Multiwalled carbon nanotubes (MWCNTs) were oxidized using a mixture of H₂SO₄ and HNO₃, and the oxidized MWCNTS were decorated with magnetite (Fe₃O₄). Finally, poly-N-isopropyl acrylamide-co-butyl acrylate (P-NIPAM) was added to obtain P-NIPAM/Fe/MWCNT nanocomposites. The nanosorbents were characterized by various techniques, including X-ray diffraction, transmission electron microscopy, scanning electron microscopy, thermogravimetric analysis, and Brunauer–Emmett–Teller analysis. The P-NIPAM/Fe/MWCNT nanocomposites exhibited increased surface hydrophobicity. Owing to their higher adsorption capacity, their kerosene removal efficiency was 95%; by contrast, the as-prepared, oxidized, and magnetite-decorated MWCNTs had removal efficiencies of 45%, 55%, and 68%, respectively. The P-NIPAM/Fe/MWCNT nanocomposites exhibited a sorbent capacity of 8.1 g/g for kerosene removal from water. The highest kerosene removal efficiency from water was obtained at a process time of 45 min, sorbent dose of 0.005 g, solution temperature of 40 °C, and pH 3.5. The P-NIPAM/Fe/MWCNTs showed excellent stability after four cycles of kerosene removal from water followed by regeneration. The reason may be the increase in the positive charge of the polymer at pH 3.5 and the increased adsorption affinity of the adsorbent toward the kerosene contaminant. The pseudo second-order model was found to be the most suitable model for studying the kinetics of the adsorption reaction.

The effectiveness and feasibility of the three biochar materials for remediation of arsenic (As) and lead (Pb) contaminated soil were explored in this study. Significant reduction of bioaccessibility and migration risks of both heavy metals have been explained mechanistically by incubation, column experiments and numerical simulation. Langmuir equation fitted As and Pb sorption isotherms better in the control and biochar (BC) amended soils, while Freundlich model was more suitable for iron modified biochar (Fe-BC) and sulfur/iron modified biochar (S/Fe-BC) amended soils, indicating that modified biochar promoted chemical adsorption process for As and Pb. For the three biochar materials, S/Fe-BC showed the best effects on reducing the bioavailability of As and Pb, with a decrease of 40.42%–64.21%. The reduction in bioaccessibility by metal portioning into available and non-available fractions was better for illustrating the mechanisms including adsorption, precipitation/coprecipitation and As(III) oxidation behind S/Fe-BC efficacy. Moreover, S/Fe-BC can effectively inhibit the leaching behavior of As and Pb under acid rain, which increased by 99.89% and 90.18%, respectively, compared with the control. The HYDRUS-1D modeling indicated that S/Fe-BC could continuously treat As (100 mg/L) and Pb (1000 mg/L) contaminated water for 16.22 years and 40.86 years, respectively, and ensure the groundwater quality criteria being met. Based on these insights, we believe that our study will provide meaningful information about the potentials of biochar derived materials for soil heavy metals’ remediation.

Oil and petroleum products are known to be among the most widespread soil pollutants. The risk of emergencies is sure to increase greatly in conditions of abnormally low temperatures. Oil and oil products are not only toxic to the environment, but can also have a negative impact on the state of the permafrost zone, accelerating the processes of permafrost degradation. The goal of the research was to study the soils and bottom sediments for oil pollution in the Arctic region of Yakutia. The research was carried out with using the complex of geochemical and microbiological methods of analysis. It had shown that at present oil pollution was mainly concentrated on the objects bearing a high technogenic load. However, some migration of hydrocarbons was observed with melt, seasonal melt and rainwaters, as a result of which the natural background of the nearby territories became technogenic character. In the Arctic conditions for the first time according to the obtained data on geochemical and microbiological studies oxidative destruction of oil pollutants in soil occurred mainly under the influence of physic and chemical environmental factors, not by microbial oxidation. Sluggish processes of mineralization of organic residues and the transformation of oil pollutants by the type of putrefaction led to the colonization of oil-polluted soils of the Arctic with putrefying and pathogenic microorganisms. The purpose of further research will be studying the possibility of intensification of soil remediation processes of technologically disturbed soils at abnormally low temperatures.

