Analysis of the disruptive effects of chemicals on lipids in invertebrates is limited by our poor knowledge of the lipid metabolic pathways and the complete lipidome. Recent studies shown that juvenoids and bisphenol A disrupted the dynamics of lipid droplets in the crustacean Daphnia magna. This study used ultra-high performance liquid chromatography/time-of-flight mass spectrometry (UHPLC/TOFMS) to study how juvenoids (pyriproxyfen and methyl farnesoate) and bisphenol A disrupt the dynamics of glycerophospholipids and glycerolipids in Daphnia adults and their allocation to eggs. Lipidomic analysis identified 234 individual lipids corresponding to three classes of glycerolipids, seven of glycerophospholipids, and one of sphingolipids, of which 194 changed according to the chemical treatments and time. Adult females in the control and bisphenol A treatment groups had low levels of triacylglycerols but high levels of glycerophospholipids, whereas those in the juvenoid treatment groups had high levels of triacylglycerols and low levels of glycerophospholipids. The opposite trend was observed for the lipid contents in the eggs produced. Because the juvenoids reduced reproduction dramatically, the females allocated less triacylglycerols to their eggs than the controls did. Interestingly, females exposed to bisphenol A allocated less triacylglycerols to their eggs despite producing a similar number of eggs as that of the controls. Thin-layer chromatography analyses confirmed the UHPLC/TOFMS results and allowed qualitative determination of cholesterol, which was also accumulated in females exposed to the juvenoids.

The sulphide-rich mine wastes accumulated in tailing dumps of La Concordia Mine (Puna of Argentina) have been exposed to the weathering action for more than 30 years. Since then, a series of redox reactions have triggered the generation of a highly acidic drainage -rich in dissolved metals-that drains into the La Concordia creek. The extent of metal and acid release in the site was analysed through field surveys and laboratory experiments. Static tests were conducted in order to predict the potential of the sulphidic wastes to produce acid, while Cu-, Zn-, Fe- and Pb-bearing phases present in the wastes were identified by XRD, SEM/EDS analysis and sequential extraction procedures. Finally, the release of these metals during sediment-water interaction was assessed in batch experiments carried out in a period of nearly two years. Field surveys indicate that the prolonged alteration of the mine wastes led to elevated electrical conductivity, pH values lower than 4 and metal concentrations that exceed the guide values for drinking water in the La Concordia stream regardless of the dominating hydrological conditions. The highly soluble Fe and Mg (hydrous)sulphates that form salt crusts on the tailings surfaces and the riverbed sediments play an important role in the control of metal mobility, as they rapidly dissolve in contact with water releasing Fe, but also Cu and Zn which are scavenged by such minerals. Another important proportion of the analysed metals is adsorbed onto Fe (hydr)oxides or form less soluble hydroxysulfates. Metals present in these phases are released to water more slowly, thus representing a potential long term source of heavy metal pollution. The obtained results are a contribution to the understanding of long term metal transformations and mobility in mine waste-impacted sites.

Chlorinated polyfluoroalkyl ether sulfonic acids (Cl-PFESAs) caused great concerns recently as novel fluorinated alternatives. However, information on their bioconcentration, bioaccumulation and biomagnification in marine ecosystems is limited. In this study, 152 biological samples including invertebrates, fishes, seabirds and mammals collected from Bohai Sea of China were analyzed to investigate the residual level, spatial distribution, bioaccumulation and biomagnification of Cl-PFESAs. 6:2 Cl-PFESA was found in concentrations ranging from <MDL (method detection limit) to 3.84 ng/g ww and it is the dominant congener when compared with concentrations of 8:2 Cl-PFESA. Compared with other bays and regions, levels of 6:2 Cl-PFESA are relatively high in bivalves and fishes from Liaodong Bay. These levels were also found to tend to increase as compared with those in 2010–2014. Logarithm bioaccumulation factors (BAFs) for 6:2 Cl-PFESA ranged from 2.23 to 4.21, implying the bioaccumulation of this compound. The trophic magnification factor (BMF) for 6:2 Cl-PFESA was determined to be 3.37 in the marine food web, indicating biomagnification potential along the marine food chain.

