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.

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.

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.

Adsorption and fractionation of Pt, Pd and Rh (defined here as platinum group elements, PGEs) onto the representative inorganic microparticles, including Fe2O3, MnO2, CaCO3, SiO2, Al2O3 and kaolinite in seawater were investigated. The effects of macromolecular organic compounds (MOCs) as the representatives of organic matter, including humic acids (HA), bovine serum albumin (BSA) and carrageenan, on the adsorption were also studied considering that organic matter is ubiquitous in seawater and indispensable to marine biogeochemical cycles. In the absence of MOCs, the representative mineral particles Fe2O3 and MnO2 had the strongest interaction with PGEs. The adsorption of PGEs onto the representative biogenic particles SiO2 and CaCO3 and lithogenic particles Al2O3 and kaolinite was similar or weaker than onto the mineral particles. MOCs inhibited the interaction between PGEs and the particles except for Pt and Pd onto the biogenic particles in artificial seawater. This impediment may be closely related to the interaction between particles, MOCs and elements. The partition coefficient (log Kd) of Pt was similar (∼4.0) in the presence of MOCs, indicating that the complexation between Pt and MOCs was less important than hydrolysis or adsorption onto the acid oxide particle surface. Rh tended to fractionate onto the mineral and lithogenic particles in the presence of HA and carrageenan, while Pd was more likely to fractionate onto the biogenic particles. However, BSA enhanced the fractionation tendency of Pd onto the mineral particles. The results indicate that the adsorption behavior of Pd onto inorganic particles was significantly affected by the composition or the type of MOCs. Hence, the interaction between PGEs and inorganic particles may be greatly affected by the macromolecular organic matter in the ocean.

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.

Secondary inorganic aerosols, including sulfate, nitrate, and ammonium contribute to a large extent to the severe haze pollution events in China. Understanding their formation mechanisms is critical for designing effective mitigation strategies to control haze pollution, especially as the role of nitrate seemed to become more important recently, especially in some megacities. In the present study, simultaneous observations were conducted in two megacities (Chengdu and Chongqing) in Sichuan Basin of southwest China, one of the regions suffering from severe aerosol pollution. One typical long-lasting pollution event in Chengdu and Chongqing was captured during wintertime from December 25, 2016 to January 5, 2017. The campaign-average of hourly concentrations of PM2.5, sulfate, and nitrate, measured by an Aerosol Analyzer (ZSF) were 101 ± 73.8 μg/m3, 15.9 ± 11.8 μg/m3, and 24.9 ± 20.6 μg/m3, respectively, in Chengdu, and were 87.7 ± 53.8 μg/m3, 19.7 ± 13.5 μg/m3, and 15.1 ± 10.1 μg/m3, respectively, in Chongqing. Nitrate contributed substantially to PM2.5 pollution when PM2.5 was lower than 150 μg/m3, largely due to the strong secondary transformation of NOX to nitrate during the occurrence of the pollution episode. Heterogeneous hydrolysis of N2O5 dominated nitrate formation during nighttime, while photochemical reactions and high-RH enhanced gas- to aqueous-phase dissolution of NH3 and HNO3 or cloud processes likely played important roles for nitrate formation during daytime. RH-dependent heterogeneous reactions contributed greatly to the formation of sulfate. NOX is confirmed to play an important role as an oxidant in accelerating the secondary transformation of SO2 to sulfate at high RH and low O3 levels under neutralization condition during heavy PM2.5 pollution episode. Results from this study identified the formation mechanism of nitrate, especially during the daytime, and addressed the importance of heterogeneous inorganic reactions in the formation of heavy aerosol pollution events.