Chokka squid (Loligo reynaudii) from three sites along the South African coast were analyzed for halogenated natural products (HNPs) and anthropogenic persistent organic pollutants (POPs). HNPs were generally more than one order of magnitude more abundant than POPs. The most prevalent pollutant, i.e. the HNP 2,3,3′,4,4′,5,5′-heptachloro-1′-methyl-1,2′-bipyrrole (Q1), was detected in all chokka squid samples with mean concentrations of 105, 98 and 45 ng/g lipid mass, respectively, at the Indian Ocean (site A), between both oceans (site B) and the South Atlantic Ocean (site C). In addition, bromine containing polyhalogenated 1′-methyl-1,2′-bipyrroles (PMBPs), 2,4,6-tribromophenol (2,4,6-TBP, up to 28 ng/g lipid mass), polybrominated methoxy diphenyl ethers, MHC-1, TBMP and other HNPs were also detected. Polychlorinated biphenyls (PCBs) were the predominant class of anthropogenic POPs. PCB 153 was the most abundant PCB congener in chokka squid from the Indian Ocean, and PCB 138 in samples from the South Atlantic Ocean and between both oceans.

Simultaneous quantification of short-, medium-, and long-chain chlorinated paraffins (CPs) in environmental matrices is challenging and has received much attention from environmental chemists. In this study, ammonium-chloride-enhanced liquid chromatography coupled with high-resolution mass spectrometry (LC-HRMS) was developed for the first time to quantify CPs in sediments and aqueous samples. Three ionization sources, including atmospheric pressure chemical ionization (APCI), electrospray ionization (ESI), and thermal-assisted-ESI, were employed to examine the performance of ammonium chloride as the chloride ion supply reagent in comparison with traditional chloride ion supply reagent, dichloromethane. Ammonium chloride can be easily used with reversed-phase liquid chromatography (LC), whereas dichloromethane is not compatible with aqueous LC mobile phase. Furthermore, other anion-supply reagents, such as ammonium formate, ammonium acetate, and ammonium bromide, were also tested. It was concluded that the adducts of the CPs with the anions were reversible and could partially dissociate into deprotonated CP ions. The yield of deprotonated CP ions was associated with the gas-phase basicity of the deprotonated CP ions and the corresponding anions. Furthermore, collision-induced dissociation curves were drawn to quantify the stability of anionic CP adducts. The ammonium-chloride-enhanced LC-HRMS was further employed for identifying CPs in sediment samples and coupled with an online SPE method for detecting CPs in aqueous samples. This study may significantly contribute to the qualification and quantification of CPs in environmental matrices.

Cadmium (Cd), a ubiquitous environmental pollutant, is known to impair placental development. However, the underlying mechanisms remain unclear. The present study used in vivo and in vitro models to investigate the effects of Cd on apoptosis and autophagy in placental trophoblasts and its mechanism. Pregnant mice were exposed to CdCl₂ (4.5 mg/kg) on gestational day (GD) 9. Human JEG-3 cells were exposed to CdCl₂ (0–40 μM) for different time points. Gestational Cd exposure obviously lowered the weight and diameter of mouse placentas. Number of TUNEL-positive cells was markedly elevated in Cd-administered mouse placentas and JEG-3 cells. Correspondingly, Cd significantly up-regulated cleaved caspase-3 protein level, a key indicator of apoptosis, in murine placentas and JEG-3 cells. Simultaneously, Cd also triggered autophagy, as determined by an elevation of LC3B-II and p62 protein, and accumulation of LC3-positive puncta, in placental trophoblasts. Chloroquine an autophagy inhibitor, obviously aggravated Cd-induced apoptosis in JEG-3 cells. By contrast, rapamycin, a specific autophagy inducer, significantly alleviated Cd-triggered apoptosis in JEG-3 cells. Mechanistically, autophagy inhibited Cd-induced apoptosis mainly via degrading caspase-9. Co-localizations of p62, a classical autophagic receptor, and caspase-9 were observed in Cd-stimulated human JEG-3 cells. Moreover, p62 siRNAs pretreatment markedly blocked the degradation of caspase 9 proteins via Cd-activated autophagy in JEG-3 cells. Collectively, our data suggest that activation of autophagy inhibits Cd-induced apoptosis via p62-mediated caspase-9 degradation in placental trophoblasts. These findings provide a new mechanistic insight into Cd-induced impairments of placental and fetal development.

