Differentiated cognition of the effects of human activities on typical persistent organic pollutants and bacterioplankton community in drinking water source.

Accelerated urbanization in developing countries led to a typical gradient of human activities (low, moderate and high human activities), which affected the pollution characteristics and ecological functions of aquatic environment. However, the occurrence characteristics of typical persistent organic pollutants, including organochlorine pesticides (OCPs) and polycyclic aromatic hydrocarbons (PAHs), and bacterioplankton associated with the gradient of human activities in drinking water sources is still lacking. Our study focused on a representative case - the upper reaches of the Dongjiang River (Pearl River Basin, China), a drinking water source characterized by a gradient of human activities. A comprehensive analysis of PAHs, OCPs and bacterioplankton in the water phase was performed using gas chromatography-mass spectrometry (GC-MS) and the Illumina platform. Moderate human activity could increase the pollution of OCPs and PAHs due to local agricultural activities. The gradient of human activities obviously influenced the bacterioplankton community composition and interaction dynamics, and low human activity resulted in low bacterioplankton diversity. Co-occurrence network analysis indicated that moderate human activity could promote a more modular organization of the bacterioplankton community. Structural equation models showed that nutrients could exert a negative influence on the composition of bacterioplankton, and this phenomenon did not change with the gradient of human activities. OCPs played a negative role in shaping bacterioplankton composition under the low and high human activities, but had a positive effect under the moderate human activity. In contrast, PAHs showed a strong positive effect on bacterioplankton composition under low and high human activities and a weak negative effect under moderate human activity. Overall, these results shed light on the occurrence characteristics of OCPs, PAHs and their ecological effects on bacterioplankton in drinking water sources along the gradient of human activities.

Mn-O Covalency Governs the Intrinsic Activity of Co-Mn Spinel Oxides for Boosted Peroxymonosulfate Activation.

Transition metal (TM)-based bimetallic spinel oxides can efficiently activate peroxymonosulfate (PMS) presumably attributed to enhanced electron transfer between TMs, but the existing model cannot fully explain the efficient TM redox cycling. Here, we discover a critical role of TM-O covalency in governing the intrinsic catalytic activity of Co3-x Mnx O4 spinel oxides. Experimental and theoretical analysis reveals that the Co sites significantly raises the Mn valence and enlarges Mn-O covalency in octahedral configuration, thereby lowering the charge transfer energy to favor MnOh -PMS interaction. With appropriate MnIV /MnIII ratio to balance PMS adsorption and MnIV reduction, the Co1.1 Mn1.9 O4 exhibits remarkable catalytic activities for PMS activation and pollutant degradation, outperforming all the reported TM spinel oxides. The improved understandings on the origins of spinel oxides activity for PMS activation may inspire the development of more active and robust metal oxide catalysts.

Degree of human activity exert differentiated influence on conventional and emerging pollutants in drinking water source.

Anthropogenic pollution poses a significant threat to drinking water sources worldwide. Previous studies have focused on the occurrence of pollutants in drinking water sources, but the impact of human activities on different types of pollutants in drinking water sources is still unclear. In this study, we chose the upper reaches of the Dongjiang River (URDR) as a case study to investigate the distribution characteristics of conventional pollutants, pesticides, and antibiotics along the gradient of human intervention. Our findings reveal that human activities can effect both conventional pollutants and emerging pollutants in the URDR to varying degrees. The escalation of human activities correlates with a rising trend in conventional pollutants, such as nitrogen (N) and phosphorus (P). Notably, only C1 (terrestrial humus) in dissolved organic matter (DOM) exhibits this increasing pattern. Pesticide and antibiotic concentrations are highest in areas with moderate and high levels of human activity, respectively, and the degree of eutrophication of drinking water closely follows the gradient of human activity. Our results also indicate that most pesticides pose a significant risk in the URDR, particularly pyrethroid pesticides (PYRs). Out of all antibiotics, only Norfloxacin (NFX) and Penicillin G (PENG) are classified as high-risk, with NFX exhibiting significant variation across different degrees of human activity. C1 and TP were the most important factors affecting the distribution of organophosphorus (OPPs) and PYRs, respectively. In conclusion, varying degrees of human activity exert differentiated influences on conventional and emerging pollutants in drinking water sources.

