Divergent Fate and Roles of Dissolved Organic Matter from Spatially Varied Grassland Soils in China During Long-Term Biogeochemical Processes.

Terrestrial dissolved organic matter (DOM) is critical to global carbon and nutrient cycling, climate change, and human health. However, how the spatial and compositional differences of soil DOM affect its dynamics and fate in water during the carbon cycle is largely unclear. Herein, the biodegradation of DOM from 14 spatially distributed grassland soils in China with diverse organic composition was investigated by 165 days of incubation experiments. The results showed that although the high humified fraction (high-HS) regions were featured by high humic-like fractions of 4-25 kDa molecular weight, especially the abundant condensed aromatics and tannins, they unexpectedly displayed greater DOM degradation during 45-165 days. In contrast, the unique proteinaceous and 25-100 kDa fractions enriched in the low humified fraction (low-HS) regions were drastically depleted and improved the decay of bulk DOM but only during 0-45 days. Together, DOM from the high-HS regions would cause lower CO2 outgassing to the atmosphere but higher organic loads for drinking water production in the short term than that from the low-HS regions. However, this would be reversed for the two regions during the long-term transformation processes. These findings highlight the importance of spatial and temporal variability of DOM biogeochemistry to mitigate the negative impacts of grassland soil DOM on climate, waters, and humans.

Bubbleless Air Shapes Biofilms and Facilitates Natural Organic Matter Transformation in Biological Activated Carbon.

The biodegradation in the middle and downstream of slow-rate biological activated carbon (BAC) is limited by insufficient dissolved oxygen (DO) concentrations. In this study, a bubbleless aerated BAC (termed ABAC) process was developed by installing a hollow fiber membrane (HFM) module within a BAC filter to continuously provide aeration throughout the BAC system. The BAC filter without an HFM was termed NBAC. The laboratory-scale ABAC and NBAC systems operated continuously for 426 days using secondary sewage effluent as an influent. The DO concentrations for NBAC and ABAC were 0.78 ± 0.27 and 4.31 ± 0.44 mg/L, respectively, with the latter providing the ABAC with greater electron acceptors for biodegradation and a microbial community with better biodegradation and metabolism capacity. The biofilms in ABAC secreted 47.3% less EPS and exhibited greater electron transfer capacity than those in NBAC, resulting in enhanced contaminant degradation efficiency and long-term stability. The extra organic matter removed by ABAC included refractory substances with a low elemental ratio of oxygen to carbon (O/C) and a high elemental ratio of hydrogen to carbon (H/C). The proposed ABAC filter provides a valuable, practical example of how to modify the BAC technology to shape the microbial community, and its activity, by optimizing the ambient atmosphere.

Goethite Formed in the Periplasmic Space of Pseudomonas sp. JM-7 during Fe Cycling Enhances Its Denitrification in Water.

Denitrification-driven Fe(II) oxidation is an important microbial metabolism that connects iron and nitrogen cycling in the environment. The formation of Fe(III) minerals in the periplasmic space has a significant effect on microbial metabolism and electron transfer, but direct evidence of iron ions entering the periplasm and resulting in periplasmic mineral precipitation and electron conduction properties has yet to be conclusively determined. Here, we investigated the pathways and amounts of iron, with different valence states and morphologies, entering the periplasmic space of the denitrifier Pseudomonas sp. JM-7 (P. JM-7), and the possible effects on the electron transfer and the denitrifying ability. When consistently provided with Fe(II) ions (from siderite (FeCO3)), the dissolved Fe(II) ions entered the periplasmic space and were oxidized to Fe(III), leading to the formation of a 25 nm thick crystalline goethite crust, which functioned as a semiconductor, accelerating the transfer of electrons from the intracellular to the extracellular matrix. This consequently doubled the denitrification rate and increased the electron transport capacity by 4-30 times (0.015-0.04 µA). However, as the Fe(II) concentration further increased to above 4 mM, the Fe(II) ions tended to preferentially nucleate, oxidize, and crystallize on the outer surface of P. JM-7, leading to the formation of a densely crystallized goethite layer, which significantly slowed down the metabolism of P. JM-7. In contrast to the Fe(II) conditions, regardless of the initial concentration of Fe(III), it was challenging for Fe(III) ions to form goethite in the periplasmic space. This work has shed light on the likely effects of iron on environmental microorganisms, improved our understanding of globally significant iron and nitrogen geochemical cycles in water, and expanded our ability to study and control these important processes.

