Nanoscale zerovalent iron (nZVI)-mediated degradation of 1,1,1-trichloro-2,2-bis(p-chlorophenyl)ethane (DDT) was investigated in a spiked soil under different conditions (iron sources, iron dosage, soil moisture, temperature, and soil types) and DDT-contaminated field. The degradation efficiency of p,p′-DDT by nZVI and nZVI coated with sodium oleate (SO-nZVI) was much higher than that by nZVI coated with polyimide (PI-nZVI). The rapid degradation of p,p′-DDT by nZVI only occurred in flooded soil. The degradation half-life of p,p′-DDT decreased significantly from 58.3 to 27.6 h with nZVI dosage from 0.5 to 2.0 % and from 46.5 to 32.0 h with temperature from 15 to 35 °C. The degradation efficiency of p,p′-DDT by nZVI differed in Jinhua (JH), Jiaxing (JX), Xiaoshan (XS), Huajiachi (HJC), and Heilongjiang (HLJ) soils. A good correlation was found between the degradation half-life of p,p′-DDT and multiple soil properties. The probable nZVI-mediated degradation pathway of p,p′-DDT in soil was proposed as DDT → DDD/DDE → DDNS → DDOH based on the metabolites identified by GC-MS. The in situ degradation efficiency of residual DDTs in a contaminated field was profoundly enhanced by the addition of nZVI as compared to the control. It is concluded that nZVI might be an efficient agent for the remediation of DDT-contaminated soil under anaerobic environment.

This study explored the association between particulate matter with an aerodynamic diameter of less than 10 μm (PM₁₀) and the cause-specific respiratory mortality. We used the ordinary kriging method to estimate the spatial characteristics of ambient PM₁₀ at 1-km × 1-km resolution across Beijing during 2008–2009 and subsequently fit the exposure-response relationship between the estimated PM₁₀ and the mortality due to total respiratory disease, chronic lower respiratory disease, chronic obstructive pulmonary disease (COPD), and pneumonia at the street or township area levels using the generalized additive mixed model (GAMM). We also examined the effects of age, gender, and season in the stratified analysis. The effects of ambient PM₁₀ on the cause-specific respiratory mortality were the strongest at lag0-5 except for pneumonia, and an inter-quantile range increase in PM₁₀ was associated with an 8.04 % (95 % CI 4.00, 12.63) increase in mortality for total respiratory disease, a 6.63 % (95 % CI 1.65, 11.86) increase for chronic lower respiratory disease, and a 5.68 % (95 % CI 0.54, 11.09) increase for COPD, respectively. Higher risks due to the PM₁₀ exposure were observed for females and elderly individuals. Seasonal stratification analysis showed that the effects of PM₁₀ on mortality due to pneumonia were stronger during spring and autumn. While for COPD, the effect of PM₁₀ in winter was statistically significant (15.54 %, 95 % CI 5.64, 26.35) and the greatest among the seasons. The GAMM model evaluated stronger associations between concentration of PM₁₀. There were significant associations between PM₁₀ and mortality due to respiratory disease at the street or township area levels. The GAMM model using high-resolution PM₁₀ could better capture the association between PM₁₀ and respiratory mortality. Gender, age, and season also acted as effect modifiers for the relationship between PM₁₀ and respiratory mortality.

Coal production negatively affects the environment by the emission of polycyclic aromatic hydrocarbons (PAHs). Two soils (KOK and KB) from a coking plant area was investigated and their total PAH concentration was 40 and 17 mg/kg for the sum (∑) 16 US EPA PAHs, respectively. A third soil was sampled from a bitumen plant area and was characterized by 9 mg/kg ∑16 US EPA PAHs. To reduce the freely dissolved concentration (Cfᵣₑₑ) of the PAHs in the soil pore water, active carbon (AC) and two biochars pyrolysed from wheat straw (biochar-S) and willow (biochar-W) were added to the soils at 0.5–5 % (w/w), each. The AC performed best and reduced the Cfᵣₑₑ by 51–98 % already at the lowest dose. The biochars needed doses up to 2.5 % to significantly reduce the Cfᵣₑₑ by 44–86 % in the biochar-S and by 37–68 % in the biochar-W amended soils. The high black carbon (BC) content of up to 2.3 % in the Silesian soils competed with the sorption sites of the carbon amendments and the performance of the remediation was a consequence of the contaminant’s source and the distribution between the BC and the AC/biochars. In contrast, the carbon amendment could best reduce the Cfᵣₑₑ in the Lublin soil where the BC content was normal (0.05 %). It is therefore crucial to know the contaminant’s source and history of a sample/site to choose the appropriate carbon amendment not only for remediation success but also for economic reasons.

