Acceleration of Fe³⁺/Fe²⁺ cycle and simultaneous reduction of particle size with enhanced stability is extremely important for iron-based heterogeneous Fenton catalysts. In this work, Fe⁰-Fe₂O₃ composite nanoparticles embedded ordered mesoporous carbon hybrid materials (Fe⁰-Fe₂O₃/OMC) were rationally designed as efficient heterogeneous Fenton catalysts. Because of the confinement and reduction of OMC, highly dispersed Fe⁰-Fe₂O₃ active species with diameter of ∼8 nm were generated by an optimized carbothermic reduction process. In addition, Fe⁰-Fe₂O₃/OMC possesses ordered mesoporous structure with uniform mesopore, high surface area and pore volume. For comparison, two other catalysts, including solely Fe⁰ nanoparticles supported on ordered mesoporous carbon (Fe⁰/OMC) and solely Fe₂O₃ nanoparticles supported on ordered mesoporous carbon (Fe₂O₃/OMC) were also prepared. The Fenton catalytic performance of synthesized catalysts was evaluated by using H₂O₂ as oxidizing agent to degrade Acid Orange II (AOII). The results show that almost 98.1% of 100 mg L⁻¹ AOII was removed by Fe⁰-Fe₂O₃/OMC in condition of neutral pH and nearly room temperature, which is much higher than those of compared catalysts. The enhanced catalytic activity of Fe⁰-Fe₂O₃/OMC for AOII removal is due to the efficient electron transfer between the Fe⁰ and iron oxide and the accelerated Fe³⁺/Fe²⁺ cycle. The stability and reusability of the catalyst was also investigated, which showed a good performance even after five consecutive runs. The as-synthesized catalyst is proved to be an attractive candidate in heterogeneous Fenton chemistry and practical application.

Stability of silver sulfide nanoparticle (Ag₂S-NP) in the environment has recently drawn considerable attention since it is associated with environmental risk. Although the overestimated stability of Ag₂S-NP in aqueous solution has already been recognized, studies on transformation of Ag₂S-NP in environmental water are still very scarce. Here we reported that Ag₂S-NP could undergo dissolution by manganese(IV) oxide (MnO₂), an important naturally occurring oxidant in the environment, even in environmental water, although the dissolved silver would probably be adsorbed onto the particles (>0.45 μm) in environmental water, mitigating the measurable levels of dissolved silver. The extent and rate of Ag₂S-NP dissolution rose with the increasing concentration of MnO₂. In addition, environmental factors including natural organic matter, inorganic salts and organic acids could accelerate the Ag₂S-NP dissolution by MnO₂, wherein an increase in dissolution extent was also observed. We further documented that Ag₂S-NP dissolution by MnO₂ was highly dependent on O₂ and it was an oxidative dissolution, with the production of SO₄²⁻. Finally, dissolution of Ag₂S-NP by MnO₂ affected zebra fish (Danio rerio) embryo viability, showing significant reduction in embryo survival and hatching rates, compared to embryos exposed to Ag₂S-NP, MnO₂ or dissolved manganese alone. These findings would further shed light on the stability of Ag₂S-NP in the natural environment - essential for comprehensive nano risk assessment.

Inhibition of reductive transformation of arsenic (As) in flooded paddy soils is of fundamental importance for mitigating As transfer into food chain. Anaerobic arsenite (As(III)) oxidizers maintain As in less mobile fraction under nitrate-reducing conditions. In this study, we explored the dynamic profile of As speciation in porewater and As distribution among the pools of differential bioavailability in soil solid phase with and without nitrate treatment. In parallel, the abundance and diversity of As(III) oxidase gene (aioA) in flooded paddy soil with nitrate amendment was examined by quantitative PCR and aioA gene clone library. Furthermore, the impact of nitrate on As accumulation and speciation in rice seedlings was unraveled. With nitrate addition (25 mmol NO₃⁻ kg⁻¹ soil), porewater As(III) was maintained at a consistently negligible concentration in the flooded paddy soil and the reductive dissolution of As-bearing Fe oxides/hydroxides was significantly restrained. Specifically, nitrate amendment kept 81% of total soil As in the nonlabile fraction with arsenate (As(V)) dominating after 30 days of flooding, compared to only 61% in the unamended control. Nitrate treatment induced 4-fold higher abundance of aioA gene, which belonged to domains of bacteria and archaea under the classes α-Proteobacteria (6%), ß-Proteobacteria (90%), ɣ-Proteobacteria (2%), and Thermoprotei (2%). By nitrate addition, As accumulation in rice seedlings was decreased by 85% with simultaneously elevated As(V) ratio in rice plant relative to control after 22 days of growth under flooded conditions. These results highlight that nitrate application can serve an efficient method to inhibit reductive dissolution of As in flooded paddy soils, and hence diminish As uptake by rice under anaerobic growing conditions.

