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.     

A novel strategy for gas mitigation during swine manure odour treatment using seaweed and a microbial consortium

• Comprehensive mitigation of gas emissions from swine manure was investigated. • Additives addition for mitigation of gas from the manure has been developed. • Sargassum horneri, seaweed masking strategy controlled gas by 90%-100%. • Immediate reduction in emitted gas and improving air quality has been determined. • Microbial consortium with seaweed completely controlled gas emissions by 100%. Gas emissions from swine farms have an impact on air quality in the Republic of Korea. Swine manure stored in deep pits for a long time is a major source of harmful gas emissions. Therefore, we evaluated the mitigation of emissions of ammonia (NH₃), hydrogen sulfide (H₂S) and amine gases from swine manure with biological products such as seaweed (Sargassum horneri) and a microbial consortium (Bacillus subtilis (1.2 × 10⁹ CFU/mL), Thiobacillus sp. (1.0 × 10¹⁰ CFU/mL) and Saccharomyces cerevisiae (2.0 × 10⁹ CFU/mL)) used as additives due to their promising benefits for nutrient cycling. Overall, seaweed powder masking over two days provided notable control of over 98%-100% of the gas emissions. Furthermore, significant control of gas emissions was especially pronounced when seaweed powder masking along with a microbial consortium was applied, resulting in a gas reduction rate of 100% for NH₃, amines and H₂S over 10 days of treatment. The results also suggested that seaweed powder masking and a microbial consortium used in combination to reduce the gas emissions from swine manure reduced odour compared with that observed when the two additives were used alone. Without the consortium, seaweed decreased total volatile fatty acid (VFA) production. The proposed novel method of masking with a microbial consortium is promising for mitigating hazardous gases, simple, and environmentally beneficial. More research is warranted to determine the mechanisms underlying the seaweed and substrate interactions.     

Fate of microplastics in a coastal wastewater treatment plant: Microfibers could partially break through the integrated membrane system

• Fate of microplastics in integrated membrane system for water reuse was investigated. • Integrated membrane system has high removal efficiency (>98%) for microplastics. • Microplastics (>93%) were mainly removed through membrane bioreactor treatment. • Small scale fiber plastics (<200 μm) could break through reverse osmosis (RO) system. • The flux of microplastics maintained at 2.7 × 10¹¹ MPs/d after the RO treatment. Rare information on the fate of microplastics in the integrated membrane system (IMS) system in full-scale wastewater treatment plant was available. The fate of microplastics in IMS in a coastal reclaimed water plant was investigated. The removal rate of microplastics in the IMS system reached 93.2% after membrane bioreactor (MBR) treatment while that further increased to 98.0% after the reverse osmosis (RO) membrane process. The flux of microplastics in MBR effluent was reduced from 1.5 × 10¹³ MPs/d to 10.2 × 10¹¹ MPs/d while that of the RO treatment decreased to 2.7 × 10¹¹ MPs/d. Small scale fiber plastics (<200 μm) could break through RO system according to the size distribution analysis. The application of the IMS system in the reclaimed water plant could prevent most of the microplastics from being discharged in the coastal water. These findings suggested that the IMS system was more efficient than conventional activated sludge system (CAS) for the removal of microplastics, while the discharge of small scale fiber plastics through the IMS system should also not be neglected because small scale fiber plastics (<200 μm) could break through IMS system equipped with the RO system.     

Evolution of humic substances in polymerization of polyphenol and amino acid based on non-destructive characterization

