Undissolved humic acid (HA) is known to substantially effect the migration and transformation of hexavalent chromium [Cr(VI)] in soils. The mechanisms of Cr(VI) retention in soils by undissolved HA have been reported; however, past studies are inconclusive about the types of HA functional groups that are involved in Cr(VI) retention and the retention mechanisms. Utilizing a two-dimensional correlation spectroscopy (2DCOS) analysis for FTIR and 13C CP/MAS NMR, this study investigated the variations of HA function groups and molecular structures after reactions with aqueous Cr(VI) under different pH conditions. Based on the changing sequence of functional groups interpreted from the 2DCOS results, a four-step mechanism for Cr(VI) retention was determined as follows: (1) electrostatic adsorption of Cr(VI) to HA surface, (2) complexation of adsorbed Cr(VI) by carboxyl and ester, (3) reduction of complexed Cr(VI) to Cr(III) by phenol and polysaccharide, and (4) complexation of reduced Cr(III) by carboxylic groups. These functional groups that are involved in Cr(VI) retention were determined to occur in aromatic domains.

Marine litter is any persistent, manufactured or processed solid material discarded, disposed of or abandoned in the marine and coastal environment. Ingestion of marine litter can have lethal and sub-lethal effects on wildlife that accidentally ingests it, and sea turtles are particularly susceptible to this threat. The European Commission drafted the 2008/56/EC Marine Strategy Framework Directive with the aim to achieve a Good Environmental Status (GES), and the loggerhead sea turtle (Caretta caretta, Linnaeus 1758) was selected for monitoring the amount and composition of litter ingested by marine animals. An analogous decision has been made under the UNEP/MAP Barcelona Convention for the protection of the Mediterranean Sea, following the Ecosystem Approach. This work provides for the first time, two possible scenarios for the Marine Strategy Framework Directive GES, both related to “Trends in the amount and composition of litter ingested by marine animals” in the Mediterranean Sea. The study validates the use of the loggerhead turtle as target indicator for monitoring the impact of litter on marine biota and calls for immediate use of this protocol throughout the Mediterranean basin and European Region. Both GES scenarios are relevant worldwide, where sea turtles and marine litter are present, for measuring the impact of ingested plastics and developing policy strategies to reduce it. In the period between 2011 and 2014, 150 loggerhead sea turtles, found dead, were collected from the Italian Coast, West Mediterranean Sea Sub-Region. The presence of marine litter was investigated using a standardized protocol for necropsies and lab analysis. The collected items were subdivided into 4 main categories, namely, IND-Industrial plastic, USE-User plastic, RUB-Non plastic rubbish, POL-Pollutants and 14 sub-categories, to detect local diversity. Eighty-five percent of the individuals considered (n = 120) were found to have ingested an average of 1.3 ± 0.2 g of litter (dry mass) or 16 ± 3 items.

Severe metal pollution due to industrial effluents releases has been documented in Jiulong River estuary, Southern China. However, integrated understanding of trace metal behavior in the sediment is lacking. In the present study, DGT (diffusive gradients in thin films) technique was employed together with sediment cores to study the porewater dynamics of trace metals as well as the benthic exchange fluxes from four sampling sites over three different months. The sedimentary environment showed distinct spatial and temporal variations due to effluent discharge and biological activities. Metal behavior was controlled by early diagenetic reactions below the interface, in suboxic layer and in deeper sediment. Precipitation as sulfides and adsorption onto Mn/Fe (hydr)oxides were important in scavenging trace metals. Estimated exchange fluxes at sediment-water interface in this estuary indicated that the overlying water was a major source for trace metals, whereas sediments could also be the source if surface remobilization (Mn/Fe reduction) dominated. Our results highlighted the impacts of both natural and anthropogenic processes on the source, fate and transformation of trace metals in this dynamic system.

