The objective of this study is to compare the consistency between column and batch experiment methods for measuring solid-phase sorption coefficients and isotherms for per and polyfluoroalkyl substances (PFAS). Perfluorooctane sulfonic acid (PFOS) and perfluorooctanoic acid (PFOA) are used as representative PFAS, and experiments are conducted with three natural porous media with differing geochemical properties. Column-derived sorption isotherms are generated by conducting multiple experiments with different input concentrations (multi-C₀ method) or employing elution-front integration wherein the entire isotherm is determined from a single breakthrough curve (BTC) elution front. The isotherms generated with the multi-C₀ column method compared remarkably well to the batch isotherms over an aqueous concentration range of 3–4 orders of magnitude. Specifically, the 95% confidence intervals for the individual isotherm variables overlapped, producing statistically identical regressions. The elution-front integration isotherms generally agreed with the batch isotherms, but exhibited noise and systematic deviation at lower concentrations in some cases. All data sets were well described by the Freundlich isotherm model. Freundlich N values ranged from 0.75 to 0.81 for PFOS and was 0.87 for PFOA and are consistent with values reported in the literature for different geomedia. The results of this study indicate that column and batch experiments can measure consistent sorption isotherms and sorption coefficients for PFOS and PFOA when robust experimental setup and data analysis are implemented.

In this paper, the degradation of three endocrine-disrupting chemicals (EDCs): bisphenol A (BPA), 17β-estradiol (E2) and 17α-ethinylestradiol (EE2) by manganite (γ-MnOOH) activated peroxymonosulfate (PMS) was investigated. Preliminary optimisation experiments showed that complete degradation of the three EDCs was achieved after 30 min of reaction using 0.1 g L⁻¹ of γ-MnOOH and 2 mM of PMS. The degradation rate constants were determined to be 0.20, 0.22 and 0.15 min⁻¹ for BPA, E2 and EE2, respectively. Combining radical scavenging approaches, Electron paramagnetic resonance (EPR) and X-ray photoelectron spectroscopy (XPS) analyses, we revealed for the first time that about 40% of EDCs degradation can be attributed to heterogeneous electron transfer reaction involving freshly generated Mn(IV), and 60% to sulfate radical degradation pathway. The influence of various inorganic ions on the γ-MnOOH/PMS system indicated that removal efficiency was slightly affected by chloride and carbonate ions, while nitrate and nitrite ions had negligible impacts. The application of γ-MnOOH/PMS system in real sewage treatment plant water (STPW) showed that degradation rate constants of EDCs decreased to 0.035–0.048 min⁻¹ and complete degradation of the three EDCs after 45 min. This study provides new insights into the reactivity of combined γ-MnOOH and PMS, and opens new ways for the application of Mn-bearing species in wastewater treatment technologies.

Carbon disulfide (CS₂) has been reported to induce disorder of glucose metabolism. However, the associations of CS₂ exposure with plasma glucose levels and risk of diabetes have not been explored in general population, and the underlying mechanisms remain unclear. We aim to examine the relationships between CS₂ exposure and fasting plasma glucose (FPG) levels, as well as diabetes, and assess the potential role of oxidative stress among the abovementioned relationships in Chinese general adults. The concentrations of urinary biomarkers of CS₂ exposure (2-thiothiazolidin-4-carboxylic acid, TTCA), and biomarkers for lipid peroxidation (8-isoprostane, 8-iso-PGF₂α) and DNA oxidative damage (8-oxo-7,8-dihydro-20-deoxyguanosine, 8-OHdG) were measured among 3338 urban adults from the Wuhan-Zhuhai cohort. Additionally, FPG levels were tested promptly. Generalized linear models and logistic regression models were used to quantify the associations among urinary TTCA, oxidative damage markers, FPG levels and diabetes risk. Mediation analysis was employed to estimate the role of oxidative damage markers in the association between urinary TTCA and FPG levels. We discovered a significant relationship between urinary TTCA and FPG levels with regression coefficient of 0.080 (95% CI: 0.002,0.157). Besides, the risk of diabetes was positively related to urinary TTCA (OR:1.282, 95% CI: 1.055,1.558), particularly among those who did not exercise regularly. Each 1% increase of urinary TTCA concentration was associated with a 0.096% and 0.037% increase in urinary 8-iso-PGF₂α and 8-OHdG, respectively. Moreover, we found an upward trend of FPG level as urinary 8-iso-PGF₂α gradually increased (Pₜᵣₑₙd<0.05), and urinary 8-iso-PGF₂α mediated 21.12% of the urinary TTCA-associated FPG increment. Our findings indicated that urinary CS₂ metabolite was associated with increased FPG levels and diabetes risk in general population. Lipid peroxidation partly mediated the association of urinary CS₂ metabolite with FPG levels.