• Humification evolution was identified with non-destructive characterization method. • Humification process from precursors to fulvic and humic acid was confirmed. • MnO₂ alone had limited oxidation ability to form HA. • MnO₂ played a key role as a catalyst to transform FA to HA in the presence of O₂. • MnO₂ could affect the structure of the humification products. Abiotic humification is important in the formation and evolution of organic matter in soil and compost maturing processes. However, the roles of metal oxides in abiotic humification reactions under micro-aerobic remain ambiguous. The aim of this study was to use non-destructive measurement methods to investigate the role of MnO₂ in the evolution of humic substances (HSs) during oxidative polymerization of polyphenol-amino acid. Our results suggested a synergistic effect between MnO₂ and O₂ in promoting the polymerization reaction and identified that MnO₂ alone had a limited ability in accelerating the transformation of fulvic acid (FA) to humic acid (HA), whereas O₂ was the key factor in the process. Two-dimensional correlation spectroscopy (2D-COS) showed that the evolution in the UV-vis spectra followed the order of 475–525 nm>300–400 nm>240–280 nm in the humification process, indicating the formation of simple organic matter followed by FA and then HA. ¹³C nuclear magnetic resonance (¹³C NMR) analysis revealed that the products under both air and N₂ conditions in the presence of MnO₂ had greater amounts of aromatic-C than in the absence of MnO₂, demonstrating that MnO₂ affected the structure of the humification products. The results of this study provided new insights into the theory of abiotic humification.     

Visible-light-driven heterostructured g-C3N4/Bi-TiO2 floating photocatalyst with enhanced charge carrier separation for photocatalytic inactivation of Microcystis aeruginosa

• Bi doping in TiO₂ enhanced the separation of photo-generated electron-hole. • The performance of photocatalytic degradation of MC-LR was improved. • Coexisting substances have no influence on algal removal performance. • The key reactive oxygen species were h⁺ and ^•OH in the photocatalytic process. The increase in occurrence and severity of cyanobacteria blooms is causing increasing concern; moreover, human and animal health is affected by the toxic effects of Microcystin-LR released into the water. In this paper, a floating photocatalyst for the photocatalytic inactivation of the harmful algae Microcystis aeruginosa (M. aeruginosa) was prepared using a simple sol-gel method, i.e., coating g-C₃N₄ coupled with Bi-doped TiO₂ on Al₂O₃-modified expanded perlite (CBTA for short). The impact of different molar ratios of Bi/Ti on CBTA was considered. The results indicated that Bi doping in TiO₂ inhibited photogenerated electron-hole pair recombination. With 6 h of visible light illumination, 75.9% of M. aeruginosa (initial concentration= 2.7 × 10⁶ cells/L) and 83.7% of Microcystin-LR (initial concentration= 100 μg/L) could be removed with the addition of 2 g/L CBTA-1% (i.e., Bi/Ti molar ratio= 1%). The key reactive oxygen species (ROSs) in the photocatalytic inactivation process are h⁺ and ^•OH. The induction of the Bi⁴⁺/Bi³⁺ species by the incorporation of Bi could narrow the bandgap of TiO₂, trap electrons, and enhance the stability of CBTA-1% in the solutions with coexisting environmental substances.     

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.     

Fate and risk assessment of emerging contaminants in reclaimed water production processes

• PPCPs had the highest removal efficiency in A²O combined with MBR process (86.8%). • ARGs and OPFRs were challenging to remove (6.50% and 31.0%, respectively). • Octocrylene and tris(2-ethylhexyl) phosphate posed high risks to aquatic organisms. • Meta-analysis was used to compare the ECs removal in wastewater treatment. • Membrane treatment technology is the most promising treatment for ECs removal. Reclaimed water has been widely applied in irrigation and industrial production. Revealing the behavior of emerging contaminants in the production process of reclaimed water is the first prerequisite for developing relevant water quality standards. This study investigated 43 emerging contaminants, including 22 pharmaceuticals and personal care products (PPCPs), 11 organophosphorus flame retardants (OPFRs), and 10 antibiotic resistance genes (ARGs) in 3 reclaimed wastewater treatment plants (RWTPs) in Beijing. The composition profiles and removal efficiencies of these contaminants in RWTPs were determined. The results indicated that the distribution characteristics of the different types of contaminants in the three RWTPs were similar. Caffeine, sul2 and tris(1-chloro-2-propyl) phosphate were the dominant substances in the wastewater, and their highest concentrations were 27104 ng/L, 1.4 × 10⁷ copies/mL and 262 ng/L, respectively. Ofloxacin and sul2 were observed to be the dominant substances in the sludge, and their highest concentrations were 5419 ng/g and 3.7 × 10⁸ copies/g, respectively. Anaerobic/anoxic/oxic system combined with the membrane bioreactor process achieved a relatively high aqueous removal of PPCPs (87%). ARGs and OPFRs were challenging to remove, with average removal rates of 6.5% and 31%, respectively. Quantitative meta-analysis indicated that tertiary treatment processes performed better in emerging contaminant removal than secondary processes. Diethyltoluamide exhibited the highest mass load discharge, with 33.5 mg/d per 1000 inhabitants. Octocrylene and tris(2-ethylhexyl) phosphate posed high risks (risk quotient>1.0) to aquatic organisms. This study provides essential evidence to screen high priority pollutants and develop corresponding standard in RWTPs.     

