The recovery of high-purity and high-value FePO4 raw materials from wastewater has great prospects in LiFePO4 battery industry due to the huge demand for new energy vehicle. However, the conventional in-situ FePO4 precipitation, as well as ex-situ PO43− adsorption-alkali regeneration, was incapable of efficiently obtaining high-purity products. To solve these problems, a dual-cycle regeneration method of Fe-NH2-polyacrylonitrile (PAN) adsorbent and H2SO4 desorbing solution was proposed to ex-situ FePO4 recovery from wastewater for Li-battery application. Benefitted from coordination interaction and electrostatic attraction, the maximum PO43− adsorption capacity of Fe-NH2-PAN reached 73.1 ± 0.4 mg/g. The average PO43− removal rate of continuous flow devices were 88.5% and 91.3% when treating low-P-concentration (0.22 mg/L) municipal wastewater (MW) and high-P-concentration (48.9 mg/L) slaughterhouse wastewater (SW) respectively. Furthermore, high-purity FePO4 analyzed by XRD spectra was achieved from the desorption solution at pH ∼1.6, resulting in the ultrahigh P recovery efficiencies of 91.4 ± 3.2%−96.3 ± 2.5% for SW and 82.7 ± 3.5% for MW. Besides, the LiFePO4/C electrodes made of recycled FePO4 exhibited a better discharge capacity (37.3−55.8 mAh/g) than that of commercial FePO4 agent (32.2−35.1 mAh/g) from 80 to 132 cycles, which showed the promising feasibility of recovering FePO4 from wastewater for Li-battery application.

1,2,5,6-tetrabromocyclooctane (TBCO) and 2,3-dibromopropyl-2,4,6-tribromophenyl ether (DPTE), as safer alternatives to traditional brominated flame retardants, have been extensively detected in various environmental media and pose emerging risks. However, much less is known about their fate in the environment. Anaerobic microbial transformation is a key pathway for the natural attenuation of contaminants. This study investigated, for the first time, the microbial transformation behaviors of β-TBCO and DPTE by Dehalococcoides mccartyi strain CG1. The results indicated that both β-TBCO and DPTE could be easily transformed by D. mccartyi CG1 with kobs values of 0.0218±0.0015 h−1 and 0.0089±0.0003 h−1, respectively. In particular, β-TBCO seemed to undergo dibromo-elimination and then epoxidation to form 4,5-dibromo-9-oxabicyclo[6.1.0]nonane, while DPTE experienced debromination at the benzene ring (ortho-bromine being removed prior to para-bromine) rather than at the carbon chain. Additionally, pronounced carbon and bromine isotope fractionations were observed during biotransformation of β-TBCO and DPTE, suggesting that C-Br bond breaking is the rate-limiting step of their biotransformation. Finally, coupled with identified products and isotope fractionation patterns, β-elimination (E2) and Sn2-nucleophilic substitution were considered the most likely microbial transformation mechanisms for β-TBCO and DPTE, respectively. This work provides important information for assessing the potential of natural attenuation and environmental risks of β-TBCO and DPTE.

A comparative study of the different advanced oxidation processes (Fe(II)-Oxone, Fe(II)-H2O2, and Fe(II)-NaClO) was carried out herein to analyze the characteristics of organic components and the migration of heavy metals in waste activated sludge. With the Fe(II)-Oxone and Fe(II)-H2O2 treatments, sludge dewaterability was significantly improved, however, sludge dewaterability was deteriorated by the Fe(II)-NaClO treatment. The enhanced sludge dewaterability by the Fe(II)-Oxone and Fe(II)-H2O2 treatments was strongly correlated with the shifted organic components, particularly proteins, in soluble extracellular polymeric substances (S-EPS), while the deteriorated sludge dewaterability by the Fe(II)-NaClO treatment was strongly correlated with the over release of organic components from bound EPS (B-EPS) to S-EPS. For both the Fe(II)-Oxone and Fe(II)-H2O2 treatments, the radicals preferentially attacked humic acid-like organic components over the protein-like organic components in S-EPS, while for the Fe(II)-NaClO treatment, interestingly, the radicals preferentially attacked the protein-like organic components in both S-EPS and B-EPS. The hydrophilic functional groups like phenolic OH and CO of polysaccharides may be more preferentially migrated to S-EPS of sludge by the Fe(II)-NaClO treatment compared to the other two treatments. With the Fe(II)-Oxone and Fe(II)-H2O2 treatments, the proportion of aliphatic compounds as well as the much oxygenated organic components with a low desaturation and a low molecular weight increased. While with the Fe(II)-NaClO treatment, the proportion of low oxygenated organic components with a high desaturation and a high molecular weight increased. The concentration of total organic carbon, particularly the concentration of proteins, may be the key factor determining the shift of Zn and Cu from sludge solid to liquid phase, along with the high oxidation extent of organic components and close binding to CHOS and CHON compounds as indicated by density functional theory (DFT) calculation. This study systematically revealed the simultaneous sludge dewatering and migration of heavy metals when the role of organic components was factored into herein.

