One of the topics gaining lots of recent attention is the antimony (Sb) pollution. We have designed a dual-functional electroactive filter consisting of one-dimensional (1-D) titanate nanowires and carbon nanotubes for simultaneous oxidation and sorption of Sb(III). Applying an external limited DC voltage assist the in-situ conversion of highly toxic Sb(III) to less toxic Sb(V). The Sb(III) removal kinetics and efficiency were enhanced with flow rate and applied voltage (e.g., the Sb(III) removal efficiency increased from 87.5% at 0 V to 96.2% at 2 V). This enhancement in kinetics and efficiency are originated from the flow-through design, more exposed sorption sites, electrochemical reactivity, and limited pore size on the filter. The titanate-CNT hybrid filters perform effectively across a wide pH range of 3–11. Only negligible inhibition was observed in the presence of nitrate, chloride, and carbonate at varying concentrations. Our analyses using STEM, XPS, or AFS demonstrate that Sb were mainly adsorbed by Ti. DFT calculations suggest that the Sb(III) oxidation kinetics can be accelerated by the applied electric field. Exhausted titanate-CNT filters can be effectively regenerated by using NaOH solution. Moreover, the Sb(III)-spiked tap water generated ∼2400 bed volumes with a >90% removal efficiency. This study provides new insights for rational design of continuous-flow filters for the decontamination of Sb and other similar heavy metal ions.

4-Nonylphenol (NP) and bisphenol A (BPA) are high-production and high-volume chemicals used to manufacture various commercial products. They are also ubiquitous contaminants that disrupt endocrine systems in wildlife and humans. We collected, from Taiwan cities with the highest food production, and analyzed, using high performance liquid chromatography tandem mass spectrometry (HPLC/MS/MS), 278 food samples for NP and BPA from 11 categories. We found background levels of 100% for NP and 72% for BPA in total samples. High levels of contamination (up to 918 and 49.4 μg/kg) were found in some foods of seafood and animal origin. We used a probabilistic approach to calculate daily dietary dose (Monte Carlo-estimated 95th percentile dietary exposure [MCS 95]) from the Taiwan National Food Consumption database for each sex- and age-specified population. For NP and BPA, the highest average daily dose (ADDs) were in the 4- to 6-year-old group (MCS 95 = 1.57/1.28 and 0.157/0.147 [Male/Female] μg/kg bw/day, respectively), and the lowest ADDs were in the ≥65-year-old group (MCS 95 = 0.674/0.581 and 0.054/0.045 [M/F] μg/kg bw/day, respectively). Based on the European Food Safety Authority (4 μg/kg bw/day for BPA) and Danish Institute of Safety and Toxicology guidelines (5 μg/kg bw/day for NP), the 95th percentile HQ of NP and BPA intake in different sex- and age-specified groups in Taiwan posed no risks through dietary exposure. The intake quantity and concentrations of grains, livestock, and seafood are important variables for the integrated risk of NP and BPA. In conclusion, a combination of multiple and long-term exposure via food consumption should be considered rather than individual endocrine-disrupting chemicals during dietary risk assessment in specific populations.The 95th percentile HQ of NP and BPA intake in different age and sex groups in Taiwan posed no risks through dietary exposure based on probabilistic and sensitive approach.

Genotoxic analyses are commonly used in ecotoxicological studies as early biomarkers to investigate the potential effects of environmental contaminants on biological models. Several pollutants can induce DNA damage and, therefore, counting micronuclei and other nuclear abnormalities are efficient tools to evaluate genotoxicity. Some pollutants such as 4-nonylphenol (NP), a detergent used mainly in industries, and Cyproterone Acetate (CPA), an antiandrogenic medicine, have already shown genotoxic effects on some vertebrates. However, although amphibians are considered bioindicators of environmental quality and their populations are declining worldwide, the effects of these compounds on anurans are not yet known and, therefore, we believe that it is important to investigate such effects on anurans. Since water contamination is one of the ultimate causes of amphibian decline, ecotoxicological studies are important to discuss the appropriate solutions to avoid species extinction. Thus, this study investigates the genotoxic effects on Rana catesbeiana tadpoles and juveniles after being exposed to 1, 10 and 100 μg/L NP and 0.025, 0.25 and 2.5 ng/L CPA, by counting the nuclear abnormalities after exposure. The laboratory experiments lasted 28 days. The experimental conditions were the same except for the water volume since tadpoles and juveniles exhibit different habits at different developmental stages. Compared to juveniles, tadpoles were more susceptible to both compounds as indicated by the increased nuclear abnormalities observed in the highest NP concentration and all tested CPA concentrations. The juveniles, on the other hand, responded only to the two highest CPA concentrations. We concluded that CPA, even at very low concentrations, is extremely harmful to both anuran developmental stages and, particularly, to tadpoles. The significant effects observed on tadpoles is an important outcome of this study since 100 μg/L or higher NP concentrations are frequently detected in the environment.