Enhanced catalytic oxidation of 2,4-dichlorophenol via singlet oxygen dominated peroxymonosulfate activation on CoOOH@Bi2O3 composite

• Bi₂O₃ cannot directly activate PMS. • Bi₂O₃ loading increased the specific surface area and conductivity of CoOOH. • Larger specific surface area provided more active sites for PMS activation. • Faster electron transfer rate promoted the generation of reactive oxygen species. • ¹O₂ was identified as dominant ROS in the CoOOH@Bi₂O₃/PMS system. Cobalt oxyhydroxide (CoOOH) has been turned out to be a high-efficiency catalyst for peroxymonosulfate (PMS) activation. In this study, CoOOH was loaded on bismuth oxide (Bi₂O₃) using a facile chemical precipitation process to improve its catalytic activity and stability. The result showed that the catalytic performance on the 2,4-dichlorophenol (2,4-DCP) degradation was significantly enhanced with only 11 wt% Bi₂O₃ loading. The degradation rate in the CoOOH@Bi₂O₃/PMS system (0.2011 min⁻¹) was nearly 6.0 times higher than that in the CoOOH/PMS system (0.0337 min⁻¹). Furthermore, CoOOH@Bi₂O₃ displayed better stability with less Co ions leaching (16.4% lower than CoOOH) in the PMS system. These phenomena were attributed to the Bi₂O₃ loading which significantly increased the conductivity and specific surface area of the CoOOH@Bi₂O₃ composite. Faster electron transfer facilitated the redox reaction of Co (III) / Co (II) and thus was more favorable for reactive oxygen species (ROS) generation. Meanwhile, larger specific surface area furnished more active sites for PMS activation. More importantly, there were both non-radical (¹O₂) and radicals (SO₄⁻•, O₂⁻•, and OH•) in the CoOOH@Bi₂O₃/PMS system and ¹O₂ was the dominant one. In general, this study provided a simple and practical strategy to enhance the catalytic activity and stability of cobalt oxyhydroxide in the PMS system.     

Enhanced triallyl isocyanurate (TAIC) degradation through application of an O3/UV process: Performance optimization and degradation pathways

• UV/O₃ process had higher TAIC mineralization rate than O₃ process. • Four possible degradation pathways were proposed during TAIC degradation. • pH impacted oxidation processes with pH of 9 achieving maximum efficiency. • CO₃^2– negatively impacted TAIC degradation while HCO₃^– not. • Cl^– can be radicals scavenger only at high concentration (over 500 mg/L Cl^–). Triallyl isocyanurate (TAIC, C₁₂H₁₅N₃O₃) has featured in wastewater treatment as a refractory organic compound due to the significant production capability and negative environmental impact. TAIC degradation was enhanced when an ozone(O₃)/ultraviolet(UV) process was applied compared with the application of an independent O₃ process. Although 99% of TAIC could be degraded in 5 min during both processes, the O₃/UV process had a 70%mineralization rate that was much higher than that of the independent O₃ process (9%) in 30 min. Four possible degradation pathways were proposed based on the organic compounds of intermediate products identified during TAIC degradation through the application of independent O₃ and O₃/UV processes. pH impacted both the direct and indirect oxidation processes. Acidic and alkaline conditions preferred direct and indirect reactions respectively, with a pH of 9 achieving maximum Total Organic Carbon (TOC) removal. Both CO₃^2– and HCO₃^– decreased TOC removal, however only CO₃^2– negatively impacted TAIC degradation. Effects of Cl^– as a radical scavenger became more marked only at high concentrations (over 500 mg/L Cl^–). Particulate and suspended matter could hinder the transmission of ultraviolet light and reduce the production of HO· accordingly.     

