Chromium-contaminated water is regarded as one of the biggest threats to human health. In this study, a novel magnetic mesoporous MnFe2O4@SiO2−CTAB composite was prepared by a facile one-step modification method and applied to remove Cr(VI). X-ray diffraction, scanning electron microscopy, transmission electron microscopy, specific surface area, and vibrating sample magnetometer were used to characterize MnFe2O4@SiO2−CTAB composites. The morphology analysis showed that the composites displayed a core-shell structure. The outer shell was mesoporous silica with CTAB and the core was MnFe2O4 nanoparticles, which ensured the easy separation by an external magnetic field. The performance of MnFe2O4@SiO2−CTAB composites in Cr(VI) removal was far better than that of bare MnFe2O4 nanoparticles. There were two reasons for the effective removal of Cr(VI) by MnFe2O4@SiO2−CTAB composites: (1) mesoporous silica shell with abundant CTA+ significantly enhanced the Cr(VI) adsorption capacity of the composites; (2) a portion of Cr(VI) was reduced to less toxic Cr(III) by MnFe2O4, followed by Cr(III) immobilized on MnFe2O4@SiO2−CTAB composites, which had been demonstrated by X-ray photoelectron spectroscopy results. The adsorption of Cr(VI) onto MnFe2O4@SiO2−CTAB followed the Freundlich isotherm model and pseudo-second-order model. Tests on the regeneration and reuse of the composites were performed. The removal efficiency of Cr(VI) still retained 92.4% in the sixth cycle. MnFe2O4@SiO2−CTAB composites exhibited a great potential for the removal of Cr(VI) from water.

Free amino acid concentrations and nitrogen (N) isotopic composition in new current-year (new), mature current-year (middle-aged) and previous-year (old) Masson pine (Pinus massoniana Lamb.) needles were determined to indicate atmospheric N deposition in Guiyang (SW China). In different areas, free amino acids (especially arginine) concentrations in new and middle-aged needles were higher than in old needles, and the variation of free amino acids (especially arginine) concentrations in new and middle-aged needles was also greater than in old needles. This indicate that free amino acids in new and middle-aged needles may be more sensitive to N deposition compared to old needles. Moreover, concentrations of total free amino acids, arginine, histidine, γ-aminobutyric acid and alanine in middle-aged needles exhibited a strong relationship with N deposition (P < 0.05). Needle δ¹⁵N values showed a strong gradient from central Guiyang to the rural area, with more positive δ¹⁵N (especially in old needles) in the city center (0–5 km) and more negative δ¹⁵N (especially in old needles) in rural area (30–35 km). These suggest that N deposition in the urban center may be dominated by ¹⁵N-enriched NOx-N from traffic exhausts, while it is dominated by isotopically light atmospheric NHx-N from agriculture in rural area. Soil δ¹⁵N decreased slightly with distance from the city center, and the difference in δ¹⁵N values between the soil and needles (especially for old needles) increased significantly with the distance gradient, indicating that atmospheric N deposition may be an important N source for needles. This study provides novel evidence that free amino acids in needles and age-dependent needle δ¹⁵N values are useful indicators of atmospheric N deposition.

Microplastics pollution is widespread in marine ecosystems and a major threat to biodiversity. Nevertheless, our knowledge of the impacts of microplastics in freshwater environments and biota is still very limited. The interaction of microplastics with freshwater organisms and the risks associated with the human consumption of organisms that ingested microplastics remain major knowledge gaps. In this study, we assessed the ingestion of microplastics by Hoplosternum littorale, a common freshwater fish heavily consumed by humans in semi-arid regions of South America. We assessed the abundance and diversity of both plastic debris and other food items found in the gut of fishes caught by local fishermen. We observed that 83% of the fish had plastic debris inside the gut, the highest frequency reported for a fish species so far. Most of the plastic debris (88.6%) recovered from the guts of fish were microplastics (<5 mm), fibres being the most frequent type (46.6%). We observed that fish consumed more microplastics at the urbanized sections of the river, and that the ingestion of microplastics was negatively correlated with the diversity of other food items in the gut of individual fish. Nevertheless, microplastics ingestion appears to have a limited impact on H. littorale, and the consequences of human consumption of this fish were not assessed. Our results suggest freshwater biota are vulnerable to microplastics pollution and that urbanization is a major factor contributing to the pollution of freshwater environments with microplastics. We suggest the gut content of fish could be used as a tool for the qualitative assessment of microplastics pollution in freshwater ecosystems. Further research is needed to determine the processes responsible for the high incidence of microplastics ingestion by H. littorale, and to evaluate the risk posed to humans by the consumption of freshwater fish that ingested microplastics.

