Diel methane emission fluxes from a landfill that was covered by vegetation were investigated to reveal the methane emission mechanisms based on the interaction of vegetation characteristics and climate factors. The methane emissions showed large variation between daytime and nighttime, and the trend of methane emissions exhibited clear bimodal patterns from both Setaria viridis- and Neyraudia reynaudiana-covered areas. Plants play an important role in methane transportation as well as methane oxidation. The notable decrease in methane emissions after plants were cut suggests that methane transportation via plants is the primary way of methane emissions in the vegetated areas of landfill. Within plants, the methane emission fluxes were enhanced due to a convection mechanism. Given that the methane emission flux is highly correlated with the solar radiation during daytime, the convection mechanism could be attributed to the increase in solar radiation. Whereas the methane emission flux is affected by a combined impact of the wind speed and pedosphere characteristics during nighttime. An improved understanding of the methane emission mechanisms in vegetated landfills is expected to develop a reliable model for landfill methane emissions and to attenuate greenhouse gas emissions from landfills.

Soils are the largest terrestrial sink for methane (CH4). However, heavy metals may exert toxicity to soil microorganisms, including methanotrophic bacteria. We tested the effect of lead (Pb), zinc (Zn) and nickel (Ni) on CH4 oxidation (1% v/v) and dehydrogenase activity, an index of the activity of the total soil microbial community in Mollic Gleysol soil in oxic and hypoxic conditions (oxia and hypoxia, 20% and 10% v/v O2, respectively). Metals were added in doses corresponding to the amounts permitted of Pb, Zn, Ni in agricultural soils (60, 120, 35 mg kg−1, respectively), and half and double of these doses. Relatively low metal contents and O2 status reflect the conditions of most agricultural soils of temperate regions. Methane consumption showed high tolerance to heavy metals. The effect of O2 status was stronger than that of metals. CH4 consumption was enhanced under hypoxia, where both the start and the completion of the control and contaminated treatment were faster than under oxic conditions. Dehydrogenase activity, showed higher sensitivity to the contamination (except for low Ni dose), with a stronger effect of heavy metals, than that of the O2 status.

With the increasing environmental application and discharge of iron-based nanoparticles (NPs), a comprehensive understanding of their fate and ecotoxicological effect in the aquatic environment is very urgent. In this study, toxicities of 4 zero-valent iron NPs (nZVI) of different sizes, 2 Fe2O3 NPs of different crystal phases, and 1 type of Fe3O4 NPs to a green alga (Chlorella pyrenoidosa) were investigated, with a focus on the effects of particle size, crystal phase, oxidation state, and environmental aging. Results show that the algal growth inhibition of nZVI increased significantly with decreasing particle size; with similar particle sizes (20–30 nm), the algal growth inhibition decreased with oxidation of the NPs with an order of nZVI > Fe3O4 NPs > Fe2O3 NPs, and α-Fe2O3 NPs presented significantly higher toxicity than γ-Fe2O3 NPs. The NP-induced oxidative stress was the main toxic mechanism, which could explain the difference in algal toxicity of the NPs. The NP-cell heteroagglomeration and physical interactions also contributed to the nanotoxicity, whereas the effect of NP dissolution was negligible. The aging in distilled water and 3 surface water samples for 3 months increased surface oxidation of the iron-based NPs especially nZVI, which decreased the toxicity to algae. These findings will be helpful for the understanding of the fate and toxicity of iron-based NPs in the aquatic environment.

The second‒order rate constants (k) of hydroxyl radical (·OH) with polychlorinated biphenyls (PCBs) in the gas phase are of scientific and regulatory importance for assessing their global distribution and fate in the atmosphere. Due to the limited number of measured k values, there is a need to model the k values for unknown PCBs congeners. In the present study, we developed a quantitative structure–activity relationship (QSAR) model with quantum chemical descriptors using a sequential approach, including correlation analysis, principal component analysis, multi−linear regression, validation, and estimation of applicability domain. The result indicates that the single descriptor, polarizability (α), plays an important role in determining the reactivity with a global standardized function of lnk = −0.054 × α ‒ 19.49 at 298 K. In order to validate the QSAR predicted k values and expand the current k value database for PCBs congeners, an independent method, density functional theory (DFT), was employed to calculate the kinetics and thermodynamics of the gas‒phase ·OH oxidation of 2,4′,5-trichlorobiphenyl (PCB31), 2,2′,4,4′-tetrachlorobiphenyl (PCB47), 2,3,4,5,6-pentachlorobiphenyl (PCB116), 3,3′,4,4′,5,5′-hexachlorobiphenyl (PCB169), and 2,3,3′,4,5,5′,6-heptachlorobiphenyl (PCB192) at 298 K at B3LYP/6–311++G**//B3LYP/6–31 + G** level of theory. The QSAR predicted and DFT calculated k values for ·OH oxidation of these PCB congeners exhibit excellent agreement with the experimental k values, indicating the robustness and predictive power of the single–descriptor based QSAR model we developed.