Coagulation/co-catalytic membrane integrated system for fouling-resistant and efficient water purification.

Low-pressure catalytic membranes allow efficient rejection of particulates and simultaneously removing organics pollutant in water, but the accumulation of dissolved organic matters (DOM) on membrane surface, which cover the catalytic sites and cause membrane fouling, challenges their stable operation in practical wastewater treatment. Here we propose a ferric salt-based coagulation/co-catalytic membrane integrated system that can effectively mitigate the detrimental effects of DOM. Ferric salt (Fe3+) serving both as a DOM coagulant to lower the membrane fouling and as a co-catalyst with the membrane-embedded MoS2 nanosheets to drive perxymonosulfate (PMS) activation and pollutant degradation. The membrane functionalized with 2H-phased MoS2 nanosheets showed improved hydrophilicity and fouling resistance relative to the blank polysulfone membrane. Attributed to the DOM coagulation and co-catalytic generation of surface-bound radicals for decontamination at membrane surface, the catalytic membrane/PMS/ Fe3+ system showed much less membrane fouling and 2.6 times higher pollutant degradation rate in wastewater treatment than the catalytic membrane alone. Our work imply a great potential of coagulation/co-catalytic membrane integrated system for water purification application.

Biological upcycling of nickel and sulfate as electrocatalyst from electroplating wastewater.

Upcycling nickel (Ni) to useful catalyst is an appealing route to realize low-carbon treatment of electroplating wastewater and simultaneously recovering Ni resource, but has been restricted by the needs for costly membranes or consumption of large amount of chemicals in the existing upcycling processes. Herein, a biological upcycling route for synchronous recovery of Ni and sulfate as electrocatalysts, with certain amount of ferric salt (Fe3+) added to tune the product composition, is proposed. Efficient biosynthesis of bio-NiFeS nanoparticles from electroplating wastewater was achieved by harnessing the sulfate reduction and metal detoxification ability of Desulfovibrio vulgaris. The optimal bio-NiFeS, after further annealing at 300 °C, served as an efficient oxygen evolution electrocatalyst, achieving a current density of 10 mA·cm-1 at an overpotential of 247 mV and a Tafel slope of 60.2 mV·dec-1. It exhibited comparable electrocatalytic activity with the chemically-synthesized counterparts and outperformed the commercial RuO2. The feasibility of the biological upcycling approach for treating real Ni-containing electroplating wastewater was also demonstrated, achieving 99.5 % Ni2+removal and 41.0 % SO42- removal and enabling low-cost fabrication of electrocatalyst. Our work paves a new path for sustainable treatment of Ni-containing wastewater and may inspire technology innovations in recycling/ removal of various metal ions.

Efficient peroxymonosulfate activation by biochar-based nanohybrids for the degradation of pharmaceutical and personal care products in aquatic environments.

Recently, pharmaceutical and personal care products (PPCPs) have been of wide concern due to their ecological toxicity, persistence, and ubiquity in aquatic environments. Peroxymonosulfate-based advanced oxidation processes (PMS-AOPs) have shown great potential for eliminating PPCPs due to their superior oxidation ability and adaptability. Biochar-based nanohybrids have been employed as emerging catalysts for peroxymonosulfate (PMS) activation. Until now, few researchers have summarized PMS activation by biochar-based catalysts for PPCPs removal. In this review, the types, sources, fates, and ecological toxicities of PPCPs were first summarized. Furthermore, various preparation and modification methods of biochar-based catalysts were systematically introduced. Importantly, the application of activating PMS with biochar-based multifunctional nanocomposites for eliminating PPCPs was reviewed. The influencing factors, such as catalysts dosage, PMS dosage, solution pH, temperature, anions, natural organic matters (NOMs), and pollutants concentration were broadly discussed. Biochar-based catalysts can act as electron donors, electron acceptors, and electron shuttles to activate PMS for the removal of PPCPs through radical pathways or/and non-radical pathways. The degradation mechanisms of PPCPs are correlated with persistent free radicals (PFRs), metal species, defective sites, graphitized degree, functional groups, electronic attributes, and the hybridization modes of biochar-based catalysts. Finally, the current problems and further research directions on the industrial application of biochar-based nanocomposites were proposed. This study provides some enlightenment for the efficient removal of PPCPs with biochar-based catalysts in PMS-AOPs.