As the metabolites of tetrabromobisphenol A (TBBPA), tetrabromobisphenol A mono- and di-methyl ethers (TBBPA MME and TBBPA DME) have been detected in various environmental media. However, knowledge of the contribution of plants to their environmental fates, especially to the interactions between TBBPA DME and TBBPA, is quite limited. In this study, the metabolism and behaviors of TBBPA DME was studied with pumpkin plants through 15-day hydroponic exposure. The TBBPA were also studied separately using in-lab hydroponic exposure for comparison. The results showed that more TBBPA DME accumulated in pumpkin roots and translocated up to stems and leaves compared with TBBPA. Transformation of TBBPA DME occurred later and more slowly than that of TBBPA. Interconversion between TBBPA DME and TBBPA was verified in intact plants for the first time. Namely, TBBPA DME can be biotransformed to TBBPA MME (transformation ratio in mole mass, TRMM 0.50%) and to TBBPA (TRMM 0.53%) within pumpkin; and TBBPA can be biotransformed to TBBPA MME (TRMM 0.58%) and to TBBPA DME (TRMM 0.62%). In addition, two single benzene-ring metabolites, 2,6-dibromo-4-(2-(2-hydroxyl)-propyl)-anisole (DBHPA, TRMM 3.4%) with an O-methyl group and 2,6-dibromo-4-(2-(2-hydroxyl)-propyl)-phenetole (DBHPP, TRMM 0.57%) with an O-ethyl group, were identified as the transformation products in the TBBPA exposure experiments. The transformation and interconversion from TBBPA DME back to TBBPA is reported as a new pathway and potential source for TBBPA in the environment.

Atmospheric pollution by polycyclic aromatic hydrocarbons (PAHs) has become a serious problem, especially in Asia, as PAHs can severely affect ecologically important mountainous areas. Using pine needles and mosses as bio-indicators, this study examined PAH pollution in a mountainous study area and evaluated the influence of transboundary PAHs. PAHs in urban areas were also evaluated for comparison. The study sites were alpine areas and urban areas (inland or coastal cities) across central Japan, in the easternmost part of Asia where atmospheric pollutants are transported from mainland Asia. The mean PAH concentrations of pine needles and mosses were 198.9 ± 184.2 ng g⁻¹ dry weight (dw) and 131.8 ± 60.7 ng g⁻¹ dw (mean ± SD), respectively. Pine needles preferentially accumulated PAHs with low molecular weights (LMW PAHs) and exhibited large differences in both PAH concentration and isomer ratios between alpine and urban sites. These differences can be explained by the strong influence of LMW PAHs emitted from domestic sources, which decreased and changed during transport from urban to alpine sites due to dry/wet deposition and photodegradation. In contrast, mosses accumulated a higher ratio of PAHs with high molecular weight (HMW PAHs). A comparison of isomer ratios showed that the PAH source for alpine moss was similar to that for northern coastal cities, which are typically influenced by long-transported PAHs from East Asia. Thus, these results indicate that alpine moss can also be strongly affected by the transboundary PAHs. It is likely that the uptake characteristics of moss, alpine climate, and alpine locations far from urban areas can strengthen the influence of transboundary pollution. Based on these results, the limitations and most effective use of bioindicators of PAH pollution for preserving alpine ecosystems are discussed.

Several aspects of the life cycle of the critically endangered European eel (Anguilla anguilla) remain poorly understood. One such aspect is the broad-versus narrow-head dimorphism, and how this impacts their overall performance at different stages of their life cycle. At the yellow eel stage, the phenotypes show a trophic divergence. We investigated whether pollutant accumulation is affected by this disparity. We show that broad-headed eels contained higher concentrations of mercury and several lipophilic organic pollutants, compared to narrow-headed ones, irrespective of their fat content. The hereby confirmed link between the phenotypic disparity, its associated feeding ecology and its impact on pollutant accumulation thus raises further concerns about their migratory and reproductive success. Considering that pollution is an important contributor to the European eel's decline, our results demonstrate that broad-headed eels are more vulnerable to detrimental pollutant accumulation. This compromises their successful contribution to their population's reproduction and its restoration.

The ingestion of microplastics (plastic particles <5 mm) has been observed in a range of marine organisms, and adverse effects have been reported in several species after high concentration exposure. However, the long-term effects of low-dose ingestion remains unclear. The aim of this study was thus to assess the chronic effects of low concentrations of polystyrene microparticles to the intertidal amphipod Echinogammarus marinus, using food consumption, growth, and moulting as endpoints. Amphipods were fed a gelatinous algal feed spiked with microbeads (8 μm) in concentrations of ∼0.9, 9 and 99 microplastics/g for 35 days. E. marinus was also analysed for retention of microplastics, and egestion rate was calculated in a separate high-dose feeding experiment. No significant effects were found in the food consumption or growth assays. There was no accumulation of microplastics in the gut, with only one microbead recorded internally in three (8%) of the exposed amphipods. The low number is likely linked to gastrointestinal functions, allowing for easy egestion of indigestible items. This assumption was supported by the observation that after high-dose exposure, 60% of E. marinus egested all microbeads within 24 h. This study suggests that ingesting low concentrations of 8 μm microplastics do not impair the feeding or growth of amphipods along the exposure period. We hope that negative results such as these may further assist in assessing the impact posed by microplastics to marine organisms.

