A “Seawater-in-Sludge” approach for capacitive biochar production via the alkaline and alkaline earth metals activation

• Capacitive biochar was produced from sewage sludge. • Seawater was proved to be an alternative activation agent. • Minerals vaporization increased the surface area of biochar. • Molten salts acted as natural templates for the development of porous structure. Sewage sludge is a potential precursor for biochar production, but its effective utilization involves costly activation steps. To modify biochar properties while ensuring cost-effectiveness, we examined the feasibility of using seawater as an agent to activate biochar produced from sewage sludge. In our proof-of-concept study, seawater was proven to be an effective activation agent for biochar production, achieving a surface area of 480.3 m²/g with hierarchical porosity distribution. Benefited from our design, the catalytic effect of seawater increased not only the surface area but also the graphitization degree of biochar when comparing the pyrolysis of sewage sludge without seawater. This leads to seawater activated biochar electrodes with lower resistance, higher capacitance of 113.9 F/g comparing with control groups without seawater. Leveraging the global increase in the salinity of groundwater, especially in coastal areas, these findings provide an opportunity for recovering a valuable carbon resource from sludge.     

Synthesis of vinasse-dolomite nanocomposite biochar via a novel developed functionalization method to recover phosphate as a potential fertilizer substitute

• Nanocomposites were prepared by adding dolomite to vinasse at different ratio. • Textural and morphological features of adsorbents were studied in detail. • CCD based RSM was used for investigation of P ion removal by nanocomposite. • The q_m based on Langmuir model for modified vinasse biochar was 178.57 mg/g. • P loaded nanocomposite improved plant growth and could be utilized as P-fertilizer. The effectiveness of phosphate (P) removal from aqueous solutions was investigated by novel low-cost biochars synthesized from vinasse and functionalized with calcined dolomite. The vinasse-derived biochar, synthesized via pyrolysis at different temperatures, showed easy preparation and a large surface area. The novel vinasse biochar nanocomposites were prepared by adding dolomite to the vinasse biochars with different weight percentages (10, 20 and 30%). The characteristics of the prepared materials were identified for further understanding of the inherent adsorption mechanism between P ions and vinasse biochars. Vinasse-dolomite nanocomposite was very effective in the adsorption of P species from aqueous media. The effect of the operational factors on Vinasse-dolomite nanocomposite was explored by applying response surface methodology (RSM). According to RSM results, the optimum condition was achieved to be contact time 90 (min), 250 (mg/L) of P concentration and pH 7. Thermodynamic isotherm and kinetic studies were applied on experimental data to understand the adsorption behavior. The Vinasse-dolomite nanocomposite revealed preferential P species adsorption in the presence of co-existing anions. The P species could be recovered by 1.0 M HCl where the efficiency was not affected up to the fifth cycle. The P-loaded Vinasse-dolomite nanocomposite was successfully tested on a plant; it significantly improved its growth and proved its potency as a P-based fertilizer substitute.     

Adsorption characteristics of ciprofloxacin onto g-MoS2 coated biochar nanocomposites

• The g-MoS₂ coated composites (g-MoS₂-BC) were synthesized. • The coated g-MoS₂ greatly increased the adsorption ability of biochar. • The synergistic effect was observed for CIP adsorption on g-MoS₂-RC700. • The adsorption mechanisms of CIP on g-MoS₂-BC were proposed. The g-MoS₂ coated biochar (g-MoS₂-BC) composites were synthesized by coating original biochar with g-MoS₂ nanosheets at 300°C(BC300)/700°C (BC700). The adsorption properties of the g-MoS₂-BC composites for ciprofloxacin (CIP) were investigated with an aim to exploit its high efficiency toward soil amendment. The specific surface area and the pore structures of biochar coated g-MoS₂ nanosheets were significantly increased. The g-MoS₂-BC composites provided more π electrons, which was favorable in enhancing the π-π electron donor-acceptor (EDA) interactions between CIP and biochar. As a result, the g-MoS₂-BC composites showed faster adsorption rate and greater adsorption capacity for CIP than the original biochar. The coated g-MoS₂ nanosheets contributed more to CIP adsorption on the g-MoS₂-BC composites due to their greater CIP adsorption capacity than the original biochar. Moreover, the synergistic effect was observed for CIP adsorption on g-MoS₂-BC700, and suppression effect on g-MoS₂-BC300. In addition, the adsorption of CIP onto g-MoS₂-BC composites also exhibited strong dependence on the solution pH, since it can affect both the adsorbent surface charge and the speciation of contaminants. It was reasonably suggested that the mechanisms of CIP adsorption on g-MoS₂-BC composites involved pore-filling effects, π-π EDA interaction, electrostatic interaction, and ion exchange interaction. These results are useful for the modification of biochar in exploiting the novel amendment for contaminated soils.     