In-situ preparation of yeast-supported Fe0@Fe2O3 as peroxymonosulfate activator for enhanced degradation of tetracycline hydrochloride.

Nano zero-valent iron (nZVI) is extensively used as a peroxymonosulfate (PMS) activator but suffers from the ease of oxidation and agglomeration due to its high surface energy and inherent magnetism. Here, green and sustainable yeast was selected as a support material to firstly in-situ prepare yeast-supported Fe0@Fe2O3 and used for activating PMS to degrade tetracycline hydrochloride (TCH), one of the common antibiotics. Due to the anti-oxidation ability of the Fe2O3 shell and the support effect of yeast, the prepared Fe0@Fe2O3/YC exhibited a superior catalytic activity for the removal of TCH as well as some other typical refractory contaminants. The chemical quenching experiments and EPR results demonstrated SO4•- was the main reactive oxygen species while O2•-, 1O2 and •OH played a minor role. Importantly, the crucial role of the Fe2+/Fe3+ cycle promoted by the Fe0 core and surface iron hydroxyl species in PMS activation was elucidated in detail. The TCH degradation pathways were proposed by LC-MS and density functional theory (DFT) calculation. In addition, the outstanding magnetic separation property, anti-oxidation ability, and high environmental resistance of the catalyst were demonstrated. Our work may inspire the development of green, efficient, and robust nZVI-based materials for wastewater treatment.

Enhanced degradation of sulfamethoxazole by non-radical-dominated peroxymonosulfate activation with Co/Zn co-doped carbonaceous catalyst: Synergy between Co and Zn.

Bimetallic catalysts are often used for peroxymonosulfate (PMS) activation in recent years due to the synergistic effects between two different metal species. However, the synergy between Zn and other transition metal in PMS activation are rarely studied because of the ease of evaporation of Zn species at high temperature. In this work, a Co/Zn co-doped carbonaceous catalyst derived from ZIF-67@ZIF-8 (Z67@8D) was prepared successfully by the core-shell replacement strategy, and used to activate PMS for sulfamethoxazole (SMX) degradation. Due to the co-existence of Co/Zn species (e.g., Co/Zn-N site), Z67@8D showed a much higher catalytic activity than that of Z8D, Z67D, and several commercial oxides. Importantly, the CoZn synergy was deeply revealed by combining experiments and density functional theory (DFT) calculations, in which Zn could adjust the electron distribution of Co, reducing the PMS adsorption energy and thus enhancing PMS decomposition and singlet oxygen (1O2) formation. Moreover, formed ZnO and graphitic structure of Z67@8D could also promote the catalytic activity. In addition, the good stability and reusability, universal applicability, and high environmental robustness of Z67@8D were demonstrated. Our findings may provide a new insight into the Zn-based bimetallic catalysts for PMS activation and pollutant degradation.

Insights into the photocatalytic peroxymonosulfate activation over defective boron-doped carbon nitride for efficient pollutants degradation.

The metal-free graphitic carbon nitride is a promising photocatalyst for peroxymonosulfate (PMS) activation towards water decontamination, but bearing low efficiency due to its electronic structure and surface chemistry. Herein, the non-metallic element boron was adopted for catalyst development. The boron dopants and defects were simultaneously introduced by potassium borohydride, resulting in an excellent activity towards PMS activation. The dominant reactive oxygen species was singlet oxygen, which was determined to originate from PMS activation over photo-induced holes initiated by an electron transfer process. Calculations based on density functional theory revealed that at excited states, due to the dopants and defects, the electron-hole distribution was altered from an even population to a significant separation, which was beneficial for photocatalytic performance. Besides, the engineered electronic structure weakened the catalyst resistance to charge transfer, enabling easier electron transfer between the catalyst and the PMS. Moreover, the strengthened and enlarged positive electrostatic potential areas on heptazine rings oriented the electron transfer process from the negatively charged PMS to the catalyst, facilitating the generation of singlet oxygen. These findings provide underlying mechanism insights into the contribution of dopants and defects to catalytic performance on persulfate-based photocatalytic water treatment.

A single microbial electrochemical system for CO2 reduction and simultaneous biogas purification, upgrading and sulfur recovery.

