A massive and dense textured layer (ca. 35–50 cm thick) of hardpan was uncovered at the top layer, which capped the unweathered sulfidic Cu-Pb-Zn tailings in depth and physically supported gravelly soil root zones sustaining native vegetation for more than a decade. For the purpose of understanding functional roles of the hardpan layer in the cover profile, the present study has characterized the microstructures of the hardpan profile at different depth compared with the tailings underneath the hardpans. A suit of microspectroscopic technologies was deployed to examine the hardpan samples, including field emission-scanning electron microscopy coupled with energy dispersive spectroscopy (FE-SEM-EDS), X-ray diffraction (XRD) and synchrotron-based X-ray absorption fine structure spectroscopy (XAFS). The XRD and Fe K-edge XAFS analysis revealed that pyrite in the tailings had been largely oxidised, while goethite and ferrihydrite had extensively accumulated in the hardpan. The percentage of Fe-phyllosilicates (e.g., biotite and illite) decreased within the hardpan profile compared to the unweathered tailings beneath the hardpan. The FE-SEM-EDS analysis showed that the fine-grained Ca-sulfate (possibly gypsum) evaporites appeared as platelet-shaped that deposited around pyrite, dolomite, and crystalline gypsum particles, while Fe-Si gels exhibited a needle-like texture that aggregated minerals together and produced contiguous coating on pyrite surfaces. These microstructural findings suggest that the weathering of pyrite and Fe-phyllosilicates coupled with dolomite dissolution may have contributed to the formation of Ca-sulfate/gypsum evaporites and Fe-Si gels. These findings have among the first to uncover the microstructure of hardpan formed at the top layer of sulfidic Cu-Pb-Zn tailings, which physically capped the unweathered tailings in depth and supported root zones and native vegetation under semi-arid climatic conditions.

The profile of 11 trace metals in two commonly used biomonitors (the native oyster Crassostrea palmula and mussel Mytella strigata) from Estero de Urias lagoon, Gulf of California, were studied for six months, covering both dry and wet seasons. Metal concentrations in these two bivalves were compared with concentrations accumulated by Artificial Mussels (AMs) deployed alongside during the same period. Significant temporal variations in Cd, Cr and Mn were observed in both bivalve species and AMs. Temporal changes were observed for Fe in both bivalve species, Pb in oyster only and Cu in both AMs and oysters, revealing seasonal changes in inputs and/or chemical forms of these metals in the lagoon. Significant correlations for Cd, Cr and Cu were found in mussels and oysters, but their Co, Fe, Mn and Zn profiles were very different, despite these two species being taxonomically closely related and often used as biomonitors for metals. Interestingly, Hg and U were detected in AMs but not in oysters and mussels. The difference in metal profile in oysters, mussels and AMs revealed in the present study clearly showed that different biomonitors and AM take up metals differentially from the same environment, and metal profile in a single biomonitor or AM alone therefore, cannot provide a good estimate on metal concentrations in the ambient environment. As such, different biomonitors and AM should be used in metal monitoring, in order to provide a comprehensive picture on metal levels in aquatic ecosystems. Concentrations of Ni and Pb in oysters, and Cr, Fe and Mn in mussels were among the highest reported in coastal waters worldwide. Concentrations of Pb in oysters exceeded legal limits set for bivalve mollusks in EU. Concentrations of Cr in mussels and oysters exceeded or were very close to, respectively, the legal limit for fish, crab-meat, oysters, prawns, and shrimps in Hong Kong. The results indicate a potential public health risk on human consumption of oysters and mussels commonly harvested from the Estero de Urias lagoon, and corresponding pollution control measures are deemed necessary.

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.

Spatiotemporal resolved models were developed predicting daily fine particulate matter (PM₂.₅) concentrations across Switzerland from 2003 to 2013. Relatively sparse PM₂.₅ monitoring data was supplemented by imputing PM₂.₅ concentrations at PM₁₀ sites, using PM₂.₅/PM₁₀ ratios at co-located sites. Daily PM₂.₅ concentrations were first estimated at a 1 × 1km resolution across Switzerland, using Multiangle Implementation of Atmospheric Correction (MAIAC) spectral aerosol optical depth (AOD) data in combination with spatiotemporal predictor data in a four stage approach. Mixed effect models (1) were used to predict PM₂.₅ in cells with AOD but without PM₂.₅ measurements (2). A generalized additive mixed model with spatial smoothing was applied to generate grid cell predictions for those grid cells where AOD was missing (3). Finally, local PM₂.₅ predictions were estimated at each monitoring site by regressing the residuals from the 1 × 1km estimate against local spatial and temporal variables using machine learning techniques (4) and adding them to the stage 3 global estimates. The global (1 km) and local (100 m) models explained on average 73% of the total,71% of the spatial and 75% of the temporal variation (all cross validated) globally and on average 89% (total) 95% (spatial) and 88% (temporal) of the variation locally in measured PM₂.₅ concentrations.