Recent efforts have been directed towards better understanding the persistency and toxicity of ionic liquids (ILs) in the context of the “benign-by-design” approach, but the assessment of their bioaccumulation potential remains neglected. This paper reports the experimental membrane partitioning of IL cations (imidazolium, pyridinium, pyrrolidinium, phosphonium), anions ([C(CN)3]-, [B(CN)4]-, [FSO2)2N]-, [(C2F5)3PF3]-, [(CF3SO2)2N]-) and their combinations as a measure for estimating the bioconcentration factor (BCF). Both cations and anions can have a strong affinity for phosphatidylcholine bilayers, which is mainly driven by the hydrophobicity of the ions. This affinity is often reflected in the ecotoxicological impact. Our data revealed that the bioconcentration potential of IL cations and anions is much higher than expected from octanol-water-partitioning based estimations that have recently been presented. For some ILs, the membrane-water partition coefficient reached levels corresponding to BCFs that might become relevant in terms of the “B” (bioaccumulation potential) classification under REACH. However, this preliminary estimation need to be confirmed by in vivo bioconcentration studies.

Beach environments are known to be conducive to fragmentation of plastic debris, and highly fragmented plastic particles can interact with smaller organisms. Even through stranded plastic debris may not interact directly with marine organisms, backwash processes may transport this debris back to coastal waters, where it may affect a wide range of marine life at different trophic levels. This study analysed the size distribution of stranded plastic debris (<10 mm) collected from eight coastal beaches in Guangdong Province, China. Polystyrene (PS) foams and fragments smaller than 7 mm were increasingly abundant in the smaller size classes, whereas resin pellets remained in their production sizes (∼3 mm). Microplastics (<5 mm) accounted for over 98% of the total plastic debris by abundance and 71% by weight, indicating that the plastic debris on these coastal beaches was highly fragmented and the majority of the plastic masses belonged to the microplastic size range. The observed size distributions of PS foams and fragments are believed to result from continued fragmentation. Previous studies found that the residence time of beached debris was less than one year on average, and no sign of plastic accumulation with depth in beach sediment was observed. Therefore, coastal beaches may represent a reservoir of highly fragmented and degraded microplastics that may be mobilised and returned to the sea during storm events. Further research on the dynamics and longevity of microplastics on beaches will help reveal the mass balance of microplastics on the shoreline and determine whether shorelines are sinks or sources of microplastics.

While the exposure assessment of polychlorinated dibenzo-p-dioxin and polychlorinated dibenzofuran (PCDD/Fs) for people living in the vicinity of municipal solid waste incinerators (MSWI) has been investigated, indirect exposure to MSWI-emitted PCDD/Fs via consumption of local foods has not been well assessed. In this study, the PCDD/F concentration in the local vegetables grown near a MSWI located in Shenzhen, South China, was determined to be 0.92 ± 0.59 pg/g wet weight (ww), significantly higher than that (0.25 ± 0.35 pg/g ww) in commercial vegetables (p < 0.05). The PCDD/F concentrations in Banyan leaf (Ficus microcarpa) samples collected from 5 sampling sites at 1 km intervals from the MSWI were found to be significantly decreased with increasing distance, suggesting that the local plants would be impacted by emissions from the MSWI. The exposure assessment of PCDD/Fs for the population living in the vicinity of MSWI was carried out by simultaneously analyzing PCDD/Fs in other food groups that were commonly consumed by the residents. If only the local vegetables were consumed and other foods were acquired commercially, the total dietary intake for a general adult was 0.94 ± 0.41 pg TEQ/kg bw/day, of which consumption of local vegetables accounted for 52.3%. If all foods consumed including vegetables were from a commercial source, the total dietary intake was 0.56 ± 0.30 pg TEQ/kg bw/day, of which consumption of commercial vegetables accounted for 20.1%. The present study for the first time reported the additional human exposure to PCDD/Fs via consumption of local vegetables impacted by emissions from MSWI.

