The objective of this work was to evaluate the adsorption capacity of alkylated modified porous biochar prepared by esterification and etherification (PSAC-2) for low concentrate volatile organic compounds (VOCs, toluene and ethyl acetate) in high humidity environment by experiments and theoretical calculations. Results showed that PSAC-2 has a large specific surface area and weak surface polarity, at 80% relative humidity, its capacities for toluene and ethyl acetate adsorption could be maintained at 92% and 87% of the initial capacities (169.9 mg/g and 96.77 mg/g). The adsorption behaviors of toluene, ethyl acetate, and water vapor were studied by adsorption isotherms, and isosteric heat was obtained. The desorption activation energy was obtained by temperature programmed desorption experiment. The outcomes manifested that the PSAC-2 can achieve strong adsorption performance for weakly polar molecules. Through density functional theory (DFT) simulations, owing to the interaction of hydrogen bonds, oxygen-containing groups became a significant factor influencing the adsorption of VOCs in humid environments. These results could provide an important reference for VOCs control in a high humidity environment.

The m-aminophenol (m-AP) is a widely used industrial chemical, which enters water, soils, and sediments with waste emissions. A common soil metal oxide, birnessite (δ-MnO2), was found to mediate the transformation of m-AP with fast rates under acidic conditions. Because of the highly complexity of the m-AP transformation, mechanism-based models were taken to fit the transformation kinetic process of m-AP. The results indicated that the transformation of m-AP with δ-MnO2 could be described by precursor complex formation rate-limiting model. The oxidative transformation of m-AP on the surface of δ-MnO2 was highly dependent on reactant concentrations, pH, temperature, and other co-solutes. The UV-VIS absorbance and mass spectra analysis indicated that the pathway leading to m-AP transformation may be the polymerization through the coupling reaction. The m-AP radicals were likely to be coupled by the covalent bonding between unsubstituted C2, C4 or C6 atoms in the m-AP aromatic rings to form oligomers as revealed by the results of activation energy and mass spectra. Furthermore, the toxicity assessment of the transformation productions indicated that the toxicity of m-AP to the E. coli K-12 could be reduced by MnO2 mediated transformation. The results are helpful for understanding the environmental behavior and potential risk of m-AP in natural environment.

Benzotriazole ultraviolet stabilizers (BUVSs) are prominent chemicals widely used in industrial and consumer products to protect against ultraviolet radiation. They are becoming contaminants of emerging concern since their residues are frequently detected in multiple environmental matrices and their toxicological implications are increasingly reported. We herein investigated the antiandrogenic activities of eight BUVSs prior to and after human CYP3A4-mediated metabolic activation/deactivation by the two-hybrid recombinant human androgen receptor yeast bioassay and the in vitro metabolism assay. More potent antiandrogenic activity was observed for the metabolized UV-328 in comparison with UV-328 at 0.25 μM ((40.73 ± 4.90)% vs. (17.12 ± 3.00)%), showing a significant metabolic activation. In contrast, the metabolized UV-P at 0.25 μM resulted in a decreased antiandrogenic activity rate from (16.08 ± 0.95)% to (6.91 ± 2.64)%, indicating a metabolic deactivation. Three mono-hydroxylated (OH) and three di-OH metabolites of UV-328 were identified by ultra-performance liquid chromatography quadrupole time of flight mass spectrometry (UPLC-Q-TOF-MS/MS), which were not reported previously. We further surmised that the hydroxylation of UV-328 occurs mainly at the alicyclic hydrocarbon atoms based on the in silico prediction of the lowest activation energies of hydrogen abstraction from C-H bond. Our results for the first time relate antiandrogenic activity to human CYP3A4 enzyme-mediated hydroxylated metabolites of BUVSs. The biotransformation through hydroxylation should be fully considered during the health risk assessment of structurally similar analogs of BUVSs and other emerging contaminants.