The North China Plain (NCP) has experienced increasingly severe groundwater nitrogen (TN) pollution. However, the factors influencing TN distribution are still poorly understood. Previous studies have identified surface soil nitrogen (TSN) loading and intrinsic groundwater vulnerability (Inv) as the main factors controlling groundwater TN pollution. However, in this study, based on 3245 shallow groundwater samples in the NCP, the multiple regression analysis results(R2=0.105, p<0.001) revealed that the TN was not mainly controlled by TSN and Inv. The lower prediction accuracy indicated the large data dispersion of TN, which might be affected by nitrogen attenuation or accumulation. Thus, the NCP was divided into balance, attenuation, and accumulation zones according to the regression equation. The attenuation zone was mainly distributed in the inter-fan and fan edge parts of the pre-mountain alluvial floodplain, as well as the west and south of the runoff area, while the accumulation zone was mainly distributed in the top part of the pre-mountain alluvial floodplain and the east of discharge area. Multi-indicators comparative analysis showed that compared to the balance (Eh= 76.2 mV) and accumulation (Eh=126.7 mV) zones, the attenuation zone has a stronger reducing environment (Eh=30.8 mV) favorable to denitrification, which can reduce the TN pollution (0.49 mg/L) caused by surface nitrogen input and consume more electron donors. Conversely, the stronger oxidizing environment in the accumulation zone limited denitrification, resulting in higher TN concentrations (19.14 mg/L) in the aquifers under the same TSN and Inv conditions as the other two zones. The standardized effects and significance on each path of the structural equation model (SEMs) fully confirmed the reliability of the above zonal analysis. Importantly, the feature importance (23.6%) of random forest and standardized effects (0.455, p<0.001) of SEMs showed that the Eh had the strongest influence on TN. Thus, the redox conditions of the aquifer, in addition to TSN and Inv, played a crucial role in controlling the TN pollution in the groundwater of a large region. The zoning work and the analysis of influencing factors are important to guide scientific prevention and control of groundwater nitrogen pollution.

Oily sewage has made serious impact on environment and people's life, and its treatment has become a global problem to be urgently solved. Oil-water separation has been considered to be an effective method to treat oily sewage at present. In this work, an underwater super-oleophobic/super-hydrophilic membrane with oil-water separation and self-cleaning properties was fabricated by electrochemical oxidation of sodium lignosulfonate doped polypyrrole. The membrane showed super-hydrophilicity for water-removal in air and super-hydrophilicity for oil-removal underwater in both oxidation and reduction states. The oil-water separation efficiency of the membranes for different organics exceeded 98.44%, no matter in oxidation or reduction state. Moreover, the membrane still exhibited excellent performance in terms of the oil-water separation efficiency and flux after 70 cycles, which were greater than 97.18% and 70.14 L·m−2·h−1, respectively. Simultaneously, through exploration of the mechanism, it was found that the larger anion kept intact in the membrane during the redox process, which made the stability of composition and performance. Thus, the membrane with advantageous properties, including underwater super-oleophobic/super-hydrophilicity, high oil-water separation efficiency, high circulating rate and stability, has significant potential in separation and collection of oily sewage.