Redox reactions of iron and manganese oxides in complex systems

• Mechanisms of redox reactions of Fe- and Mn-oxides were discussed. • Oxidative reactions of Mn- and Fe-oxides in complex systems were reviewed. • Reductive reaction of Fe(II)/iron oxides in complex systems was examined. • Future research on examining the redox reactivity in complex systems was suggested. Conspectus Redox reactions of Fe- and Mn-oxides play important roles in the fate and transformation of many contaminants in natural environments. Due to experimental and analytical challenges associated with complex environments, there has been a limited understanding of the reaction kinetics and mechanisms in actual environmental systems, and most of the studies so far have only focused on simple model systems. To bridge the gap between simple model systems and complex environmental systems, it is necessary to increase the complexity of model systems and examine both the involved interaction mechanisms and how the interactions affected contaminant transformation. In this Account, we primarily focused on (1) the oxidative reactivity of Mn- and Fe-oxides and (2) the reductive reactivity of Fe(II)/iron oxides in complex model systems toward contaminant degradation. The effects of common metal ions such as Mn²⁺ , Ca²⁺, Ni²⁺, Cr³⁺ and Cu²⁺, ligands such as small anionic ligands and natural organic matter (NOM), and second metal oxides such as Al, Si and Ti oxides on the redox reactivity of the systems are briefly summarized.     

Sorption of aromatic organophosphate flame retardants on thermally and hydrothermally produced biochars

• TPhP showed faster and higher sorption on biochars than TPPO. • Pyrochars had higher sorption capacity for TPPO than hydrochar. • Hydrophobic interactions dominated TPhP sorption by biochars. • The π-π EDA and electrostatic interactions are involved in sorption. Aromatic organophosphate flame retardant (OPFR) pollutants and biochars are commonly present and continually released into soils due to their increasingly wide applications. In this study, for the first time, the sorption of OPFRs on biochars was investigated. Although triphenyl phosphate (TPhP) and triphenylphosphine oxide (TPPO) have similar molecular structures and sizes, TPhP exhibited much faster and higher sorption than TPPO due to its stronger hydrophobicity, suggesting the dominant role of hydrophobic interactions in TPhP sorption. The π-π electron donor–acceptor (EDA) interactions also contributed to the sorption process, as suggested by the negative correlation between the sorption capacity of the aromatic OPFRs and the aromatic index (H/C atomic ratios) of biochar. Density functional theory calculations further showed that one benzene ring of aromatic OPFRs has no electrons, which may interact with biochar via π-π EDA interactions. The electrostatic attraction between the protonated P = O in OPFRs and the negatively charged biochar was found to occur at pH below 7. This work provides insights into the sorption behaviors and mechanisms of aromatic OPFRs by biochars.     

Nanoscale zero-valent iron supported on biochar for the highly efficient removal of nitrobenzene

• Biochar supported nanoscale zero-valent iron composite (nZVI/BC) was synthesized. • nZVI/BC quickly and efficiently removed nitrobenzene (NB) in solution. • NB removal by nZVI/BC involves simultaneous adsorption and reduction mechanism. • nZVI/BC exhibited better catalytic activity, stability and durability than nZVI. The application of nanoscale zero-valent iron (nZVI) in the remediation of contaminated groundwater or wastewater is limited due to its lack of stability, easy aggregation and iron leaching. To address this issue, nZVI was distributed on oak sawdust-derived biochar (BC) to obtain the nZVI/BC composite for the highly efficient reduction of nitrobenzene (NB). nZVI, BC and nZVI/BC were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). For nZVI/BC, nZVI particles were uniformly dispersed on BC. nZVI/BC exhibited higher removal efficiency for NB than the simple summation of bare nZVI and BC. The removal mechanism was investigated through the analyses of UV-Visible spectra, mass balance and XPS. NB was quickly adsorbed on the surface of nZVI/BC, and then gradually reduced to aniline (AN), accompanied by the oxidation of nZVI to magnetite. The effects of several reaction parameters, e.g., NB concentration, reaction pH and nZVI/BC aging time, on the removal of NB were also studied. In addition to high reactivity, the loading of nZVI on biochar significantly alleviated Fe leaching and enhanced the durability of nZVI.     