In this work, a single microbial electrochemical system was developed for multiple goals simultaneously - CO2 reduction, biogas purification, upgrading and sulfur recovery. This system consists of a methanogen-inoculated biocathode for CO2 reduction and a ferrous ion (Fe2+)-mediated abiotic anode for hydrogen sulfide (H2S) oxidation. In the cathodic chamber, methane production rate of 20.6 ± 1.0 µmol·h-1 and high upgrading level (up to 98.3% methane content) were achieved. In the anodic chamber, H2S was completely removed and selectively converted into elemental sulfur particles. The system showed stable performance during continuous operation for treating both pure CO2 and mixed gases, with a cathodic coulombic efficiency of up to 85.2%. This simple system holds a great potential for practical application for biogas upgrading and sulfur recovery from waste water/gases.

Interactions between chlorophenols and peroxymonosulfate: pH dependency and reaction pathways.

A non-radical reaction between peroxysulfates and phenolic compounds, as important structural moieties of natural organic matters, has been reported recently, implying new opportunities for environmental remediation without need for catalyst or energy input. However, this approach seems to be ineffective for halogenated aromatic compounds, an important disinfection by-products (DBPs). Here, we shed light on the interactions between peroxymonosulfate (PMS) and chlorophenols and the influential factors. The results show that the chlorophenols transformation kinetics were highly dependent on the solution pH and chlorophenol species: raising the pH significantly accelerated the chlorophenols degradation, and at alkaline pH the removal rates of different chlorophenols were in the order of trichlorophenol > dichlorophenol > chlorophenol > tetrachlorophenol. The faster degradation of pollutants with more chlorine groups was mainly due to their relatively higher dissociation degree, which favors a direct pollutant-PMS interaction to generate radicals for their degradation. The chlorophenol degradation intermediate (i.e. benzoquinone) further mediated the generation of singlet oxygen at alkaline pH, thereby contributing to accelerated pollutant removal. The slower degradation of tetrachlorophenol than other chlorophenols was likely due to its strong electrostatic epulsion to PMS which restricted the reaction. Our work unveils the chlorophenols degradation mechanisms in PMS reaction system, which may facilitate a better understanding and optimization of advanced oxidation processes for pollution control to reduce potential DBPs accumulation.

Modeling of acetate-type fermentation of sugar-containing wastewater under acidic pH conditions.

In this study, a kinetic model was developed based on Anaerobic Digestion Model No. 1 to provide insights into the directed production of acetate and methane from sugar-containing wastewater under low pH conditions. The model sufficiently described the dynamics of liquid-phase and gaseous products in an anaerobic membrane bioreactor by comprehensively considering the syntrophic bioconversion steps of sucrose hydrolysis, acidogenesis, acetogenesis and methanogenesis under acidic pH conditions. The modeling results revealed a significant pH-dependency of hydrogenotrophic methanogenesis and ethanol-producing processes that govern the sucrose fermentative pathway through changing the hydrogen yield. The reaction thermodynamics of such acetate-type fermentation were evaluated, and the implications for process optimization by adjusting the hydraulic retention time were discussed. This work sheds light on the acid-stimulated acetate-type fermentation process and may lay a foundation for optimization of resource-oriented processes for treatment of food wastewater.

Biogenic FeS accelerates reductive dechlorination of carbon tetrachloride by Shewanella putrefaciens CN32.

Dissimilatory metal reducing bacteria (DMRB) widely exist in the subsurface environment and are involved in various contaminant degradation and element geochemical cycling processes. Recent studies suggest that DMRB can biosynthesize metal nanoparticles during metal reduction, but it is unclear yet how such biogenic nanomaterials would affect their decontamination behaviors. In this study, we found that the dechlorination rates of carbon tetrachloride (CT) by Shewanella putrefaciens CN32 was significantly increased by 8 times with the formation of biogenic ferrous sulfide (FeS) nanoparticles. The pasteurized biogenic FeS enabled 5 times faster dechlorination than abiotic FeS that had larger sizes and irregular structure, confirming a significant contribution of the biogenic FeS to CT bioreduction resulting from its good dispersion and relatively high dechlorination activity. This study highlights a potentially important role of biosynthesized nanoparticles in environmental bioremediation.