Herein, a pH-independent interpenetrating polymeric networks (Fe-SA-C) were fabricated from graphitic biochar (BC) and iron-alginate hydrogel (Fe-SA) for removal of Cr(VI) and Pb(II) in aqueous solution. Fourier transform infrared spectroscopy (FTIR), Raman spectroscopy and scanning electron microscope (SEM) results demonstrated that graphitic BC interpenetration increased surface porosity and distorted surfaces of Fe-SA, which boosted availability of hydroxyl (-OH) group. Fe³⁺ as a cross-linking agent of the alginate endowed Fe-SA-C with positive surfaces (positive zeta potential) and excellent pH buffering capacity, while excessive Fe³⁺ was soldered on Fe-SA-C matrix as FeO(OH) and Fe₂O₃. Cr(VI) removal at pH of 3 by Fe-SA-C (20.3 mg g⁻¹) were 30.3% and 410.6% greater than that by Fe-SA and BC, respectively. Fe-SA-C exhibited minor pH dependence over pH range of 2–7 towards Cr(VI) retention. Greater zeta potential of Fe-SA-C over Fe-SA conferred a better electrostatic attraction with Cr(VI). FTIR and XPS of spent sorbents confirmed the reduction accounted for 98.5% for Cr(VI) removal mainly due to participation of –OH. Cr(VI) reduction was further favored by conductive carbon matrix in Fe-SA-C, as evidenced by more negative Tafel corrosion potential. Reductively formed Cr(III) was subsequently complexed with carboxylic groups originating from oxidation of –OH. Thus, Cr(VI) removal invoked electrostatic attraction, reduction, and surface complexation mechanisms. Pb(II) removal with excellent pH independence was mainly ascribed to surface complexation and possible precipitation. Thus, the functionalized, conductive, and positively-charged Fe-SA-C extended its applicability for Cr(VI) and Pb(II) removal from aqueous solutions in a wide pH range. This research could expand the application of hydrogel materials for removal of both cationic and anionic heavy metals in solutions over an extended pH range.

Pyriproxyfen is a juvenile hormone analogue insecticide used worldwide. At present, the potential threat of pyriproxyfen to aquatic organism has not been well explored. In this work, the bioaccumulation, metabolic profile and toxicity of pyriproxyfen and its metabolites to zebrafish were studied, and the enantioselectivity of pyriproxyfen and the major chiral metabolites were also determined. Sixteen metabolites of pyriproxyfen in zebrafish were identified. Hydroxylation, ether linkage cleavage and oxidation in phase I metabolism, followed by sulfate and glucuronic acid conjugation. The bioconcentration factors ranged from 1175 to 1246. Hydroxylation metabolites of pyriproxyfen showed enantioselective behavior in zebrafish with enantiomer fractions (EFs) of 4′–OH– pyriproxyfen and 5″–OH– pyriproxyfen ranged from 0.50 to 0.71. Toxicological indexes including acute toxicity, joint toxicity and oxidative stress were tested. Among all the metabolites, 4′–OH– pyriproxyfen was found 2 folds more toxic to zebrafish than pyriproxyfen. (−)-Pyriproxyfen was found 2 folds more toxic than rac- and (+)-pyriproxyfen. Antagonistic effects were found in binary joint toxicity of pyriproxyfen and its hydroxylated metabolites. Pyriproxyfen and its metabolites also showed oxidative stress damage by inhibiting the activity of CAT and SOD and increasing MDA. This work provided deep insight into the metabolism and the potential risks of pyriproxyfen to aquatic organisms.