Structural Variation of Precipitates Formed by Fe(II) Oxidation and Impact on the Retention of Phosphate.

The oxidation-precipitation process of Fe(II) is ubiquitous in the environment and critically affects the fate of contaminants and nutrients in natural systems where Fe(II) is present. Here, we explored the effect of H2O2 concentration on the structure of precipitates formed by Fe(II) oxidation and compared the precipitates to those formed by Fe(III) hydrolysis. Additionally, the phosphate retention under different H2O2 concentrations was evaluated. XRD, TEM, PDA, XPS, and UV-visible absorbance spectroscopy were used to characterize the structure of the formed precipitates; UV-visible absorbance spectroscopy was also used to determine the residual phosphate and Fe(II) in solution. It was found that the predominant precipitates in Fe(II) solution changed from planar-shaped crystalline lepidocrocite (γ-FeOOH) to poor short-range order (poorly crystalline) spherical-shaped hydrous ferric oxide (HFO) with increasing H2O2 concentrations. Although the HFO precipitates formed from Fe(II) resembled those formed from Fe(III) hydrolysis, the former was larger and had clearer lattice fringes. During the formation of γ-FeOOH, both Fe(II)-Fe(III) complexes and ligand-to-metal charge transfer processes were observed, and it was found that Fe(II) was present in the planar-shaped precipitates. Fe(II) might be present in the interior of precipitates as Fe(OH)2, which could serve as a nucleus for the epitaxial growth of γ-FeOOH. In addition, the extent of phosphate retention increased with the H2O2 concentration, indicating the increased reactivity of formed precipitates with H2O2 concentration. More phosphate was retained via coprecipitation with Fe than adsorption on the preformed Fe precipitates due to the incorporation of phosphate within the structure of the formed Fe hydroxyphosphate via coprecipitation.

Discovery of Welcome Biopolymers in Surface Water: Improvements in Drinking Water Production.

The presence of biopolymers in surface waters and their significance for potable water supply have received little attention previously owing to their low concentrations. In this paper, we present the results of an extensive study that has investigated the role and benefits of biopolymers during the purification of surface water with reference to their specific biological and physico-chemical properties. Using samples collected from two representative surface waters in China and the United Kingdom, macromolecular biopolymers were separated and concentrated for subsequent investigation of their role in coagulation, metal ion adsorption, and membrane separation. Our results show that biopolymers significantly improve the antifouling capability of membrane nanofiltration, in combination with the enhanced conventional coagulation performance and additional security against several unhealthy metal pollutants (e.g., Fe, Al, and Cr). We believe this is the first study that reveals the versatile benefits and the fate of natural biopolymers in surface water purification processes.

Capabilities of Microbial Consortia from Disparate Environment Matrices in the Decomposition of Nature Organic Matter by Biofiltration.

Dissolved organic matter (DOM) plays a pivotal role in drinking water treatment, influencing the performance of unit processes and final water quality (e.g. disinfection byproduct risk). Biofiltration is an effective method of reducing DOM, but currently lacks a comprehensive appreciation of the association between microbial profiles and biofiltration performance. In this study, bench-scale biofiltration units inoculated with microbial consortia from river and soil matrices were operated successively for comparing their efficacy in terms of DOM removal. The results showed that biofiltration units receiving soil microbes were significantly superior (p < 0.05) to those receiving river inoculated microbes in terms of decomposing DOM recalcitrant fractions and reducing DBP formation potential, resulting in DOC and DBP precursor removals of up to 58.4 % and 87.9 %, respectively. Characterization of the taxonomic composition revealed that differences in the microbial assembly of the two biofilter groups were subject to deterministic rather than stochastic factors. Furthermore, more complicated interspecific relationships and niche structures in soil inoculated biofilters were deciphered by co-occurrence network, providing a plausible profile on a taxonomic division of labor in DOM stepwise degradation. Accordingly, the contribution of microbial compositions was found to be of greater importance than the GAC mass and biomass attached to the media. Thus, this study has advanced the understanding of microbial-mediated DOM decomposition in biofiltration, and also provided a promising strategy for enhancing the process for water use via developing appropriate engineered consortia of bacteria.

Exploring the influence of aquatic phosphate on Fe floc dynamics in water treatment.

