It has been proposed that non-protein thiols and organic acids play a major role in cadmium phytoavailability and distribution in plants. In the Cd-hyperaccumulator Solanum nigrum and non-accumulator Solanum melongena, the role of these organic ligands in the accumulation and detoxification mechanisms of Cd are debated. In this study, we used X-ray absorption spectroscopy to investigate Cd speciation in these plants (roots, stem, leaves) and in the soils used for their culture to unravel the plants responses to Cd exposure. The results show that Cd in the 100 mg.kg-1 Cd-doped clayey loam soil is sorbed onto iron oxyhydroxides. In both S. nigrum and S. melongena, Cd in roots and fresh leaves is mainly bound to thiol ligands, with a small contribution of inorganic S ligands in S. nigrum leaves. We interpret the Cd binding to sulfur ligands as detoxification mechanisms, possibly involving the sequestration of Cd complexed with glutathione or phytochelatins in the plant vacuoles. In the stems, results show an increase binding of Cd to -O ligands (>50% for S. nigrum). We suggest that Cd is partly complexed by organic acids for transportation in the sap.

In this study, surface seawater, sediment and zooplankton samples were collected from three different sampling stations in Marseille Bay (NW Mediterranean Sea) and were analyzed for both microplastics and organic plastic additives including seven phthalates (PAEs) and nine organophosphate esters (OPEs). PAE concentrations ranged from 100 to 527 ng L-1 (mean 191±123 ng L-1) in seawater, 12 to 610 ng g-1 dw (mean 194±193 ng g-1 dw) in sediment and 0.9 to 47 μg g-1 dw (mean 7.2±10 μg g-1 dw) in zooplankton, whereas OPE concentrations varied between 9-1013 ng L-1 (mean 243±327 ng L-1) in seawater, 13-49 ng g-1 dw (mean 25±11 ng g-1 dw) in sediment and 0.4-4.6 μg g-1 dw (mean 1.6±1.0 μg g-1 dw) in zooplankton. Microplastic counts in seawater ranged from 0 to 0.3 items m-3 (mean 0.05±0.05 items m-3). We observed high fluctuations in contaminant concentrations in zooplankton between different sampling events. However, the smallest zooplankton size class generally exhibited the highest PAE and OPE concentrations. Field-derived bioconcentration factors (BCFs) showed that certain compounds are prone to bioaccumulate in zooplankton, including some of the most widely used chlorinated OPEs, but with different intensity depending on the zooplankton size-class. The concentration of plastic additives in surface waters and the abundance of microplastic particles were not correlated, implying that they are not necessarily good indicators for each other in this compartment. This is the first comprehensive study on the occurrence and temporal variability of PAEs and OPEs in the coastal Mediterranean based on the parallel collection of water, sediment and differently sized zooplankton samples.

Copper oxide nanoparticles (CuO-NP) are used as an efficient alternative to conventional Cu in agriculture and might end up in soils. They show a high toxicity towards cells and microorganisms, but only low toxicity towards soil invertebrates. However, most existing soil ecotoxicological studies were conducted in a sandy reference soil and at test concentrations ≥100 mg Cu/kg soil. Therefore, there is a knowledge gap concerning the effect of soil texture on the toxicity of CuO-NP at lower, more realistic test concentrations. In our study, a sandy reference soil and three loamy soils were spiked with CuO-NP at up to four concentrations, ranging from 5 to 158 mg Cu/kg. We investigated 28-day reproduction as well as weight and Cu content after 14-day bioaccumulation and subsequent 14-day elimination for the springtail Folsomia candida. For the first time we analysed the size distribution of CuO-NP in aqueous test soil extracts by single particle-ICP-MS which revealed that the diameter of CuO-NP significantly increased with increasing concentration, but did not vary between test soils. Negative effects on reproduction were only observed in loamy soils, most pronounced in a loamy-acidic soil (−61%), and they were always strongest at the lowest test concentration. The observed effects were much stronger than reported by other studies performed with sandy soils and higher CuO-NP concentrations. In the same soil and concentration, a moderate impact on growth (−28%) was observed, while Cu elimination from springtails was inhibited. Rather than Cu body concentration, the diameter of the CuO-NP taken up, as well as NP-clay interactions might play a crucial role regarding their toxicity. Our study reports for the first time toxic effects of CuO-NP towards a soil invertebrate at a low, realistic concentration range. The results strongly suggest including lower test concentrations and a range of soil types in nanotoxicity testing.