For the purpose of investigating the effect of landfill leachate on the characteristics of organic matter in groundwater, groundwater samples were collected near and in a landfill site, and dissolved organic matter (DOM) was extracted from the groundwater samples and characterized by excitation–emission matrix (EEM) fluorescence spectra combined with fluorescence regional integration (FRI) and self-organizing map (SOM). The results showed that the groundwater DOM comprised humic-, fulvic-, and protein-like substances. The concentration of humic-like matter showed no obvious variation for all groundwater except the sample collected in the landfill site. Fulvic-like substance content decreased when the groundwater was polluted by landfill leachates. There were two kinds of protein-like matter in the groundwater. One kind was bound to humic-like substances, and its content did not change along with groundwater pollution. However, the other kind was present as “free” molecules or else bound in proteins, and its concentration increased significantly when the groundwater was polluted by landfill leachates. The FRI and SOM methods both can characterize the composition and evolution of DOM in the groundwater. However, the SOM analysis can identify whether protein-like moieties was bound to humic-like matter.

The influence of molybdenum oxide nanoparticles (MoO₃) on the growth and survival of Eisenia fetida was established. The activity of antioxidant enzymes and changes in concentration of molybdenum in the body of E. fetida were determined. The degree of bacterial bioluminescence inhibition in extracts of substrates and worm was studied using luminescent strain Escherichia coli K12 TG1. The enzymatic activity of substrates before and after exposure with nanoparticles and worms was assessed. Nanoparticles have concentrations of 10, 40, and 500 mg/kg of dry matter, and substrata are made of artificial soil (substrate A) and microcrystalline cellulose (substrate B). Spherical nanoparticles MoO₃, yellow in color, with size 92 ± 0.3 nm, Z-potential 42 ± 0.52 mV, molybdenum content 99.8 mass/%, and specific area 12 m²/g were used in the study. A significant decrease by 23.3 % in weight was registered (for MoO₃ NPs at 500 mg/kg) on substrate A (p ≤ 0.05). On substrate B, the maximum decrease in weight by 20.5, 33.3, and 16.9 % (p ≤ 0.05) was registered at a dose of 10, 40, and 500 mg/kg, respectively; mortality was from 6.6 to 73 %. After the assessment of bacterial bioluminescence inhibition in substrates A and B (extracts) and before worms were put, the toxicity of substrates was established at doses of 40 and 500 mg/kg, expressed in inhibitory concentration (IC) 30 and IC 50 values. Comparatively, on days 7 and 14, after exposure in the presence of E. fetida, no inhibition of bioluminescence was registered in extracts of substrates A and B, indicating the reduction in toxicity of substrates. The initial content of molybdenum in E. fetida was 0.9 ± 0.018 mg/kg of dry matter. The degree of molybdenum accumulation in worm tissue was dependent on the dose and substrate quality. In particular, 2–7 mg/kg of molybdenum accumulated from substrate A, while up to 15 kg/kg of molybdenum accumulated from substrate B (day 7). Molybdenum concentration decreased by 64.8 and 57.4 % at doses 40 and 500 mg/kg, respectively, on day 14. The reaction of antioxidant enzymes was shown in an insignificant increase of glutathione reductase (GSR) and catalase (CAT) at concentrations of 10 and 40 mg/kg in substrate A, followed by the subsequent reduction of their activity at the dose of 500 mg/kg MoO₃. The activity of GSR in substrate B against the presence of MoO₃ nanoparticles decreased, with significant difference of 33.5 % (p ≤ 0.05) at the dose of 500 mg/kg compared with untreated soil. In experiments with substrate A, an increase of catalase activity was registered for the control sample. The presence of MoO₃ nanoparticles at the concentration of 10 mg/kg in the environment promoted enzymatic activity on days 7 and 14, respectively. A further increase of nanoparticle concentration resulted in the decrease of catalase activity with a minimum value at the concentration of MoO₃ of 500 mg/kg. In the experiment with substrate B at the concentration of MoO₃ nanoparticles of 40 mg/kg, enzymatic activity increases on day 7 of exposure. However, the stimulating effect of nanoparticles stops by day 14 of the experiment and further catalase activity is dose dependent with the smallest value in the experiment with MoO₃ having the concentration of 500 mg/kg.