The formation of flocs is crucial in the coagulation process of water treatment. However, the nature of ligand exchange on the surface of primary nanoparticles (PNPs) during floc formation requires further investigation to enhance our understanding of the coagulation mechanism. Phosphate (P) is a ubiquitous nutrient ion in aquatic surface water, in this study, the impact of P on floc growth under different pH conditions were investigated. The results revealed that floc growth patterns depended on both P dosage and pH. The mode of ligand exchange between P and in-situ formed ferric hydroxide within a pH range of 5 to 10 was further explored, and remarkable disparities in pH changes induced by P addition were observed. At lower pH levels, OH- release occurred relatively slowly, stabilizing with continued P addition. At neutral pH, OH- release was comparatively higher with P addition, while under alkaline conditions, both the quantity of OH- and its release rate decreased. It was deduced that Fe-OH21/2+ sites function as "active sites," while Fe-OH1/2- sites act as "inert sites" on the surface of PNPs formed during flocculation. These sites are crucial in the interconnections between flocs formed during coagulation and in floc growth. Analyses of Fe PNPs by Scanning Electron Microscopy (SEM) and Transmission Electron Microscopy (TEM), with and without P addition, revealed that the introduction of P inhibits or interferes with the self-crystallization of Fe PNPs through chemical coordination reactions. The results offer deeper insights into the coagulation mechanism and the transformation of Fe flocs in raw waters containing P during water treatment practices.

Simultaneous removal of NOM and sulfate in a bioelectrochemical integrated biofilter treating reclaimed water.

Biofiltration is an environmentally 'green' technology that is compatible with the recently proposed sustainable development goals, and which has an increasingly important future in the field of water treatment. Here, we explored the impacts of bioelectrochemical integration on a bench-scale slow rate biofiltration system regarding its performance in reclaimed water treatment. Results showed that the short-term (<3 months) integration improved the removal of natural organic matter (NOM) (approximately 8.8%). After long-term (5 months and thereafter) integration, the cathodic charge transfer resistance was found to have a significant reduction from 2662 to 1350 Ω. Meanwhile, bioelectrochemical autotrophic sulfate (SO42-) reduction (over 27.6% reduction) through the syntrophic metabolism between hydrogen oxidation strains (genus Hydrogenophaga) and sulfate-reducing microbes (genera Dethiobacter, Desulfovibrio, and Desulfomicrobium) at the cathodic region was observed. More significantly, the microbial-derived chromophoric humic substances were found to act as electron shuttles at the cathodic region, which might facilitate the process of bioelectrochemical SO42- reduction. Overall, this study provided valuable insights into the potential application of bioelectrochemical-integrated biofilter for simultaneous reduction of NOM and SO42- treating reclaimed water.

Uncovering the neglected role of anions in trivalent cation-based coagulation processes.

Coagulation efficiency is heavily contingent upon a profound comprehension of the underlying mechanisms, facilitated by the evolution of coagulation theory. However, the role of anions, prevalent components in raw and wastewaters, has been relatively overlooked in this context. To address this gap, this study has investigated the impact of three common anions (i.e., chloride, sulfate, and phosphate) on Al-based coagulation. The results have shown that the influence of anions on coagulation depends predominantly on their ability to compete with hydroxyl groups throughout the entire coagulation process, encompassing hydrolysis, aggregation, and the growth of large flocs. Moreover, this competition is subject to the dual influence of both anion concentration and hydroxyl concentration (i.e., pH). The results have revealed the intricate interplay between anions and coagulants, their impact on floc structure, and their importance in optimizing coagulation efficiency and ensuring the production of high-quality water.

Fouling behavior of BTEX in petrochemical wastewater treated by nanofiltration (NF).