Utilization of MSWI fly ash as partial cement or sand substitute with focus on cementing efficiency and health risk assessment

• Washed MSWI fly ash was used as partial cement or sand substitute. • Sand replacing is beneficial for strength, while cement replacement reduces strength. • Cementing efficiency factor and mortar pore structure explain the strength results. • Health risk assessment was conducted for MSWI fly ash blended cement mortar. • CR and HI contributed by different exposures and heavy metals were analyzed. The strength of cement substituted mortar decreases with the increase in fly ash amount, whereas the strength increases when the fly ash is blended as sand substitute. A mortar with highest strength (compressive strength= 30.2 Mpa; flexural strength= 7.0 Mpa) was obtained when the sand replacement ratio was 0.75%. The k value (cementing efficiency) of fly ash varied between 0.36 and 0.15 for the fly ash fraction in binder between 5% and 25%. The k values of fly ash used for sand replacement were all significantly above that used for cement substitution. The macropores assigned to the gaps between particles decreased when the fly ash was used as sand replacement, providing an explanation for the strength enhancement. The waste-extraction procedure (toxicity-sulphuric acid and nitric acid method (HJ/T 299-2007)) was used to evaluate metal leaching, indicating the reuse possibility of fly ash blended mortar. For the mortar with the mass ratio of fly ash to binder of 0.5%, the carcinogenic risks (CR) and non-carcinogenic hazard quotient (HQ) in sensitive scenario for blended mortar utilization were 9.66 × 10^-7 and 0.06, respectively; these results were both lower than the threshold values, showing an acceptable health risk. The CR (9.89 × 10^-5) and HQ (3.89) of the non-sensitive scenario for fly ash treatment exceeded the acceptable threshold values, indicating health risks to onsite workers. The main contributor to the carcinogenic and non-carcinogenic risk is Cr and Cd, respectively. The CR and HQ from inhalation was the main route of heavy metal exposure.     

Metagenomic analysis on resistance genes in water and microplastics from a mariculture system

• Total 174 subtypes of ARGs were detected by metagenomic analysis. • Chloramphenicol resistance genes were the dominant ARGs in water and microplastics. • The abundances of MRGs were much higher than those of ARGs. • Proteobacteria, Bacteroidetes, and Actinobacteria were the dominant phylum. • Microplastics in mariculture system could enrich most of MRGs and some ARGs. Microplastics existing widely in different matrices have been regarded as a reservoir for emerging contaminants. Mariculture systems have been observed to host microplastics and antibiotic resistance genes (ARGs). However, more information on proliferation of ARGs and metal resistance genes (MRGs) in mariculture system at the presence of microplastics is needed. This study used metagenomic analysis to investigate the distribution of ARGs and MRGs in water and microplastics of a typical mariculture pond. Total 18 types including 174 subtypes of ARGs were detected with the total relative abundances of 1.22/1.25 copies per 16S rRNA copy for microplastics/water. Chloramphenicol resistance genes were the dominant ARGs with the abundance of 0.35/0.42 copies per 16S rRNA copy for microplastics/water. Intergron intI1 was dominant gene among 6 detected mobile genetic elements (MGEs) with the abundance of 75.46/68.70 copies per 16S rRNA copy for water/microplastics. Total 9 types including 46 subtypes of MRGs were detected with total abundance of 5.02 × 10²/6.39 × 10² copies per 16S rRNA copy for water/ microplastics while genes resistant to copper and iron served as the dominant MRGs. Proteobacteria, Bacteroidetes, and Actinobacteria accounted for 84.2%/89.5% of total microbial community. ARGs with relatively high abundance were significantly positively related to major genera, MGEs, and MRGs. Microplastics in mariculture system could enrich most of MRGs and some ARGs to serve as potential reservoir for these pollutants. The findings of this study will provide important information on resistance gene pollution at presence of microplastics in the mariculture system for further proposing suitable strategy of environmental management.     