Drilled seeds are an important food resource for many farmland birds but may pose a serious risk when treated with pesticides. Most compounds currently used as seed treatment in the EU have low acute toxicity but may still affect birds in a sub-chronic or chronic way, especially considering that the sowing season lasts several weeks or months, resulting in a long exposure period for birds. Tebuconazole is a triazole fungicide widely used in agriculture but its toxicity to birds remains largely unknown. Our aim was to test if a realistic scenario of exposure to tebuconazole treated seeds affected the survival and subsequent reproduction of the red-legged partridge (Alectoris rufa). We fed captive partridges with wheat seeds treated with 0%, 20% or 100% of tebuconazole application rate during 25 days in late winter (i.e. tebuconazole dietary doses were approximately 0.2 and 1.1 mg/kg bw/day). We studied treatment effects on the physiology (i.e. body weight, biochemistry, immunology, oxidative stress, coloration) and reproduction of partridges. Exposed birds did not reduce food consumption but presented reduced plasmatic concentrations of lipids (triglycerides at both exposure doses, cholesterol at high dose) and proteins (high dose). The coloration of the eye ring was also reduced in the low dose group. Exposure ended 60 days before the first egg was laid, but still affected reproductive output: hatching rate was reduced by 23% and brood size was 1.5 times smaller in the high dose group compared with controls. No significant reproductive effects were found in the low dose group. Our results point to the need to study the potential endocrine disruption mechanism of this fungicide with lagged effects on reproduction. Risk assessments for tebuconazole use as seed treatment should be revised in light of these reported effects on bird reproduction.

The most promising technique for directly converting solar energy into clean fuels and environmental remediation by organic dye degradation is photoelectrochemical (PEC) process. We introduced Sn⁴⁺/Ti⁴⁺ doped α-Fe₂O₃@CuₓO heterojunction photoanode with complete optimization for PEC hydrogen (H₂) generation and organic dye degradation. Improvement of photocurrent photo and reducing overpotentials under optimized conditions lead to enhancing PEC performances, degradation efficiency of organic compounds, and H₂ generation generation rate. The optimized heterojunction photoanode (5TiFe@CuₓO-D) showed IPCE exceeding 42% compared with pristine hematite (Fe₀.₀₁–800₆ₕ) nanostructures (28%). Additionally, all the optimized photoanodes showed higher PEC stability for 10 h. Time-resolved PL spectra confirm the improved average lifetime for heterojunction photoanodes, supporting the enhanced PEC performance. Optimized 5TiFe@CuₓO-D material achieved PEC H₂ generation of ∼300 μL h⁻¹.cm⁻² which is two times higher than pristine hematite’s activity (150 μL h⁻¹.cm⁻²) and almost 99% degradation efficiency within 120 min of irradiation time. Therefore, a state-of-the-art study has been explored for hematite-based heterojunction photoanodes reflecting the superior PEC performance and hydrogen, methyl orange (MO) dye degradation activities. The improved results were reported because of stable morphology and better crystallinity acquired through systematic investigation of thermal effects and hydrothermal duration, improved electrical properties by Sn/Ti doping into the lattice of α-Fe₂O₃ and optimization of CuₓO deposition methods. The formation of well-defined heterojunction minimizes the recombination of the charge carrier and leads to effective transportation of excited electrons for the enhanced PEC performance.

Per- and polyfluoroalkyl substances (PFAS) concentrations of groundwater in three cities of the Nakdong River Basin in South Korea were quantified to investigate PFAS contamination and the effect of PFAS leakage incident that occurred in the study area in 2018. Groundwater PFASs concentration ranged from non-detectable (N.D.) to 36.9 ng/L (mean 14.1 ng/L), in which, perfluorooctanoic acid (PFOA), perfluorohexanoic acid (PFHxA), perfluoropentanoic acid (PFPeA), and perfluorohexane sulfonate (PFHxS) were commonly observed. Compared to long-chain (C ≥ 8) PFAS, short-chain (<C8) PFAS are more commonly detected in groundwater. Statistical differences were found between the groundwater obtained from different land use. PFAS detected in groundwater from industrial land use were significant different (p<0.01) than other land usages. Spatial difference of PFAS concentrations and distributions in groundwater were also found. PFAS concentrations in groundwater at the furthest downstream area (mean 26.4 ng/L) were the highest followed by the middle reaches (mean 16.2 ng/L), and the upstream area (mean 4.3 ng/L). PFHxS, which was detected dominantly in the middle reach areas, contributed 51% of the total PFAS concentration, but was not detected in the upstream area. There was no health risk by drinking groundwater but found the effect of PFHxS leakage incident on groundwater.