Membrane fouling generated by small molecular-weight aromatic compounds with poor biodegradability is a major barrier to advanced petrochemical wastewater treatment using nanofiltration (NF) technology. In this study, the fouling behavior of ten BTEX with different substituent existing in petrochemical wastewater on the NF membrane was systematically investigated. By examining the effect of the number, position, and type of substituents on the permeability of NF membranes and membrane resistance analysis, combined with XDLVO theory and correlation analysis, we found that stronger dipole-dipole interactions of BTEX with higher polarity and hydrogen bonding effects between substituents and the membrane surface were verified to be the main forces driving the attachment to the surface of membranes. Furthermore, by analyzing the effect of common inorganic ions in petrochemical wastewater on membrane fouling, it was found that electron-donating substituents (-CH3, -C2H5, and -NH2) enhanced the electron cloud density of the benzene ring, a process that exacerbated membrane fouling by strengthening electrostatic interactions between the benzene ring and Ca2+ ions. The fouling potential of electron-withdrawing substituted (-NO2, -OH) BTEX exhibited the opposite trend. Overall, this study provides a theoretical basis for developing effective membrane fouling control strategies in NF advanced treatment of petrochemical wastewater. ENVIRONMENTAL IMPLICATION: Aromatic chemicals in petrochemical effluent are difficult to degrade, and their accumulation will cause significant harm to humans and ecological systems. Determine the composition of small molecule BTEX in petrochemical wastewater, gain an in-depth comprehension of the membrane fouling behavior of nanofiltration membrane filtration, identify the primary forces causing irreversible membrane surface fouling using experimental data and model fitting, and propose viable anti-fouling membrane modification strategies. Establish a technical foundation for membrane fouling management in the long-term operation of petrochemical wastewater membrane treatment.

New insights into the concentration-dependent regulation of membrane biofouling formation via continuous nanoplastics stimulation.

The release of nanoplastics (NPs) into the environment is growing due to the extensive use of plastic products. Numerous studies have confirmed the negative effects of NPs on microorganisms, which poses uncertainties concerning their impact on nanofiltration (NF) membrane biofouling. This study investigated the initial cell adhesion process, NF membrane biofouling kinetic processes and bacterial responses of Pseudomonas aeruginosa (P. aeruginosa) exposed to varied NPs concentrations (0-50 mg·L-1). Transcriptome analysis demonstrated that low concentration of NPs (0.1 mg·L-1) promoted bacterial quorum sensing, energy metabolism, exopolysaccharide biosynthesis and bacterial secretion systems. Correspondingly, the polysaccharide content increased remarkably to 2.77 times the unexposed control, which served as a protective barrier for bacteria to avoid the impact of NPs-induced stress. Suppressed homologous recombination, microbial metabolic potentials and flagellar assembly were detected in bacteria exposed to a high concentration (50 mg·L-1) of NPs, mainly due to the triggered reactive oxygen species (ROS) generation, genomic DNA damage, and decreased energy production. Overall, enhanced formation of the extracellular polymeric substances (EPS) and aggravated membrane flux decline were observed when NPs interacted with the membrane surface by cell secretions (low NPs levels) or cell lysis (high NPs levels). These findings shed light on understanding the microbial metabolism mechanism and membrane biofouling propensity with NPs stress at both the molecular and gene levels.

Bioinspired stormwater control measure for the enhanced removal of truly dissolved polycyclic aromatic hydrocarbons and heavy metals from urban runoff.

Stormwater harvesting (SWH) addresses the UN's Sustainable Development Goals (SDGs). Conventional stormwater control measures (SCMs) effectively remove particulate and colloidal contaminants from urban runoff; however, they fail to retain dissolved contaminants, particularly substances of concern like polycyclic aromatic hydrocarbons (PAHs) and heavy metals (HMs), thereby hindering the SWH applicability. Here, inspired by protein folding in nature, we reported a novel biomimetic SCM for the efficient removal of dissolved PAHs and HMs from urban runoff. Lab-scale tests were conducted together with a more mechanistic investigation on how the contaminants were removed. By integrating hydrophobic organic chains with low-cost hydrophilic flocculant matrixes, our biomimetic flocculants achieved a 1.4-9.5 times removal of all detected dissolved PAHs and HMs, while enhancing the removal of a wide-spectrum of particulate and colloidal contaminants, compared to existing SCMs. Ecotoxicity, as indicated by newborn Daphnia magna as experimental organisms, was reduced from "acute toxicity" of the original runoff sample (toxic unit of ∼2.6) to "non-toxicity" (toxic unit < 0.4) of the treated water. The improved performance is attributed to the protein-folding-like features of the bioinspired flocculants providing: (i) stronger binding to PAHs (via hydrophobic association) and HMs (via coordination), and (ii) the ability of spontaneous aggregation. The bio-inspired approach in this work holds strong promise as an alternative or supplementary component in SCM systems, and is expected to contribute to sustainable water management practices in relation to SDGs.

A comprehensive evaluation of the temporal and spatial fouling characteristics of RO membranes in a full-scale seawater desalination plant.