Excitation-emission matrix (EEM) fluorescence spectroscopy for characterization of organic matter in membrane bioreactors: Principles,methods and applications

• Principles and methods for fluorescence EEM are systematically outlined. • Fluorophore peak/region/component and energy information can be extracted from EEM. • EEM can fingerprint the physical/chemical/biological properties of DOM in MBRs. • EEM is useful for tracking pollutant transformation and membrane retention/fouling. • Improvements are still needed to overcome limitations for further studies. The membrane bioreactor (MBR) technology is a rising star for wastewater treatment. The pollutant elimination and membrane fouling performances of MBRs are essentially related to the dissolved organic matter (DOM) in the system. Three-dimensional excitation-emission matrix (3D-EEM) fluorescence spectroscopy, a powerful tool for the rapid and sensitive characterization of DOM, has been extensively applied in MBR studies; however, only a limited portion of the EEM fingerprinting information was utilized. This paper revisits the principles and methods of fluorescence EEM, and reviews the recent progress in applying EEM to characterize DOM in MBR studies. We systematically introduced the information extracted from EEM by considering the fluorescence peak location/intensity, wavelength regional distribution, and spectral deconvolution (giving fluorescent component loadings/scores), and discussed how to use the information to interpret the chemical compositions, physiochemical properties, biological activities, membrane retention/fouling behaviors, and migration/transformation fates of DOM in MBR systems. In addition to conventional EEM indicators, novel fluorescent parameters are summarized for potential use, including quantum yield, Stokes shift, excited energy state, and fluorescence lifetime. The current limitations of EEM-based DOM characterization are also discussed, with possible measures proposed to improve applications in MBR monitoring.     

Insight into fluorescence properties of 14 selected toxic single-ring aromatic compounds in water: Experimental and DFT study

• The fluorescence peak location of 14 compounds interpreted at protein-like region. • The p-electron system inside aromatic ring contributes to the fluorophore region. • Functional group variation effects the emission spectra. • Decrease in quantum yield and increase in DE is due to atomic weight F>Cl>Br>I. • Theoretically results are in line with experimental ones. Various single-ring aromatic compounds in water sources are of great concern due to its hazardous impact on the environment and human health. The fluorescence excitation-emission matrix (EEMs) spectrophotometry is a useful method to identify organic pollutants in water. This study provides a detailed insight into the fluorescence properties of the 14 selected toxic single-ring aromatic compounds by experimental and theoretical analysis. The theoretical analysis were done with Time-Dependent Density Functional Theory (TD-DFT) and B3LYP/6-31G (d,p) basis set, whereas, Polarizable Continuum Model (PCM) was used to consider water as solvent. The selected compounds displayed their own specific excitation-emission (Ex/Em) wavelengths region, at Ex<280 nm and Em<340 nm, respectively. Whereas the theoretical Ex/Em was observed as, Ex at 240 nm–260 nm and Em at 255 nm–300 nm. Aniline as a strong aromatic base has longer Em (340 nm) than alkyl, carbonyl, and halogens substituted benzenes. The lone pair of electrons at amide substituent serves as a p-electron contributor into the aromatic ring, hence increasing the stability and transition energy, which results in longer emission and low quantum yield for the aniline. The fluorescence of halogenated benzenes illustrates an increase in the HOMO-LUMO energy gap and a decrease in quantum yield associated with atomic size (F>Cl>Br>I). In this study the theoretical results are in line with experimental ones. The understanding of fluorescence and photophysical properties are of great importance in the identification of these compounds in the water.     

Ammonia and phosphorus removal from agricultural runoff using cash crop waste-derived biochars