In modern water industry, trace organic contaminants are usually subjected to multiple treatment barrier. Structural modification triggered by pretreatment (e.g., prechlorination) may influence the further transformation and fate of contaminants in downstream treatment unit processes. However, our knowledge on this aspect is still limited. In this contribution, we investigated the chlorination of chloroxylenol (PCMX), an antimicrobial agent extensively used during COVID-19 pandemic, and the photoreactivity of its halogenated derivatives. Our results indicated that chlorination of PCMX mainly occurred through electrophilic substitution to give chlorinated products, including Cl- and 2Cl-PCMX. Addition of bromide (Br−) shifted the halogenated derivatives to bromine-containing products such as Br- and 2Br-PCMX. Owing to the bathochromic and “heavy atom” effects of halogen substituents, these products have increased light absorption and photoreactivity. Toxicity evaluation suggested that these halo-derivatives also have much higher persistence, bioaccumulation, and toxicity (PBT) than the parent PCMX. Results of this contribution advance our understanding of the transformation of PCMX during chlorination and the photochemical activity of its halogenated derivatives in sequential UV disinfection process or sunlit surface waters.

Photosensitized biohybrid system (PBS) enables bacteria to exploit light energy harvested by semiconductors for rapid pollutants transformation, possessing a promising future for water reclamation. Maintaining a biocompatible environment under photocatalytic conditions is the key to developing PBS-based treatment technologies. Natural microbial cell is surrounded by extracellular polymeric substances (EPS) that either be tightly bound to the cell wall (i.e., tightly bound EPS, tbEPS) or loosely associated with cell surface (i.e., loosely bound EPS, lbEPS), which provides protection from unfavorable environment. We hypothesized that providing EPS fractions can enhance bacterial viability under adverse environment created by photocatalytic reactions. We constructed a model PBS consisting of Shewanella oneidensis and CdS using Cr(VI) as the target pollutant. Results showed complete removal of 25 mg/L Cr(VI) within 90 minutes without an electron donor, which may mainly rely on the synergistic effect of CdS and bacteria on photoelectron transfer. Further sustainability evaluation of pristine PBS and PBS with extra EPS fractions (including lbEPS and tbEPS) for Cr(VI) treatment showed that PBS with extra lbEPS achieved efficient Cr(VI) removal within five consecutive batch treatment cycles, compared to the three cycles both in pristine PBS and PBS with tbEPS. After addition of lbEPS, the accumulation of reactive oxygen species (ROS) was greatly reduced via the EPS-capping effect and quenching effect, and the toxic metal internalization potential was lowered by complexation with Cd and Cr, resulting in enhanced bacterial viability during photocatalysis. This facile and efficient cytoprotective method helps the rational design of PBS for environmental remediation.

Hundreds of millions of people are exposed to excessive levels of fluoride in drinking water predominately in low-resource communities. Activated alumina is recognized as the Best Available Technology for fluoride removal from drinking water by the US Environmental Protection Agency, but it has substantial economic and environmental costs. Bonechar is a more environmentally friendly and potentially lower cost alternative adsorbent. Here, fluoride adsorption from groundwater (pH 8.1±0.2) by activated alumina was compared with bonechar primarily produced from bovines bones at peak heating temperatures between 400-1,100°C in a modular top-lit updraft drum (TLUD) stove (using a bone-wood mixture) and furnace. TLUD and furnace bonechar produced at peak temperatures 650-1,000°C and 400-800°C, respectively, outperformed activated alumina in batch tests (i.e., required smaller doses to achieve 90% fluoride removal). The impact of using bovine versus porcus bones to produce bonechar had a negligible impact on fluoride adsorption. A wide range of peak temperatures in the TLUD achieved by varying primary air flow rates and fuel selection (e.g., bone-to-wood mass ratios) produced efficient fluoride adsorbents. This finding demonstrates that a TLUD can be a robust, operationally flexible production system. Fluoride removal by TLUD and furnace bonechars showed strong, negative correlations (R2 ≥0.88) with organic matter content. Bonechar pilot column tests indicated that the mass transfer zone was captured (i.e., immediate fluoride breakthrough was not observed) at an empty bed contact time (EBCT) of 5 min, increasing EBCT to 30 min had a minimal impact on adsorption efficiency, and intermittent operation (3-10 d shut-off periods) decreased effluent fluoride concentrations. Furnace bonechars produced at peak temperatures 400-700°C outperformed activated alumina in pilot columns. Differences in adsorption efficiencies in batch and column tests were associated with the linearity of fluoride adsorption. A theoretical model quantifying adsorption linearity with Freundlich 1/n values was able to predict adsorber performance solely based on batch test data.