Exposure of wildlife to Active Pharmaceutical Ingredients (APIs) is likely to occur but studies of risk are limited. One exposure pathway that has received attention is trophic transfer of APIs in a water-fish-osprey food chain. Samples of water, fish plasma and osprey plasma were collected from Delaware River and Bay, and analyzed for 21 APIs. Only 2 of 21 analytes exceeded method detection limits in osprey plasma (acetaminophen and diclofenac) with plasma levels typically 2–3 orders of magnitude below human therapeutic concentrations (HTC). We built upon a screening level model used to predict osprey exposure to APIs in Chesapeake Bay and evaluated whether exposure levels could have been predicted in Delaware Bay had we just measured concentrations in water or fish. Use of surface water and BCFs did not predict API concentrations in fish well, likely due to fish movement patterns, and partitioning and bioaccumulation uncertainties associated with these ionizable chemicals. Input of highest measured API concentration in fish plasma combined with pharmacokinetic data accurately predicted that diclofenac and acetaminophen would be the APIs most likely detected in osprey plasma. For the majority of APIs modeled, levels were not predicted to exceed 1 ng/mL or method detection limits in osprey plasma. Based on the target analytes examined, there is little evidence that APIs represent a significant risk to ospreys nesting in Delaware Bay. If an API is present in fish orders of magnitude below HTC, sampling of fish-eating birds is unlikely to be necessary. However, several human pharmaceuticals accumulated in fish plasma within a recommended safety factor for HTC. It is now important to expand the scope of diet-based API exposure modeling to include alternative exposure pathways (e.g., uptake from landfills, dumps and wastewater treatment plants) and geographic locations (developing countries) where API contamination of the environment may represent greater risk.

Mercury (Hg) is a persistent and widespread heavy metal with neurotoxic effects in wildlife. While bioaccumulation of Hg has historically been studied in aquatic food webs, terrestrial consumers can become contaminated with Hg when they feed on aquatic organisms (e.g., emergent aquatic insects, fish, and amphibians). However, the extent to which dietary connectivity to aquatic ecosystems can explain patterns of Hg bioaccumulation in terrestrial consumers has not been well studied. Bats (Order: Chiroptera) can serve as a model system for illuminating the trophic transfer of Hg given their high dietary diversity and foraging links to both aquatic and terrestrial food webs. Here we quantitatively characterize the dietary correlates of long-term exposure to Hg across a diverse local assemblage of bats in Belize and more globally across bat species from around the world with a comparative analysis of hair samples. Our data demonstrate considerable interspecific variation in hair total Hg concentrations in bats that span three orders of magnitude across species, ranging from 0.04 mg/kg in frugivorous bats (Artibeus spp.) to 145.27 mg/kg in the piscivorous Noctilio leporinus. Hg concentrations showed strong phylogenetic signal and were best explained by dietary connectivity of bat species to aquatic food webs. Our results highlight that phylogeny can be predictive of Hg concentrations through similarity in diet and how interspecific variation in feeding strategies influences chronic exposure to Hg and enables movement of contaminants from aquatic to terrestrial ecosystems.

While (N-ethyl perfluorooctanesulfonamido ethanol)-based phosphates (SAmPAPs) have been proposed as a group of perfluorooctanesulfonate (PFOS) precursors, investigation of their occurrence and fate has been limited to SAmPAP diester. In this study, SAmPAP diester and triester were simultaneously determined in freshwater sediment from Taihu Lake using a newly developed UPLC-MS/MS method, and their biotransformation to PFOS in lake sediment was investigated. SAmPAP diester and triester were detected in sediments with a detection frequency of 56% and 88%, and their mean concentrations were 0.24 ± 0.11 ng/g dry weight (dw) and 0.12 ± 0.03 ng/g dw, respectively. The SAmPAP diester/triester ratio in sediment was 1.1 ± 4.2, much lower than that (6.7) observed in the technical product, and the positive correlation was found between the concentrations of SAmPAP diester and PFOS in sediments (r² = 0.45, p = 0.01), suggesting that SAmPAP diester would be biotransformed to PFOS in the lake sediment. The microbial degradation test in the lake sediments further clarified that SAmPAP diester was biodegraded to PFOS, but SAmPAP triester was highly recalcitrant to microbial degradation. This study suggests that the occurrence of SAmPAP diester in freshwater lake sediments may be an important precursor of PFOS.