Although epoxiconazole is the worldwidely used fungicide, limited information is known about its toxic effects and bioaccumulation behavior in freshwater ecosystems. In this study, zebrafish were exposed to epoxiconazole at concentrations of 100 and 1000 μg L−1 for 21 d. 1H NMR-based metabolomics analysis showed that low- and high-dose epoxiconazole exposure resulted in two similar but not identical patterns for the change of endogenous metabolites related to energy, lipid and amino acid metabolism. The expression of genes associated with mitochondrial respiratory chain, ATP synthesis and fatty acid β-oxidation were further measured to explore the reason for the disturbed energy metabolism, finding epoxiconazole had an inhibition effect on the genes expression of the above ways. Significant enantioselectivity was observed with (+)-epoxiconazole enrichment in the bioaccumulation process. These results will be of great importance in understanding the toxic effects induced by epoxiconazole and provide important basis for its comprehensive environmental assessment.

Nanoscale zero-valent iron (nZVI) is an effective arsenic (As) scavenger. However, spent nZVI may pose a higher environmental risk than our initial thought in the presence of As-reducing bacteria. Therefore, our motivation was to explore the As redox transformation and release in spent nZVI waste residue in contact with Pantoea sp. IMH, an arsC gene container adopting the As detoxification pathway. Our incubation results showed that IMH preferentially reduce soluble As(V), not solid-bound As(V), and was innocent in elevating total dissolved As concentrations. μ-XRF and As μ-XANES spectra clearly revealed the heterogeneity and complexity of the inoculated and control samples. Nevertheless, the surface As local coordination was not affected by the presence of IMH as evidenced by similar As-Fe atomic distance (3.32–3.36 Å) and coordination number (1.9) in control and inoculated samples. The Fe XANES results suggested that magnetite in nZVI residue was partly transformed to ferrihydrite, and the IMH activity slowed down the nZVI aging process. IMH distorted Fe local coordination without change its As adsorption capacity as suggested by Mössbauer spectroscopy. Arsenic retention is not inevitably enhanced by in situ formed secondary Fe minerals, but depends on the relative As affinity between the primary and secondary iron minerals.

A simultaneous sampling campaign was undertaken to study the pollution by 21 per- and polyfluoroalkyl substances (PFASs) in rivers, drain outlets and their receiving Bohai Sea of China. Chlorinated polyfluoroalkyl ether sulfonic acids (Cl-PFESAs) are being used as fluorinated alternatives and they were included in this study. In comparison with other regions and countries, high concentrations of ∑21PFASs in seawater samples from the Bohai Sea, ranging from 5.03 to 41 700 ng/L (median: 64.8 ng/L), were observed. The spatial distribution of PFAS levels in this sea area was in the ranking of Laizhou Bay > Liaodong Bay > Bohai Bay > other sea areas. By comparing the levels and composition profiles of PFASs in the seawater and their sources (rivers and drain outlets), it was concluded that rivers and drain outlets are the primary sources of PFAS contamination to the Bohai Sea. These PFAS levels varied seasonally among the rivers and drain outlets, but statistically significant changes were not observed. Levels of 6:2 and 8:2 Cl-PFESAs in rivers, drain outlets and receiving sea were firstly reported in the present study. Relatively high concentrations of 6:2 Cl-PFESA were found in drain outlets, ranging from below method limits of quantification (MLQ) to 7600 ng/L, but 8:2 Cl-PFAES detection was infrequent and all median concentration below MLQ. Mass discharges to the sea of 6:2 Cl-PFESA from rivers and drain outlets to the sea were estimated to be 37 and 17 kg/y, respectively.

Traditional tea (Camellia sinensis) and herbal tea are being consumed across the world. However, long term consumption of tea can increase the chances of fluorosis owing to the presence of fluoride (F) in teas. Therefore, it is imperative to assess the health risk associated with tea consumption. The main objectives of this study were to: 1) estimate total F in 47 popular teas, including traditional and herbal teas and F concentrations in 1% (w/v) infusion of 5 min, and 2) assess the exposure risks of F from tea consumption in children and adults. The data showed that total F was the least in herbal teas (33–102 mg/kg) and their infusions (0.06–0.69 mg/L) compared to traditional teas (296–1112 mg/kg) and their infusions (1.47–6.9 mg/L). During tea infusion, 6–96% and 18–99% of the F was released into the water from herbal and traditional teas, respectively. Ten samples of traditional teas, including five green teas had chronic daily intake (CDI) values of F > 0.05 mg/d/kg bw, the stipulated permissible limits of F intake from all sources. Although the F from teas posed no immediate health hazards with hazard quotient <1, some tea samples could potentially contribute >4 mg F/d, thereby adding to the overall F burden. Therefore, together with F from food and water sources, daily F consumptions from teas might increase its health risks to humans. So, caution should be excised when drinking teas containing high F.