Understanding response of bacterioplankton community responsible for maintaining ecological functions of aquatic ecosystems to environmental disturbance is an important subject. However, it remains largely unclear how bacterioplankton generalists and specialists responding to dredging disturbance. Illumina MiSeq sequencing and statistical analyses were used to evaluate landscape patterns, evolutionary potentials, environmental adaptability, and community assembly processes of generalists and specialists in response to dredging in eutrophic Lake Nanhu. The Proteobacteria and Actinobacteria dominated bacterioplankton communities of generalists and specialists, and abundances of Proteobacteria decreased and Actinobacteria increased after dredging. The generalists displayed higher phylogenetic distance, richness difference, speciation rate, extinction rate, and diversification rate as well as stronger environmental adaptation than that of specialists. In contrast, the specialists rather than generalists showed higher community diversity, taxonomic distance, and species replacement as well as closer phylogenetic clustering. Stochastic processes dominated community assemblies of generalists and specialists, and stochasticity exhibited a larger effect on community assembly of generalists rather than specialists. Our results emphasized that lake dredging could change landscape patterns of bacterioplankton generalists and specialists, whereas the short-term dredging conducted within one year was unable to reverse community difference between generalists and specialists. Our findings extend our understanding of how bacterioplankton generalists and specialists responding to dredging disturbance, and these findings might in turn call on long-term dredging for better ecological restoration of eutrophic lakes.

High-frequency nitrate-N (NO3−−N) data are increasingly available, while accurate assessments of in-stream NO3−−N retention in large streams and rivers require a better capture of complex river hydrodynamic conditions. This study demonstrates a fusion framework between high-frequency water quality data and hydrological transport models, that (1) captures river hydraulics and their impacts on solute signal propagation through river hydrodynamic modeling, and (2) infers in-stream retention as the differences between conservatively traced and reactively observed NO3−−N signals. Using this framework, continuous 15-min estimates of NO3−−N retention were derived in a 6th-order reach of the lower Bode River (27.4 km, central Germany), using long-term sensor monitoring data during a period of normal flow from 2015-2017 and a period of drought from 2018-2020. The unique NO3−−N retention estimates, together with metabolic characteristics, revealed insightful seasonal patterns (from high net autotrophic removal in late-spring to lower rates, to net heterotrophic release during autumn) and drought-induced variations of those patterns (reduced levels of net removal and autotrophic nitrate removal largely buffered by heterotrophic release processes, including organic matter mineralization). Four clusters of diel removal patterns were identified, potentially representing changes in dominant NO3−−N retention processes according to seasonal and hydrological conditions. For example, dominance of autotrophic NO3−−N retention extended more widely across seasons during the drought years. Such cross-scale patterns and changes under droughts are likely co-determined by catchment and river environments (e.g., river primary production, dissolved organic carbon availability and its quality), which resulted in more complex responses to the sequential droughts. Inferences derived from this novel data-model fusion provide new insights into NO3− dynamics and ecosystem function of large streams, as well as their responses to climate variability. Moreover, this framework can be flexibly transferred across sites and scales, thereby complementing high-frequency monitoring to identify in-stream retention processes and to inform river management.

