Perfluoroalkyl acids (PFAAs) are persistent in the environment, highly bio-accumulative in the body, and likely hepatotoxic in humans. There is evidence of sex-specific physiological responses to PFAA exposure. However, epidemiological studies seldom stratify the analyses by sex. Given the high prevalence of liver disease in general population adolescents, this study was designed to determine whether or not there is association between exposure to PFAAs and biomarkers of liver function in adolescent participants of the 2013–2016 National Health and Nutrition Examination Survey, and whether or not such association is sex-specific. Multivariate linear regressions were performed to examine the association between single PFAAs [perfluorooctane sulfonic acid (PFOS); linear form of perfluorooctanoic acid (PFOA); perfluorohexane sulfonic acid (PFHxS); perfluorononanoic acid (PFNA)], and biomarkers of liver function — gamma glutamyltransferase (GGT), aspartate aminotransferase (AST), alanine aminotransferase (ALT), and total bilirubin. Multivariate logistic regressions were performed to estimate adjusted odd ratios (aOR) of elevated ALT, AST and GGT. The study results show that, in females, there was a positive association of the highest PFOA quartile with increased ALT, AST and GGT, and the highest PFNA quartile with increased ALT and AST. Conversely, in male adolescents there was an association of the highest linear PFOA quartile with decreased ALT, and the highest PFNA quartile with ALT and AST. Females had higher odds of clinically-defined elevated ALT with increased PFOA (aOR = 1.79; 95% CI: 1.05, 3.04) or PFNA (aOR = 2.28; 95% CI: 1.08, 2.28), whereas males had decreased odds of clinically-defined elevated ALT with increased n-PFOA (aOR = 0.43; 95% CI: 0.20, 0.93) or PFNA (aOR = 0.5; 95% CI: 0.28, 0.89). In conclusion, there were sex differences in the association between serum PFAA levels and biomarkers of liver function. These results may provide support for analyzing sex-based adverse effects of PFAAs.

Vegetable production in solar greenhouses in northern China results in the excessive use of nitrogen (N) fertilizers and water via flooding irrigation. Both factors result in low N use efficiency and high environmental costs because groundwater becomes contaminated with nitrate (NO3−). Four consecutive tomato (Lycopersicum esculentum Mill.) cropping seasons were tested whether drip fertigation and/or the incorporation of maize straw (S) may significantly reduce NO3− and dissolved organic N (DON) leaching while increasing the water-use efficiency (WUE) and partial factor productivity of applied N (PFPN) of the tomatoes. The following treatments were used: ① conventional flooding irrigation with overfertilization (CIF, 900 kg N ha−1 season−1), ② CIF + S, ③ drip irrigation with optimized fertilization (DIF, 400 kg N ha−1 season−1), ④ DIF + S. We found that (1) DIF significantly increases the PFPN and WUE by 262% and 73% without compromising the yield compared with CIF, respectively. (2) For CIF, approximately 50% of the total N input was leached at a NO3−/DON ratio of approximately 2:1. (3) Compared with CIF, DIF reduced NO3− and DON leaching by 88% and 90%, respectively. Water percolation was positively correlated with N leaching (p < 0.001). (4) Straw application only reduced NO3− leaching losses in the first year and did not affect DON leaching overall, although DON leaching was increased in DIF in the first growing season. In conclusion, DIF significantly reduces NO3− and DON leaching losses by approximately 90% compared with the current farmer practice (CIF). Considering the significant DON leaching losses, which have been overlooked because previous measurements focused on NO3−, DON should be considered as a primary factor of environmental pollution in conventional solar greenhouse vegetable production systems.

Tetracycline (TC) can enter the human body via the soil-vegetable-human food chain; therefore, it is necessary to understand the toxicity of TC to humans through vegetables grown on contaminated soils. The present study combined an enzyme-linked immunosorbent assay method and an HL-7702 cell model and assessed the bioavailability and toxicity of TC from pak choi (Brassica campestris L. ssp. chinensis) grown on TC-contaminated soils. The results showed that the degradation rate of TC in black soil was significantly higher than that in purplish clay, while the results for TC uptake in pak choi were opposite. The bioaccessibility of TC was found to be higher in pak choi grown on purplish clay (5.67–7.59%) than in that grown on black soil (5.22–6.77%). It is suggested that soil properties contribute to the uptake of TC by pak choi. More fertile soil contained lower TC concentrations and thus mediated lower TC toxicity to humans. It may seem comforting that TC concentrations in the edible parts of pak choi are often found to be below safe limits. However, the TC diagnosis method showed that even moderate increases in TC concentrations in pak choi may induce oxidative stress, liver injury, mitochondrial cristae and rough endoplasmic reticulum swelling, and early apoptosis in liver cells HL-7702. The pak choi grown in purplish clay showed higher TC cytotoxicity than that grown in black soil. The TC cytotoxicity of raw pak choi was found to be higher than that of cooked pak choi. These results provide direct evidence of effective ways to prevent TC toxicity in humans.

