Acceleration of Fe³⁺/Fe²⁺ cycle and simultaneous reduction of particle size with enhanced stability is extremely important for iron-based heterogeneous Fenton catalysts. In this work, Fe⁰-Fe₂O₃ composite nanoparticles embedded ordered mesoporous carbon hybrid materials (Fe⁰-Fe₂O₃/OMC) were rationally designed as efficient heterogeneous Fenton catalysts. Because of the confinement and reduction of OMC, highly dispersed Fe⁰-Fe₂O₃ active species with diameter of ∼8 nm were generated by an optimized carbothermic reduction process. In addition, Fe⁰-Fe₂O₃/OMC possesses ordered mesoporous structure with uniform mesopore, high surface area and pore volume. For comparison, two other catalysts, including solely Fe⁰ nanoparticles supported on ordered mesoporous carbon (Fe⁰/OMC) and solely Fe₂O₃ nanoparticles supported on ordered mesoporous carbon (Fe₂O₃/OMC) were also prepared. The Fenton catalytic performance of synthesized catalysts was evaluated by using H₂O₂ as oxidizing agent to degrade Acid Orange II (AOII). The results show that almost 98.1% of 100 mg L⁻¹ AOII was removed by Fe⁰-Fe₂O₃/OMC in condition of neutral pH and nearly room temperature, which is much higher than those of compared catalysts. The enhanced catalytic activity of Fe⁰-Fe₂O₃/OMC for AOII removal is due to the efficient electron transfer between the Fe⁰ and iron oxide and the accelerated Fe³⁺/Fe²⁺ cycle. The stability and reusability of the catalyst was also investigated, which showed a good performance even after five consecutive runs. The as-synthesized catalyst is proved to be an attractive candidate in heterogeneous Fenton chemistry and practical application.

Long-term genotoxic effects of two auxinic herbicide formulations, namely, the 58.4% 2,4-dichlorophenoxyacetic acid (2,4-D)-based DMA® and the 57.7% dicamba (DIC)-based Banvel® were evaluated on Cnesterodon decemmaculatus. Primary DNA lesions were analyzed by the single-cell gel electrophoresis methodology. Two sublethal concentrations were tested for each herbicide corresponding to 2.5% and 5% of the LC50₉₆ₕ values. Accordingly, fish were exposed to 25.2 and 50.4 mg/L or 41 and 82 mg/L for 2,4-D and DIC, respectively. Fish were continuously exposed for 28 days with replacement of test solutions every 3 days. Genotoxicity was evaluated in ten individuals from each experimental point at the beginning of the exposure period (0 day) and at 7, 14, 21 and 28 days thereafter. Results demonstrated for first time that 2,4-D-based formulation DMA® induced primary DNA strand breaks after 7–28 days exposure on C. decemmaculatus regardless its concentration. On the other hand, DIC-based formulation Banvel® exerted its genotoxic effect after exposure during 7–14 days and 7 days of 2.5 and 5% LC50₉₆ₕ, respectively. The present study represents the first evidence of primary DNA lesions induced by two widely employed auxinic herbicides on C. decemmaculatus, namely 2,4-D and DIC, following long-term exposure.

The increase of production and consumption of copper oxide nanostructures in several areas contributes to their release into aquatic ecosystems. Toxic effects of copper oxide nanoparticles (CuO NPs), in particular, on tropical aquatic organisms are still unknown, representing a risk for biota. In this study, the effects of rod-shaped CuO NPs on the Neotropical species Ceriodaphnia silvestrii and Hyphessobrycon eques were investigated. We also compared the toxicity of CuO NPs and CuCl₂ on these species to investigate the contribution of particles and cupper ions to the CuO NPs toxicity. Considering the low copper ions release from CuO NPs (<1%), our results revealed that the toxicity of CuO NPs to C. silvestrii and H. eques was mainly induced by the NPs. The 48 h EC₅₀ for C. silvestrii was 12.6 ± 0.7 μg Cu L⁻¹ and for H. eques the 96 h LC₅₀ was 211.4 ± 57.5 μg Cu L⁻¹ of CuO NPs. There was significant decrease in reproduction, feeding inhibition and increase in reactive oxidative species (ROS) generation in C. silvestrii exposed to CuO NPs. In fish H. eques, sublethal exposure to CuO NPs caused an increase in ROS generation in gill cells and an increase in cells number that were in early apoptotic and necrotic stages. Our results showed that CuO NPs caused toxic effects to C. silvestrii and H. eques and ROS play an important role in the toxicity pathway observed. Data also indicated that C. silvestrii was among the most sensitive species for CuO NPs. Based on predicted environmental concentration in water bodies, CuO NPs pose potential ecological risks for C. silvestrii and H. eques and other tropical freshwater organisms.

