Herein, magnetic porous pinecone-derived hydrochar (MPHCMW) co-activated by KHCO₃ and K₂FeO₄ through one-step microwave-assisted pyrolysis was innovatively synthesized for hexavalent chromium (Cr(VI)) and anthracene (ANT) removal from water. The analyses of characterization consequences and co-activation mechanisms not merely proved the high specific surface area (703.97 m²/g) and remarkable microporous structures of MPHCMW caused by the synergistic chemical activation of KHCO₃ and K₂FeO₄, but also testified successful loading of Fe⁰ and Fe₃O₄ on MPHCMW by the process of carbothermal reduction between K₂FeO₄ and carbon matrix of hydrochar. The resultant MPHCMW possessed pH-dependence for Cr(VI), while adsorption for ANT was hardly impacted by the pH of solution. Moreover, the adsorption processes of MPHCMW could attain equilibrium within 60 min for Cr(VI) and 30 min for ANT with multiple kinetics, and the corresponding adsorption capacity for Cr(VI) and ANT was 128.15 and 60.70 mg/g, respectively. Additionally, the adsorption percentages of MPBCMW for Cr(VI)/ANT was maintained at 87.87/82.64% after three times of adsorption-desorption cycles. Furthermore, pore filling, complexation, electrostatic interaction, reduction and ion exchange were testified to enhance the removal of Cr(VI), while the ANT removal was achieved via π-π stacking, complexation, pore filling and hydrogen bonding force.

The occurrence of excessive ammonium in groundwater threatens human and aquatic ecosystem health across many places worldwide. As the fate of ammonium in groundwater systems is often affected by a complex mixture of transport and biogeochemical transformation processes, identifying the sources of groundwater ammonium is an important prerequisite for planning effective mitigation strategies. Elevated ammonium was found in both a shallow and an underlying deep groundwater system in an alluvial aquifer system beneath an agricultural area in the central Yangtze River Basin, China. In this study we develop and apply a novel, indirect approach, which couples the random forest classification (RFC) of machine learning method and fluorescence excitation-emission matrices with parallel factor analysis (EEM-PARAFAC), to distinguish multiple sources of ammonium in a multi-layer aquifer. EEM-PARAFAC was applied to provide insights into potential ammonium sources as well as the carbon and nitrogen cycling processes affecting ammonium fate. Specifically, RFC was used to unravel the different key factors controlling the high levels of ammonium prevailing in the shallow and deep aquifer sections, respectively. Our results reveal that high concentrations of ammonium in the shallow groundwater system primarily originate from anthropogenic sources, before being modulated by intensive microbially mediated nitrogen transformation processes such as nitrification, denitrification and dissimilatory nitrate reduction to ammonium (DNRA). By contrast, the linkage between high concentrations of ammonium and decomposition of soil organic matter, which ubiquitously contained nitrogen, suggested that mineralization of soil organic nitrogen compounds is the primary mechanism for the enrichment of ammonium in deeper groundwaters.

Stable nitrogen isotope (δ¹⁵N) technology has often been used as a powerful tool to separate nitrogen oxides (NOₓ) produced by residential combustion (i.e., biomass burning and coal combustion) from other sources. However, the insufficient measurement of δ¹⁵N-NOₓ fingerprints of these emissions limits its application, especially in North China where residential emissions are significant. This study conducted combustion experiments to determine the δ¹⁵N-NOₓ of typical residential fuels in North China, including ten biomass fuels and five types of coal. The results showed that the δ¹⁵N of biomass varied between −6.9‰ and 2.3‰, which was lower than the δ¹⁵N of residential coal (−0.2‰–4.6‰). After combustion, the δ¹⁵N of biomass residues increased greatly, while that of coal residues showed no significant upward trend (p > 0.05). The δ¹⁵N-NOₓ produced by biomass burning ranged from −5.6‰ to 3.2‰ (−0.4‰ ± 2.4‰), showing a significant linear relation with δ¹⁵N-biomass. Comparatively, the δ¹⁵N-NOₓ derived from residential coal combustion was much higher (16.1‰ ± 3.3‰), ranging from 11.7‰ to 19.7‰. It was not well correlated with δ¹⁵N-coal, and only slightly lower than the estimated δ¹⁵N-NOₓ of industrial coal combustion (17.9‰, p > 0.05). These observations indicate that the δ¹⁵N-NOₓ of residential coal combustion is a result of the mixture of thermal- and fuel-released NOₓ. Based on the isotopic characteristics observed in this study, we analyzed the reported δ¹⁵N-NOₓ, and provided more statistically robust δ¹⁵N-NOₓ distributions for biomass burning (1.3‰ ± 4.3‰; n = 101) and coal combustion (17.9‰ ± 3.1‰; n = 26), which could provide guidance for scientific studies aiming to quantify the origin of NOₓ in North China and in other regions.