The fouling of seawater reverse osmosis (SWRO) membranes remains a persistent challenge in desalination. Previous research has focused mainly on fouling separately; however, organic, inorganic, and biofouling can coexist and influence each other. Hence, in-depth study of the spatiotemporal changes in actual combined fouling in full-scale seawater desalination will provide more effective information for fouling investigation and control. In this study, we monitored (i) the operational performance of a full-scale desalination plant for 7 years and (ii) the development and characterization of membrane and spacer fouling at different locations of spiral-wound membrane modules sampled after 2.5-, 3.5-, and 7-year operation. The findings showed that (i) operational performance indicators declined with time (normalized flux 40 % reduction, salt rejection 2 % in 7 years), with a limited effect of the 20-day cleaning frequency, (ii) fouling accumulation in the membrane module mainly occurred at the feed side of the lead module and the microbial community in these area exhibited the highest diversity, (iii) the dominant microbial OTUs belonged mainly to Proteobacteria (43-70 %), followed by Bacteroidetes (10-11 %), (iv) Phylogenetic molecular ecological networks and Spearman correlation analysis revealed that Chloroflexi (Anaerolineae) and Planctomycetes were keystone species in maintaining the community structure and biofilm maturation and significantly impacted the foulant content on the SWRO membrane, even with low abundance, and that (v) fouling accumulation was composed of polysaccharides, soluble microbial products, marine humic acid-like substances, and inorganic Ca/Fe/Mg/Si dominate the fouling layer of both the membrane and spacer. Overall, variation partitioning analysis quantitatively describes the increasing contribution of biofouling over time. Ultimately, the organic‒inorganic-biofouling interaction (70 %) significantly contributed to the overall fouling of the membrane after 7 years of operation. These results can be used to develop more targeted fouling control strategies to optimize SWRO desalination plant design and operation.

Enhanced removal of trace pesticides and alleviation of membrane fouling using hydrophobic-modified inorganic-organic hybrid flocculants in the flocculation-sedimentation-ultrafiltration process for surface water treatment.

Pesticide concentrations in surface water occasionally exceed regulated values due to seasonal events (rainy season in high intensity agricultural areas) or intermittent discharges (leakage, spillage, or other emergency events). The need to remove pesticide compounds in these situations poses a challenge for drinking water treatment plants (DWTPs). In this work, the performance of dosing hydrophobic-modified inorganic-organic hybrid flocculants (HOC-M; lower acute toxicity than corresponding metal salt coagulants; acceptable economic costs when M=Al or Fe; prepared in large-scale quantities), for the removal of four different pesticides (each initial concentration: 0.25 µg/L) from Yangtze River water, and in mitigating membrane fouling, by an integrated flocculation-sedimentation-ultrafiltration (FSUF) process, was evaluated over a period of 40 days; the FSUF is well-established in many DWTPs. The mechanisms underlying the treatment were unveiled by employing a combination of instrumental characterizations, chemical computations, material flow analyses, and statistical analyses. Efficient pesticide removal (80.3%∼94.3%) and membrane fouling reduction (26.6%∼37.3% and 28.3%∼57.6% for reversible and irreversible membrane resistance, respectively) in the FSUF process were achieved by dosing HOC-M, whereas conventional inorganic coagulants were substantially inferior for pesticide removal (< 50%) and displayed more severe fouling development. Hydrophobic association between the pesticides and the hydrophobic organic chain of HOC-M played a predominant role in the improvement in pesticide removal; coexisting particulate/colloid inorganic minerals and natural organic matter with HOC-M adsorbed on the surface, acting as floc building materials, provided sites for the indirect combination of pesticides into flocs. The observed fouling alleviation from dosing HOC-M was ascribed to both the pre-removal of fouling-causing materials in the flocculation-sedimentation prior to UF, and a stable hydrophilization modification effect of residual HOC-M in the UF unit. The latter effect resulted from a hydrophobic association between the PVDF substrate of the membranes and the hydrophobic organic chains of the HOC-M, causing the hydrophilic ends of the HOC-M to be exposed away from the membrane surface, thereby inhibiting foulant accumulation. This work has not only demonstrated the superior performance of dosing HOC-M in the FSUF process for trace pesticide removal in DWTPs, but also clarified the underlying mechanisms.

Protein-folding-inspired approach for UF fouling mitigation using elevated membrane cleaning temperature and residual hydrophobic-modified flocculant after flocculation-sedimentation pre-treatment.