Cultivation of Chlorella sp. HQ in inland saline-alkaline water under different light qualities

• Optimal growth of Chlorella in inland saline-alkaline water was achieved by blue LED. • Lipids of Chlorella sp. HQ were mainly composed of C16:0 and C18:2 under various LEDs. • The BiodieselAnalyzer^© software was used to evaluate the Chlorella biodiesel quality. • Chlorella sp. HQ was a high-quality feedstock for biodiesel production. Inland saline-alkaline water can be used for the low-cost cultivation of microalgae, but whether algal biomass under various light sources has the potential to produce biodiesel remains to be developed. Herein, the influence of different light-emitting diode (LEDs) light colors (blue, red, white, mixed blue-red, and mixed blue-white LED) on the growth performance, lipid accumulation, and fatty acid composition of Chlorella sp. HQ cultivated in inland saline-alkaline water was investigated. The highest algal density was obtained under blue LEDs at the end of cultivation, reaching 1.93±0.03 × 10⁷ cells/mL. White LEDs can improve biomass yield, total lipid yield, and triacylglycerol yield per algal cell. The main fatty acid components of Chlorella from inland saline-alkaline water were palmitic acid and linoleic acid. The BiodieselAnalyzer^© software was used to predict algal biodiesel quality by estimating different quality parameters. The cetane number, kinematic viscosity, and density of Chlorella biodiesel were 51.714–67.69, 3.583–3.845 mm²/s, and 0.834–0.863 g/cm³, respectively. This further proved that the Chlorella biomass obtained from inland saline-alkaline water has the potential to be used as a high-quality biodiesel feedstock.     

Effects of hydraulic retention time on net present value and performance in a membrane bioreactor treating antibiotic production wastewater

• The membrane bioreactor cost decreased by 38.2% by decreasing HRT from 72 h to 36 h. • Capital and operation costs contributed 62.1% and 37.9% to decreased costs. • The membrane bioreactor is 32.6% cheaper than the oxidation ditch for treatment. • The effluent COD also improved from 709.93±62.75 mg/L to 280±17.32 mg/L. • Further treatment also benefited from lower pretreatment investment. A cost sensitivity analysis was performed for an industrial membrane bioreactor to quantify the effects of hydraulic retention times and related operational parameters on cost. Different hydraulic retention times (72–24 h) were subjected to a flat-sheet membrane bioreactor updated from an existing 72 h oxidation ditch treating antibiotic production wastewater. Field experimental data from the membrane bioreactor, both full-scale (500 m³/d) and pilot (1.0 m³/d), were used to calculate the net present value (NPV), incorporating both capital expenditure (CAPEX) and operating expenditure. The results showed that the tank cost was estimated above membrane cost in the membrane bioreactor. The decreased hydraulic retention time from 72 to 36 h reduced the NPV by 38.2%, where capital expenditure contributed 24.2% more than operational expenditure. Tank construction cost was decisive in determining the net present value contributed 62.1% to the capital expenditure. The membrane bioreactor has the advantage of a longer lifespan flat-sheet membrane, while flux decline was tolerable. The antibiotics decreased to 1.87±0.33 mg/L in the MBR effluent. The upgrade to the membrane bioreactor also benefited further treatments by 10.1%–44.7% lower direct investment.     

The size distribution of airborne bacteria and human pathogenic bacteria in a commercial composting plant