Coastal tourist and industrial cities are most likely to have differential effects on the distance dilution of antibiotic resistance genes (ARGs) in an estuary system. This study used high-throughput fluorescence quantitative polymerase chain reaction to identify sediment ARGs in two typical estuaries of coastal tourist and industrial cities (Xiamen and Taizhou) in China. The distance dilution of ARGs and its relationship with key environmental factors were analysed. The results indicated that along the river inlet towards the sea, the distance dilution effect on ARG abundance in estuary sediments of Taizhou was approximately double that in Xiamen, and the macrolide, lincosamide, and streptogramin B (MLSB) and vancomycin genes were replaced by the fluoroquinolone, quinolone, florfenicol, chloramphenicol, and amphenicol (FCA) and β-lactam genes in Taizhou, whereas β-lactam genes succeeded the MLSB and sul genes in Xiamen. The abundance and number of ARGs and mobile genetic elements (MGEs) were positively correlated with the particle size and total organic carbon (TOC) contents of sediments, whereas they were negatively associated with the oxidation and reduction potential (Eₕ) and pH of sediments, as well as the seawater salinity. The sediment particle size (SPZ) was the dominant physicochemical factor affecting the abundance of ARGs (r = 0.826, p < 0.05) and MGEs (r = 0.850, p < 0.01). These findings suggest that although the distance dilution effect on the ARG abundance of estuary sediments of the industrial city is greater than that of the tourist city, the larger SPZ, higher TOC content, and lower salinity, pH, and Eₕ in estuary regions adjacent to the industrial city can more significantly facilitate the proliferation and propagation of ARGs in the sediments.

Photosensitization of natural organic matter (NOM) is an important natural source of reactive bromine species (RBrS) in the environment. Up to now, quantitative information about RBrS was mainly based on model sensitizers. Whether the behavior of model compounds could represent those of complex NOM remains unknown. In this study, we employed a chemical probe (3,5-dimethyl-1-H-pyrazole) to measure RBrS in humic acid (HA)-containing solutions and investigated their influential factors. The formation rate, decay rate constant, steady-state concentration, and lifetimes of RBrS were 3.87(±0.16) × 10⁻¹³ mol L⁻¹·s⁻¹, 1.99(±0.20) × 10⁴ s⁻¹, 2.04(±0.13) × 10⁻¹⁷ mol L⁻¹, and 5.06(±1.05) × 10⁻⁵ s, respectively. Measured steady-state concentrations of RBrS were 3–5 orders of magnitude lower than those in model sensitizer system. Results showed that HA drove the RBrS generation, and about 0.12–0.70% of triplet-state HA (³HA*) would be transformed into RBrS. HA structures strongly affected this process. Phenolic-like groups suppressed the formation, while aromatic ketone-like moieties facilitated it. Last, HA also altered the transformation pathways. The contribution of ·OH dependent and direct oxidation pathways was almost equal, while the direct oxidation was predominant in the model system. Thus, careful consideration should be taken into photochemical formation of RBrS in NOM-involved solution, due to their complexity and multiple roles.

Biochar is often applied to paddy soils as a soil improver, as it retains nutrients and increases C sequestration; as such, it is a tool in the move towards C-neutral agriculture. Nitrogen (N) fertilizers have been excessively applied to rice paddies, particularly in small farms in China, because N is the major limiting factor for rice production. In paddy soils, dynamic changes in iron (Fe) continuously affect soil emissions of methane (CH₄) and carbon dioxide (CO₂); however, the links between Fe dynamics and greenhouse gas emissions, dissolved organic carbon (DOC), and rice yields following application of biochar remain unclear. The aims of this study were to examine the effects of two rates of nitrogen (N)-enriched biochar (4 and 8 t ha⁻¹ y⁻¹) on paddy soil C emissions and storage, rice yields, and Fe dynamics in subtropical early and late rice growing seasons. Field application of N-enriched biochar at 4 and 8 t ha⁻¹ increased C emissions in early and late rice, whereas application at 4 t ha⁻¹ significantly increased rice yields. The results of a culture experiment and a field experiment showed that the application of N-enriched biochar increased soil Fe²⁺concentration. There were positive correlations between Fe²⁺concentrations and soil CO₂, CH₄, and total C emissions, and with soil DOC concentrations. On the other way around, these correlations were negative for soil Fe³⁺concentrations. In the soil culture experiment, under the exclusion of plant growth, N-enriched biochar reduced cumulative soil emissions of CH₄ and CO₂. We conclude that moderate inputs of N-rich biochar (4 t ha⁻¹) increase rice crop yield and biomass, and soil DOC concentrations, while moderating soil cumulative C emissions, in part, by the impacts of biochar on soil Fe dynamics. We suggest that water management strategies, such as dry-wet cycles, should be employed in rice cultivation to increase Fe²⁺ oxidation for the inhibition of soil CH₄ and CO₂ production. Overall, we showed that application of 4 t ha⁻¹ of N-enriched biochar may represent a potential tool to improve sustainable food production and security, while minimizing negative environmental impacts.