Nanoparticles (NPs), heavy metal and natural organic matter (NOM) may simultaneously exist in the aquatic environment, where they will affect the behavior of each other and may enhance their toxicities. Studies on the influences of interactions between NOM and heavy metal ions on the behavior of NPs are scarce. In this study, combined effects of Pb²⁺ and HA on the aggregation behavior of TiO₂ NPs in water environment were investigated by Dynamic light scattering (DLS) and Nanoparticle tracking analysis (NTA). The results illustrated that interactions between Pb²⁺ and HA could case the aggregation of TiO₂ NPs obviously. The concurrence of Pb²⁺ and HA resulted in decreased critical coagulation concentration (CCC) and increased attachment efficiencies. Meanwhile, we found that the addition sequences of HA and heavy metal clearly influenced the aggregation kinetics of TiO₂ NPs. At different addition sequences, the complex reaction between Pb²⁺ and HA changed the surface charge of TiO₂ NPs, and caused the different aggregation behavior which depended on the complex locations and complex sites. Furthermore, the excitation-emission-matrix (EEM) fluorescence spectra was used to verify the significant effects of the complex interactions between Pb²⁺ and HA on the aggregation of TiO₂ NPs. Our results would be significant for interpreting TiO₂ behavior in the complicated water system.The complexation between Pb²⁺ and HA promoted the aggregation of TiO₂ NPs, meanwhile, complex locations and complex sites played an important role.

Previous in vitro studies have implied that triphenyl phosphate (TPHP) may act as an obesogen. However, its specific contributions to the progression of obesity and related metabolic diseases are still unclear in vivo in mice. In this study, we evaluated the effects of in utero and lactational exposure to three doses of TPHP (10, 100, and 1000 μg/kg BW) on obesity and metabolic dysfunctions in adult male mice fed a low-fat diet (LFD) or high-fat diet (HFD), by examining body weight, liver weight, histopathology, blood biochemistry, gene expression, and gut microbiota compositions and metabolic functions. Results showed that TPHP exposure led to increased body weight, liver weight, fat mass, hepatic steatosis, impaired glucose homeostasis, and insulin resistance, and mRNA levels of genes involved in lipid metabolism, especially lipogenesis and lipid accumulation, were significantly altered by TPHP treatment. Gas chromatography-mass spectrometry (GC-MS) analysis further supported the changes in fatty acid composition. Intestinal flora measurements by 16S rRNA gene sequencing and ¹H NMR based fecal metabolomics indicated that TPHP treatment modulated gut microbiome composition and influenced host-gut co-metabolism, especially for bile acids and short chain fatty acids (SCFAs). These results suggest that fetal exposure to TPHP can promote the development of obesity and metabolic dysfunctions in adult mice.

In standard terrestrial ecotoxicological tests, soils usually are spiked with highly soluble metal salts leading to overestimation of bioavailability and introducing counterions that may contribute to toxicity. Leaching is suggested as an efficient method to avoid the effects of the associated counterions. The present study aimed at investigating the effects of leaching on the bioavailability and toxicity of Pb(NO₃)₂ and PbO to the potworm Enchytraeus crypticus in LUFA 2.2 soil freshly spiked or after 18 months ageing. Percolation decreased porewater Pb concentrations as well as the toxicity of both Pb forms. The influence of percolation differed between the two Pb forms and between freshly spiked and aged soils. Percolation slightly increased LC50s based on total soil Pb concentrations for Pb(NO₃)₂, but not for PbO, and only affected Pb toxicity to enchytraeid reproduction in freshly spiked soils. The differences in Pb uptake in E. crypticus and toxicity between the two Pb forms as well as between different treatments could be minimized by relating them to 0.01 M CaCl₂-extractable concentrations. In addition, body Pb concentrations could well explain enchytraeid survival across all soils and treatments, indicating its suitability as a good proxy for Pb toxicity in soil.

The issue of potential long-term or hereditary effects for both humans and wildlife exposed to low doses (or dose rates) of ionising radiation is a major concern. Chronic exposure to ionising radiation, defined as an exposure over a large fraction of the organism's lifespan or even over several generations, can possibly have consequences in the progeny. Recent work has begun to show that epigenetics plays an important role in adaptation of organisms challenged to environmental stimulae. Changes to so-called epigenetic marks such as histone modifications, DNA methylation and non-coding RNAs result in altered transcriptomes and proteomes, without directly changing the DNA sequence. Moreover, some of these environmentally-induced epigenetic changes tend to persist over generations, and thus, epigenetic modifications are regarded as the conduits for environmental influence on the genome.Here, we review the current knowledge of possible involvement of epigenetics in the cascade of responses resulting from environmental exposure to ionising radiation. In addition, from a comparison of lab and field obtained data, we investigate evidence on radiation-induced changes in the epigenome and in particular the total or locus specific levels of DNA methylation. The challenges for future research and possible use of changes as an early warning (biomarker) of radiosensitivity and individual exposure is discussed. Such a biomarker could be used to detect and better understand the mechanisms of toxic action and inter/intra-species susceptibility to radiation within an environmental risk assessment and management context.