The inorganic content of the well-preserved 3.2-m record of Las Conchas bog (NW Spain), covering 8000 cal yr BP., was analysed. To study natural vs. human contributions, we applied an innovative approach, namely the sequential study of multivariate statistics (factor analysis followed by clustering of the factor score matrix) and enrichment factors (EFs). The increasing weight of potentially toxic elements (PTEs) such as the geochemical association of Zn, Pb and Cd (EFs higher than 10, 20 and 40 in the last two centuries) was revealed, and corroborated by the contrast between the contents of anthropogenic Pb and total Rare Earth Elements (a suitable proxy for natural geogenic supplies). Furthermore, elements such as Hg, Tl and As also showed enrichment in the most recent samples of the study core. Some of them are commonly associated with global atmospheric transport; however, in this case, their increasing contents could also be explained by nearby industrial and mining activities.In summary, severe pollution was observed in the uppermost part of the record, thereby pointing to an important environmental concern. Given that local and regional sources of PTEs, such as mining and heavy industry, especially Zn smelting, were probably the main historical causes of this contamination and that some of these industries are still active, we consider that our findings deserve further attention.

Airborne lower-chlorinated PCBs are vulnerable to metabolization to PCB sulfates through further sulfation of the hydroxylated metabolites (OH-PCBs). However, studies on the toxic effects and mechanisms of PCB sulfates are still very limited. Here, we investigated for the first time the potential endocrine disruption effects of PCB sulfates through estrogen-related receptor γ (ERRγ) in comparison with their OH-PCBs precursors and PCB parent compounds. The binding affinity of thirteen PCBs/OH-PCBs/PCB sulfates was measured by using fluorescence competitive binding assays based on fluorescence polarization (FP). All of the tested chemicals could bind to ERRγ with the Kd (dissociation constant) values ranging from not available (NA) to 3.2 μM 4′–OH–PCB 12 showed the highest binding affinity with Kd value of 3.2 μM, which was comparable to that of a synthetic ERRγ agonist GSK4716. The effects of the thirteen chemicals on the ERRγ transcriptional activity were determined by using the luciferase reporter gene assay. We found the PCBs/OH-PCBs/PCB sulfates acted as agonists for ERRγ, with the lowest observed effective concentration reaching 3 μM. The binding affinity and agonistic activity of PCBs towards ERRγ were both enhanced after hydroxylation, while further sulfation of OH-PCBs decreased the activity instead. Molecular docking simulation showed that OH-PCBs had lower binding energy than the corresponding PCBs and PCB sulfates, indicating that OH-PCBs had higher binding affinity theoretically. In addition, OH-PCBs could form hydrogen bonds with amino acids Glu316 and Arg247 while PCBs and PCB sulfates could not, which might be the main factor impacting the binding affinity and agonistic activity. Overall, ERRγ is a novel target for lower-chlorinated PCBs and their metabolites.

Graphene with atomic layer of sp²-hybridized carbon atoms in a hexagonal structure has attracted multidisciplinary attention since its discovery. Due to the inherent advantages of large specific surface area and abundant functional groups, its derivative graphene oxide (GO) nanomaterials have achieved large-scale development in effective pollution treatment. In the past few years, novel GO-based nanomaterials through coupling with other nanomaterials have been synthesized with significant process and applied for efficient elimination of different kinds of pollutants. This paper aims to summarize recent research results on the excellent removal ability of GO-based nanomaterials for various heavy metal ions in aqueous solutions. The synthesis, adsorption process characteristics and interaction mechanism of the adsorbent are emphasized and discussed. The effects of various environmental conditions are outlined. At last, a brief summary, perspective and outlook are presented. This review is intended to provide some thrilling information for the design and manufacture of GO-based nanomaterials for the elimination of heavy metal ions from wastewater in environmental pollution management.

Natural environments are receiving an increasing number of contaminants. Therefore, the evaluation and identification of early responses to pollution in these complex habitats is an urgent and challenging task. Doñana National Park (DNP, SW Spain) has been widely used as a model area for environmental studies because, despite its strictly protected core, it is surrounded by numerous threat sources from agricultural, mining and industrial activities. Since many pollutants often induce oxidative stress, redox proteomics was used to detect redox-based variations within the proteome of Mus spretus mice captured in DNP and the surrounding areas. Functional analysis showed that most differentially oxidized proteins are involved in the maintenance of homeostasis, by eliciting mechanisms to respond to toxic substances and oxidative stress, such as antioxidant and biotransformation processes, immune and inflammatory responses, and blood coagulation. Furthermore, changes in the overall protein abundance were also analysed by label-free quantitative proteomics. The upregulation of phase I and II biotransformation enzymes in mice from Lucio del Palacio may be an alert for organic pollution in the area located at the heart of DNP. Metabolic processes involved in protein turnover (proteolysis, amino acid catabolism, new protein biosynthesis and folding) were activated in response to oxidative damage to these biomolecules. Consequently, aerobic respiratory metabolism increased to address the greater ATP demands. Alterations of cholesterol metabolism that could cause hepatic steatosis were also detected. The proteomic detection of globally altered metabolic and physiological processes offers a complete view of the main biological changes caused by environmental pollution in complex habitats.