Endocrine disrupting chemicals (EDCs) are a matter of great concern. They are ubiquitous in the environment, are considered harmful to humans and wildlife, yet remain challenging to identify based on current international test guidelines and regulatory frameworks. For a compound to be identified as an EDC within the EU regulatory system, a plausible link between an endocrine mode-of-action and an adverse effect outcome in an intact organism must be established. This requires in-depth knowledge about molecular pathways regulating normal development and function in animals and humans in order to elucidate causes for disease. Although our knowledge about the role of the endocrine system in animal development and function is substantial, it remains challenging to predict endocrine-related disease outcomes in intact animals based on non-animal test data. A main reason for this is that our knowledge about mechanism-of-action are still lacking for essential causal components, coupled with the sizeable challenge of mimicking the complex multi-organ endocrine system by methodological reductionism. Herein, we highlight this challenge by drawing examples from male reproductive toxicity, which is an area that has been at the forefront of EDC research since its inception. We discuss the importance of increased focus on characterizing mechanism-of-action for EDC-induced adverse health effects. This is so we can design more robust and reliable testing strategies using non-animal test methods for predictive toxicology; both to improve chemical risk assessment in general, but also to allow for considerable reduction and replacement of animal experiments in chemicals testing of the 21st Century.

Microplastics (MPs) serve as vectors for microorganisms and antibiotic resistance genes (ARGs) and contribute to the spread of pathogenic bacteria and ARGs across various environments. Patterns of microbial communities and ARGs in the biofilm on the surface of MPs, also termed as plastisphere, have become an issue of global concern. Although antibiotic resistome in the plastisphere has been detected, how watershed urbanization affects patterns of potential pathogens and ARGs in the microplastic biofilms is still unclear. Here, we compared the bacterial communities, the interaction between bacterial taxa, pathogenic bacteria, and ARGs between the plastisphere and their surrounding water, and revealed the extensive influence of urbanization on them. Our results showed that bacterial communities and interactions in the plastisphere differed from those in their surrounding water. Microplastics selectively enriched Bacteroidetes from water. In non-urbanized area, the abundance of Oxyphotobacteria was significantly (p < 0.05) higher in plastisphere than that in water, while α-Proteobacteria was significantly (p < 0.05) higher in plastisphere than those in water of urbanized area. Pathogenic bacteria, ARGs, and mobile genetic elements (MGEs) were significantly (p < 0.05) higher in the urbanized area than those in non-urbanized area. MPs selectively enriched ARG-carrying potential pathogens, i.e., Klebsiella pneumoniae and Enterobacter cloacae, and exhibited a distinct effect on the relative abundance of ARG and pathogens in water with different urbanization levels. We further found ARGs were significantly correlated to MGEs and pathogenic bacteria. These results suggested that MPs would promote the dissemination of ARGs among microbes including pathogenic bacteria, and urbanization would affect the impact of MPs on microbes, pathogens, and ARGs in water. A high level of urbanization could enhance the enrichment of pathogens and ARGs by MPs in aquatic systems and increase microbial risk in aquatic environments. Our findings highlighted the necessity of controlling the spread of ARGs among pathogens and the usage of plastic products in ecosystems of urban areas.

Atmospheric nitrogen (N) deposition is becoming an increasingly important factor affecting the nutrient level of lakes, especially considering the long-term control measures for external N inputs in developed regions. However, few studies have investigated the effects of atmospheric N deposition and the respective ecological significance in eutrophic waters. In this study, bulk and wet deposition rates of all N species and water N concentrations in Lake Taihu were determined based on the long-term (2010–2018) high-resolution (weekly or monthly) systematic observations. The results indicated that the decline in wind speed and change in land-use type likely decreased the N deposition rate. The bulk N deposition rates decreased from 45.77 kg N ha⁻¹ yr⁻¹ in 2012 to 22.06 kg N ha⁻¹ yr⁻¹ in 2018, which could account for decrease of 1.01 mg N L⁻¹ in the lake N concentrations via a rough estimation, and this value was close to the actual variation in N concentration in Lake Taihu. The correlation between N concentrations and atmospheric deposition fluxes was stronger than that between N concentrations and riverine N inputs or lake storage, which further indicated that change in atmospheric N deposition was the key reason for the variation in N concentrations. The direct bulk N deposition into Lake Taihu accounted for 17.5% and 51.4% of the riverine N inputs and lake N inventory, respectively. Moreover, atmospheric N deposition was concentrated in summer, which was dominated by reduced N, and it may be important for the duration of algal blooms. Therefore, external N inputs, including atmospheric N deposition, should be further controlled for an effective mitigation of eutrophication and algal blooms in Lake Taihu.