We evaluated three types of functionalized, graphene-based materials for activating persulfate (PS) and removing (i.e., sorption and oxidation) sulfamethoxazole (SMX) as a model emerging contaminant. Although advanced oxidative water treatment requires PS activation, activation requires energy or chemical inputs, and toxic substances are contained in many catalysts. Graphene-based materials were examined herein as an alternative to metal-based catalysts. Results show that nitrogen-doped graphene (N-GP) and aminated graphene (NH2-GP) can effectively activate PS. Overall, PS activation by graphene oxide was not observed in this study. N-GP (50 mg L−1) can rapidly activate PS (1 mM) to remove >99.9% SMX within 3 h, and NH2-GP (50 mg L−1) activated PS (1 mM) can also remove 50% SMX within 10 h. SMX sorption and total removal was greater for N-GP, which suggests oxidation was enhanced by increasing proximity to PS activation sites. Increasing pH enhanced the N-GP catalytic ability, and >99.9% SMX removal time decreased from 3 h to 1 h when pH increased from 3 to 9. However, the PS catalytic ability was inhibited at pH 9 for NH2-GP. Increases in ionic strength (100 mM NaCl or Na2SO4) and addition of radical scavengers (500 mM ethanol) both had negligible impacts on SMX removal. With bicarbonate addition (100 mM), while the catalytic ability of N-GP remained unaltered, NH2-GP catalytic ability was inhibited completely. Humic acid (250 mg L−1) was partially effective in inhibiting SMX removal in both N-GP and NH2-GP systems. These results have implications for elucidating oxidant catalysis mechanisms, and they quantify the ability of functionalization of graphene with hetero-atom doping to effectively catalyze PS for water treatment of organic pollutants including emerging contaminants.

Steroidal estrogens (SEs), widespread in aquatic systems, have a potential to disrupt the endocrine system of wildlife species and humans. In our experiments, the performance of ε-MnO2 nanorods in transforming 17β-estradiol (E2) was investigated, and the effect of humic acid (HA) on the reaction behaviors was systematically characterized. Reconfiguration of humic molecules was also investigated by high-performance size exclusion chromatography (HPSEC). Results indicated that ε-MnO2 nanomaterials ensured efficient removal of E2 from the aqueous solution. The presence of HA hindered the transformation of E2, while enhanced the cross-coupling between E2 and humic molecules. In particular, we used a mixture of un-labeled E2 and 13C3-labeled E2 at a 1: 1 set ratio (w/w) to probe the reaction products via high-resolution mass spectrometry (HRMS). The combination of HRMS and 13C3-labeling revealed the intermediate products including estrone (E1), and hydroxylated, quinone-like, and ring-opened species, as well as E2 dimer and trimer. More importantly, possible cross-coupling products between E2 and HA were also identified. A reaction mechanism including two-electron oxidation and single-electron oxidation was proposed. The applied analytical approach using HRMS along with 13C3-labeling for reaction-product identification is crucial to understanding the role of HA in the transformation of SEs.

Permanently increasing in the amount of sludge resulted in the serious environment burden. This work reports a novel carbothermal process for converting the Fe-rich waste sludge into cleaner nano-flake Fenton-like catalyst to relieve the crisis. The transformation of Fe species at different carbothermal temperature was evaluated by XRD analysis. SEM and XPS analyses were involved to characterize the morphology and chemical bonds of the catalysts. Results shown that the resulted catalyst carbonized at 800 °C (Fe-SC-800) was composed of Fe0 and Fe3O4, performing nano-flake-like structure. The Fe-SC-800 has the highest catalytic activity in degradation of AOII in C0 = 200 mg/L. The efficiency achieves at 98% within 30 min at neutral pH, which is ascribed to the hydroxyl radical oxidation. Moreover, no iron is leached and the Fe-SC-800 could be recycled for three times at least. Thus, the Fe rich sludge could be reutilized as a valuable source for eco-friendly catalyst production, constituting an ecological way to manage these sludge wastes and eliminate the sludge and organic pollution to environment.