Hydrophobic-modified flocculants have demonstrated considerable promise in the removal of emerging contaminants by flocculation. However, there is a lack of information about the impacts of dosing such flocculants on the performance of subsequent treatment unit(s) in the overall water treatment process. In this work, inspired by the ubiquitous protein folding phenomenon, an innovative approach using an elevated membrane cleaning temperature as the means to induce residual hydrophobic-modified chitosan flocculant (TRC), after flocculation-sedimentation, to reduce membrane fouling in a subsequent ultrafiltration was proposed; this was evaluated in a continuous flocculation-sedimentation-ultrafiltration (FSUF) process treating samples of the Yangtze River. The hydrophobic chains of TRC had similar temperature-dependent hydrophobicity to those of natural proteins. In the 40-day operation of the FSUF system with combined dosing of alum and TRC, a moderately elevated cleaning water temperature (45 °C) of both backwash with air-bubbling and soaking with sponge-scrubbing cleaning, significantly reduced reversible and irreversible fouling resistance by 49.8%∼61.3% and 73.9%∼83.3%, respectively, compared to the system using cleaning water at 25 °C. Material flow analysis, statistical analysis, instrumental characterizations, and computational simulations, showed that the enhanced fouling mitigation originated from three factors: the reduced contaminant accumulation onto membranes, the strengthened membrane-surface-modification role of TRC, and the weakened structure of the fouling material containing TRC, at the elevated cleaning temperature. Other measures of the performance, these being water purification, membrane stability and economic aspects, also confirmed the potential and feasibility of the proposed approach. This work has provided new insights into the role of hydrophobic-modified flocculants in membrane fouling control, in addition to emerging contaminant removal, in a FSUF surface water treatment process.

FexO/FeNC modified activated carbon packing media for biological slow filtration to enhance the removal of dissolved organic matter in reused water.

The biological slow filtration reactor (BSFR) process has been found to be moderately effective for the removal of refractory dissolved organic matter (DOM) in the treatment of reused water. In this study, bench scale experiments were conducted using a mixture of landscape water and concentrated landfill leachate as feed water, to compare a novel iron oxide (FexO)/FeNC modified activated carbon (FexO@AC) packed BSFR, with a conventional activated carbon packed BSFR (AC-BSFR), operated in parallel. The results showed that the FexO@AC packed BSFR had a refractory DOM removal rate of 90%, operated at a hydraulic retention time (HRT) of 10 h at room temperature for 30 weeks, while under the same conditions the removal by the AC-BSFR was only 70%. As a consequence, the treatment by the FexO@AC packed BSFR substantially reduced the formation potential of trihalomethanes, and to a less extent, haloacetic acids. The modification of FexO/FeNC media raised the conductivity and the oxygen reduction reaction (ORR) efficiency of the AC media to accelerate the anaerobic digestion by consuming the electrons that are generated by anaerobic digestion itself, which lead to the marked improvement in refractory DOM removal.

Extending granular activated carbon (GAC) bed life: A column study of in-situ chemical regeneration of pesticide loaded activated carbon for water treatment.

In-situ chemical regeneration of granular activated carbon (GAC) may represent an advantageous alternative to conventional off-site thermal regeneration in water treatment applications. The performance of chemical regeneration of carbon exhausted by metaldehyde and isoproturon was investigated using rapid small-scale column tests, performed using a sequence of pesticide adsorption and chemical regeneration cycles with a novel alkaline-organic regenerant solution. A fresh regenerant solution was able to achieve 82% and 45% regeneration of carbon exhausted by metaldehyde and isoproturon, respectively. After the first regeneration, the performance declined slightly to 79%, and to 36% after the fourth regeneration. A comparison using a thermally regenerated (operational) carbon suggested that chemical regeneration was more beneficial for carbon exhausted by metaldehyde. The regenerant solution has a potential to be re-used multiple times, thereby minimizing the amount of waste chemicals generated. A series of carbon characterization tests showed that chemical regeneration did not alter the surface area, pore size distribution and surface chemistry of the carbon. As part of the evaluation, the adsorption thermodynamics of virgin and chemically regenerated carbons were determined using isothermal titration calorimetry to evaluate the adsorption behaviour of the pesticides on the carbon samples. The relatively high regeneration efficiency achieved by chemical regeneration, and minimal deleterious effect to the physico-chemical properties of the carbon, demonstrated the beneficial potential of this process as an alternative to conventional thermal regeneration of GAC.

Towards microplastics contribution for membrane biofouling and disinfection by-products precursors: The effect on microbes.

