Effects of human activities on atmospheric nitrate (NO₃⁻) formation remain unclear, though the knowledge is critical for improving atmospheric chemistry models and nitrogen deposition reduction strategies. A potentially useful way to explore this is to compare NO₃⁻ oxidation processes in urban and rural atmospheres based upon the oxygen stable isotope composition of NO₃⁻ (Δ¹⁷O–NO₃⁻). Here we compared the Δ¹⁷O–NO₃⁻ from three-years of daily-based bulk deposition in urban (Shenyang) and forested rural sites (Qingyuan) in northeast China and quantified the relative contributions of different formation pathways based on the SIAR model. Our results showed that the Δ¹⁷O in Qiangyuan (26.2 ± 3.3‰) is significantly higher (p < 0.001) than in Shenyang (24.0 ± 4.0‰), and significantly higher in winter (Shenyang: 26.1 ± 6.7‰, Qingyuan: 29.6 ± 2.5‰) than in summer (Shenyang: 22.7 ± 2.9‰, Qingyuan: 23.8 ± 2.4‰) in both sites. The lower values in the urban site are linked with conditions that favored a higher relative contribution of nitrogen dioxide reaction with OH pathway (0.76-0.91) than in rural site (0.47-0.62), which should be induced by different levels of human activities in the two sites. The seasonal variations of Δ¹⁷O–NO₃⁻ in both sites are explained by a higher relative contribution of ozone-mediated oxidation chemistry and unfavorable conditions for the OH pathway during winter relative to summer, which is affected by human activities and seasonal meteorological condition change. Based on Δ¹⁷O, wintertime conditions led to a contribution of O₃ related pathways (NO₃ + DMS/HC and N₂O₅ hydrolysis) of 0.63 in Qingyuan and 0.42 in Shenyang, while summertime conditions led to 0.15 in Qingyuan and 0.05 in Shenyang. Our comparative study on Δ¹⁷O–NO₃⁻ between urban and rural sites reveals different anthropogenic effects on nitrate formation processes on spatial and temporal scales, illustrating different responses of reactive nitrogen chemistry to changes in human activities.

In this study, magnetic biochar (MAB) and humic acid (HA)-coated magnetic biochar produced from apple branches without and after cellulase hydrolysis (HMAB and CHMAB, respectively) were prepared and tested as adsorbents of enrofloxacin (ENR) and moxifloxacin (MFX) in aqueous solution. Compared with MAB and HMAB, novel adsorbent CHMAB possessed a superior mesoporous structure, greater graphitization degree and abundant functional groups. When antibiotic solutions ranged from 2 to 20 mg L⁻¹, the theoretical maximum adsorption capacities of CHMAB for ENR and MFX were 48.3 and 61.5 mg g⁻¹ at 35 °C with adsorbent dosage of 0.4 g L⁻¹, respectively, while those of MAB and HMAB were 39.6 and 54.4 mg g⁻¹, and 44.7 and 59.0 mg g⁻¹, respectively. The pseudo-second-order kinetic model and Langmuir model presented a better fitting to the spontaneous and endothermic adsorption process. The maximum adsorption capacity of ENR and MFX onto CHMAB was achieved at initial pH values of 5 and 8, respectively. Additionally, the adsorption capacity of ENR and MFX decreased with increasing concentrations of K⁺ and Ca²⁺ (0.02–0.1 mol L⁻¹). Synergism between the pore-filling effect, π-π electron-donor-acceptor interactions, regular and negative charge-assisted H-bonding, surface complexation, electrostatic interactions and hydrophobic interactions may dominate the adsorption process. This study demonstrated that a novel magnetic biochar composite prepared through pyrolysis of agricultural waste lignocellulose hydrolyzed by cellulase in combination with HA coating was a promising adsorbent for eliminating quinolone antibiotics from aqueous media.

Fomesafen (FSA) is widely used in soybean fields for weed control. However, the persisting characteristics of FSA in the agricultural soil or water may become a hidden danger causing environmental pollution and phytotoxicity to succession crops. In this study, the growth and physiological responses of rice to FSA were investigated. It was found that the growth of rice seedlings was obviously inhibited by FSA exposure especially at over 0.1 mg L⁻¹. To gain an insight into the molecular mechanisms for the potential ecotoxicology, four libraries of rice roots and shoots exposed to FSA were created and subjected to the global RNA-sequencing (RNA-Seq) combined with HRLC-Q-TOF-MS/MS analytical technologies to comprehensively characterize the biochemical processes and catalytic reactions involved in FSA metabolism in rice. Compared with those without FSA, 499 and 450 up-regulated genes in roots and shoots with FSA were detected. Many of them were closely correlated with the tolerance to environmental stress, detoxification of xenobiotics and molecular metabolism process including cytochrome P450, glutathione S-transferases and acetyltransferase. A total of eight metabolites and fourteen conjugates in the reactive pathways of hydrolysis, substitution, reduction, methylation, glycosylation, acetylation, and malonylation were characterized by HRLC-Q-TOF-MS/MS. The relationship between the metabolized derivatives of FSA and enhanced expression the corresponding enzymatic regulators was established. This study will help understand the mechanisms and pathways of FSA metabolism and inspire the further research on FSA degradation in the paddy crops and environmental or health risks.