The present study is a literature-based analysis investigating occurrence and the possible consequences of polycyclic aromatic hydrocarbons (PAH) in marine protected areas (MPAs) of Latin America and Caribbean. The approach using overlapping of georeferenced MPA polygons with data compiled from peer-reviewed literature, published during the last 15 years, showed 341 records of PAH in 9 countries. PAH was reported to occur within the boundaries of 36 MPAs located in Argentina, Brazil, Colombia, Mexico, Nicaragua and Uruguay. According to quality guidelines, low to moderate impacts are expected in MPAs categorized in different management classes. Considering sediment samples, 13% of the records presented concentrations enough to cause occasional toxicity. Such level of risk was also seen in Ramsar sites and in Amazonian MPAs. In addition, based on concentrations reported in biota, occasional deleterious effects on organisms from Biosphere Reserves might occur. Diagnostic ratios pointed out petrogenic and pyrolytic processes as PAH predominant sources, and were mainly attributed to the proximity to ports, industries and urban areas. MPAs located in the vicinity of impact-generating areas may be under threat and require government attention and action, mainly through implementation of contamination monitoring programs.

Bio-stimulation of the indigenous microbial community is considered as an effective strategy for the bioremediation of polluted environments. This examination explored the near effects of various bio-stimulants on pyrene degradation, prokaryotic community compositions, and functions using 16S rRNA amplicon sequencing and qPCR. At first, the results displayed significant differences (p < 0.05) between the prokaryotic community structures of the control group, PYR (contains pyrene only), and bio-stimulants amended groups. Among the bio-stimulants, biochar, oxalic acid, salicylate, NPK, and ammonium sulfate augmented the pyrene degradation potential of microbial communities. Moreover, the higher abundance of genera, such as Flavobacterium, Hydrogenophaga, Mycobacterium, Rhodococcus, Flavihumibacter, Pseudomonas, Novosphingobium, etc., across the treatments indicated that these genera play a vital role in pyrene metabolism. Based on the higher abundance of GP-RHD and nidA genes, we speculated that Gram-positive prokaryotic communities are more competent in pyrene dissipation than Gram-negative. Furthermore, the marked abundance of nifH, and pqqC genes in the NPK and SA treatments, respectively, suggested that different bio-stimulants might enrich certain bacterial assemblages. Besides, the significant distinctions (p < 0.05) between the bacterial consortia of HA (humic acid) and SA (sodium acetate) groups from NPK, OX (oxalic acid), UR (urea), NH4, and SC (salicylate) groups also suggested that different bio-stimulants might induce distinct ecological impacts influencing the succession of prokaryotic communities in distinct directions. This work provides new insight into the bacterial degradation of pyrene using the bio-stimulation technique. It suggests that it is equally important to investigate the community structure and functions along with studying their impacts on degradation when devising a bio-stimulation technology.

Terrestrial mosses are promising tracers for research concerning metal atmospheric deposition and pollution. Concentrations of Cr, Co, Ni, Zn, Sr, Cd, Ba, and Pb in different moss species from Mountain Gongga, China were analyzed to investigate the effects of growth substrates, geographic elevation, and type of moss species on the accumulation characteristics of heavy metals, as well as to identify heavy metal sources. The ability of heavy metals to accumulate in moss varied significantly, with low concentrations of Cd and Co; medium concentrations of Cr, Ni, and Pb; and high concentrations of Zn, Sr, and Ba. Elevation significantly influenced the accumulation characteristics of heavy metals, with high concentrations found at lower elevations due to proximal pollution. Growth substrate and moss species were found to have certain influence on the bioconcentration capacities of heavy metals in moss in this study. Correlation analysis showed similar sources for Sr, Zn, and Ba, as well as for Ni, Co, and Cr. The positive matrix factorization (PMF) model was consistent with atmospheric deposition of Pb and Cd; substrate sources of Cr, Co, and Ni; and anthropogenic sources of Ba, Sr, and Zn. This research characterized the accumulation characteristics of heavy metals and their influence factors in different mosses found in alpine ecosystems and provides a reference for future studies in similar areas.

Indoor environment constitutes an important source of industrial additive chemicals to human exposure. We hypothesized that the influence of residential environment on human exposure varies among different types of additive chemicals and differs between children and mothers. This study determined a suite of additive chemicals in house dust from South China dwellings (n = 47) and urine from child-mother pairs. Concentrations of phthalates (PAEs; median 601 μg/g) were 2–3 orders of magnitude greater than those of parabens (0.82 μg/g), bisphenols (3.31 μg/g), and benzophenone-related chemicals (2.69 μg/g). Urinary concentrations differed between children and mothers, but the pattern of differences varied between chemical groups. Children exhibited greater urinary levels of mono-PAEs than mothers (510 versus 395 ng/mL, p = 0.152), while the latter population exhibited greater levels of parabens and benzophenones. Regression analyses indicate a lack of association between dust and urinary levels for most chemicals, suggesting that other exposure pathways can complicate human exposure scenarios. Indeed, we estimated that the daily intake via dust ingestion only constituted 0.002–0.81% of total daily intake estimated based on urine data for mothers and 0.04–5.61% for children. Future efforts are needed to better characterize source-specific exposure for different populations.