Sewage sludge contains Ag₂S-NPs causing NP exposure of soil fauna when sludge is applied as soil amendment. Earthworm bioturbation is an important process affecting many soil functions. Bioturbation may be affected by the presence of Ag₂S-NPs, but the earthworm activity itself may also influence the displacement of these NPs that otherwise show little transport in the soil. The aim of this study was to determine effects of Ag₂S-NPs on earthworm bioturbation and effect of this bioturbation on the vertical distribution of Ag₂S-NPs. Columns (12 cm) of a sandy loamy soil with and without Lumbricus rubellus were prepared with and without 10 mg Ag kg⁻¹, applied as Ag₂S-NPs in the top 2 cm of the soil, while artificial rainwater was applied at ∼1.2 mm day⁻¹. The soil columns were sampled at three depths weekly for 28 days and leachate collected from the bottom. Total Ag measurements showed more displacement of Ag to deeper soil layers in the columns with earthworms. The application of rain only did not significantly affect Ag transport in the soil. No Ag was detected in column leachates. X-ray tomography showed that changes in macro porosity and pore size distribution as a result of bioturbation were not different between columns with and without Ag₂S-NPs. Earthworm activity was therefore not affected by Ag₂S-NPs at the used exposure concentration. Ag concentrations along the columns and the earthworm density allowed the calculation of the bioturbation rate. The effect on the Ag transport in the soil shows that earthworm burrowing activity is a relevant process that must be taken into account when studying the fate of nanoparticles in soils.

Biochar as a porous carbon material could be used for improving soil physical and chemical properties, while insufficient attention has been paid to potential risks induced by infiltration of heavy metals in the runoff water flowing through biochar-amended soil. Four different soil-biochar matrices with same volumes were constructed including soil alone (M1), biochar alone (M2), soil-biochar layering (M3) and soil-biochar mixing (M4). Leaching experiments were conducted with Pb, Cu, and Zn contaminated runoff water. Results showed that biochar amendment greatly improved the water permeation, and the infiltration rates in M2, M3, and M4 were 2.85–23.0 mm min⁻¹, being much higher than those in M1 (1.33–4.05 mm min⁻¹), though the rates decreased as the leaching volumes increased. However, biochar induced more Pb, Cu, and Zn infiltrated through soil-biochar matrix. After 350-L leaching, M1 retained about 95% Pb, 90% Cu, and 36% Zn, while M2 only retained 4.80% Pb, 17.4% Cu, and 4.01% Zn; about 30% Pb, 80% Cu, and 15% Zn were retained in M3 and M4. Notably, Zn was trapped first and then re-leached into the filtrate, which resulted in a much higher effluent Zn than the influent Zn at the later stage. However, the unit weight of biochar showed a higher capacity for retaining heavy metals compared to per unit of soil. Under the dynamic water flow, all benefits and disadvantages induced by biochar were weakened with its physical disintegration. Biochar as soil amendment can enhance plant growth via ameliorating soil structure, while it would pose risks to environment because of large penetration of heavy metals. If biochar was compacted to form a denser physical structure, perhaps more heavy metals could be retained.

The influence of anthropogenic outdoor sources on the geochemical composition of house dust material in large cities is poorly understood. In this study, we investigate the magnetic signature and the concentrations of potentially toxic elements (PTEs) in randomly selected house dust samples from the metropolitan area of Athens, the most populated city in Greece. Environmental magnetic measurements, including isothermal remanent magnetization and thermomagnetism, indicated that the main magnetic mineral is coarse-grained low-coercivity magnetite. Detailed microscopic observations of the magnetically extracted material revealed the presence of three different kinds of Fe-rich particles deriving from both combustion-related and non-exhaust vehicular sources: irregularly-shaped grains and spherules of Fe-oxides, and particles consisting of metallic Fe. Further study of the morphology of single anthropogenic magnetic spherules (size > 30 μm) identified the presence of magnetite spherical particles, typically formed by industrial combustion processes. Enrichment factors (EFs) for the PTEs calculated against the Athens urban soil showed that the house dusts were very highly enriched in Cd, Cu, Zn and significantly enriched in Pb (median EF values of 34.1, 26.2, 25.4 and 10.3, respectively). The oral bioaccessibility of PTEs in the house dust, evaluated using a simulated gastric solution (0.4 M glycine), was in the order Pb > Zn > Mn > Cd > Ni > Cu > Cr > Fe. Concentrations of Pb increased with the house age. Principal component and cluster analysis demonstrated the close association of anthropogenic Cu, Pb and Zn with the magnetic susceptibility of the house dusts. We conclude that both traffic-related and industrial sources trigger the occurrence of magnetic Fe/PTEs- rich particles in house dust. These results reinforce the use of environmental magnetism determinations for assessing anthropogenic contamination of PTEs in the indoor environment in large cities.