It is necessary to better characterize plastic marine debris in order to understand its fate in the environment and interaction with organisms, the most common type of debris being made of polyethylene (PE) and polypropylene (PP). In this work, plastic debris was collected in the North Atlantic sub-tropical gyre during the Expedition 7th Continent sea campaign and consisted mainly in PE. While the mechanisms of PE photodegradation and biodegradation in controlled laboratory conditions are well known, plastic weathering in the environment is not well understood. This is a difficult task to examine because debris comes from a variety of manufactured objects, the original compositions and properties of which vary considerably. A statistical approach was therefore used to compare four sample sets: reference PE, manufactured objects, mesoplastics (5–20 mm) and microplastics (0.3–5 mm). Infrared spectroscopy showed that the surface of all debris presented a higher oxidation state than the reference samples. Differential scanning calorimetry analysis revealed that the microplastics were more crystalline contrarily to the mesoplastics which were similar to references samples. Size exclusion chromatography showed that the molar mass decreased from the references to meso- and microplastics, revealing a clear degradation of the polymer chains. It was thus concluded that the morphology of marine microplastic was much altered and that an unambiguous shortening of the polymer chains took place even for this supposedly robust and inert polymer.

Sixteen U.S. EPA priority polycyclic aromatic hydrocarbons (PAHs) and eleven non-priority isomers including some dibenzopyrenes were analyzed to evaluate health risk attributable to inhalation exposure to ambient PAHs and contributions of the non-priority PAHs in a megacity Nanjing, east China. The annual average mass concentration of the total 16 EPA priority PAHs in air was 51.1 ± 29.8 ng/m³, comprising up to 93% of the mass concentration of all 27 PAHs, however, the estimated Incremental Lifetime Cancer Risk (ILCR) due to inhalation exposure would be underestimated by 63% on average if only accounting the 16 EPA priority PAHs. The risk would be underestimated by 13% if only particulate PAHs were considered, though gaseous PAHs made up to about 70% of the total mass concentration. During the last fifteen years, ambient Benzo[a]pyrene decreased significantly in the city which was consistent with the declining trend of PAHs emissions. Source contributions to the estimated ILCR were much different from the contributions for the total mass concentration, calling for the introduce of important source-oriented risk assessments. Emissions from gasoline vehicles contributed to 12% of the total mass concentration of 27 PAHs analyzed, but regarding relative contributions to the overall health risk, gasoline vehicle emissions contributed 45% of the calculated ILCR. Dibenzopyrenes were a group of non-priority isomers largely contributing to the calculated ILCR, and vehicle emissions were probably important sources of these high molecular weight isomers. Ambient dibenzo[a,l]pyrene positively correlated with the priority PAH Benzo[g,h,i]perylene. The study indicates that inclusion of non-priority PAHs could be valuable for both PAH source apportionment and health risk assessment.

Experimental work was undertaken to test whether gaseous perfluorooctanoic acid (PFOA) sorbs to glass fibre filters (GFFs) during air sampling, causing an incorrect measure of the gas-particle equilibrium distribution. Furthermore, tests were performed to investigate whether deactivation by siliconisation prevents sorption of gaseous PFOA to filter materials. An apparatus was constructed to closely simulate a high-volume air sampler, although with additional features allowing introduction of gaseous test compounds into an air stream stripped from particles. The set-up enabled investigation of the sorption of gaseous test compounds to filter media, eliminating any contribution from particles. Experiments were performed under ambient outdoor air conditions at environmentally relevant analyte concentrations. The results demonstrate that gaseous PFOA sorbs to GFFs, but that breakthrough of gaseous PFOA on the GFFs occurs at trace-level loadings. This indicates that during high volume air sampling, filters do not quantitatively capture all the PFOA in the sampled air. Experiments with siliconised GFFs showed that this filter pre-treatment reduced the sorption of gaseous PFOA, but that sorption still occurred at environmentally relevant air concentrations. We conclude that deactivation of GFFs does not allow for the separation of gaseous and particle bound perfluorinated carboxylic acids (PFCAs) during active air sampling. Consequently, the well-recognised theory that PFCAs do not prevail as gaseous species in the atmosphere may be based on biased measurements. Caution should be taken to ensure that this artefact will not bias the conclusions of future field studies.