•Bacterial concentrations from eight stages were 10⁴–10⁵copies/m³. •Diameter influenced clustering of bacterial and HPB lineages. •Dg of 8 HPB ranged from 2.42 to 5.09 μm in composting areas. •Dg of 8 HPB ranged from 3.70 to 8.96 μm in packaging areas. •HPB had high concentrations and small sizes in composting areas. Composting plants are regarded as one of the important sources of environmental bioaerosols. However, limitations in the size distribution of airborne bacteria have prevented our comprehensive understanding of their risk to human health and their dispersal behavior. In this study, different sizes of airborne bacteria were collected using an eight-stage impactor from a full-scale composting facility. Size-related abundance and communities of airborne bacteria as well as human pathogenic bacteria (HPB) were investigated using 16S rRNA gene sequencing coupled with droplet digital PCR. Our results indicate that the bacterial concentrations from the eight stages were approximately 10⁴–10⁵copies/m³. Although no statistical correlation was detected between the particle size and the Shannon index, the influence of size on bacterial lineages was observed in both composting and packaging areas. For airborne bacteria from different stages, the dominant phyla were Firmicutes, Proteobacteria, and Actinobacteria, and the dominant genera was Bacillus. Seven out of eight HPB with a small geometric mean aerodynamic diameter had a high concentration in composting areas. Based on diameters of 2.42 to 5.09 μm, most HPB in the composting areas were expected to be deposited on the bronchus and secondary bronchus. However, in the packaging areas, the deposition of HPB (diameters 3.70 to 8.96 μm) occurred in the upper part of the respiratory tract. Our results on the size distribution, abundance, and diversity of these bacteria offer important information for the systematic evaluation of bacterial pathogenicity and the potential health impacts on workers in composting plants and the surrounding residents.     

Label-free colorimetric nanosensor with improved sensitivity for Pb2+ in water by using a truncated 8–17 DNAzyme

• Unmodified-AuNP based, colorimetric nanosensor was constructed for Pb²⁺ detection. • 5-nucleotide truncation in DNAzyme made complete substrate detachment upon Pb²⁺. • Ultrasensitive and selective detection of Lead (II) was achieved with 0.2×10^-9 mol/L LOD. Water pollution accidents, such as the Flint water crisis in the United States, caused by lead contamination have raised concern on the safety of drinking water distribution systems. Thus, the routine monitoring of lead in water is highly required and demands efficient, sensitive, cost-effective, and reliable lead detection methods. This study reports a label-free colorimetric nanosensor that uses unmodified gold nanoparticles (AuNPs) as indicators to enable rapid and ultra-sensitive detection of lead in environmental water. The 8–17 DNAzyme was truncated in this study to facilitate the detachment of single-stranded DNA fragments after substrate cleavage in the presence of Pb²⁺. The detached fragments were adsorbed over AuNPs and protected against salt concentration-induced aggregation. Accordingly, high Pb²⁺ would result in rapid color change from blue to pink. The established sensing principle achieved a sensitive limit of detection of 0.2×10^-9 mol/L Pb²⁺, with a linear working range of two orders of magnitude from 0.5×10^-9 mol/L to 5×10^-9 mol/L. The selectivity of the nanosensor was demonstrated by evaluating the interfering metal ions. The developed nanosensor can serve as a substitute for the rapid analysis and monitoring of trace lead levels under the drinking water distribution system and even other environmental water samples.     

Zero-valent manganese nanoparticles coupled with different strong oxidants for thallium removal from wastewater

• Nano zero-valent manganese (nZVMn, Mn⁰) is synthesized via borohydrides reduction. • Mn⁰ combined with persulfate/hypochlorite is effective for Tl removal at pH 6-12. • Mn⁰ can activate persulfate to form hydroxyl and sulfate radicals. • Oxidation-induced precipitation and surface complexation contribute to Tl removal. • Combined Mn⁰-oxidants process is promising in the environmental field. Nano zero-valent manganese (nZVMn, Mn⁰) was prepared through a borohydride reduction method and coupled with different oxidants (persulfate (S₂O₈²⁻), hypochlorite (ClO⁻), or hydrogen peroxide (H₂O₂)) to remove thallium (Tl) from wastewater. The surface of Mn⁰ was readily oxidized to form a core-shell composite (MnO_x@Mn⁰), which consists of Mn⁰ as the inner core and MnO_x (MnO, Mn₂O₃, and Mn₃O₄) as the outer layer. When Mn⁰ was added alone, effective Tl(I) removal was achieved at high pH levels (>12). The Mn⁰-H₂O₂ system was only effective in Tl(I) removal at high pH (>12), while the Mn⁰-S₂O₈²⁻ or Mn⁰-ClO⁻ system had excellent Tl(I) removal (>96%) over a broad pH range (4–12). The Mn⁰-S₂O₈²⁻ oxidation system provided the best resistance to interference from an external organic matrix. The isotherm of Tl(I) removal through the Mn⁰-S₂O₈²⁻ system followed the Freundlich model. The Mn⁰ nanomaterials can activate persulfate to produce sulfate radicals and hydroxyl radicals. Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy suggested that oxidation-induced precipitation, surface adsorption, and electrostatic attraction are the main mechanisms for Tl(I) removal resulting from the combination of Mn⁰ and oxidants. Mn⁰ coupled with S₂O₈²⁻/ClO⁻ is a novel and effective technique for Tl(I) removal, and its application in other fields is worthy of further investigation.     