Elemental sulfur packed-bed (S0PB) bioreactors for autotrophic denitrification have gained more attention in wastewater treatment due to their organic carbon-free operation, low operating cost, and minimal carbon emissions. However, the rapid development of microbial S0-disproportionation (MS0D) in S0PB reactor during deep denitrification poses a significant drawback to this new technology. MS0D, the process in which sulfur is used as both an electron donor and acceptor by bacteria, plays a crucial role in the microbial-driven sulfur cycle but remains poorly understood in wastewater treatment setups. In this study, we induced MS0D in a pilot-scale S0PB reactor capable of denitrifying over 1000 m3/d nitrate-containing wastewater. Initially, the S0PB reactor stably removed 6.6 mg-NO3−-N/L nitrate at an empty bed contact time (EBCT) of 20 mins, which was designated the S0-denitrification stage. To induce MS0D, we reduced the influent nitrate concentrations to allow deep nitrate removal, resulted in the production of large quantities of sulfate and sulfide (SO42−:S2− 3.2 w/w). Meanwhile, other sulfur-heterologous electron acceptors (SHEAs), e.g., nitrite and DO, were also kept at non-detectable levels. The negative correlations between the SHEAs concentrations and the sulfide productions indicated that the absence of SHEAs was a primary inducing factor to MS0D. The microbial community drastically diverged in response to the depletion of SHEAs during the switch from S0-denitrification to S0-disproportionation. An evident enrichment of sulfur-disproportionating bacteria (SDBs) was found at the S0-disproportionation stage, accompanied by the decline of sulfur-oxidizing bacteria (SOBs). In the end, we discovered that shortening the EBCT and increasing the reflux ratio could inhibit sulfide production by reducing it from 43.9 mg/L to 3.2 mg/L or 25.5 mg/L. In conclusion, our study highlights the importance of considering MS0D when designing and optimizing S0PB reactors for sustainable autotrophic sulfur denitrification in real-life applications.

Despite the significance of rivers and streams as pathways for microplastics (MP) entering the marine environment, limited research has been conducted on the behavior of MP within fluvial systems. Specifically, there is a lack of understanding regarding the infiltration and transport dynamics of MP across the streambed interface and within the hyporheic sediments. In this study, transport and retention of MP are investigated using a new numerical modeling approach. The model is built as a digital twin of accompanying flume experiments, which are used to validate the simulation results. The model accurately represents particle transport in turbulent water flow and within the hyporheic zone (HZ). Simulations for transport and infiltration of 1 µm MP particles into a sandy streambed demonstrate that the advection-dispersion equation can be used to adequately represent particle transport for pore-scale sized MP within the HZ. To assess the applicability of the modeling framework for larger MP, the experiment was repeated using 10 µm particles. The larger particles exhibited delayed infiltration and transport behavior, and while the model successfully represented the spatial extent of particle transport through the HZ, it was unable to fully replicate hyporheic transit times. This study is the first to combine explicit validation against experimental data, encompassing qualitative observations of MP concentration patterns and quantification of fluxes. By that, it significantly contributes to our understanding of MP transport processes in fluvial systems. The study also highlights the advantages and limitations of employing a fully integrated modeling approach to investigate the transport and retention behavior of MP in rivers and streams.

Mn-modified biochars (BCs) were developed by pre-treatment of feedstock (MBCs) or post-modification of biochar (BCM), for simultaneous adsorption and degradation of a model pollutant, cephalexin. The apparent removal rates of cephalexin in the presence of MBCs (2.49 - 6.39 × 10−2 h−1) and BCM (13.3 × 10−3 h−1) were significantly higher than that in the presence of biochar prepared under similar conditions (4.2 × 10−3 h−1). While the •OH generated from the activation of dissolved O2 by the persistent free radicals (PFRs) and phenolic -OH on BC could cause degradation of cephalexin, its removal was drastically enhanced through direct oxidation by the MnOx and related Mn species on Mn-modified BCs. The removal of cephalexin by MBCs decreased as the solution pH was raised from 5.0 to 9.0, which supports the critical role played by Mn3O4 in its oxidation. Removal of cephalexin in the presence of MBCs and Mn3O4 was enhanced with the introduction of Mn(II) ions, suggesting that the Mn3O4 present on MBCs facilitates the re-oxidation of Mn(II) to highly reactive Mn(III). While MnO2 anchored on BCM also enhanced the cephalexin oxidation, the active sites of BC and MnO2 were partially destroyed during post-modification of BC, compromising the redox cycling of Mn(II)/Mn(III) and the generation of •OH. As a result, the performance of BCM in oxidizing cephalexin was inferior to that of MBCs. These findings shed new light on the development of environmentally benign sorbents capable of simultaneously adsorbing and oxidizing organic pollutants.