Public awareness of plastic pollution and its impact on the ecosystem has increased rapidly. The microplastics in raw waters and their removal during drinking water treatment is receiving growing attention, but the impact on the efficiency of ultrafiltration has not been examined previously, especially in regard to the formation potential of disinfection by-products (DBPs-FP) in effluent water. In this study, two bench-scale continuous-flow ultrafiltration systems, with and without microplastics, were operated to examine the effect of microplastics on ultrafiltration. Results showed that the microplastics not only increased microbial growth, but also affected the microbial community (e.g. families Xanthobacteraceae, Sphingomonadaceae, Leptolyngbyaceae), which can promote the production of extracellular polymeric substances and nitrogen fixation, causing rapid membrane fouling. The formation potential of THM (TCM and BDCM) and N-DBP (TCNM) species in UF permeate increased with the presence of microplastics, due to changes in water quality. Statistical analysis indicated that tyrosine-like components (C3), ammonium (NH4+-N) and tryptophan-like component (C1) can be used as indicators of the DBPs-FP. This study provides new insights into the relationship between microplastics, membrane biofouling and DBPs-FP, and the potential adverse impact of microplastics on drinking water treatment.

Beneficial role of pre- and post-ozonation in a low rate biofiltration-ultrafiltration process treating reclaimed water.

Previous studies have shown that the combination of biological and ozone oxidation processes can achieve a greater performance in treating natural surface water than each process individually. In this work, we designed and tested an ozonation-gravity-driven up-flow slow rate (0.01 m/h) biofiltration-ozonation (O3-GUSB-O3) process for the pre-treatment of reclaimed water prior to ultrafiltration (UF), with the aim of producing high quality drinking water and a significantly reduced degree of UF fouling. Results showed that O3 coupled with GUSB can effectively remove aromatic compounds (∼ 84.8%), dissolved organic carbon (DOC, ∼ 83.4%), and biopolymers in surface water. In addition, post-ozonation greatly contributed to the reduction of the UF membrane fouling (∼ 6 times greater flux). With regard to the disinfection by-product formation potential (DBPFP) of the final treated water, both trihalomethane formation potential (THMFP) and haloacetic acid formation potential (HAAFP) were greatly reduced (86.4% and 84.8% for THMs and HAAs, respectively). The relationship between DBPFP and various spectral indexes revealed that aromatic compounds and amino acids were more likely to generate DBPs during the disinfection stage. Among these, humic substances were more likely to generate THMs, while low molecular weight carboxylate and carbonyl organic compounds were associated with the generation of HAAs. Moreover, the dosage of O3 during the post-ozonation stage was found to influence directly the generation of DBPs. Overall, this study has conducted a detailed evaluation of a novel multi-ozone biofilter UF process for treating surface water, and the results provide a valuable basis for subsequent studies at larger scale to demonstrate the potential of the treatment process for practical applications.

Stoichiometric carbocatalysis via epoxide-like C-S-O configuration on sulfur-doped biochar for environmental remediation.

Heteroatom doping is a promising technique to enhance biochar for effective environmental remediation. However, development of electroactive heteroatom-doped biochars, e.g., sulfur-doped biochar, has been hindered due to complex nature of non-stoichiometric biomass-derived carbon and changeable electrochemical state of dopants. Herein, we produced a series of wood waste-derived biochars with customized levels of minerals and redox-active moieties, aiming to unravel the crucial factors for sulfur doping. Calcium (Ca) in biochar was found to preferentially coordinate with sulfur to form inactive inorganic sulfur minerals (i.e., CaSO4 and CaS) with inferior catalytic reactivity. After diminishing the inherent Ca minerals beforehand, we could introduce surface phenoxyl-type radicals (C-O•) and vacancy defects on the biochar to develop an electrophilic C-S-O bonding configuration, which guaranteed a high affinity towards peroxymonosulfate (PMS, 2.08 mM g-1, 30 min) and efficient removal of bisphenol A (BPA, 91.1%, 30 min). Scavenging experiments and in-situ Raman analyses indicated that the epoxide-like C-S-O structure induced nucleophilic addition of PMS to generate surface-bound singlet oxygen (1O2, major) and hydroxyl radicals (•OH, minor) through a preservative and stoichiometric interfacial reaction. Overall, the proposed approach overcomes the major hurdles in science-informed fabrication of sulfur-doped biochar and advances its development for environmental remediation.