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.

Diethyl phthalate (DEP), as a kind of universally used plasticizer, has aroused considerable public concern owing to its wide detection, environmental stability, and potential health risks. In this work, the highly efficient removal of DEP by ferrate (VI) (Fe(VI)) was systematically explored in soil environment. The effects of the oxidant dosages, soil types, as well as the presence of coexisting cations and anions in tested soil on DEP removal were evaluated. When the dosage of Fe(VI) was 20 mM, complete removal of DEP (50 μg/g) was achieved in the tested soil after 2 min of reaction. Furthermore, the removal rate of DEP was closely related to the soil types, and the degradation rates were decreased obviously in red soil (RS), black soil (BS) and paddy soil (PS), probably due to the acidic condition and high content of organic matters. Moreover, the presence of Ca²⁺, Mg²⁺ and Al³⁺ in soil can inhibit the removal of DEP by Fe(VI), while SO₄²⁻ has an slightly promotion effect. Six oxidation intermediates were detected in the reaction process of DEP, product analysis revealed that the transformation of DEP was mainly through two pathways, including hydrolysis and hydroxylation reactions, which were probably mediated by oxygen atom transfer process of Fe(VI). Based on the frontier electron density theory calculation, two ester groups of DEP were prone to be attacked by Fe(VI), and the hydroxyl addition tended to occur at the para-position of one of the ester groups on the benzene ring. This study provides a novel approach for phthalate esters removal from soil using Fe(VI) oxidation and shows new insights into the oxidation mechanisms.

In this paper, the acute toxicity of monobutyl phthalate (MBP), the main hydrolysis product of dibutyl phthalate, on adult zebrafish liver antioxidant system was studied. Compared the toxicity effect of MBP and DBP by histopathology and apoptosis experiments, we speculated that the toxic effects of DBP on animals may be caused by its metabolite MBP. The results indicated that the antioxidant Nrf2-Keap1 pathway was insufficient to resist MBP-induced hepatotoxicity and led to an imbalance of membrane ion homeostasis and liver damage. Decreased cell viability, significant tissue lesions and early hepatocyte apoptosis were observed in the zebrafish liver in MBP exposure at high concentration (10 mg/L). The activities of antioxidant enzymes and ATPases in zebrafish liver were inhibited with increased malondialdehyde (MDA) content and alanine aminotransferase (ALT) and aspartate aminotransferase (AST) activities. Integrated biomarker response (IBR) calculation results indicated that MBP mainly inhibited catalase (CAT) activity. Simultaneously, the expression of antioxidant-related genes (SOD, CAT, GPx, Nrf2, HO-1) was down-regulated, while apoptosis-related genes (p53, bax, cas3) were significantly up-regulated.

Macro (BC), colloidal (CBC) and nanobiochar (NBC) were examined for the particle size effect for adsorptive removal of oxytetracycline (OTC) and co-occurring nutrients, which are present in synthetic hydrolyzed human urine. The surface morphologies and functionality of biochars were characterized using Scanning Electron Microscopy (SEM), Brunauer-Emmett-Teller (BET) specific surface area and Fourier Transform Infra-Red (FTIR) Spectroscopy. Experiments for the removal of OTC were performed at the natural pH (pH 9.0) of hydrolyzed human urine using solid-solutions of 3 types of chars (1 g/L) with a contact time of 5 h, at initial OTC concentration of 50 mg/L where isotherm experiments were investigated with OTC concentrations from 25 to 1000 mg/L. The highest maximum adsorption capacity of 136.7 mg/g was reported for CBC, while BC reported slightly low value (129.34 mg/g). Interestingly, NBC demonstrated a two-step adsorption process with two adsorption capacities (16.9 and 113.2 mg/g). Colloidal biochar depicted the highest adsorption for NH₄⁺, PO₄³⁻, and SO₄²⁻ nutrients. All 3 types of chars showed strong retention with a poor desorption (6% in average) of OTC in synthetic hydrolyzed urine medium. CBC and NBC demonstrated both physisorption and chemisorption, whereas the OTC removal by BC was solely via physisorption. Nevertheless, CBC biochar demonstrated the best performance in adsorptive removal of OTC and nutrients in hydrolyzed human urine and its capability towards wastewater treatment. As the removal of nutrients were low, the treated urine can possibly be used as a safe fertilizer.