Microcystin-LR is the most poisonous and commonly encountered hepatotoxin produced by cyanobacteria in an aquatic ecosystem, and it may cause thyroid dysfunction in fish. The present study aimed to reveal the effects of transgenerational toxicity of MCLR on the thyroid endocrine system under sub-chronic exposure conditions. Adult zebrafish (F0) were exposed to environmentally relevant concentrations (1, 5 and 25 μg/L) of MCLR for 45 days. The produced F1 embryos were then tested without further MCLR treatment. In the F0 generation, exposure to 25 μg/L MCLR reduced thyroxine (T4) but not 3, 5, 3′-triiodothyronine (T3) levels in females, while the T4 and T3 levels were unchanged in males. After parental exposure to MCLR, we observed a decreased hatching and growth retardation correlated with reduced thyroid hormone levels in the F1 offspring. The gene transcription and protein expression along the hypothalamic-pituitary-thyroid axis were detected to further investigate the possible mechanisms of MCLR-induced thyroid disruption. Our results indicated MCLR could disturb the thyroid endocrine system under environmentally relevant concentrations and the disrupting effects could be remarkably transmitted to its F1 offspring. We regard these adverse effects as a parental transgenerational toxicity of MCLR.

Mercury is a toxic compound to which humans are exposed by consumption of fish. Current fish consumption advisories focus on minimizing the risk posed by the species that are most likely to have high levels of mercury. Less accounted for is the variation within species, and the potential role of the geographic origin of a fish in determining its mercury level. Here we surveyed the mercury levels in 117 yellowfin tuna caught from 12 different locations worldwide. Our results indicated significant variation in yellowfin tuna methylmercury load, with levels that ranged from 0.03 to 0.82 μg/g wet weight across individual fish. Mean mercury levels were only weakly associated with fish size (R2 < 0.1461) or lipid content (R2 < 0.00007) but varied significantly, by a factor of 8, between sites. The results indicate that the geographic origin of fish can govern mercury load, and argue for better traceability of fish to improve the accuracy of exposure risk predictions.

Chemical contamination of aquatic systems often co-occurs with dramatic changes in surrounding terrestrial vegetation. Plant leaf litter serves as a crucial resource input to many freshwater systems, and changes in litter species composition can alter the attributes of freshwater communities. However, little is known how variation in litter inputs interacts with chemical contaminants. We investigated the ecological effects resulting from changes in tree leaf litter inputs to freshwater communities, and how those changes might interact with the timing of insecticide contamination. Using the common insecticide malathion, we hypothesized that inputs of nutrient-rich and labile leaf litter (e.g., elm [Ulmus spp.] or maple [Acer spp.]) would reduce the negative effects of insecticides on wetland communities relative to inputs of recalcitrant litter (e.g., oak [Quercus spp.]). We exposed artificial wetland communities to a factorial combination of three litter species treatments (elm, maple, and oak) and four insecticide treatments (no insecticide, small weekly doses of 10 μg L−1, and either early or late large doses of 50 μg L−1). Communities consisted of microbes, algae, snails, amphipods, zooplankton, and two species of tadpoles. After two months, we found that maple and elm litter generally induced greater primary and secondary production. Insecticides induced a reduction in the abundance of amphipods and some zooplankton species, and increased phytoplankton. In addition, we found interactive effects of litter species and insecticide treatments on amphibian responses, although specific effects depended on application regime. Specifically, with the addition of insecticide, elm and maple litter induced a reduction in gray tree frog survival, oak and elm litter delayed tree frog metamorphosis, and oak and maple litter reduced green frog tadpole mass. Our results suggest that attention to local forest composition, as well as the timing of pesticide application might help ameliorate the harmful effects of pesticides observed in freshwater systems.

The complex QDs-Indolicidin (QDs-Ind) has been previously shown to be a good antimicrobial system with a low acute toxicity on Daphnia magna (D. magna). However, multigenerational effects caused by exposure to QDs-Ind and after subsequent recovery are still unknown. In this study, we performed multigenerational exposure tests and we evaluated individual fitness, population growth, DNA alteration, expression of Dhb (haemoglobin), Vtg (vitellogenin), CYP4 (cytochrome P450s CYP4 family), and CYP314 (cytochrome P450s mitochondrial family 314) genes on three generation of D. magna. Results showed that the total amount of eggs produced per female and total number of brood per female and body lengths were significantly decreased, Dhb, CYP4 were upregulated while Vtg was down-regulated except at reproduction days when it was slightly up-regulated under QDs-Ind exposure. Random Amplification of Polymorphic DNA (RAPD) method has proven to be useful to qualitative assess of DNA damage during generation and to underline modification in somatic or germinal cells. The results of the study suggest that effects of chronic exposure cannot be ignored.