The main objective of this study was to unravel the chemical reactions and processes dictating the potential bioavailability of vanadium (V). In environmental solutions V exists in two stable oxidation states, +IV and +V, of which + V is considered to be more toxic. In this study, the effect of speciation and soil pH on the chemical accessibility of V was investigated with two soils: 1) field soil rather rich in soil organic matter (SOM) and 2) coarse mineral soil low in SOM. Fresh soil samples treated with V(+V) (added as NaVO3) or V(+IV) (added as VOSO4) (pH adjusted to the range 4.0–6.9) were incubated for 3 months at 22 °C. The adsorption tendency of V species was explored by water extraction (Milli-Q water, 1:50 dw/V) and by sequential extraction (0.25 M KCl; 0.1 M KH2/K2HPO4; 0.1 M NaOH; 0.25 M H2SO4, 1:10 dw/V). The potential bioavailability of V was found to be dictated by soil properties. SOM reduced V(+V) to V(+IV) and acted as a sorbent for both species, which lowered the bioaccessibility of V. A high pH, in turn, favored the predominance of the V(+V) species and thus increased the chemical accessibility of V.

Nanoparticulate mackinawite (FeS) can be an important host-phase for arsenic (As) in sulfidic, subsurface environments. Although not previously investigated, phosphate (PO43−) may compete with As for available sorption sites on FeS, thereby enhancing As mobility in FeS-bearing soils, sediments and groundwater systems. In this study, we examine the effect of PO43− on sorption of arsenate (As(V)) and arsenite (As(III)) to nanoparticulate FeS at pH 6, 7 and 9. Results show that PO43− (at 0.01–1.0 mM P) did not significantly affect sorption of either As(V) or As(III) to nanoparticulate FeS at initial aqueous As concentrations ranging from 0.01 to 1.0 mM. At pH 9 and 7, sorption of both As(III) and As(V) to nanoparticulate FeS was similar, with distribution coefficient (Kd) values spanning 0.76–15 L g−1 (which corresponds to removal of 87–98% of initial aqueous As(III) and As(V) concentrations). Conversely, at pH 6, the sorption of As(III) was characterized by substantially higher Kd values (6.3–93.4 L g−1) than those for As(V) (Kd = 0.21–0.96 L g−1). Arsenic K-edge X-ray absorption near edge structure (XANES) spectroscopy indicated that up to 52% of the added As(V) was reduced to As(III) in As(V) sorption experiments, as well as the formation of minor amounts of an As2S3-like species. In As(III) sorption experiments, XANES spectroscopy also demonstrated the formation of an As2S3-like species and the partial oxidation of As(III) to As(V) (despite the strictly O2-free experimental conditions). Overall, the XANES data indicate that As sorption to nanoparticulate FeS involves several redox transformations and various sorbed species, which display a complex dependency on pH and As loading but that are not influenced by the co-occurrence of PO43−. This study shows that nanoparticulate FeS can help to immobilize As(III) and As(V) in sulfidic subsurface environments where As co-exists with PO43−.

Understanding of xenobiotic metabolism is necessary for risk assessment as well as toxicological research. In the present study, nanoLC/LTQ-Orbitrap mass based non-targeted metabolomics method coupled with ultra-performance liquid chromatography (UPLC)/triple quadrupole mass based targeted metabolomics method was carried out to investigate the stereoselective metabolism of benalaxyl in mouse hepatic microsomes. As a result, 7 metabolites of benalaxyl were identified, including 5 previously reported and 2 newly identified metabolites in present work. Hydroxylation, oxidation and esterolysis were major biotransformation reactions of benalaxyl in mouse hepatic microsomes. For stereoselective metabolism study, (−)-R-benalaxyl degraded much faster than its antipode with the t1/2 of 81.24 and 190.38 min for (−)-R- and (+)-S-benalaxyl, respectively. More importantly, stereoselectivity was also observed in the formation of the identified metabolites. In conclusion, the combined use of the mass spectrometry based targeted and non-targeted metabolomics provided a new approach to investigate stereoselective metabolism and identify novel metabolites of chiral pesticides. This study highlights the stereoselective metabolic profile of benalaxyl enantiomers and provides reliable data for benalaxyl toxicological risk assessment in mammal.