Development of non-noble metal cluster catalysts, aiming at concurrently high activity and stability, for emission control systems has been challenging because of sintering and overcoating of clusters on the support. In this work, we reported the role of well-dispersed copper nanoclusters supported on TiO₂ in CO oxidation under industrially relevant operating conditions. The catalyst containing 0.15 wt% Cu on TiO₂ (0.15 CT) exhibited a high dispersion (59.1%), a large specific surface area (381 m²/gCᵤ), a small particle size (1.77 nm), and abundant active sites (75.8% Cu₂O). The CO oxidation activity measured by the turnover frequency (TOF) was found to be enhanced from 0.60 × 10⁻³ to 3.22 × 10⁻³ molCO·molCᵤ⁻¹·s⁻¹ as the copper loading decreased from 5 to 0.15 wt%. A CO conversion of approximately 60% was still observed in the supported cluster catalyst with a Cu loading of 5 wt% at 240 °C. No deactivation was observed for catalysts with low copper loading (0.15 and 0.30 CT) after 8 h of time-on-stream, which compares favorably with less stable Au cluster-based catalysts reported in the literature. In contrast, catalysts with high copper loading (0.75 and 5 CT) showed deactivation over time, which was ascribed to the increase in copper particle size due to metal cluster agglomeration. This study elucidated the size-activity threshold of TiO₂-supported Cu cluster catalysts. It also demonstrated the potential of the supported Cu cluster catalyst at a typical temperature range of diesel engines at light-load. The supported Cu cluster catalyst could be a promising alternative to noble metal cluster catalysts for emission control systems.

The determination of both stable nitrogen (δ¹⁵N–NO₃⁻) and stable oxygen (δ¹⁸O–NO₃⁻) isotopic signatures of nitrate in PM₂.₅ has shown potential for an approach of assessing the sources and oxidation pathways of atmospheric NOx (NO+NO₂). In the present study, daily PM₂.₅ samples were collected in the megacity of Beijing, China during the winter of 2017–2018, and this new approach was used to reveal the origin and oxidation pathways of atmospheric NOx. Specifically, the potential of field δ¹⁵N–NO₃⁻ signatures for determining the NOx oxidation chemistry was explored. Positive correlations between δ¹⁸O–NO₃⁻ and δ¹⁵N–NO₃⁻ were observed (with R² between 0.51 and 0.66, p < 0.01), and the underlying environmental significance was discussed. The results showed that the pathway-specific contributions to NO₃⁻ formation were approximately 45.3% from the OH pathway, 46.5% from N₂O₅ hydrolysis, and 8.2% from the NO₃+HC channel based on the δ¹⁸O-δ¹⁵N space of NO₃⁻. The overall nitrogen isotopic fractionation factor (εN) from NOx to NO₃⁻ on a daily scale, under winter conditions, was approximately +16.1‰±1.8‰ (consistent with previous reports). Two independent approaches were used to simulate the daily and monthly ambient NOx mixtures (δ¹⁵N-NOx), respectively. Results indicated that the monthly mean values of δ¹⁵N-NOx compared well based on the two approaches, with values of −5.5‰ ± 2.6‰, −2.7‰ ± 1.9‰, and −3.2‰ ± 2.2‰ for November, December, and January (2017–2018), respectively. The uncertainty was in the order of 5%, 5‰ and 5.2‰ for the pathway-specific contributions, the εN, and δ¹⁵N-NOx, respectively. Results also indicated that vehicular exhaust was the key contributor to the wintertime atmospheric NOx in Beijing (2017–2018). Our advanced isotopic perspective will support the future assessment of the origin and oxidation of urban atmospheric NOx.