The process improvement, a pilot remediation test and the decontamination mechanism of microwave-induced steam distillation (MISD) for petroleum hydrocarbons (PHs) removal were conducted. Processes of multistage steam distillation and carbon reinforcement were compared to determine the best remediation process. Pilot project was then carried out to explore the applicability of MISD in site-scale remediation. The remediation efficiency, procedures and influencing factors of site-scale MISD project were studied by monitoring variations of soil moisture, temperature and PHs concentrations. Furthermore, the decontamination mechanisms of PHs were clarified based on kinetic analysis. The results showed that the multistage steam distillation could improve 10%∼15% remediation efficiency, and the carbon reinforcement could shorten remediation duration of each steam distillation stage by 50%. Pilot MISD project adopted multistage steam distillation process and went through four (initial, rapid heating-up, gentle heating-up and quasi-equilibrium) remediation stages (overall temperature ≤100 °C). The final PHs removal rate was about 60%, which would get better with greater proportion of low boiling points components and stronger vapor extraction. Kinetic studies showed that PHs was removed by steam stripping and limited by intraparticle diffusion in the “steam distillation zone”, while local high temperature (＞100 °C) greatly improved PHs volatilization and provided activation energy for PHs desorbed and degraded in the “selective heating zone".

Thermogravimetric analysis and pyrolyzer-gas chromatography/mass spectrometry measurements were taken to examine the kinetic behavior and product distribution on the thermal and catalytic pyrolysis of different types of sewage sludge. Compared to livestock manure sewage sludge (LMSS), municipal sewage sludge (MSS) had larger ash (30.3%) and lower fixed carbon (7.9%) contents. The peak intensities for the 1ˢᵗ decomposition region (200–380 °C) on the derivative thermogravimetric curve of MSS were higher than those of LMSS. In contrast, the peak height in the 2ⁿᵈ temperature region (>380 °C) of MSS was lower than that of LMSS. The activation energy for the pyrolysis of MSS (Avg. 186.5 kJ/mol) was lower than that of LMSS (Avg. 263.4 kJ/mol) over the entire conversion range. MSS produced larger amounts of fatty acids and cholesterol than LMSS. The in-situ catalytic pyrolysis of MSS over HBeta using a pyrolyzer-gas chromatography/mass spectrometry also produced larger amounts of aromatic hydrocarbons than LMSS, suggesting that its better feedstock properties strongly influence the final product oil quality.

In this study, a weather-based multicomponent model was developed based on the unique biostructures and metabolic processes of mushrooms to evaluate their uptake of pesticides from soils, and the effects of temperature and relative humidity on the bioaccumulation of pesticides in mushrooms was comprehensively quantified. Additionally, a new pseudo-partition coefficient between mushrooms and soils was introduced to assess the impacts of different physiochemical properties on the pesticide uptake process. The results indicate that, in general, the pseudo-partition coefficient increases as the relative humidity increases for both the air and soil according to Fick’s law of gas diffusion and the spatial competition of molecules, respectively. Meanwhile, the effect of temperature on the pesticide bioaccumulation process is more complex. For most pesticides (e.g., atrazine), the pseudo-partition coefficient that was computed from the transpiration component had a maximum value at a specific temperature due to the temperature dependency of the transpiration and biodegradation processes. For some pesticides (e.g., ethoprophos), the pseudo-partition coefficient of the air-deposition component had a maximum value at a certain temperature that was caused by the ratio of the soil–air internal transfer energy and degradation activation energy of the pesticide. It was also concluded that for relatively low-volatility pesticides, transpiration dominated the bioaccumulation process; this was mainly determined from the pesticide water solubility. For nonbiodegradable pesticides (e.g., lindane), the computed coefficient values were relatively low due to their insolubility in water, which inhibits bioaccumulation in mushrooms and is one of the main reasons for their long-term persistence in soils.

Aiming at realizing heavy metal recycling and resource utilization, a carbon-based iron catalyst (Fe@C) was synthesized through a resin carbonization method, and adopted for peroxymonosulfate (PMS) activation to remove bisphenol S (BPS), an emerging aquatic contaminant. This study demonstrated that Fe@C exhibited excellent catalytic potential for BPS degradation with a relatively low activation energy (Ea = 29.90 kJ/mol). Kinetic factors affecting the activation performance were thoroughly investigated. The obtained results indicated that Fe@C composite exhibited the superior uniformity with carbon as the framework and granular iron oxide as the coverage. pH increase could cause the inhibitive effect on BPS degradation, while the increasing catalyst loading (0.05–0.5 g/L) was conducive for the catalytic performance of Fe@C, with an optimal PMS concentration at 1.0 mM. A negative influence on BPS degradation was obtained in the presence of SO42−, HCO3− and lower concentration of Cl− (0–20 mM), compared to the promotion at higher concentration of Cl− (>50 mM). Based on the electron spin resonance (ESR) monitoring and radical scavenging results, it is demonstrated that singlet oxygen, a non-radical species, emerged together with ·SO4− and ·OH for BPS degradation. A three-channel catalytic mechanism was verified through typical characterizations. Furthermore, the degradation pathway of BPS was proposed based on the identified intermediates. This novel carbon-based activator for PMS showed notable potential for the waste resin recycling and water decontamination.A novel Fe-based activator carbonized from a saturated resin exhibits excellent performance for Bisphenol S degradation with activated peroxymonosulfate.