Although the abiotic and biotic transformation/degradation (T/D) processes of tetrabromobisphenol A (TBBPA) have been widely investigated in model experiments, few reviews have focused on these processes along with their metabolites or degradation products. In this paper, we summarize the current knowledge on the T/D of TBBPA and its derivatives, including abiotic and biotic T/D strategies/conditions, mechanisms, metabolites and environmental occurrences. Various treatments, such as pyrolysis, photolysis, chemical reactions and biotransformation, have been employed to study the metabolic mechanism of TBBPA and its derivatives and to remediate associated contaminated environments. To date, more than 100 degradation products and metabolites have been identified, dominated by less brominated compounds such as bisphenol A, 2,6-dibromo-4-isopropylphenol, 2,6-dibromo-4-hydroxyl-phenol, 2,6-dibromophenol, isopropylene-2,6-dibromophenol, 4-(2-hydroxyisopropyl)-2,6-dibromophenol, etc. It can be concluded that the T/D of TBBPA mainly takes place through debromination and β-scission. In some environmental media and human and animal tissues, brominated metabolites, glucoside and sulfate derivatives are also important T/D products. Here, the T/D products of TBBPA and its derivatives have been most comprehensively presented from the literature in recent 20 years. This review will enhance the understanding of the environmental behaviors of TBBPA-associated brominated flame retardants along with their ecological and health risks.

Bisphenols and triclosan (TCS) are widely used in consumer products. However, knowledge on human exposure to these anthropogenic chemicals has remained limited in China, especially for children. In this study, concentrations of seven bisphenols and TCS were determined in 283 urine samples collected from South China children aged between 3 and 11 years old. Bisphenol A (BPA), bisphenol S (BPS) and TCS were frequently detected in urine samples, with a detection rate of 93%, 89%, and 95%, respectively. Urinary concentrations of Σ7BPs (the sum concentrations of the seven bisphenols) ranged from 0.43 to 31.5 μg/L, with a median value of 0.91 μg/L, while TCS concentrations ranged from < limit of quantification to 21.9 μg/L (median: 0.21 μg/L). BPA was the predominant analogue (median: 0.35 μg/L), accounting for 49.8% of Σ7BPs. The urinary BPA concentrations in children from Guangzhou were significantly greater than those from Shenzhen. Correlation analysis suggested that multiple exposure sources to South China children likely existed for BPA, BPS, and TCS. Age, but not gender, was negatively associated with urinary residues of BPA and BPS (p < 0.05) and positively with TCS concentrations (p < 0.05). The estimated daily intake of Σ7BPs (23.9 ng/kg bw/day) or TCS (5.63 ng/kg bw/day) was below the tolerant reference dose of BPA, indicating no considerable health hazard to South China children.

Bisphenol A (BPA) exposure receives great ecotoxicological concern. However, gaps in knowledge, such as metabolism of BPA and inconsistent reports on reproductive toxicity, still exist. In this study, a marine fish model (Oryzias melastigma) was exposed to serial concentrations of BPA throughout its whole life cycle. The level of BPA-glucuronide (BPAG) dramatically increased throughout the embryonic stage since 4 dpf. Accordingly, the mRNA level and enzymatic activity of UDP-glucuronosyltransferases (UGTs) increased across the embryonic stage. The mRNA level of UGT2 subtype rather than UGT1 or UGT5 showed a concentration dependent response to BPA exposure. BPA exposure led to the morphological disruption of the chorion and villi as shown by scanning electron microscopy; however, the hatchability was not significantly influenced after exposure. Newly hatching larvae were continuously exposed to BPA for 120 days. Lower mRNA levels of hormone metabolism-related genes, decreased ratio of E2/T, slower ovary development and decreased egg production confirmed the inhibitory effect of BPA on reproduction. Overall, our results showed the conjugation of BPA into BPAG by UGT2 at the embryonic stage and convinced the reproductive toxicity from multiple levels after whole life exposure to BPA.

Despite of their ubiquitous distribution in marine sediments, the role of benthic fauna in microplastic transport at the sea floor has received little attention yet. The present study investigated the influence of bioturbation activity of the polychaete Arenicola marina on microplastic transport and burial in marine sediments. Sediment ingestion was assessed in a long term mesocosm experiment with exposure times ranging from 106 to 240 days, using three particle tracers with different particle diameters (microplastic: 500 and 1000 μm, respectively; luminophores: 130 μm). Sediment grain size distributions were assessed after experiment termination in all feeding layers at 8–12 cm depth to determine the influence of size-selective feeding of A. marina on median grain size and microplastic retention. Burial of microplastic occurred in all mesocosms up to a depth of 20 cm and was strongly dependent on individual sediment feeding rates. For low bioturbation conditions, both microplastic and luminophore concentrations exhibited an exponential decrease with increasing sediment depth, indicating particle burial via feeding funnel transport. Particle concentrations remained high in the uppermost 4 cm of the sediment. At high bioturbation rates, no microplastic particles remained in near-surface sediment layers, but a distinct accumulation of microplastic was observed in the feeding layer, suggesting the discrimination of plastic particles during feeding. In contrast, luminophores displayed a similar accumulation, but additionally showed uniform distributions above feeding layers, indicating ingestion and defecation by polychaetes. In accordance with these findings, an overall coarsening of median grain sizes was observed in all feeding layers, indicating the retention of large microplastic due to size-selective feeding. These findings demonstrate the ability of the conveyor belt-feeding polychaete A. marina to promote unidirectional transports of microplastic ≥500 μm and the potential for the long-term retention of these particles in marine sediments.