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.

Aluminum dialkyl phosphinates (ADPs) are a promising class of chemicals offering superior flame retardance. However, knowledge on their behavior in vivo is scarce. Hydrolysis has been suggested as one of the major routes of environmental degradation of ADPs. Herein, aluminum methylcyclohexyl phosphinic (AMHP), a kind of ADPs with industrial production in China, and its hydrolysate methyl cyclohexyl phosphinic acid (MHPA) were continuously exposed to Sprague Dawley (SD) rats for 28 days in this study. The same ratio of MHPA in organs to serum and the same daily excretion of MHPA were observed for AMHP exposure group and MHPA exposure group, suggesting the hydrolysis of AMHP in vivo. The hydrolysis of AMHP to MHPA was further confirmed by in vitro simulated human gastric intestinal juice. Therefore, both AMHP and MHPA distributed in liver, kidney and even brain in the form of MHPA. More than 80% of AMHP and MHPA could be excreted by feces and urine. Feces are the main route of excretion of AMHP and MHPA. The denseness of the inflammatory cell in the hepatic portal area and biochemical indexes showed the obvious dose-effect relationship. However, the toxicity of AMHP and MHPA was quite low even with exposure level up to 100 mg/kg dw/day. The low cumulative ability and mild toxicity indicated AMHP as a promising substitute for brominated flame retardant.

Perfluoroalkyl acids (PFAAs) were measured in aqueous and suspended particulate matter (SPM) fractions in the final effluents from 12 wastewater treatment facilities located around the Connecticut shoreline. Aqueous phase concentrations ranged from 53 to 198 ng/L for ∑PFAAs with ≤7 perfluorinated carbons (CF₂) and 2–73 ng/L for >7 CF₂ PFAAs. Predominant PFAAs associated with effluent derived SPM were perfluorodecanoic acid and perflurorooctane sulfonic acid, detected in 48% and 52% of samples in concentrations ranging from <LOQ–1770 ng/g and <LOQ–2750 ng/g respectively. Based on the range of concentrations detected and the average flow of final effluent to the Long Island Sound (LIS), average total annual PFAA mass loads from wastewater treatment facilities to the LIS is estimated in the range of 70–315 kg/year, with 4–100 kg/year consisting of >7 CF₂ PFAAs. Partitioning coefficients (log KOC) derived for effluent water and SPM phases (4.2 ± 0.3, 4.4 ± 0.4, 5.1 ± 0.2 and 5.3 ± 0.2 for PFOA, PFNA PFDA and PFUnA; 4.5 ± 0.2 and 5.2 ± 0.2 for PFOS and PFHsX respectively) were found to be of similar magnitude to aeration tank particles, though 0.5 to 2 log units greater than sludge solids and to natural system particulates including riverine SPM, estuarine SPM and sediments. Results from this study suggest that effluent derived suspended particulate matter could be an effective vector in the transport of long-chained PFAAs through wastewater treatment into receiving waters, and a potential vector to the local food chain.