Decabromodiphenyl ether (BDE-209) is commonly used as a flame retardant, usually in products that were utilized in electronic equipment, plastics, furniture and textiles. To identify the impacts of BDE-209 on the male reproductive system and the underlying toxicological mechanisms, 40 male ICR mice were randomly divided into four groups, which were then exposed to BDE-209 at 0, 7.5, 25 and 75 mg kg−1 d−1 for four weeks, respectively. With regard to the in vitro study, GC-2spd cells were treated with BDE-209 at 0, 2, 8 and 32 μg mL−1 for 24 h, respectively. The results from the in vivo experiments showed that BDE-209 resulted in damage to the testis structure, led to cell apoptosis in testis and decreased sperm number and motility, while sperm malformation rates were significantly increased. Moreover, BDE-209 could induce oxidative stress with decreased testosterone levels, result in DNA damage and activate DNA damage response signaling pathways (ATM/Chk2, ATR/Chk1 and DNA-PKcs/XRCC4/DNA ligase Ⅳ). The data from the in vitro experiments showed that BDE-209 led to cytotoxicity by reducing cell viability and increasing LDH release as well. BDE-209 also induced DNA strand breaks, cell cycle arrest at G1 phase and elevated reactive oxygen species (ROS) level in GC-2 cells. These results suggested that BDE-209 could lead to male reproductive toxicity by inducing DNA damage and failure of DNA damage repair which resulted in cell cycle arrest and apoptosis of spermatogenic cell. The present study provided new evidence to elucidate the potential mechanism of male reproductive toxicity induced by BDE-209.

Metal pollution has been associated with anthropogenic activities, such as effluents and emissions from mines. Soil could be exposure route of wild rats to metals, especially in mining areas. The aim of this study was to verify whether soil exposure under environmentally relevant circumstances results in metal accumulation and epigenetic modifications. Wistar rats were divided to three groups: 1) control without soil exposure, 2) low-metal exposure group exposed to soil containing low metal levels (Pb: 75 mg/kg; Cd: 0.4), and 3) high-metal exposure group exposed to soil (Pb: 3750; Cd: 6). After 1 year of exposure, the metal levels, Pb isotopic values, and molecular indicators were measured. Rats in the high-group showed significantly greater concentrations of Pb and Cd in tissues. Higher accumulation factors (tissue/soil) of Cd than Pb were observed in the liver, kidney, brain, and lung, while the factor of Pb was higher in the tibia. The obtained results of metal accumulation ratios (lung/liver) and stable Pb isotope ratios in the tissues indicated that the respiratory exposure would account for an important share of metal absorption into the body. Genome-wide methylation status and DNA methyltransferase (Dnmt 3a/3b) mRNA expressions in testis were higher in the high-group, suggesting that exposure to soil caused metal accumulation and epigenetic alterations in rats.

Oxygenated polycyclic aromatic hydrocarbons (oxy-PAHs) are a group of environmental pollutants found in complex mixtures together with PAHs. In contrast to the extensively studied PAHs, which have been established to have mutagenic and carcinogenic properties, much less is known about the effects of oxy-PAHs. The present work aimed to investigate the genotoxic potency of a set of environmentally relevant oxy-PAHs along with environmental soil samples in human bronchial epithelial cells (HBEC). We found that all oxy-PAHs tested induced DNA strand breaks in a dose-dependent manner and some of the oxy-PAHs further induced micronuclei formation. Our results showed weak effects in response to the oxy-PAH containing subfraction of the soil sample. The genotoxic potency was confirmed in both HBEC and HepG2 cells following exposure to oxy-PAHs by an increased level of phospho-Chk1, a biomarker used to estimate the carcinogenic potency of PAHs in vitro. We further exposed zebrafish embryos to single oxy-PAHs or a binary mixture with PAH benzo[a]pyrene (B[a]P) and found the mixture to induce comparable or greater effects on the induction of DNA strand breaks compared to the sum of that induced by B[a]P and oxy-PAHs alone. In conclusion, oxy-PAHs were found to elicit genotoxic effects at similar or higher levels to that of B[a]P which indicates that oxy-PAHs may contribute significantly to the total carcinogenic potency of environmental PAH mixtures. This emphasizes further investigations of these compounds as well as the need to include oxy-PAHs in environmental monitoring programs in order to improve health risk assessment.