Lindane persists in the environment and bioaccumulates as an organochlorine pesticide and can pose risks to ecological environments and human health. To explore the long-term toxicity and underlying mechanisms of lindane, Caenorhabditis elegans was chosen as an animal model for toxicological study. The indicators of physiological, oxidative stress and cell apoptosis were examined in nematodes chronically exposed to environmentally relevant concentrations of lindane (0.01–100 ng/L). The data suggested that exposure to lindane at doses above 0.01 ng/L induced adverse physiological effects in C. elegans. Significant increases of ROS production and lipofuscin accumulation were observed in 100 ng/L of lindane-exposed nematodes, suggesting that lindane exposure induced oxidative stress in nematodes. Exposure to 10–100 ng/L of lindane also significantly increased the average number of germ cell corpses, which indicated cell apoptosis induced by lindane in C. elegans. Moreover, chronic exposure to 100 ng/L lindane significantly influenced the expression of genes related to oxidative stress and cell apoptosis (e.g., isp-1, sod-3, ced-3, and cep-1 genes). These results indicated that oxidative stress and cell apoptosis could play an important role in toxicity induced by lindane in nematodes.

Pyriproxyfen is a juvenile hormone analogue insecticide used worldwide. At present, the potential threat of pyriproxyfen to aquatic organism has not been well explored. In this work, the bioaccumulation, metabolic profile and toxicity of pyriproxyfen and its metabolites to zebrafish were studied, and the enantioselectivity of pyriproxyfen and the major chiral metabolites were also determined. Sixteen metabolites of pyriproxyfen in zebrafish were identified. Hydroxylation, ether linkage cleavage and oxidation in phase I metabolism, followed by sulfate and glucuronic acid conjugation. The bioconcentration factors ranged from 1175 to 1246. Hydroxylation metabolites of pyriproxyfen showed enantioselective behavior in zebrafish with enantiomer fractions (EFs) of 4′–OH– pyriproxyfen and 5″–OH– pyriproxyfen ranged from 0.50 to 0.71. Toxicological indexes including acute toxicity, joint toxicity and oxidative stress were tested. Among all the metabolites, 4′–OH– pyriproxyfen was found 2 folds more toxic to zebrafish than pyriproxyfen. (−)-Pyriproxyfen was found 2 folds more toxic than rac- and (+)-pyriproxyfen. Antagonistic effects were found in binary joint toxicity of pyriproxyfen and its hydroxylated metabolites. Pyriproxyfen and its metabolites also showed oxidative stress damage by inhibiting the activity of CAT and SOD and increasing MDA. This work provided deep insight into the metabolism and the potential risks of pyriproxyfen to aquatic organisms.

Spatial variation of the levels of polycyclic aromatic hydrocarbons (PAHs) was evaluated within an urban-industrial district where the main anthropogenic pressures are a 15 MW biomass power plant (BPP) and road traffic. The use of a high-density lichen transplant network and wind quantitative relationships made it possible to perform a hierarchical analysis of contamination. Combined uni-bi and multivariate statistical analyses of the resulting databases revealed a dual pattern. In its surroundings (local scale), the BPP affected the bioaccumulation of fluoranthene, pyrene and total PAHs, although a confounding effect of traffic (mostly petrol/gasoline engines) was evident. Spatial variation of the rate of diesel vehicles showed a significant association with that of acenaphthylene, acenaphthene, fluorene, anthracene and naphthalene. The series of high-speed wind values suggests that wind promotes diffusion rather than dispersion of the monitored PAHs. At the whole study area scale, the BPP was a source of acenaphthylene and acenaphthene, while diesel vehicles were a source of acenaphthylene. PAHs contamination strongly promotes oxidative stress (a threefold increase vs pre-exposure levels) in lichen transplants, suggesting a marked polluting effect of anthropogenic sources especially at the expense of the mycobiont. The proposed monitoring approach could improve the apportionment of the different contributions of point and linear anthropogenic sources of PAHs, mitigating the reciprocal biases affecting their spatial patterns.