Uranium(VI) biosorption from aqueous solutions was investigated in batch studies by using fungus Pleurotus ostreatus biomass. The optimal biosorption conditions were examined by investigating the reaction time, biomass dosage, pH, temperature, and uranium initial concentration. The interaction between fungus biomass and uranium was confirmed using Fourier transformed infrared (FT-IR), scanning electronic microscopy energy dispersive X-ray (SEM-EDX), and X-ray photoelectron spectroscopy (XPS) analysis. Results exhibited that the maximum biosorption capacity of uranium on P. ostreatus was 19.95 ± 1.17 mg/g at pH 4.0. Carboxylic, amine, as well as hydroxyl groups were involved in uranium biosorption according to FT-IR analysis. The pseudo-second-order model properly evaluated the U(VI) biosorption on fungus P. ostreatus biomass. The Langmuir equation provided better fitting in comparison with Freundlich isotherm models. The obtained thermodynamic parameters suggested that biosorption is feasible, endothermic, and spontaneous. SEM-EDX and XPS were additionally conducted to comprehend the biosorption process that could be described as a complex process involving several mechanisms of physical adsorption, chemisorptions, and ion exchange. Results obtained from this work indicated that fungus P. ostreatus biomass can be used as potential biosorbent to eliminate uranium or other radionuclides from aqueous solutions.

The origin and evolution of brine and saline groundwater have always been a challenged work for geochemists and hydrogeologists. Chemical and isotopic data of brine and saline waters were used to trace the sources of salinity and therefore to understand the transport mechanisms of groundwater in Xishanzui, Inner Mongolia. Both Cl/Br (molar) versus Na/Br (molar) and Cl (meq/L) versus Na (meq/L) indicated that salinity was from halite dissolution or at least a significant impact by halite dissolution. The logarithmic plot of the concentration trends of Cl (mg/L) versus Br (mg/L) for the evaporation of seawater and the Qinghai Salt Lake showed that the terrestrial halite dissolution was the dominated contribution for the salinity of this brine. The stable isotope ratios of hydrogen and oxygen suggested that the origin of brine was from paleorecharge water which experienced mixing of modern water in shallow aquifer. δ³⁷Cl values ranged from −0.02 to 3.43 ‰ (SMOC), and reflecting mixing of different sources. The Cl isotopic compositions suggest that the dissolution of halite by paleometeoric water had a great contribution to the salinity of brine, and the contributions of the residual seawater and the dissolution of halite by the Yellow River water could be excluded.

This study aimed to evaluate the effects of two rehabilitation systems in sites contaminated by Zn, Cu, Pb, and Cd on biological soil attributes [microbial biomass carbon (Cmic), basal and induced respiration, enzymatic activities, microorganism plate count, and bacterial and fungal community diversity and structure by denaturing gradient gel electrophoresis (DGGE)]. These systems (S₁ and S₂) consisted of excavation (trenching) and replacement of contaminated soil by uncontaminated soil in rows with Eucalyptus camaldulensis planting (S₁-R and S₂-R), free of understory vegetation (S₁-BR), or completely covered by Brachiaria decumbens (S₂-BR) in between rows. A contaminated, non-rehabilitated (NR) site and two contamination-free sites [Cerrado (C) and pasture (P)] were used as controls. Cmic, densities of bacteria and actinobacteria, and enzymatic activities (β-glucosidase, acid phosphatase, and urease) were significantly higher in the rehabilitated sites of system 2 (S₂-R and S₂-BR). However, even under high heavy metal contents (S₁-R), the rehabilitation with eucalyptus was also effective. DGGE analysis revealed similarity in the diversity and structure of bacteria and fungi communities between rehabilitated sites and C site (uncontaminated). Principal component analysis showed clustering of rehabilitated sites (S₂-R and S₂-BR) with contamination-free sites, and S₁-R was intermediate between the most and least contaminated sites, demonstrating that the soil replacement and revegetation improved the biological condition of the soil. The attributes that most explained these clustering were bacterial density, acid phosphatase, β-glucosidase, fungal and actinobacterial densities, Cmic, and induced respiration.