• Orange tree residuals biochar had a better ability to adsorb ammonia. • Modified tea tree residuals biochar had a stronger ability to remove phosphorus. • Partially-modified biochar could remove ammonia and phosphorus at the same time. • The real runoff experiment showed an ammonia nitrogen removal rate of about 80%. • The removal rate of total phosphorus in real runoff experiment was about 95%. Adsorption of biochars (BC) produced from cash crop residuals is an economical and practical technology for removing nutrients from agricultural runoff. In this study, BC made of orange tree trunks and tea tree twigs from the Laoguanhe Basin were produced and modified by aluminum chloride (Al-modified) and ferric sulfate solutions (Fe-modified) under various pyrolysis temperatures (200°C–600°C) and residence times (2–5 h). All produced and modified BC were further analyzed for their abilities to adsorb ammonia and phosphorus with initial concentrations of 10–40 mg/L and 4–12 mg/L, respectively. Fe-modified Tea Tree BC 2h/400°C showed the highest phosphorus adsorption capacity of 0.56 mg/g. Al-modified Orange Tree BC 3h/500°C showed the best performance for ammonia removal with an adsorption capacity of 1.72 mg/g. FTIR characterization showed that P = O bonds were formed after the adsorption of phosphorus by modified BC, N-H bonds were formed after ammonia adsorption. XPS analysis revealed that the key process of ammonia adsorption was the ion exchange between K⁺ and NH₄⁺. Phosphorus adsorption was related to oxidation and interaction between PO₄^3– and Fe³⁺. According to XRD results, ammonia was found in the form of potassium amide, while phosphorus was found in the form of iron hydrogen phosphates. The sorption isotherms showed that the Freundlich equation fits better for phosphorus adsorption, while the Langmuir equation fits better for ammonia adsorption. The simulated runoff infiltration experiment showed that 97.3% of ammonia was removed by Al-modified Orange tree BC 3h/500°C, and 92.9% of phosphorus was removed by Fe-modified Tea tree BC 2h/400°C.     

Phosphorus transformation under the influence of aluminum,organic carbon,and dissolved oxygen at the water-sediment interface: A simulative study

• The three simulation factors caused various changes in both water and sediment. • Responses to simulations differed with the reported natural lakes and wetlands. • Al has dominant effects on sediment P release control among the three factors. • Adding sediment Al can be effective and safe under the simulated conditions. • Polyphosphates were not generated, while added phytate was rather stable. The effects of sediment aluminum (Al), organic carbon (OC), and dissolved oxygen (DO) on phosphorus (P) transformation, at the water-sediment interface of a eutrophic constructed lake, were investigated via a series of simulative experiments. The above three factors had various influences on dissolved P concentration, water pH, water and surface sediment appearance, and P fractions. Additions of Al had the greatest effect on suppressing P release, and the water pH remained alkaline in the water-sediment system under various OC and DO conditions. No dissolution of the added Al was detected. ³¹P-NMR characterization suggested that OC addition did not promote biological P uptake to polyphosphates under oxic conditions. The simulation result on the added phytate indicated the absence of phytate in the original lake sediment. As compared to the reported natural lakes and wetland, the water-sediment system of the constructed lake responded differently to some simulative conditions. Since Al, OC, and DO can be controlled with engineering methods, the results of this study provide insights for the practical site restorations.     

Mechanism of dichloromethane disproportionation over mesoporous TiO2 under low temperature

• Mechanism of DCM disproportionation over mesoporous TiO₂ was studied. • DCM was completely eliminated at 350℃ under 1 vol.% humidity. • Anatase (001) was the key for disproportionation. • A competitive oxidation route co-existed with disproportionation. • Disproportionation was favored at low temperature. Mesoporous TiO₂ was synthesized via nonhydrolytic template-mediated sol-gel route. Catalytic degradation performance upon dichloromethane over as-prepared mesoporous TiO₂, pure anatase and rutile were investigated respectively. Disproportionation took place over as-made mesoporous TiO₂ and pure anatase under the presence of water. The mechanism of disproportionation was studied by in situ FTIR. The interaction between chloromethoxy species and bridge coordinated methylenes was the key step of disproportionation. Formate species and methoxy groups would be formed and further turned into carbon monoxide and methyl chloride. Anatase (001) played an important role for disproportionation in that water could be dissociated into surface hydroxyl groups on such structure. As a result, the consumed hydroxyl groups would be replenished. In addition, there was another competitive oxidation route governed by free hydroxyl radicals. In this route, chloromethoxy groups would be oxidized into formate species by hydroxyl radicals transfering from the surface of TiO₂. The latter route would be more favorable at higher temperature.     