In order for Alberta's thick bitumen to be transported through pipelines, condensates are added creating a diluted bitumen (dilbit) mixture. Recent pipeline expansion projects have generated concern about potential dilbit spills on aquatic wildlife health. Studies have suggested that polycyclic aromatic compounds (PACs) are toxic to aquatic vertebrates and could potentially also interfere with their endocrine system. The research objectives of this study were to investigate the toxicity of dilbit to developing frog embryos and to identify the molecular mechanisms of action involved. Fertilized embryos of Western clawed frog (Silurana tropicalis) were exposed for 72 h to water accommodated fractions (WAF; 0.7–8.9 μg/L TPACs) and chemically-enhanced WAFs (CEWAF; 0.09–56.7 μg/L TPACs) of Access Western Blend (AWB) and Cold Lake Blend (CLB) dilbits. Both dilbit's CEWAFs significantly increased embryonic mortality and malformation incidence in the highest treatments tested, while WAF treatments led to no visible toxic effects. Increases of the cytochrome P450 1A (cyp1a) mRNA levels were observed for all WAF and CEWAF dilbit treatments suggesting that phase I detoxification is activated in the dilbit-exposed larvae. When exposed to PAC concentrations ranging from 0.09 to 8.9 μg/L, the frogs displayed no observable malformations, but expressed significant increases of cyp1a mRNA levels (2- to 25-fold; indicating a suitable biomarker of exposure); however, when concentrations were of 46.6 μg/L or higher, both malformed frog phenotype and induction of cyp1a mRNA level (>250-fold) were measured (indicating a suitable biomarker of response). The expression of several genes related to cellular detoxification and endocrine disruption were also measured, but were not significantly altered by the treatments. In sum, cyp1a mRNA level is a highly sensitive endpoint to measure subtle molecular changes induced by PAC exposure in the frog embryos and larvae, and data suggest that PAC concentration higher than 46 μg/L would be toxic to the developing S. tropicalis.

Increasing amount of aluminum (Al) gets into aquatic ecosystem through anthropogenic activity, but the knowledge about Al migration and relationships with sediments possessing different physico-chemical properties in eutrophic lakes is limited. Here, the Al migration rule and relationships with sediment nutritions in the Hangzhou West Lake, China was investigated, where a certain amount of residual Al-salts can enter because of the pre-treatment of the Qiantang River diversion project every day. Results revealed the obvious spatial distribution heterogeneity of Al in sediment vertical direction and horizontal direction following water flow. The Al content in sediment ranged 0.463–1.154 g kg⁻¹ in Maojiabu Lake, and ranged 9.862–40.442 g kg⁻¹ in Xiaonanhu Lake. Higher Al content distributed in upper layer sediment in lake with more disturbance. Total nitrogen (TN) contents were higher 0.917–3.387 mg g⁻¹ and 0.627–0.786 mg g⁻¹ in upper layer sediment than that in lower layer in Maojiabu Lake and Xiaonanhu Lake, respectively. Total phosphorus (TP) content ranged 0.779–2.580 mg g⁻¹, in which IP and Fe/Al-P contributed 24.9–80.8% and 17.0–51.6%, respectively. Correlations between Al content with nutrition, humic acid (HA) etc. of sediment regionally varied in Maojiabu and Xiaonanhu Lake. Spatial distribution of Al-salt in eutrophic lakes closely related with the physico-chemical characteristics of nutrients, humus, human disturbance and water division parameters. Results provides new insight into Al-salts migration and references for Al-risk evaluating in eutrophic lakes.

A field study was conducted to clarify sources of atmospheric black carbon and related carbonaceous components at Rishiri Island, Japan. We quantified equivalent black carbon (eBC) particle mass and the absorption Ångström exponent (AAE), atmospheric CO and CH₄, in addition to levoglucosan in total suspended particles, a typical tracer of biomass burning. Sixteen high eBC events were identified attributable to either anthropogenic sources or biomass burning in Siberia/China. These events were often accompanied by increases of co-emitted gases such as CH₄ and CO. Specifically, we observed pollution events with elevated eBC, AAE, levoglucosan, and CH₄CO slope in late July 2014, which were attributed to forest fires in Siberia by reference to the FLEXPART model footprint and fire hotspots. In autumn, drastic increases of eBC, AAE, and levoglucosan were observed, accompanied by an eBC–CO slope of >15 ng m⁻³/ppb, resulting from long-range transport of emissions from extensive burning of crop residue on the Northeast China Plain. Other than the sources of fossil fuel combustion in China and forest fires in Siberia, we report for the first time that pollution events in northern Japan are caused by crop residue burning in China. This study elucidated valuable information that will improve understanding of the effects of biomass burning in East Asia on atmospheric carbonaceous components.