The role of a single water molecule on the atmospheric reaction of HONO + ClO is systematically investigated employing quantum chemical calculation combined with harmonic transition state theory. Two reaction pathways, cis-HONO + ClO and trans-HONO + ClO, are identified for the naked reaction, which depends on the configurations of HONO. When adding a single water molecule to this reaction, the rate constants of cis-HONO + ClO and trans-HONO + ClO pathways are 7.97 × 10⁻²¹ and 2.29 × 10⁻¹⁷ cm³ molecule⁻¹ s⁻¹, respectively, larger than the corresponding naked reaction. To further understand the role of water on the HONO + ClO reaction, it is necessary to calculate the effective rate constant by considering the concentration of water. It shows that the effective rate constants of water-assisted cis-HONO + ClO pathway are much smaller than those of the naked reaction, whereas the presence of water accelerates the trans-HONO + ClO at room temperature. This study demonstrates that water has a positive role in the pathway of trans-HONO + ClO by modifying the stabilities of reactant complexes and transition states through the hydrogen bond formation, which contributes to the sink of atmospheric HONO. In addition, the kinetic branching ratio indicates that the favorable reaction is the trans-HONO + ClO instead of the cis-HONO + ClO pathway, in contrast to the naked reaction. These results reveal the importance of water in the evaluation of the fate of active species in the atmosphere. Graphical Abstract

The application of biosorption operation has gained attention in the removal and retrieval of toxic metal ions from water bodies. Wastewater from industrial activity generally presents great complexity due to the coadsorption of cations to the inactive biomass binding sites. In this work, the competitive biosorption of Cu(II) and Ag(I) ions was studied in batch systems. A kinetic study applying a non-acidified and acidified waste of Sargassum filipendula in equimolar and non-equimolar metal samples was carried out and the acidified biosorbent was selected due to higher removal rates and selectivity of silver ions. The assays were performed with 2 g L⁻¹ of biosorbent concentration at 25 °C for 12 h and pH was controlled at around 5.0. Copper presented higher affinity for the biosorbent and a fast biosorption kinetic profile, while silver equilibrium times exhibited dependence on the copper concentration. External diffusion is the rate-limiting step in Cu(II) ion removal and it might also limit the kinetic rates of Ag(I) ions with intraparticle diffusion, depending on the initial concentration of metal cations. The ion-exchange mechanism is evidenced and complexation and electrostatic attraction mechanisms might be suggested, explained by simultaneous chemisorption and physisorption processes during the operation. Calcium and sodium were released in considerable amounts by the ion-exchange mechanism. Characterization analyses confirmed the role of several functional groups in the competitive biosorption accompanied by a homogenous covering of both metal ions on the surface of the particles. Particle porosity analyses revealed that the material is macroporous and an appreciable amount of macropores are filled with metal cations after biosorption.

In this study, the catalytic activity and kinetic characteristics of the aromatic hydrocarbon dioxygenase system and the possibility of substituting its ferredoxin and ferredoxin reductase components were evaluated. The genes encoding toluene dioxygenase and toluene dihydrodiol dehydrogenase were cloned from Pseudomonas putida F1, and the corresponding enzymes were overexpressed and purified to homogeneity. Oxidative hydroxylation of toluene to cis-toluene dihydrodiol was catalyzed by toluene dioxygenase, and its subsequent dehydrogenation to 3-methylcatechol was catalyzed by toluene dihydrodiol dehydrogenase. The specific activity of the dioxygenase was 2.82 U/mg-protein, which is highly remarkable compared with the values obtained in previous researches conducted with crude extracts or insoluble forms of enzymes. Kinetic parameters, as characterized by the Hill equation, were vₘₐₓ = 497.2 μM/min, KM = 542.4 μM, and nH = 2.2, suggesting that toluene dioxygenase has at least three cooperative binding sites for toluene. In addition, the use of alternative ferredoxins and reductases was examined. Ferredoxin cloned from CYP153 could transfer electrons to the iron sulfur protein component of toluene dioxygenase. The ferredoxin could be reduced by ferredoxin, rubredoxin, and putidaredoxin reductases of CYP153, alkane-1 monooxygenase, and camphor 5-monooxygenase, respectively. The results provide useful information regarding the effective enzymatic biotreatment of hazardous aromatic hydrocarbon contaminants.