The use of dynamic membranes as a low-cost alternative for conventional membrane for the treatment of landfill leachate (LFL) was investigated in this study. For this purpose a lab-scale, submerged pre-anoxic and post-aerobic bioreactor configuration was used with nylon mesh as dynamic membrane support. The study was conducted at ambient temperature and LFL was fed to the bioreactor in gradually increasing concentration mixed with tap water (from 20% to 100%). The results of this study demonstrated that lower mesh pore size of 52 μm achieved better results in terms of solid-liquid separation performance (turbidity <10 NTU) of the formed dynamic membrane layer as compared to 200 and 85 μm meshes while treating LFL. Consistently high NH₄⁺-N conversion efficiency of more than 98% was achieved under all nitrogen loading conditions, showing effectiveness of the formed dynamic membrane in retaining slow growing nitrifying species. Total nitrogen removal reached more than 90% however, the denitrification activity showed a fluctuating profile and found to be inhibited by elevated concentrations of free nitrous acid and NO₂⁻-N at low pH values inside the anoxic bioreactor. A detailed metagenomic analysis allowed a taxonomic investigation over time and revealed the potential biochemical pathways involved in NH₄⁺-N conversion. This study led to the identification of a dynamic system in which nitrite concentration is determined by the contribution of NH₄⁺ oxidizers (Nitrosomonas), and by a competition between nitrite oxidizers (Nitrospira and Nitrobacter) and reducers (Thauera).

Thirteen secondary organic aerosol (SOA) tracers of isoprene (SOAI), monoterpenes (SOAM), sesquiterpenes (SOAS) and aromatics (SOAA) in fine particulate matter (PM2.5) were measured at a Pearl River Delta (PRD) regional site for one year. The characteristics including their seasonal cycles and the factors influencing their formation in this region were studied. The seasonal patterns of SOAI, SOAM and SOAS tracers were characterized over three enhancement periods in summer (I), autumn (II) and winter (III), while the elevations of SOAA tracer (i.e., 2,3-dihydroxy-4-oxopentanoic acid, DHOPA) were observed in Periods II and III. We found that SOA formed from different biogenic precursors could be driven by several factors during a one-year seasonal cycle. Isoprene emission controlled SOAI formation throughout the year, while monoterpene and sesquiterpene emissions facilitated SOAM and SOAS formation in summer rather than in other seasons. The influence of atmospheric oxidants (Ox) was found to be an important factor of the formation of SOAM tracers during the enhancement periods in autumn and winter. The formation of SOAS tracer was influenced by the precursor emissions in summer, atmospheric oxidation in autumn and probably also by biomass burning in both summer and winter. In this study, we could not see the strong contribution of biomass burning to DHOPA as suggested by previous studies in this region. Instead, good correlations between observed DHOPA and Ox as well as [NO2][O3] suggest the involvement of both ozone (O3) and nitrogen dioxide (NO2) in the formation of DHOPA. The results showed that regional air pollution may not only increase the emissions of aromatic precursors but also can greatly promote the formation processes.

Sediments nearby harbors are dredged regularly, and the sediments require the stringent treatment to meet the regulations on reuse and mitigate the environmental burdens from toxic pollutants. In this study, FeCl₃ was chosen as an extraction agent to treat marine sediment co-contaminated with Cu, Zn, and total petroleum hydrocarbons (TPH). In chemical extraction process, the extraction efficiency of Cu and Zn by FeCl₃ was compared with the conventional one using inorganic acids (H₂SO₄ and HCl). Despite the satisfactory level for extraction of Cu (78.8%) and Zn (73.3%) by HCl (0.5 M) through proton-enhanced dissolution, one critical demerit, particularly acidified sediment, led to the unwanted loss of Al, Fe, and Mg by dissolution. Moreover, the vast amount of HCl required the huge amounts of neutralizing agents for the post-treatment of the sediment sample via the washing process. Despite a low concentration, extraction of Cu (70.1%) and Zn (69.4%) was done by using FeCl₃ (0.05 M) through proton-enhanced dissolution, ferric-organic matter complexation, and oxidative dissolution of sulfide minerals. Ferric iron (Fe³⁺) was reduced to ferrous iron (Fe²⁺) with sulfide (S²⁻) oxidation during FeCl₃ extraction. In consecutive chemical oxidations using hydrogen peroxide (H₂O₂) and persulfate (S₂O₈²⁻), the resultant ferrous iron was used to activate the oxidants to effectively degrade TPH. S₂O₈²⁻ using FeCl₃ solution (molar ratio of ferrous to S₂O₈²⁻ is 19.8–198.3) removed 42.6% of TPH, which was higher than that by H₂O₂ (molar ratio of ferrous to H₂O₂ is 1.2–6.1). All experimental findings suggest that ferric is effectively accommodated to an acid washing step for co-contaminated marine sediments, which leads to enhanced extraction, cost-effectiveness, and less environmental burden.