Fipronil, a phenyl-pyrazole insecticide, has a wide range of uses, from agriculture to veterinary medicine. Due to its large-scale applications, the risk of environmental and occupational exposure and bioaccumulation raises concerns. Moreover, relatively little is known about the intracellular mechanisms of fipronil in trophoblasts and the endometrium involved in implantation. Here, we demonstrated that fipronil reduced the viability of porcine trophectoderm and luminal epithelial cells. Fipronil induced cell cycle arrest at the sub-G1 phase and apoptotic cell death through DNA fragmentation and inhibition of DNA replication. These reactions were accompanied by homeostatic changes, including mitochondrial depolarization and cytosolic calcium depletion. In addition, we found that exposure to fipronil compromised the migration and implantation ability of pTr and pLE cells. Moreover, alterations in PI3K-AKT and MAPK-ERK1/2 signal transduction were observed in fipronil-treated pTr and pLE cells. Finally, the antiproliferative and apoptotic effects of fipronil were also demonstrated in 3D cell culture conditions. In summary, our results suggest that fipronil impairs implantation potentials in fetal trophectoderm and maternal endometrial cells during early pregnancy.

Tissue distribution of legacy and emerging per-and polyfluoroalkyl substances (PFASs) in several kinds of edible fishes collected from Meiliang bay of Taihu Lake, China were investigated and the related human health risks were assessed. Perfluorooctanesulfonate (PFOS), perfluorooctanesulfonamide (PFOSA) and 6:2 fluorotelomer phosphate diester (6:2 diPAP) were the most abundant legacy perfluoroalkyl acid (PFAA), PFOS related precursor (PreFOS), and the emerging PFASs in all fish tissues, respectively. Similar to the legacy PFAAs, 6:2 diPAP and 6:6 perfluorophosphinate (6:6 PFPiA) had the highest levels in the fish liver, whereas the highest level of PFOSA was in kidney, which might be due to its intensive transformation in fish liver. The concentrations of PFASs were generally positively correlated with the trophic levels. The profiles of PFASs were significantly different among bitterling, crucian and other fish, which might be related to their different metabolic capacities. Bioaccumulation factors (BAFs) of PreFOSs, 6:2 diPAP, and 6:6 PFPiA were lower than those of PFAAs with the same number of perfluorinated carbons. The calculated hazard ratios (HR) of PFOS (Range: 0.0100–0.655) and perfluorooctanoic acid (PFOA) (<0.00200) in all fish muscles were less than 1.0. However, the HR of the ∑PFASs in crucian muscle was 1.04, which implied that frequent consumption of crucian collected from Meiliang Bay might pose potential risks to human health.

Microplastic pollution is emerging as a global environmental issue, and its potential for transferring hazardous chemicals to aquatic organisms is gaining attention. Studies have investigated the transfer of chemicals, mainly sorbed chemicals, through ingestion of microplastics by organisms, but limited information is available regarding chemical additives and uptake via the aqueous route through plastic leaching. In this study, we compared two bioaccumulation pathways of the additive hexabromocyclododecane (HBCD) by exposing mussels (Mytilus galloprovincialis) to two different sizes of expanded polystyrene (EPS): inedible size (4.2–5.5 mm) for leachate uptake and edible size (20–770 μm) for particle ingestion and leachate uptake. Over 10 days, the HBCD concentration increased significantly in mussels in the EPS exposure groups, indicating that EPS microplastic acts as a source of HBCD to mussels. The concentration and isomeric profiles of HBCD in mussels show that uptake through the aqueous phase is a more significant pathway for bioaccumulation of HBCD from EPS to mussels than particle ingestion. HBCD levels measured in EPS, leachate and exposed mussels from this study are environmentally relevant concentration. The fate and effects of chemical additives leached from plastic debris in ecosystem requires further investigation, as it may affect numerous environments and organisms through the aqueous phase.

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.