High retention membrane bioreactors (HR-MBR) combine a high retention membrane separation process such as membrane distillation, forward osmosis, or nanofiltration with a conventional activated sludge (CAS) process. Depending on the physicochemical properties of the trace organic contaminants (TrOCs) as well as the selected high retention membrane process, HR-MBR can achieve effective removal (80–99%) of a broad spectrum of TrOCs. An in-depth assessment of the available literature on HR-MBR performance suggests that compared to CAS and conventional MBRs (using micro- or ultra-filtration membrane), aqueous phase removal of TrOCs in HR-MBR is significantly better. Conceptually, longer retention time may significantly improve TrOC biodegradation, but there are insufficient data in the literature to evaluate the extent of TrOC biodegradation improvement by HR-MBR. The accumulation of hardly biodegradable TrOCs within the bioreactor of an HR-MBR system may complicate further treatment and beneficial reuse of sludge. In addition to TrOCs, accumulation of salts gradually increases the salinity in bioreactor and can adversely affect microbial activities. Strategies to mitigate these limitations are discussed. A qualitative framework is proposed to predict the contribution of the different key mechanisms of TrOC removal (i.e., membrane retention, biodegradation, and sorption) in HR-MBR.

In this work, two recyclable phosphotungstic acid salts/reduced graphene oxides were successfully prepared. The prepared samples were characterized by X-ray diffraction analysis (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), infrared spectroscopy (IR), X-ray photoelectron spectroscopy (XPS), thermo-gravimetric analysis (TGA), Raman spectroscopy, and photoluminescence spectroscopy (PL). The structure and catalytic performance of two composites were comparatively investigated, and the reduced graphene oxide mass ratios in K₃[PW₁₂O₄₀]/reduced graphene oxide (denoted as KPW-RGO) and (NH₄)₃[PW₁₂O₄₀]/reduced graphene oxide (denoted as NH₄PW-RGO) were optimized and their roles in them were explored. The results indicate that the Keggin structures of KPW and NH₄PW are still kept after being anchored on the RGO surface, but their morphologies change a lot in composites. The photocatalytic activities of KPW-3RGO (0.01989 min⁻¹) are 5.42 times than that of KPW (0.00367 min⁻¹), and NH₄PW-1RGO (0.0184 min⁻¹) is 2.26 times than that of NH₄PW (0.00814 min⁻¹). The enhanced photocatalytic activity is mainly ascribed to photo-induced interfacial charge transfer on the heterojunction between RGO and NH₄PW or KPW and strong adsorption ability of RGO towards MO. Moreover, NH₄PW-1RGO and KPW-3RGO had much better photocatalytic activity, good recyclable ability, and stability compared to HPW-RGO, which cannot be recycled.

To insight the urban volatile organic compound (VOC) profiles and its contribution to ozone, four-time per day (8:00–9:00, 15:00–16:00, 19:00–20:00, and 23:00–24:00) off-line VOC samples were collected from 16th July to 28th July 2018 for a summer investigation campaign over Xi’an, China. The diurnal variation was significant that the lowest TVOC concentrations were observed in the midnight period (28.4 ± 25.6 ppbv) while the highest was shown in the morning (49.6 ± 40.1 ppbv). The differences of total non-methane VOCs (TVOCs) between weekdays and weekend were also significant that the weekend showed significantly high VOC levels than weekdays (p < 0.05) but did not lead to significant ambient O₃ increase (p > 0.05). Isopentane, a general marker for vehicle exhaust, showed descending concentrations from morning to midnight and good correlation with vehicle numbers on road, indicating a potential source to the VOCs at this site. The results from PMF proved that vehicular exhaust was the largest source to the VOCs in this study (64.4%). VOC categories showed a reverse sequence in abundance of concentrations and OFP contributions that alkenes showed the highest OFPs although with the lowest abundance in TOVCs due to their high reactivity in photochemical reactions. High OFPs from ethylene and isopentane indicated that vehicular emissions could be the largest potential OFP source in this site. OFPs from isoprene (from 1.85 to 13.4 ppbv) indicated that biogenic VOCs should not be negligible in urban Xi’an city when controlling O₃ pollutants. Comparison of two OFP methods was conducted and MIR method was proved to be more reasonable and scientific in summer Xi’an. Therefore, vehicular emission, the largest contributor to ambient VOCs and also OFPs, as well as biological source should be priority controlled in guiding VOC emissions and reducing O₃ control policies.

In this study, nine OPEs were measured in 60 street dust samples collected from the central province of Henan, China. The total concentrations of OPEs (∑₉OPEs) in street dust range from 2.77 to 505 μg/kg (median 59.3 μg/kg). Chlorinated OPEs are dominant in street dust with median concentration of 33.5 μg/kg, followed by aryl OPEs (median 9.05 μg/kg), and alkyl OPEs (median 6.19 μg/kg). No significant correlations are found between ∑₉OPEs and parameters, such as population (p = 0.931), population density (p = 0.602), car ownership (p = 0.618), and gross domestic product (p = 0.863). Principal component analysis (PCA) result reveals that road traffic could be a major source of OPEs in street dust because of their extensive use in various vehicles. The total average (median) and high-level exposure (95th percentile) of OPEs are 1.01 × 10⁻², 7.17 × 10⁻² ng/kg bw/d for adults and 6.03 × 10⁻², 0.43 ng/kg bw/d for children, respectively. Hazard quotient (HQ) values are 5–6 orders of magnitude lower than the acceptable risk level (HQ < 0.1), indicating there is still a low risk to local residents at current levels.

