the consumption of contaminated fish. Most of the available research regarding microplastic toxicity has focused on marine organisms through direct feeding or waterborne exposures at the individual level. However, little is known about the trophic transfer of microplastics through the aquatic food chain. Freshwater zooplankton Daphnia magna (hereafter Daphnia), and the fathead minnow Pimephales promelas (FHM), are well-known model species used in standard toxicological studies and ecological risk assessments that provide a simple model for trophic transfer. The aim of this study was to assess the tissue translocation, trophic transfer, and depuration of two concentrations (20 and 2000-part ml⁻¹) of 6 μm polystyrene (PS) microplastics particles between Daphnia and FHM. Bioconcentration factors (BCF) and bioaccumulation factors (BAF) were determined. Fluorescent microscopy was used to determine the number of particles in the water media and within the organs of both species. Throughout the five days of exposure, PS particles were only found within the GI tract of both species. The BCF for Daphnia was 0.034 ± 0.005 for the low concentration and 0.026 ± 0.006 for the high concentration. The BAF for FHM was 0.094 ± 0.037 for the low concentration and 0.205 ± 0.051 for the high concentration. Between 72 and 96 h after exposure all microplastic particles were depurated from both species. The presence of food had a significant effect on the depuration of microplastic particles from Daphnia but not for FHM. Based on the low BCF and BAF values for both species, rapid depuration rates, and null translocation of microplastic particles to organs and tissues from the GI tract, there is a low probability that microplastics will bioconcentrate and bioaccumulate under environmental conditions.

Fluralaner is a novel isoxazoline insecticide which shows high insecticidal activity against parasitic, sanitary and agricultural pests, but there is little information about the effect of fluralaner on non-target organisms. This study reports the acute toxicity, bioconcentration, elimination and antioxidant response of fluralaner in zebrafish. All LC50 values of fluralaner to zebrafish were higher than 10 mg L⁻¹ at 24, 48, 72 and 96 h. To study the bioconcentration and elimination, the zebrafish were exposed to sub-lethal concentrations of fluralaner (2.00 and 0.20 mg L⁻¹) for 15 d and then held 6 d in clean water. The results showed medium BCF of fluralaner with values of 12.06 (48 h) and 21.34 (144 h) after exposure to 2.00 and 0.20 mg L⁻¹ fluralaner, respectively. In the elimination process, a concentration of only 0.113 mg kg⁻¹ was found in zebrafish on the 6th day after removal to clean water. After exposure in 2.00 mg L⁻¹ fluralaner, the enzyme activities of SOD, CAT, and GST, GSH-PX, CarE and content of MDA were measured. Only CAT and CarE activities were significantly regulated and the others stayed at a stable level compared to the control group. Meanwhile, transcriptional expression of CYP1C2, CYP1D1, CYP11A were significantly down-regulated at 12 h exposed to 2.00 mg L⁻¹ of fluralaner. Except CYP1D1, others CYPs were up-regulated at different time during exposure periods.Fluralaner and its formulated product (BRAVECTO®) are of low toxicity to zebrafish and are rapidly concentrated in zebrafish and eliminated after exposure in clean water. Antioxidant defense and metabolic systems were involved in the fluralaner-induced toxicity. Among them, the activities of CAT and CarE, and most mRNA expression level of CYPs showed fast response to the sub-lethal concentration of fluralaner, which could be used as a biomarker relevant to the toxicity.

The synthetic polycyclic musks HHCB (Galaxolide®) and AHTN (Tonalide®) were monitored in fathead minnows (FHMs) caged for a month at various locations in the North Saskatchewan River (NSR), upstream and downstream of the Gold Bar wastewater treatment plant that serves the city of Edmonton, AB, Canada. In addition, the distribution of these musk compounds in the river was predicted using the fugacity-based Quantitative Water Air Sediment Interface (QWASI) model. In FHMs caged 0.15 km downstream of the wastewater outfall, mean concentrations of HHCB and AHTN were 7.4 and 0.4 μg g−1 wet weight, respectively. These are among the highest reported concentrations of these musk compounds in fish exposed to treated wastewater. The musk concentrations in FHMs were significantly lower further downstream of the outfall. High bioconcentration factors (BCFs) in FHMs that exceeded 104 higher than estimated concentrations in water indicated that there were low rates of biotransformation of the musks in the fish. In the FHMs caged at the site closest to the wastewater outfall, HHCB concentrations in FHMs were comparable to the body burdens that have been reported to moderate expression of vitellogenin in female rainbow trout, indicating that fish in the NSR downstream of the wastewater outfall may be at risk of anti-estrogenic effects. The QWASI model applied to six individual river sections of the NSR predicted that the largest fluxes of HHCB and AHTN would be for downstream transport in water, which explains why FHMs accumulated elevated concentrations of the musks at the furthest downstream site, 9.9 km from the wastewater discharge.