Increasing evidence shows that impaired telomere function is associated with male infertility, and various environmental factors are believed to play a pivotal role in telomerase deficiency and telomere shortening. Benzo[a]pyrene (B[a]P), a ubiquitous pollutant of polycyclic aromatic hydrocarbons (PAHs), can act as a reproductive toxicant; however, the adverse effect of B[a]P on telomeres in male reproductive cells has never been studied, and the related mechanisms remain unclear. In this study, we explored the effects of benzo[a]pyrene-7,8-dihydrodiol-9,10-epoxide (BPDE), the active metabolite of B[a]P, on telomere dysfunction in mouse spermatocyte-derived cells (GC-2) and also the potential role of telomerase in BPDE-induced spermatogenic cell damage. The results showed that BPDE induced cell viability inhibition, senescence, and apoptosis in GC-2 cells in a dose-dependent manner. Shortened telomeres, telomere-associated DNA damage, reduced telomerase activity, and TERT expression were also observed in BPDE-treated cells, accompanied with the activation of DNA damage response pathway (ATM/Chk1/p53/p21). Moreover, by establishing the TERT knockdown and re-expression cell models, we found that TERT regulated telomere length and the expression of DNA damage response-related proteins to influence senescence and apoptosis in GC-2 cells. These in vitro findings were further confirmed in vivo in the testicular cells of rats orally administrated with B[a]P for 7 days. B[a]P treatment resulted in histological lesions, apoptosis, and senescence in the testes of rats, which were accompanied by shortened telomeres, reduced levels of TERT protein, and increased expression of DNA damage response-related proteins. In conclusion, it can be concluded that TERT-mediated telomere dysfunction contributes to B[a]P- and BPDE-induced senescence and apoptosis through DNA damage response in male reproductive cells.

Sulfur (S) fertilizer application in rice (Oryza sativa L.) is crucial in determining rice grain productivity and quality. However, little information is available concerning the effect of S supply on cadmium (Cd) uptake and translocation in rice. In this study, both hydroponic and soil experiments were conducted to investigate the influence of S supply on Cd accumulation in rice under two Cd levels (0 and 50 μM), combined with three S concentrations (0, 2.64 and 5.28 mM). The moderate and excessive S supply (2.64 and 5.28 mM) tended to increase plant growth, root length, root and shoot dry weights of rice seedlings, and significantly decreased Cd concentrations in rice plants and grains in the absence or presence of Cd. The subcellular distribution and chemical forms of Cd in roots and shoots also varied with S supply levels. The decreased Cd uptake and translocation in rice grains could be ascribed to the enhanced formation of iron (Fe) plaque on the root surfaces and increased Cd chelation and vacuolar sequestration in roots, since Fe, Mn concentrations in Fe plaque, glutathione and phytochelatins contents, as well as phytochelatin synthase (OsPCS) and tonoplast heavy metal ATPase (OsHMA3) expressions in roots significantly increased with increased S supply. This work provides more insight into the mechanisms of Cd uptake and translocation in rice, and will be helpful for developing strategies to reduce rice grain Cd through S fertilizer application in Cd-contaminated soil.

Plastic pollution is ubiquitous throughout the marine environment, with microplastic (i.e. <5 mm) contamination a global issue of emerging concern. The lack of universally accepted methods for quantifying microplastic contamination, including consistent application of microscopy, photography, an spectroscopy and photography, may result in unrealistic contamination estimates. Here, we present and apply an analysis workflow tailored to quantifying microplastic contamination in marine waters, incorporating stereomicroscopic visual sorting, microscopic photography and attenuated total reflectance (ATR) Fourier transform infrared (FTIR) spectroscopy. The workflow outlines step-by-step processing and associated decision making, thereby reducing bias in plastic identification and improving confidence in contamination estimates. Specific processing steps include (i) the use of a commercial algorithm-based comparison of particle spectra against an extensive commercially curated spectral library, followed by spectral interpretation to establish the chemical composition, (ii) a comparison against a customised contaminant spectral library to eliminate procedural contaminants, and (iii) final assignment of particles as either natural- or anthropogenic-derived materials, based on chemical type, a compare analysis of each particle against other particle spectra, and physical characteristics of particles. Applying this workflow to 54 tow samples collected in marine waters of North-Western Australia visually identified 248 potential anthropogenic particles. Subsequent ATR-FTIR spectroscopy, chemical assignment and visual re-inspection of photographs established 144 (58%) particles to be of anthropogenic origin. Of the original 248 particles, 97 (39%) were ultimately confirmed to be plastics, with 85 of these (34%) classified as microplastics, demonstrating that over 60% of particles may be misidentified as plastics if visual identification is not complemented by spectroscopy. Combined, this tailored analysis workflow outlines a consistent and sequential process to quantify contamination by microplastics and other anthropogenic microparticles in marine waters. Importantly, its application will contribute to more realistic estimates of microplastic contamination in marine waters, informing both ecological risk assessments and experimental concentrations in effect studies.