Microbes are sensitive indicators of estuarine processes because they respond rapidly to dynamic disturbance events. As most of the world's population lives in urban areas and climate change-related disturbance events are becoming more frequent, estuaries bounded by cities are experiencing increasing stressors, at the same time that their ecosystem services are required more than ever. Here, using a multidisciplinary approach, we determined the response of planktonic microbial assemblages in response to seasonality and a rainfall disturbance in an urban estuary bounded by Australia's largest city, Sydney. We used molecular barcoding (16S, 18S V4 rRNA) and microscopy-based identification to compare microbial assemblages at locations with differing characteristics and urbanisation histories. Across 142 samples, we identified 8,496 unique free-living bacterial zOTUs, 8,175 unique particle associated bacterial zOTUs, and 1,920 unique microbial eukaryotic zOTUs. Using microscopy, we identified only the top 10 µm), however quantification was possible. The site with the greater history of anthropogenic impact showed a more even community of associated bacteria and eukaryotes, and a significant increase in dissolved inorganic nitrogen following rainfall, when compared to the more buffered site. This coincided with a reduced proportional abundance of Actinomarina and Synechococcus spp., a change in SAR 11 clades, and an increase in the eukaryotic microbial groups Dinophyceae, Mediophyceae and Bathyoccocaceae, including a temporary dominance of the harmful algal bloom dinoflagellate Prorocentrum cordatum (syn. P. minimum). Finally, a validated hydrodynamic model of the esturary supported these results, showing that the more highly urbanised and upstream location consistently experienced a higher magnitude of salinity reduction in response to rainfall events during the study period. The best abiotic variables to explain community dissimilarities between locations were TDP, PN, modelled temperature and salinity (r = 0.73) for the free living bacteria, TP for the associated bacteria (r = 0.43), and modelled temperature (r = 0.28) for the microbial eukaryotic communities. Overall, these results show that a minor disturbance such as a brief rainfall event can significantly shift the microbial assemblage of an anthropogenically impacted area within an urban estuary to a greater degree than a seasonal change, but may result in a lesser response to the same disturbance at a buffered, more oceanic influenced location. Fine scale research into the factors driving the response of microbial communities in urban estuaries to climate related disturbances will be necessary to understand and implement changes to maintain future estuarine ecosystem services.

The importance of controlling internal phosphorus (P) pollution in lakes has been recognized by scientists, and the application of P-inactivating materials to immobilize sediment P is often considered. However, sediment resuspension, a typical physical process occurring in lakes, has been demonstrated to increase the uncertainty of immobilization. In this study, we explored the characteristics of P immobilization in the horizontal direction under the effects of resuspension using annular flume tests based on drinking water treatment residuals (DWTR). The results showed that resuspension caused the mobile P and bioavailable P to be heterogeneously distributed in sediment planes after DWTR addition, resulting in varying P immobilization efficiencies at different depths. In particular, the coefficient of variation was 14.2–24.5% for mobile P horizontally distributed in the planes, resulting in a range of mobile P decreasing efficiencies at 24.0–47.8%. Further analysis indicated that variations in horizontal distribution were typically due to the varied migration of particles of different sizes. Specifically, P immobilization in sediment planes at different depths was regulated by promoting the migration of 63 μm DWTR (to the bottom) with the mixing of <8 μm DWTR in the sediment plane at different depths. The varying horizontal distributions of total P, resulting from the migration of 16–32 μm sediment, could enhance the heterogeneities of the P immobilization. Thus, the particle size of materials and lake background conditions, for example, the hydrodynamic characteristics and P distributions in differently sized sediments, should be used as key bases to select or develop P-inactivating materials to design proper remediation strategies for controlling internal P pollution in lakes.