Antioxidative potential of metformin: Possible protective mechanism against generating OH radicals

• Metformin consumes O₂−• and OH• induced by PM are proposed. • OH• dominated the oxidation of metformin compared with O₂−• • Metformin can prevent the harm of ROS induced by PM to human health. • Antioxidative potential of metformin was first proposed to provide measures. Exposure to particulate matter (PM) can lead to the excessive accumulation of reactive oxygen species (ROS), which causes oxidative stress and endangers human health. In this study, the effects of metformin on PM-induced radicals were investigated, and the antioxidation reaction mechanism of metformin was analyzed by the density functional theory (DFT) method. The corresponding results revealed that the consumption rate of dithiothreitol (DTT) increased as the metformin concentration (0–40 mmol/L) increased under exposure to PM active components. Moreover, the OH radical content decreased as the metformin concentration increased. This result may be related to the consumption of PM-induced OH radicals by metformin, which promotes the DTT consumption rate. Additionally, because the initiation reaction has a high barrier, the oxidation reaction rate between metformin and •O₂− is not very fast, although various catalysts may be present in the human environment. Importantly, we found that the barrier of metformin induced by OH radicals is only 9.6 kcal/mol while the barrier of metformin induced by oxygen is 57.9 kcal/mol, which shows that the rate of the •OH-initiated oxidative reaction of metformin is much faster and that this reaction path occurs more easily. By sample analysis, the mean OH radical generation was 55 nmol/min/g (ranging from 5 to 105 nmol/min/g) on haze days and 30 nmol/min/g (ranging from 10 to 50 nmol/min/g) on non-haze days. Moreover, OH radical generation was higher on haze days than on neighboring non-haze days. Taken together, all data suggest that metformin could consume the PM-induced radicals, such as OH radicals and •O₂−, thereby providing health protection.     

Distribution of aromatic amines,phenols, chlorobenzenes,and naphthalenes in the surface sediment of the Dianchi Lake,China

• The total organic pollutant concentrations in sediment were 27.4-1620 ng/g. • The phenol concentrations were relatively high in the sediment of the Dianchi Lake. • Average total concentrations decreased as follows: Caohai>Waihai>Haigeng Dam. • 1,4-dichlorobenzene, 3- or 4-methylphenol, 1,2,4-trichlorobenzene might be risks. Organic pollutants are widespread environmental pollutants with high toxicity, persistence, and bioaccumulation. Our aim was to investigate the distribution of aromatic amines, phenols, chlorobenzenes, and naphthalenes in the surface sediment of the Dianchi Lake, China. Nineteen surface sediment samples were collected from the Dianchi Lake, and 40 types of organic pollutants were analyzed via gas chromatography–mass spectrometry. The total organic pollutant concentrations in the surface sediment of the Dianchi Lake varied from 27.4 to 1.62 × 10³ ng/g. The concentrations of phenols were much higher than those in other water bodies but still within a controllable range, whereas the concentrations of the other organic pollutant classes were similar or even lower. The detection ratio of 3- or 4-methylphenol was the highest (100.00%) among the pollutants. The average total organic pollutant concentrations decreased in the following order: Caohai (540 ng/g)>the middle of Waihai (488 ng/g)>the edge of Waihai (351 ng/g)>Haigeng Dam (90.4 ng/g). Pearson analysis showed a strong correlation among 1-methylnaphthalene, 2-methylnaphthalene, 1,3-dinitronaphthalene, and 1,4-dinitronaphthalene (p<0.01). Caohai, the north lakeshore of Waihai and the south of Waihai showed higher risk because of high concentration; meanwhile, 1,4-dichlorobenzene, 3- or 4-methylphenol and 1,2,4-trichlorobenzene were more likely to cause risks.     