Per-and polyfluoroalkyl substances (PFASs) have attracted extensive attention since this century due to their wide distribution, persistence, bioaccumulation/biomagnification potential, and (eco)toxicity. In the present study, we investigated the sorption kinetics, sorption isotherms and desorption behaviors of legacy and emerging PFASs with different chain lengths and functional end groups onto marine sediments at four different salinities (0, 10, 20, and 30 practical salinity units (psu)). Results revealed that the sorption of PFASs onto sediment can be well described by the pseudo-second-order kinetic model. PFASs sorption was influenced by both compound-specific and solution-specific parameters. The distribution coefficient (Kd) for PFASs were increased with the increase of perfluorocarbon chain length and salinity, suggesting that hydrophobic and electrostatic interactions were involved in the adsorption process. 6:2 FTSA showed the lowest adsorption among PFASs with eight carbon atoms (6:2 FTSA, PFOA and PFOS). The increase of perfluorocarbon chain length of PFASs and salinity would result in the decrease of desorption rate of PFASs from sediment. In addition, PFCAs were desorbed more easily from the sediment than the PFSAs with the same perfluorocarbon chain length at all salinity groups. The present study demonstrated that salinity can apparently influence the fate of PFASs in aquatic environment and provided valuable data for modeling the fate of PFASs in real environment.

The toxicological status of bisphenol A (BPA) is under strong debate. Whereas in vitro it is an agonist of the estrogen receptor with a potency ca. 10⁵-fold lower than the natural female hormone estradiol, in vivo exposure causes only mild effects at concentration thresholds environmentally not relevant and inconsistent among species. By using a proteomic approach, shotgun liver proteome analysis, we show that 7-d exposure to 10 μg/L of the BPA metabolite, 4-methyl-2,4-bis(4-hydroxyphenyl)pent-1-ene (MBP), and not the same exposure to the parental molecule BPA, alters the liver proteome of male Cyprinodon variegatus fish. Different physiological and environmental conditions leading to biotransformation of BPA to MBP may partly explain the conflicting results so far reported for in vivo BPA exposures. The pattern of alteration induced by MBP is similar to that caused by estradiol, and indicative of estrogenic endocrine disruption. MBP enhanced ribosomal activity, protein synthesis and transport, with upregulation of 91% of the ribosome-related proteins, and 12 proteins whose expression is regulated by estrogen-responsive elements, including vitellogenin and zona pellucida. Whey acidic protein (WAP) was the protein most affected by MBP exposure (FC = 68). This result points at WAP as novel biomarker for xenoestrogens.

Preconception and prenatal exposure to phthalates has been associated with an increased risk of preterm birth. However, it is unclear whether there are periods of heightened susceptibility during pregnancy. This prospective cohort study included 386 women undergoing fertility treatment who gave birth to a singleton infant during 2005 through 2018. Eleven phthalate metabolites were measured in spot urine samples collected at each trimester. In approximately 50% of participants, two metabolites of 1,2-cyclohexane dicarboxylic acid diisononyl ester (DINCH), a phthalate substitute, were also measured. The molar sum of four di(2-ethylhexyl) phthalate metabolites (∑DEHP) was calculated. We evaluated the associations of mean maternal biomarker concentrations with risk of preterm birth using modified log-binomial models and utilized multiple informant models to compare trimester-specific associations. We examined the relative biomarker concentration across gestation comparing women with preterm birth to women with term delivery using quadratic mixed model. The risk ratio for preterm birth associated with a one-unit increase in the natural log-transformed urinary concentrations of ∑DEHP (mean during pregnancy) was 1.21 (95% confidence interval (CI): 0.84, 1.72). In multiple informant models, these associations were strongest in the third trimester (RR = 1.51; 95% CI: 1.17, 1.95). Estimated mean ∑DEHP concentrations were higher among women with preterm than term delivery, especially late in gestation. Associations with preterm birth were also observed for each of the four individual DEHP metabolites. Detection of cyclohexane-1,2-dicarboxylic acid monocarboxyisooctyl ester (MCOCH), a metabolite of DINCH, appeared to be positively related to preterm birth. In this prospective cohort of subfertile couples, maternal ∑DEHP metabolite concentrations during pregnancy were associated with an increased risk of preterm birth, particularly during late gestation.

This study reports the results obtained from toxicological analyses of different types of baits referred to the laboratory of the Toxicology Area (Faculty of Veterinary Medicine, Cáceres, Spain) over a 17-year period (2002–2018). These baits were suspicious materials found in the environment of the region of Extremadura (Western Spain), where such malpractices are a problem to be addressed, as wide livestock farming and hunting activities are combined with a significant wealth of wildlife (especially birds of prey). A total of 246 baits, including 32 commercial chemical products to be used in baits, were analysed. Samples from 183 cases were received and classified according to the material used for their preparation and the toxic substance found. Overall, the most common bait consisted of meat preparations (56.3% of cases) intended to eliminate predators considered ‘annoying’ for livestock and hunting practices, such as carnivores and scavengers. It should be noted that contact baits (as fenthion-impregnated perches) were also detected (7.6%). Regarding the substances detected, anticholinesterase compounds (organophosphates and carbamates) were the most commonly used substances for the preparation of baits (detected in 85.3% of positive baits). Moreover, 8% of the positive baits presented more than one toxic substance in their composition. Due to the types of toxic compounds and the methods used to prepare the baits, this study shows that the malicious use of highly toxic substances in the environment to kill wildlife is a common and current issue and poses a serious risk to different species.