Simultaneous removal of NOx and chlorobenzene on V2O5/TiO2 granular catalyst: Kinetic study and performance prediction

• A V₂O₅/TiO₂ granular catalyst for simultaneous removal of NO and chlorobenzene. • Catalyst synthesized by vanadyl acetylacetonate showed good activity and stability. • The kinetic model was established and the synergetic activity was predicted. • Both chlorobenzene oxidation and SCR of NO follow pseudo-first-order kinetics. • The work is of much value to design of multi-pollutants emission control system. The synergetic abatement of multi-pollutants is one of the development trends of flue gas pollution control technology, which is still in the initial stage and facing many challenges. We developed a V₂O₅/TiO₂ granular catalyst and established the kinetic model for the simultaneous removal of NO and chlorobenzene (i.e., an important precursor of dioxins). The granular catalyst synthesized using vanadyl acetylacetonate precursor showed good synergistic catalytic performance and stability. Although the SCR reaction of NO and the oxidation reaction of chlorobenzene mutually inhibited, the reaction order of each reaction was not considerably affected, and the pseudo-first-order reaction kinetics was still followed. The performance prediction of this work is of much value to the understanding and reasonable design of a catalytic system for multi-pollutants (i.e., NO and dioxins) emission control.     

Sustainable wood-based nanotechnologies for photocatalytic degradation of organic contaminants in aquatic environment

•Wood and its reassemblies are ideal substrates to develop novel photocatalysts. •Synthetic methods and mechanisms of wood-derived photocatalysts are summarized. •Advances in wood-derived photocatalysts for organic pollutant removal are summed up. •Metal doping, morphology control and semiconductor coupling methods are highlighted. •Structure-activity relationship and catalytic mechanism of photocatalysts are given. Wood-based nanotechnologies have received much attention in the area of photocatalytic degradation of organic contaminants in aquatic environment in recent years, because of the high abundance and renewability of wood as well as the high reaction activity and unique structural features of these materials. Herein, we present a comprehensive review of the current research activities centering on the development of wood-based nanocatalysts for photodegradation of organic pollutants. This review begins with a brief introduction of the development of photocatalysts and hierarchical structure of wood. The review then focuses on strategies of designing novel photocatalysts based on wood or its recombinants (such as 1D fiber, 2D films and 3D porous gels) using advanced nanotechnology including sol-gel method, hydrothermal method, magnetron sputtering method, dipping method and so on. Next, we highlight typical approaches that improve the photocatalytic property, including metal element doping, morphology control and semiconductor coupling. Also, the structure-activity relationship of photocatalysts is emphasized. Finally, a brief summary and prospect of wood-derived photocatalysts is provided.     

Co-pyrolysis of sludge and kaolin/zeolite in a rotary kiln: Analysis of stabilizing heavy metals

• Adding kaolin/zeolite promotes the formation of stable heavy metals. • The potential ecological risk index of co-pyrolysis biochar is extremely low. • Increasing the pyrolysis temperature reduces the leaching toxicity of heavy metals. • The toxicity of biochar reduces with the increasing content of stable heavy metals. Pyrolysis is a promising technique used for treating of sewage sludge. However, the application of pyrolysis products is limited due to the presence of heavy metals. In this study, sewage sludge mixed with kaolin/zeolite was pyrolyzed in a rotary kiln, aiming to improve the immobilization of heavy metals in pyrolytic carbon. The total concentrations, speciation distributions, leaching toxicities, and potential ecological risk indices of heavy metals in pyrolysis biochar were explored to examine the effects of kaolin/zeolite and pyrolytic temperature on immobilizing heavy metals. Further, mineral composition and surface morphology of biochar were characterized by X-ray diffraction and scanning electron microscopy to reveal the potential mechanism of immobilizing heavy metals. Increasing pyrolysis temperature facilitated the stabilization of heavy metals in pyrolysis biochar. The proportions of stable heavy metals in biochar obtained at 650℃ were 54.50% (Cu), 29.73% (Zn), 79.29% (Cd), 68.17% (Pb) and 86.70% (Cr). Compared to sewage sludge, the potential contamination risk index of pyrolysis biochar obtained at 650℃ was reduced to 17.01, indicating a low ecological risk. The addition of 7% kaolin/zeolite further reduced the risk index of co-pyrolysis biochar prepared at 650℃ to 10.86/15.28. The characterization of biochar revealed that increase in the pyrolysis temperature and incorporation of additives are conducive to the formation of stable heavy metal-inorganics. This study demonstrates that the formation of stable mineral compounds containing heavy metals is the key to stabilizing heavy metals in pyrolysis biochar.     