Preparation of nZVI embedded modified mesoporous carbon for catalytic persulfate to degradation of reactive black 5

• The MCNZVI is prepared as an interesting material for PS activation. • Graphitized carbon shells facilitate electron transfer from Fe⁰. • The MCNZVI exhibits excellent performance to degrade RB5 by ¹O₂. • The MCNZVI has high stability and reusability in the oxidation system. High-efficiency and cost-effective catalysts with available strategies for persulfate (PS) activation are critical for the complete mineralization of organic contaminants in the environmental remediation and protection fields. A nanoscale zero-valent iron-embedded modified mesoporous carbon (MCNZVI) with a core-shell structure is synthesized using the hydrothermal synthesis method and high-temperature pyrolysis. The results showed that nZVI could be impregnated within mesoporous carbon frameworks with a comparatively high graphitization degree, rich nitrogen doping content, and a large surface area and pore volume. This material was used as a persulfate activator for the oxidation removal of Reactive Black 5 (RB5). The effects of the material dosage, PS concentration, pH, and some inorganic anions (i.e., Cl⁻, SO₄²⁻) on RB5 degradation were then investigated. The highest degradation efficiency (97.3%) of RB5 was achieved via PS (20 mmol/L) activation by the MCNZVI (0.5 g/L). The pseudo-first-order kinetics (k = 2.11 × 10⁻² min⁻¹) in the MCNZVI/PS (0.5 g/L, 20 mmol/L) was greater than 100 times than that in the MCNZVI and PS. The reactive oxygen species (ROS), including ¹O₂, SO₄^·−, HO^·, and ·O₂⁻, were generated by PS activation with the MCNZVI. Singlet oxygen was demonstrated to be the primary ROS responsible for the RB5 degradation. The MCNZVI could be reused and regenerated for recycling. This work provides new insights into PS activation to remove organic contamination.     

Experimental and computational assessment of 1,4-Dioxane degradation in a photo-Fenton reactive ceramic membrane filtration process

• 1,4-Dioxane was degraded via the photo-Fenton reactive membrane filtration. • Degradation efficiency and AQY were both enhanced in photocatalytic membrane. • There is a tradeoff between photocatalytic degradation and membrane permeation flux. • Degradation pathways of 1,4-Dioxane is revealed by DFT analysis. The present study evaluated a photo-Fenton reactive membrane that achieved enhanced 1,4-Dioxane removal performance. As a common organic solvent and stabilizer, 1,4-Dioxane is widely used in a variety of industrial products and poses negative environmental and health impacts. The membrane was prepared by covalently coating photocatalyst of goethite (α-FeOOH) on a ceramic porous membrane as we reported previously. The effects of UV irradiation, H₂O₂ and catalyst on the removal efficiency of 1,4-Dioxane in batch reactors were first evaluated for optimized reaction conditions, followed by a systematical investigation of 1,4-Dioxane removal in the photo-Fenton membrane filtration mode. Under optimized conditions, the 1,4-Dioxane removal rate reached up to 16% with combination of 2 mmol/L H₂O₂ and UV₃₆₅ irradiation (2000 µW/cm²) when the feed water was filtered by the photo-Fenton reactive membrane at a hydraulic retention time of 6 min. The removal efficiency and apparent quantum yield (AQY) were both enhanced in the filtration compared to the batch mode of the same photo-Fenton reaction. Moreover, the proposed degradation pathways were analyzed by density functional theory (DFT) calculations, which provided a new insight into the degradation mechanisms of 1,4-Dioxane in photo-Fenton reactions on the functionalized ceramic membrane.