Through an analysis of data gathered from Chinese firms surveyed by the Carbon Disclosure Project (CDP), this paper studies the motivations of Chinese firms to respond to the CDP. The results indicate that (1) Chinese firms are more inclined to respond to the CDP survey for the sense-making motivation; (2) Chinese firms are less inclined to respond to the CDP survey due to the existence of proprietary costs for information disclosure; (3) self-interested political motivation is a negative motivation for Chinese firms to respond to the CDP survey; state-owned enterprises (SOEs) are less inclined to respond to the CDP survey than are non-SOEs; and (4) Chinese firms did not consider a financing motivation when deciding whether to respond to the CDP survey. However, the results of our further research show that if firms actively respond to the CDP survey, their financing constraints can be significantly reduced. This paper studies the four motivations for Chinese firms to respond to the CDP survey, contributing to the research of carbon emission disclosure. This paper highlights the importance of corporate carbon awareness for carbon emission disclosure, builds an understanding of the internal driving forces of response to the CDP survey among Chinese firms, and thus promotes the increase of Chinese corporate disclosure of carbon emission.

Fishmeal is a fundamental ingredient of feedstuffs and is used globally in aquaculture. However, there are few data on the antibiotic resistance genes (ARGs) and human pathogenic bacteria in fishmeal and little understanding of the potential risks of fishmeal application in mariculture systems. Here, we investigated the high-throughput profiles of ARGs and human potential pathogenic bacteria (HPPB) in representative fishmeals (n = 5) and the potential impact of fishmeal on mariculture sediments. ARGs were quantified with microbial DNA quantitative PCR arrays and HPPB were analyzed with Illumina sequencing of 16S rRNA genes. The impact of the fishmeal on the aquaculture sediments was assessed in a microcosm study. Twenty-four unique ARGs (3–14 per sample) and 25 HPPB species were detected in the fishmeal samples. The most prevalent ARGs were fluoroquinolone resistance genes. The overall abundance of HPPB was 5.0–25.5%, and the HPPB species were dominated by Vibrio parahaemolyticus, Clostridium novyi, and Escherichia coli. In the mariculture microcosm sediment, fishmeal significantly increased the normalized abundance of the class I integrase gene (25.4-fold), which plays an important role in the dissemination of ARGs. Dosing with fishmeal also contributed to increases in a resident sulfanilamide resistance gene (sulI gene) and the emergence of a macrolide resistance gene (ermB gene) in the sediment. These findings demonstrated that fishmeal itself is an underestimated reservoir and source of ARGs and HPPBs, and that the application of fishmeal facilitates the dissemination of ARGs in aquaculture sediments. Our results extend our knowledge of the ARGs and HPPB within fishmeal and may provide a feasible and effective approach to the detection of ARGs and HPPB in fishmeal during food safety inspection. Graphical abstract ᅟ

The photochemical role of Fe(III)-citrate complex is significant in natural waters due to its ubiquitous existence and excellent photoreactivity at near neutral pH. Although there are many reports on the photoinduced degradation of pollutants in the Fe(III)-citrate system, the optimum pH for its photoreactivity is yet not clearly understood. Here, for the first time, we demonstrated that the optimum pH was 5.5 for the photoproduction of •OH in the Fe(III)-citrate system via kinetics modeling based on the steady-state approximation. According to the experimental results, the •OH photoproduction increased with increasing pH until 5.5 and then decreased in Fe(III)-citrate solution, which agreed well with the prediction trend of kinetic modeling. The effect of the common ligand oxalate on the photoreactivity of Fe(III)-citrate system was also investigated. The addition of oxalate promoted the photoproduction of •OH in Fe(III)-citrate solutions, and the measured [•OH]ₛₛ increased with oxalate concentration under a fixed Fe(III)-to-citrate ratio. Little synergistic effect exists in Fe(III)-citrate-oxalate system at pH 4.0–5.5. In contrast, an appreciable synergistic effect was observed at near neutral pH (6.0–8.0). Higher oxalate-to-citrate ratio facilitated the synergistic effect. Furthermore, antifungal drug fluconazole could be removed efficiently in the Fe(III)-citrate-oxalate system. The photodegradation kinetics also verified the optimum pH of Fe(III)-citrate system and synergistic effect of oxalate. By LC-ESI-MS/MS analyses, the photoproducts of fluconazole in the Fe(III)-citrate-oxalate system were identified and the reaction mechanism involving hydroxylation substitution and subsequent cleavage of heterocyclic amine was proposed. These findings suggest that Fe(III)-citrate exhibits best photoreactivity at pH 5.5, and the coexistence of reactive ligands will enhance its photoreactivity at circumneutral pH, indicating potential application in wastewater treatment via addition of appropriate citrate and co-ligands.