Manganese (Mn) oxides are extensively used to oxidize As(III) present in ground, drinking, and waste waters to the less toxic and more easily removable As(V). The common presence of multiple other cations in natural waters, and more especially of redox-sensitive ones such as Fe2+, may however significantly hamper As(III) oxidation and its subsequent removal. The present work investigates experimentally the influence of Mn(III) chelating agents on As(III) oxidation process in such environmentally relevant complex systems. Specifically, the influence of sodium pyrophosphate (PP), an efficient Mn(III) chelating agent, on As(III) oxidation by birnessite in the presence of Fe(II) was investigated using batch experiments at circum-neutral pH. In the absence of PP, competitive oxidation of Fe(II) and As(III) leads to Mn oxide surface passivation by Fe(III) and Mn(II/III) (oxyhydr)oxides, thus inhibiting As(III) oxidation. Addition of PP to the system highly enhances As(III) oxidation by birnessite even in the presence of Fe(II). PP presence prevents passivation of Mn oxide surfaces keeping As and Fe species in solution while lower valence Mn species are released to solution. In addition, reactive oxygen species (ROS), tentatively identified as hydroxyl radicals (•OH), are generated under aerobic conditions through oxygen activation by Fe(II)–PP complexes, enhancing As(III) oxidation further. The positive influence of Mn(III) chelating agents on As(III) oxidation most likely not only depend on their affinity for Mn(III) but also on their ability to promote formation of these active radical species. Finally, removal of As(V) through sorption to Fe (oxyhydr)oxides is efficient even in the presence of significant concentrations of PP, and addition of such Mn(III) chelating agents thus appears as an efficient way to enhance the oxidizing activity of birnessite in large-scale treatment for arsenic detoxification of groundwaters.

Peracetic acid (PAA) may be used in drinking water treatment for pre-oxidation and mussel control at the intake. PAA may exert a downstream chlorine demand, but full details of this reaction have not been reported. There are three possible mechanisms of this demand: (1) PAA may react directly with chlorine; (2) PAA exists in equilibrium with hydrogen peroxide, which is known to react with chlorine; and (3) as H2O2 reacts with chlorine, PAA will hydrolyze to form more H2O2 to re-establish PAA/H2O2 equilibrium, thereby serving as an indirect reservoir of chlorine demand. While the H2O2 reaction with chlorine is well known, the other mechanisms of possible PAA-induced chlorine demand have not previously been investigated. The observed molar stoichiometric ratio of PAA to free chlorine (n) for the presumed direct PAA + free chlorine reaction was determined to be approximately 2, and the corresponding observed reaction rate coefficients at pH 6, 7, 8, and 9 were 2.76, 3.14, 1.61, 10.1 M−n·s−1, respectively (at 25°C). With these estimated values, a kinetic model was built to predict the chlorine demand by PAA. The results suggest that chlorine demand from PAA is likely to be negligible over the course of several days (e.g., 8) and high PAA:Cl2 molar ratios (e.g., >2:1).

Estuaries are significant sources of the ozone-depleting greenhouse gas N2O. However, owing to large spatial heterogeneity and discrete measurements, N2O emissions from estuaries are considerably uncertain. Microbial processes are disputed in terms of the dominant N2O production under severe human disturbance. Herein, combining real-time and high-resolution measurements with bioinformatics analysis, we accurately mapped the consecutive two-dimensional N2O distribution in the Pearl River Estuary (PRE), China, and revealed its underlying microbial community processes and mechanisms. Both the horizontal and vertical distributions of N2O concentrations varied greatly at fine scales. Supersaturated N2O concentrations (9.1 to 132.2 nmol/L) in the surface water decreased along the estuarine salinity gradient, with several emission hotspots scattered upstream. The vertical N2O distribution showed marked differences from complete mixing upstream to incomplete mixing downstream, with constant or changeable concentrations with increasing depth. Furthermore, spatially varied denitrifying and nitrifying microorganisms controlled the N2O production and distribution in the PRE, with denitrification playing the dominant role. The nirK-type and nirS-type denitrifying bacteria were the primary producers of N2O in the water and sediment columns, respectively. In addition, substrate concentration (NO3− and DOC) regulated N2O production by affecting key microbial processes, while physical influences (water-mass mixing and salt wedges) reshaped N2O distribution. With this information, a conceptual model of estuarine N2O production and distribution was constructed to generalize the possible biochemical processes under environmental constraints, which could provide insights into the N2O biogeochemical cycle and emission mitigation from a mechanistic perspective.