Compound-specific isotope analysis (CSIA) was firstly applied to explore the biodegradation of hexachlorcyclohexane (HCH) isomers in contaminated soil. Concentrations and compound-specific carbon isotope ratio profiles of HCH in different specific ex-situ pilot-scale contaminated soil mesocosms were determined. The addition of nutrients and Sphingobium spp. significantly enhanced the degradation of HCH in contaminated soils within 90 days. Isomer specific biodegradation of HCHs was observed with α- and γ-HCH being more degradable than β and δ-HCH. Stable carbon isotope fractionation of HCH was observed and the δ¹³C values shifted from −28.8 ± 0.3‰ to −24.8 ± 0.7‰ upon 87.3% removal, −27.9 ± 0.2‰ to −25.9 ± 0.5‰ upon 72.8% removal, −29.4 ± 0.3‰ to −19.9 ± 0.6‰ upon 95.8% removal, and −27.8 ± 0.5‰ to −23.6 ± 0.7‰ after 96.9% removal for α, β, γ, and δ-HCH, respectively. Furthermore, the enrichment factor ε for α, β, γ, and δ-HCH biodegradation in soil was obtained for the first time as −2.0‰, −1.5‰, −3.2‰, and −1.4‰, which could play a critical role in assessing in situ biodegradation of HCH isomers in field site soil. Results from ex-situ pilot-scale experiments clearly demonstrated that CSIA could be a promising tool to qualitatively and quantitatively evaluate in situ biodegradation of HCH in contaminated field site.

Solubilization of arsenate in guts of deposit-feeders is a key process for their dietary uptake of arsenate from contaminated sediments. The present study explored this digestive solubilization with in vitro extraction experiments that quantified arsenic (As) release from substrates (natural sediment and As-enriched iron oxides) in the presence of various digestive agents (proteins, amino acids and surfactants collected from gut fluid of a sipunculan worm). To investigate potential mechanisms for the influence of digestive agents, analyses determined correlations between As and Fe concentrations, the size distribution of the As bound to the digestive agents, and the adsorption of the digestive agents on the substrates. Both the digestive surfactants and proteinaceous materials increased arsenate mobilization, with the surfactants enhancing the effects of the proteinaceous materials. Arsenate reduction and reductive dissolution of iron oxides were not observed and correlations between the concentrations of released As and Fe were weak. These findings indicate that dissolution release of Fe did not appear to be the main route by which the digestive agents mobilized particle-associated As. Most of the released As (>70%) was distributed in the <10 kDa fraction of the digestive agents, showing that the As mobilization was also not caused by complexation with proteins in the digestive agents. In contrast, adsorption of the digestive agents occurred along with the release of arsenate from the arsenate-rich substrates, suggesting that competitive adsorption was the mechanism by which the digestive agents mobilized sedimentary arsenate. Our work demonstrated that the presence of digestive surfactants significantly enhances arsenate availability during deposit feeding.

Although effluent from municipal wastewater treatment plants (WWTPs) is a major stressor in receiving environments, relatively few studies have addressed how its discharge affects natural fish communities. Here, we assessed fish community composition over three years along a gradient of effluent exposure from two distinct WWTPs within an International Joint Commission Area of Concern on the Great Lakes (Hamilton Harbour, Canada). We found that fish communities changed with distance from both WWTPs, and were highly dissimilar between sites that were closest to and furthest from the wastewater outfall. Despite differences in the size and treatment technology of the WWTPs and receiving habitats downstream, we found that the sites nearest the outfalls had the highest fish abundances and contained a common set of signature fish species (i.e., round goby Neogobius melanostomus, green sunfish Lepomis cyanellus). Non-native and stress tolerant species were also more abundant near one of the studied WWTPs when compared to the reference site, and the number of young-of-the-year fish collected did not vary along the effluent exposure gradients. Overall, we show that fish are attracted to wastewater outfalls raising the possibility that these sites may act as an ecological trap.

Microcystis aeruginosa is one of the main species of cyanobacteria that causes water blooms. M. aeruginosa can release into the water several types of microcystins (MCs), which are harmful to aquatic organisms and even humans. However, few studies have investigated the hepatotoxicity of M. aeruginosa itself in zebrafish in environments that simulate natural aquatic systems. The objective of this study was to evaluate the hepatotoxicity of M. aeruginosa in adult zebrafish (Danio rerio) after short-term (96 h) exposure and to elucidate the potential underlying mechanisms. Distinct histological changes in the liver, such as enlargement of the peripheral nuclei and sinusoids and the appearance of fibroblasts, were observed in zebrafish grown in M. aeruginosa culture. In addition, antioxidant enzyme activity was activated and protein phosphatase (PP) activity was significantly decreased with increasing microalgal density. A proteomic analysis revealed alterations in a number of protein pathways, including ribosome translation, immune response, energy metabolism and oxidative phosphorylation pathways. Western blot and real-time PCR analyses confirmed the results of the proteomic analysis. All results indicated that M. aeruginosa could disrupt hepatic functions in adult zebrafish, thus highlighting the necessity of ecotoxicity assessments for M. aeruginosa at environmentally relevant densities.