Nano zero valent iron/Ni bimetal materials (nZVI/Ni) were prepared by borohydride reduction method to remediate toxic Cr(Ⅵ) contaminated in soil leachate. nZVI/Ni was characterized using scanning electron microscopy (SEM), X-ray diffraction (XRD) and X-ray Photoelectron Spectroscopy (XPS). Different factors including pH value of soil leachate, reaction time, temperature, humic acid and coexisting anions (SO42-, NO3−, HCO3−, CO32-) were studied to analyze the reduction rate. Results showed that the reduction rate of Cr(Ⅵ) could reach 99.84% under the condition of pH of 5 and temperature of 303 K. pH values and temperature of soil leachate had a significant effect on the reduction efficiency, while humic acid had inhibition effect for the reduction reaction. SO42-, HCO3− and CO32- had inhibition effect for reduction rate, while NO3− barely influenced the reduction process of nZVI/Ni. Moreover, Langumir-Hinshelwood first order kinetic model was studied and could describe the reduction process well. The thermodynamic studies indicated that the reaction process was endothermic and spontaneous. Activation energy was 143.80 kJ mol−1, showing that the reaction occurred easily. Therefore, the study provides an idea for nZVI/Ni further research and practical application of nZVI/Ni in soil remediation.

Concentrations of the insecticide endosulfan (α- and β-isomer) and its degradation product endosulfan sulfate in air, seawater and soil are calculated with the global environmental fate model CliMoChem. As model input, physicochemical properties of all three compounds were assembled and a latitudinally and temporally resolved emission inventory was generated. For concentrations in air, model and measurements are in good agreement; a bimodal seasonality with two peaks in spring and fall as it is observed in Arctic air is reproduced by the model. For seawater, the agreement of model and measurements depends on the values of the hydrolysis activation energy of endosulfan used in the model; with relatively high values around 100kJ/mol, model results match field data well. The results of this assessment of the levels, persistence, and global distribution of endosulfan are also relevant for the evaluation of endosulfan as a Persistent Organic Pollutant under the Stockholm Convention.

Development of efficient, green and low-cost natural mineral-based reductive materials is promising to remediation of hexavalent chromium(Cr(VI))-contaminated soil. Considering the synergetic effect between pyrite and zerovalent iron (ZVI), an activated pyrite supported ZVI(ZVI/FeS₂) with high reducing activity was developed by ball milling activation of natural pyrite and sulfidation of ZVI. The remediation property of ZVI/FeS₂ for Cr(VI)-contaminated soil was evaluated with different ZVI/FeS₂ dosage, soil-water ratio, initial pH, time and temperature, as well as the stability of Cr. The results showed that ZVI/FeS₂ possessed high reduction activity with soil Cr(VI) removal rate up to 99 % even under alkaline condition, and soil with different pH values eventually converged to neutral after 90 days, indicating that ZVI/FeS₂ has a good self-regulating alkaline ability. The reduction process conformed to Langmuir-Hinshelwood first-order kinetics and was a spontaneous and endothermic process. The lower activation energy of 17.97 kJ mol⁻¹ (usually 60–250 kJ mol⁻¹) indicated that the reduction reaction of Cr(VI) was particularly easy to occur. The speciation change of Cr in soil within 30 days demonstrated that the Cr in the soil was converted from a readily migratable state to a more stable state, where the Fe–Mn oxide bound fraction reached 85.03 % due to the generation of Cr(III)/Fe(III) co-precipitation. The results of long-term stability experiments showed that the leaching concentrations of Cr(VI) and total Cr decreased significantly after the ZVI/FeS₂ treatment and remained stable at very low levels for 180 days. This study provided a sustainable way to fully utilize natural pyrite minerals to obtain iron-bearing reductive materials for feasible, effective and long-term stable immobilization of Cr(VI) in soil.