Bisphenol analogues (BPs) and natural estrogens (NEs) as two important groups of endocrine-disrupting compounds (EDCs) in drinking water treatment plants (DWTPs) have been hardly investigated except bisphenol A (BPA) and three major NEs including estrone (E1), 17β-estradiol (E2) and estriol (E3). In this study, a GC-MS analytical method was firstly established and validated for trace simultaneous determination of ten BPs and twelve NEs in drinking water, which included BPA, bisphenol B (BPB), bisphenol C (BPC), bisphenol E (BPE), bsiphenol F (BPF), bsiphenol P (BPP), bisphenol S (BPS), bisphenol Z (BPZ), bisphenol AF (BPAF), bisphenol AP (BPAP), E1, E2, E3, 17α-estradiol (17α-E2), 2-hydroestrone (2OHE1), 16hydroxyestrone (16α-OHE1), 4-hydroestrone (4OHE1), 2-hydroxyesstradiol (2OHE2), 4-hydroxyestradiol (4OHE2), 17-epiestriol (17epiE3), 16-epiestriol (16epiE3) and 16keto-estraiol (16ketoE2). This investigation showed that eighteen out of twenty-two targeted compounds were detected in drinking source waters of eight DWTPs with concentrations ranging from not detected to 142.8 ng/L. Although the conventional treatment process of DWTP could efficiently remove both BPs and NEs with respective removal efficiencies of 74.1%-90.9% and 74.5%-100%, BPA, BPS, BPE, BPZ, E1, 2OHE1, and 2OHE2 were found in the finished drinking waters. Chlorination could remove part of BPs and NEs, but the efficiency varied greatly with DWTP and the reason was unknown. In the finished drinking waters of eight DWTPs, the highest chemically calculated estrogen equivalence (EEQ) derived from BPs and NEs was up to 6.11 ngE2/L, which was over 22 times that could do harm to zebrafish, indicating a potential risk to human health. Given the fact that many chlorination products of BPs and NEs likely have higher estrogenic activities, the estrogenic effect of BPs and NEs in finished drinking water should be accurately examined urgently with the inclusion of BPs, NEs as well as their main chlorinated by-products. This study shed new light on the occurrence, removal, and potential estrogenic effects of BPs and NEs in DWTPs.

Harmful algal blooms negatively impact freshwater, estuarine, and marine systems worldwide, including those used for drinking water, recreation, and aquaculture, through the production of toxic and non-toxic secondary metabolites as well as hypoxic events that occur when algal blooms degrade. Consequently, water resource managers often utilize chemical, bacterial, physical, and/or plant-based treatments to control algal blooms and improve water quality. However, awareness of available treatments may be limited, and there is ambiguity among the effects of algal bloom treatments across studies. Such variation within the literature and lack of knowledge of other tested treatments leave uncertainty for water resource managers when deciding what treatments are best to control algal blooms and improve water quality. Our primary objective was to synthesize data from 39 published and unpublished studies that used one of 28 chemical, bacterial, physical, and/or plant-based treatments in field experiments on various water quality measurements, including phytoplankton pigments and cell density, cyanobacterial toxins (microcystin), and common off-flavors (i.e., taste and odor compounds; geosmin and 2-methylisoborneol). We hypothesized that treatments would improve water quality. Across all studies and treatment types (227 effect sizes), water quality improvements were observed when measured at the time of greatest decline following treatment or at the end of the experiment. However, these findings were primarily mediated by only four chemicals, namely copper sulfate, hydrogen peroxide, peracetic acid, and simazine. None of the bacterial, physical, or plant-based treatments were shown to significantly improve water quality by themselves. Results from this synthesis quantitatively showed that most treatments fail to improve water quality in the field and highlight the need for more research on existing and alternative treatments.