PM-support interfacial effect and oxygen mobility in Pt,Pd or Rh-loaded (Ce,Zr,La)O2 catalysts

• Pt/CZL exhibits the optimum catalytic performance for HC and NO_x elimination. • The strong PM-Ce interaction favors the oxygen mobility and DOSC. • Pd/CZL shows higher catalytic activity for CO conversion due to more O_latt species. • Great oxygen mobility at high temperature broadens the dynamic operation window. • The relationship between DOSC and catalytic performance is revealed. The physicochemical properties of Pt-, Pd- and Rh- loaded (Ce,Zr,La)O₂ (shorted for CZL) catalysts before/after aging treatment were systematically characterized by various techniques to illustrate the relationship of the dynamic oxygen storage/release capacity and redox ability with their catalytic performances for HC, NO_x and CO conversions. Pt/CZL catalyst exhibits the optimum catalytic performance for HC and NO_x elimination, which mainly contribute to its excellent redox ability and dynamic oxygen storage/release capacity (DOSC) at lower temperature due to the stronger PM (precious metals)-support interaction. However, the worse stability of Pt-O-Ce species and volatile Pt oxides easily result in the dramatical decline in catalytic activity after aging. Pd/CZL shows higher catalytic activity for CO conversion by reason of more O_latt species as the active oxygen for CO oxidation reaction. Rh/CZL catalyst displays the widest dynamic operation window for NO_x elimination as a result of greater oxygen mobility at high temperature, and the ability to retain more Rh-O-Ce species after calcined at 1100°C effectively restrains sintering of active RhO_x species, improving the thermal stability of Rh/CZL catalyst.     

Enhanced carbon tetrachloride degradation by hydroxylamine in ferrous ion activated calcium peroxide in the presence of formic acid

• Complete CT degradation was achieved by employing HA to CP/Fe(II)/FA process. • Quantitative detection of Fe(II) regeneration and HO• production was investigated. • Benzoic acid outcompeted FA for the reaction with HO•. • CO₂•⁻ was the dominant reductive radical for CT removal. • Effects of solution matrix on CT removal were conducted. Hydroxyl radicals (HO•) show low reactivity with perchlorinated hydrocarbons, such as carbon tetrachloride (CT), in conventional Fenton reactions, therefore, the generation of reductive radicals has attracted increasing attention. This study investigated the enhancement of CT degradation by the synergistic effects of hydroxylamine (HA) and formic acid (FA) (initial [CT] = 0.13 mmol/L) in a Fe(II) activated calcium peroxide (CP) Fenton process. CT degradation increased from 56.6% to 99.9% with the addition of 0.78 mmol/L HA to the CP/Fe(II)/FA/CT process in a molar ratio of 12/6/12/1. The results also showed that the presence of HA enhanced the regeneration of Fe(II) from Fe(III), and the production of HO• increased one-fold when employing benzoic acid as the HO• probe. Additionally, FA slightly improves the production of HO•. A study of the mechanism confirmed that the carbon dioxide radical (CO₂•⁻), a strong reductant generated by the reaction between FA and HO•, was the dominant radical responsible for CT degradation. Almost complete CT dechlorination was achieved in the process. The presence of humic acid and chloride ion slightly decreased CT removal, while high doses of bicarbonate and high pH inhibited CT degradation. This study helps us to better understand the synergistic roles of FA and HA for HO• and CO₂•⁻ generation and the removal of perchlorinated hydrocarbons in modified Fenton systems.     

Persistent free radicals in humin under redox conditions and their impact in transforming polycyclic aromatic hydrocarbons

• Regulation of redox conditions promotes the generation of free radicals on HM. • HM-PFRs can be fractionated into active and inactive types depending on stability. • The newly produced PFRs readily release electrons to oxygen and generate ROS. • PFR-induced ROS mediate the transformation of organic contaminants adsorbed on HM. The role of humic substance-associated persistent free radicals (PFRs) in the fate of organic contaminants under various redox conditions remains unknown. This study examined the characterization of original metal-free peat humin (HM), and HM treated with varying concentrations of H₂O₂ and L-ascorbic acid (VC) (assigned as H₂O₂-HM and VC-HM). The concentration of PFRs in HM increased with the addition of VC/H₂O₂ at concentrations less than 0.08 M. The evolution of PFRs in HM under different environmental conditions (e.g., oxic/anoxic and humidity) was investigated. Two types of PFRs were detected in HM: a relatively stable radical existed in the original sample, and the other type, which was generated by redox treatments, was relatively unstable. The spin densities of VC/H₂O₂-HM readily returned to the original value under relatively high humidity and oxic conditions. During this process, the HM-associated “unstable” free radicals released an electron to O₂, inducing the formation of reactive oxygen species (ROS, i.e., ^•OH and ^•O₂⁻). The generated ROS promoted the degradation of polycyclic aromatic hydrocarbons based on the radical quenching measurements. The transformation rates followed the order naphthalene>phenanthrene>anthracene>benzo[a]pyrene. Our results provide valuable insight into the HM-induced transformation of organic contaminants under natural conditions.     