To investigate the removal characteristics of ammonium-nitrogen (NH₄⁺-N), nitrite-nitrogen (NO₂⁻-N), nitrate-nitrogen (NO₃⁻-N), and total nitrogen from groundwater by a degradable composite active medium, kinetics, thermodynamics, and equilibrium adsorption, experiments were performed using scoria and degrading bacteria immobilized on scoria. Removal of NH₄⁺-N, NO₂⁻-N, and NO₃⁻-N was conducted in adsorption experiments using different times, initial concentrations, pH values, and groundwater chemical compositions (Ca²⁺, Mg²⁺, HCO₃⁻, CO₃²⁻, Fe²⁺, Mn²⁺, and SO₄²⁻). The results showed that the removal of nitrogen by the composite active medium was obviously better than that of scoria alone. The removal rates of NH₄⁺-N (C₀ = 5 mg/L), NO₂⁻-N (C₀ = 5 mg/L), and NO₃⁻-N (C₀ = 100 mg/L) by the composite active medium within 1 h were 96.05%, 82.40%, and 83.16%, respectively. The adsorption kinetics were well fitted to a pseudo-second order model, whereas the equilibrium adsorption agreed with the Freundlich model. With changes in the pH, variation in the removal could be attributed to the combined effect of hydrolysis and competitive ion adsorption, and the optimum pH was 7. Different concentration conditions, hardness, alkalinity, anions, and cations showed different promoting and inhibiting effects on the removal of nitrogen. A careful examination of ionic concentrations in adsorption batch experiments suggested that the sorption behavior of nitrogen onto the immobilized medium was mainly controlled by ion exchange. The degrading bacteria on the scoria surface were eluted and analyzed by metagenomic sequencing. There were significant differences in the number of operational taxons, relative abundances, and community diversity among degrading bacteria after adsorption of the three forms of nitrogen. The relative abundance of degrading bacteria was highest after NO₃⁻-N removal, and the diversity was highest after NO₂⁻-N removal. Pseudomonas and Serratia were the dominant genera that could efficiently remove NH₄⁺-N and NO₂⁻-N.

The biodegradation of polychlorinated-p-dioxins and dibenzofurans (PCDD/Fs) has been recently demonstrated in a single reactor under hypoxic conditions. Maintaining hypoxic conditions through periodic aerations results in a marked fluctuation of reduction–oxidation (redox) potential. To further assess the effects of redox fluctuations, we operated two fed-batch continuously stirred tank reactors (CSTRs) with sophisticated redox controls at different anoxic/oxic fluctuations to reduce PCDD/Fs in contaminated soil. The results of long-term reactor operation showed that the CSTR with redox fluctuations at a narrow range (−63 ± 68 mV) (CSTR_A) revealed a higher substrate hydrolysis level and PCDD/F degradation rate than did the CSTR with a redox potential that fluctuated at a broad range (−13 ± 118 mV) (CSTR_B). In accordance with analyses of bacterial 16S rRNA genes, the designated hypoxic conditions with added compost supported survival of bacterial populations at a density of approximately 10⁹ copies/g slurry. The evolved core microbiome was dominated by anoxic/oxic fluctuation-adapted Bacteroidetes, Alphaproteobacteria, and Actinobacteria, with higher species diversity and functionality, including hydrolysis and degradation of dioxin-like compounds in CSTR_A than in CSTR_B. Taken together, the overall results of this study expand the understanding of redox fluctuations in association with the degradation of recalcitrant substrates in soil and the corresponding microbiome.

The role of sediment–bound organic phosphorus (Pₒ) as an additional nutrient source is a component of internal P budgets in lake system that is usually neglected. Here we examined the relative importance of sediment Pₒ to internal P load and the role of bioavailable Pₒ in algal growth in Lake Erhai, China. Lake Erhai sediment extractable Pₒ accounted for 11–43% (27% average) of extractable total P, and bioavailable Pₒ accounted for 21–66% (40%) of Pₒ. The massive storage of bioavailable Pₒ represents an important form of available P, essential to internal loads. The bioavailable Pₒ includes mainnly labile monoester P and diester P was identified in the sequential extractions by H₂O, NaHCO₃, NaOH, and HCl. 40% of H₂O−Pₒ, 39% of NaHCO₃−Pₒ, 43% of NaOH−Pₒ, and 56% of HCl−Pₒ can be hydrolyzed to labile monoester and diester P, suggesting that the bioavailability of Pₒ fractions was in decreasing order as follows: HCl−Pₒ > NaOH−Pₒ > H₂O−Pₒ > NaHCO₃−Pₒ. It is implied that traditional sequential fractionation of Pₒ might overestimate the availability of labile Pₒ in sediments. Furthermore, analysis of the environmental processes of bioavailable Pₒ showed that the stabler structure of dissloved organic matter (DOM) alleviated the degradation and release of diester P, abundant alkaline phosphatase due to higher algal biomass promoted the degradation of diester P. The stability of DOM structure and the degradation of diester P might responsible for the spatial differences of labile monoester P. The biogeochemical cycle of bioavailable Pₒ replenishs available P pools in overlying water and further facilitate algal growth during the algal blooms. Therefore, to control the algal blooms in Lake Erhai, an effective action is urgently required to reduce the accumulation of Pₒ in sediments and interrupt the supply cycle of bioavailable Pₒ to algal growth.