Albatrosses (Diomedeidae) are iconic pelagic seabirds whose life-history traits (longevity, high trophic position) put them at risk of high levels of exposure to methylmercury (MeHg), a powerful neurotoxin that threatens humans and wildlife. Here, we report total Hg (THg) concentrations in body feathers from 516 individual albatrosses from 35 populations, including all 20 taxa breeding in the Southern Ocean. Our key finding is that albatrosses constitute the family of birds with the highest levels of contamination by Hg, with mean feather THg concentrations in different populations ranging from moderate (3.8 μg/g) to exceptionally high (34.6 μg/g). Phylogeny had a significant effect on feather THg concentrations, with the mean decreasing in the order Diomedea > Phoebetria > Thalassarche. Unexpectedly, moulting habitats (reflected in feather δ13C values) was the main driver of feather THg concentrations, indicating increasing MeHg exposure with decreasing latitude, from Antarctic to subtropical waters. The role of moulting habitat suggests that the majority of MeHg eliminated into feathers by albatrosses is from recent food intake (income strategy). They thus differ from species that depurate MeHg into feathers that has been accumulated in internal tissues between two successive moults (capital strategy). Since albatrosses are amongst the most threatened families of birds, it is noteworthy that two albatrosses listed as Critical by the World Conservation Union (IUCN) that moult and breed in temperate waters are the most Hg-contaminated species (the Amsterdam and Tristan albatrosses). These data emphasize the urgent need for robust assessment of the impact of Hg contamination on the biology of albatrosses and they document the high MeHg level exposure of wildlife living in the most remote marine areas on Earth.

The parameter AOX (adsorbable organic halogens) indicates the total amount of organic halogens in an environment. Seawater and surface sediment samples from 12 sample sites in the Hangzhou Bay (HZB), China, were analyzed for AOX to investigate its contamination status. In this study, the AOX concentration ranged from 140.6 ± 45.6 μg/L to 716.1 ± 62.3 μg/L in seawater of the HZB, and from 11.3 ± 2.4 mg/kg to 112.7 ± 7.2 mg/kg in the sediment. Ocean currents, fluvial currents and the Yangtze River exerted profound influences on the distribution of AOX in the HZB. The point sources around the HZB, represented by wastewater treatment plants, discharged at least 645.4 t AOX into the HZB every year, most of which was generated by industrial activities rather than the human daily activities.

Vehicular emissions have become one of the main source of pollution of urban soils; this highlights the need for more detailed research on various traffic-related emissions and related distribution patterns. Since the banning of asbestos in the European Union, its substitution with antimony (Sb) in brake linings has led to increased inputs of this toxic metalloid to environmental compartments. The objective of this study was to provide detailed information about the spatial distribution patterns of Sb and to assess its mobility and bioavailability. Roadside soils along an arterial road (approx. 9000 vehicles per day) in Cologne (Germany) were studied along five transects, at four soil depths and at seven sampling points set at varying distances from the road (n = 140). For all samples, comprehensive soil characterization was performed and inverse aqua regia-extractable trace metal content was determined being pseudo-total contents. Furthermore, for one transect, also total Sb and a chemical sequential extraction procedure was applied (n = 28). Pseudo-total Sb for all transects decreased significantly with soil depth and distance from the road, reflecting a distribution pattern similar to that of other trace metals associated with brake lining emissions. Conversely, metals associated with exhaust emissions showed a convex distribution. The geochemical fractionation of Sb revealed the following trends: i) non-specifically sorbed Sb was <5%; ii) specifically sorbed Sb was only detected within 1 m distance from the road and decreased with depth; iii) Sb associated with poorly-crystalline Fe oxides decreased with distance from the road; and iv) content of Sb bounded to well-crystalline Fe oxides, and Sb present in the residual fraction remained relatively constant at each depth. Consequently, roadside soils appear to inhibit brake lining-related Sb contamination, with significant but rather low ecotoxicological potential for input into surface and groundwater.