National and international regulations require that ships' ballast water is treated to minimize the risk of introducing potentially invasive species. A common approach employed by commercial ballast water management systems is chlorination. This study presents the algal toxicity findings for three chlorination-based BWMS and their implications to environmental safety of port waters receiving treated ballast water from ships. Discharged treated ballast water from all three BWMS was toxic to algae with IC25s (25% growth inhibition) ranging from 9.9% to 17.9%, despite having total residual oxidant concentrations below 0.02 mg/l, based on Whole Effluent Toxicity assays. When held at 4 °C, some of the ballast water samples continued to exhibit toxic effects with no observed effect concentrations as low as 18% after a 134 day holding time. Thirteen individual disinfection by-products were measured above the detected limit at the time of discharge. No correlation between DBPs and algal toxicity was observed.

In this study, the performance of oxidation with actived persulfate (PS) by graphene oxide-TiO₂ nanosheet (GO-TiO₂) was investigated for diclofenac (DCF) removal, an anti-inflammatory analgesic being widely used in human health care and veterinary treatment. GO-TiO₂ containing oxygen functional groups is employed as an activator for the activation of PS used as the oxidizing agent. Modeling and optimization of the process were performed by central composite design (CCD) as a response surface methodology (RSM). The effects of various factors, including PS concentration, GO-TiO₂ amount, initial pH of DCF solution, and reaction time on DCF oxidation, were evaluated. When the estimated values of the full quadratic model obtained with CCD were compared with the actual experimental results, a strong agreement was obtained with an R² value of 0.9553. Besides, the model consistency was verified by analysis of variance (ANOVA) with a value of 20.17 of F value and P value of less than 0.05. After the optimization run, maximum DCF removal of 93.06% occurred with contact time of 14 min, pH of 5.54, PS concentration of 10 g/L, and 0.1 g of GO-TiO₂ as optimal variable values.

It is well-established that aquatic wildlife is exposed to natural and synthetic endocrine disrupting compounds which are able to interfere with the hormonal system. Although advanced oxidation processes (AOPs) have shown to be effective, their application is limited by a relatively high operational cost. In order to reduce the cost of energy consumed in the AOPs, widely available solar energy instead of UV light may be applied either as photocatalytic oxidation or as photosensitized oxidation. The main goal of the present study was to investigate the sunlight photodegradation of paraben mixture. Two processes, namely the photocatalytic oxidation with modified TiO₂ nanoparticles and photosensitized oxidation with photosensitive chitosan beads, were applied. The oxidants were identified as singlet oxygen and hydroxyl radicals for photosensitized and photocatalytic oxidation, respectively. The toxicity, as well as ability to water disinfection of both processes under natural sunlight, has been investigated. Application of sunlight for the processes led to degradation of parabens. The efficiency of both processes was comparable. Despite the fact that singlet oxygen is weaker oxidant than hydroxyl radicals, the photosensitized oxidation seems to be more promising for wastewater purification, due to the possibility of chitosan bead reuse and more effective water disinfection. Graphical Abstract ᅟ

Accurate estimation of oxidant consumption during in situ chemical oxidation (ISCO) is the key to determining the treatment effectiveness in contaminated sites. We established the estimation model of soil oxidant demand (SOD) and simulation equations of potassium permanganate (KMnO₄) dynamic consumption based on the reaction equation of KMnO₄ with reductive minerals and the estimation model of SOD. Model validation, model application, and simulation assessment had been accomplished. Results indicated that the simulations are in good agreement with measured data. The confidence level of the SOD estimation model of KMnO₄ was over 80%, with sensitivity in decreasing order as follows: organic matter content > initial KMnO₄ concentration > reductive minerals (RMs). Particularly, the organic matter played a dominate role in the SOD model estimation. The coefficient of determination (R²) of the SOD dynamic consumption simulation equation was above 0.9. Among the various types of soils, the overall trend of SOD value and reaction period decreased as follows: clay > loam > sand. However, the consumption rate of KMnO₄ decreased in the order of clay > sand > loam. In addition, SOD value, reaction period, and reaction rate all increased as the initial concentration of KMnO₄ went up. This work can provide a methodology and reference for selecting and estimating of the optimal oxidant doses and reaction period during field application.