The increasing use of nanoparticles (NPs) worldwide has raised some concerns about their impact on the environment. The aim of the study was to assess the toxicity of metal oxide nanoparticles, singly or combined, in a freshwater fish (Carassius auratus). The fish were exposed for 7, 14, and 21 days to different concentrations of NPs (10 μg Al₂O₃.L⁻¹, 10 μg ZnO.L⁻¹, 10 μg Al₂O₃.L⁻¹ plus 10 μg ZnO.L⁻¹, 100 μg Al₂O₃.L⁻¹, 100 μg ZnO.L⁻¹, and 100 μg Al₂O₃.L⁻¹ plus 100 μg ZnO.L⁻¹). At the end of each exposure period, antioxidant enzyme activity (catalase, glutathione-S-transferase, and superoxide dismutase), lipid peroxidation, and histopathology were assessed in the gills and livers of C. auratus. The results show an increase in catalase (CAT) and superoxide dismutase (SOD) activity in the gills and livers of fish, especially after 14 days of exposure to single and combined NPs, followed by a reduction at 21 days. An increase in glutathione S-transferase (GST) was observed in gills after 7 days for all tested NP concentrations (single and combined); while in livers, a significant increase was determined after 14 days of exposure to 100 μg.L⁻¹ of both single ZnO and Al₂O₃ NPs. Lipid peroxidation (LPO) significantly increased in gills after 7 days of exposure to 100 μg.L⁻¹ Al₂O₃ NPs (single or combined). In livers, LPO increased significantly after 7 days of exposure to all tested concentrations of both single ZnO and Al₂O₃ (except for 10 μg Al₂O₃.L⁻¹), and after 14 days of exposure to ZnO (10 and 100 μg.L⁻¹) and Al₂O₃ (100 μg.L⁻¹). The results from histological observations suggest that exposure to metal oxide NPs affected both livers and gills, presenting alterations such as gill hyperplasia and liver degeneration. However, the most pronounced effects were found in gills. In general, this study shows that the tested NPs, single or combined, are capable of causing sub-lethal effects on C. auratus, but when combined, NPs seem to be slightly more toxic than when added alone.

Chiral polychlorinated biphenyl (PCB) congeners, such as PCB 136, are atropselectively metabolized to various hydroxylated PCB metabolites (HO-PCBs). The present study investigates the effect of two thiol antioxidants, glutathione and N-acetyl-cysteine (NAC), on profiles and chiral signatures of PCB 136 and its HO-PCB metabolites in rat liver microsomal incubations. Liver microsomes prepared from rats pretreated with phenobarbital were incubated with PCB 136 (5 μM) in the presence of the respective antioxidant (0–10 mM), and levels and chiral signatures of PCB 136 and its HO-PCB metabolites were determined. Three metabolites, 5-136 (2,2′,3,3′,6,6′-hexachlorobiphenyl-5-ol), 4-136 (2,2′,3,3′,6,6′-hexachlorobiphenyl-4-ol), and 4,5-136 (2,2′,3,3′,6,6′-hexachlorobiphenyl-4,5-diol), were detected in all incubations, with 5-136 being the major metabolite. Compared to microsomal incubations without antioxidant, levels of 4,5-136 increased with increasing antioxidant concentration, whereas levels of PCB 136 and both mono-HO-PCBs were not affected by the presence of either antioxidant. PCB 136, 4-136, and 5-136 displayed significant atropisomeric enrichment; however, the direction and extent of the atropisomeric enrichment was not altered in the presence of an antioxidant. Because 4,5-136 can either be conjugated to a sulfate or glucuronide metabolite that is readily excreted or further oxidized a potentially toxic PCB 136 quinone, the effect of both thiol antioxidants on 4,5-136 formation suggests that disruptions of glutathione homeostasis may alter the balance between both metabolic pathways and, thus, PCB 136 toxicity in vivo.