Pesticides in stormwater runoff−A mini review

• The sources and pathways of pesticides into stormwater runoff were diverse. • Factors affecting pesticides in stormwater runoff were critically reviewed. • Pesticides mitigation strategies were included in this review. • The current knowledge gap of the pesticides in stormwater runoff was identified. Recently, scientific interest has grown in harvesting and treating stormwater for potable water use, in order to combat the serious global water scarcity issue. In this context, pesticides have been identified as the key knowledge gap as far as reusing stormwater is concerned. This paper reviewed the presence of pesticides in stormwater runoff in both rural and urban areas. Specifically, the sources of pesticide contamination and possible pathways were investigated in this review. Influential factors affecting pesticides in stormwater runoff were critically identified as: 1) characteristics of precipitation, 2) properties of pesticide, 3) patterns of pesticides use, and 4) properties of application surface. The available pesticide mitigation strategies including best management practice (BMP), low impact development (LID), green infrastructure (GI) and sponge city (SC) were also included in this paper. In the future, large-scale multi-catchment studies that directly evaluate pesticide concentrations in both urban and rural stormwater runoff will be of great importance for the development of effective pesticides treatment approaches and stormwater harvesting strategies.     

Review on remediation technologies for arsenic-contaminated soil

• Recent progress of As-contaminated soil remediation technologies is presented. • Phytoextraction and chemical immobilization are the most widely used methods. • Novel remediation technologies for As-contaminated soil are still urgently needed. • Methods for evaluating soil remediation efficiency are lacking. • Future research directions for As-contaminated soil remediation are proposed. Arsenic (As) is a top human carcinogen widely distributed in the environment. As-contaminated soil exists worldwide and poses a threat on human health through water/food consumption, inhalation, or skin contact. More than 200 million people are exposed to excessive As concentration through direct or indirect exposure to contaminated soil. Therefore, affordable and efficient technologies that control risks caused by excess As in soil must be developed. The presently available methods can be classified as chemical, physical, and biological. Combined utilization of multiple technologies is also common to improve remediation efficiency. This review presents the research progress on different remediation technologies for As-contaminated soil. For chemical methods, common soil washing or immobilization agents were summarized. Physical technologies were mainly discussed from the field scale. Phytoextraction, the most widely used technology for As-contaminated soil in China, was the main focus for bioremediation. Method development for evaluating soil remediation efficiency was also summarized. Further research directions were proposed based on literature analysis.     

TiO2@palygorskite composite for the efficient remediation of oil spills via a dispersion-photodegradation synergy

• A novel and multi-functional clay-based oil spill remediation system was constructed. • TiO₂@PAL functions as a particulate dispersant to break oil slick into tiny droplets. • Effective dispersion leads to the direct contact of TiO₂ with oil pollutes directly. • TiO₂ loaded on PAL exhibits efficient photodegradation for oil pollutants. • TiO₂@PAL shows a typical dispersion-photocatalysis synergistic remediation. Removing spilled oil from the water surface is critically important given that oil spill accidents are a common occurrence. In this study, TiO₂@Palygorskite composite prepared by a simple coprecipitation method was used for oil spill remediation via a dispersion-photodegradation synergy. Diesel could be efficiently dispersed into small oil droplets by TiO₂@Palygorskite. These dispersed droplets had an average diameter of 20–30 mm and exhibited good time stability. The tight adsorption of TiO₂@Palygorskite on the surface of the droplets was observed in fluorescence and SEM images. As a particulate dispersant, the direct contact of TiO₂@Palygorskite with oil pollutants effectively enhanced the photodegradation efficiency of TiO₂ for oil. During the photodegradation process, •O₂⁻and •OH were detected by ESR and radical trapping experiments. The photodegradation efficiency of diesel by TiO₂@Palygorskite was enhanced by about 5 times compared with pure TiO₂ under simulated sunlight irradiation. The establishment of this new dispersion-photodegradation synergistic remediation system provides a new direction for the development of marine oil spill remediation.