Phosphorus recovery from sewage sludge via Mg-air battery system.

A pressing issue in contemporary society is the resource scarcity of phosphorus. Operating on the principle of electrochemical reactions between Mg as the anode and oxygen from air as the cathode, Mg-air batteries (MAB) have been employed to provide new prospects for phosphorus recovery in struvite form. Different phosphorus concentrations and reaction time impact struvite generation in MAB systems; however, the exact mechanism has rarely been investigated. We investigated how varying the initial phosphorus concentration and the reaction time affects phosphorus recovery, electricity generation, and the efficiency of struvite production in MAB. Additionally, we examine the impact of solid carbon sources on phosphorus transformation in sludge. The findings revealed that the incorporation of solid carbon sources facilitated the release of phosphate by changing phosphorus speciation. The electrolyte derived from the conditioned sludge filtrate exhibited a remarkable phosphorus removal efficiency of 91.7 % within 1 h, yielding the highest struvite purity of ∼70 %, whereas that using raw sludge filtrate or extending the reaction time was found to be less effective, even reducing struvite formation. Furthermore, different electrolytes influence the system's ability to passivate anode, and electrolytes with higher phosphorus concentrations have better electricity production performance. The results by Visual MINTEQ model confirmed that longer reaction times and lower initial phosphorus concentrations can negatively affect struvite formation by introducing Mg3(PO4)2 and Mg(OH)2. The integration of agricultural waste as carbon sources with MAB for phosphorus recovery represents a potential methodology for struvite recuperation from sewage sludge, thereby heralding a sustainable strategy for resource recovery.

Computational-aided analysis of the pathway and mechanism of dichloroacetonitrile formation from phenylalanine upon chloramination.

Dichloroacetonitrile (DCAN) is an emerging disinfection by-product (DBP) that is widespread in drinking water. However, the pathway for DCAN formation from aromatic amino acids remains unclear, leading to a lack of an understanding of its explicit fate during chloramination. In this study, we investigated the specific formation mechanism of DCAN during the chloramination of phenylalanine based on reaction kinetics and chemical thermodynamics. The reason for differences between aldehyde and decarboxylation pathways was explained, and kinetic parameters of the pathways were obtained through quantum chemistry calculations. The results showed that the reaction rate constant of the rate-limiting step of the aldehyde pathway with 1.9 × 10-11 s-1 was significantly higher than that of decarboxylation (3.6 × 10-16 s-1 M-1), suggesting that the aldehyde pathway is the main reaction pathway for DCAN formation during the chloramination of phenylalanine to produce DCAN. Subsequently, theoretical calculations were performed to elucidate the effect of pH on the formation mechanism, which aligned well with the experimental results. Dehydrohalogenation was found to be the rate-limiting step under acidic conditions with reaction rate constants higher than those of the rate-limiting step (expulsion of amines) under neutral conditions, increasing the rate of DCAN formation. This study highlights the differences in DCAN formation between the decarboxylation and aldehyde pathways during the chloramination of precursors at both molecular and kinetic levels, contributing to a comprehensive understanding of the reaction mechanisms by which aromatic free amino acids generate DCAN.

Application of fluorescence spectra and molecular weight analysis in the identification of algal organic matter-based disinfection by-product precursors.

Algal organic matter (AOM) is considered to be threatening for the consumption of disinfectants and the formation of disinfection by-products (DBPs) during the disinfection process. Incompatible parameters in the conventional pretreatment of algal-laden water will lead to counterproductive results, such as AOM release. Therefore, the generation of AOM and its conversion to DBPs during pretreatment should be observed. The characteristics of DBPs from extracellular organic matter (EOM) and intracellular organic matter (IOM) were epitomized and simulation experiments were conducted in deionized (DI) water and source water under pretreatment conditions. Differences in DBP formation between the different backgrounds during chlorination and powdered activated carbon (PAC) treatment were investigated. Instead of monotonous excitation-emission matrix (EEM) spectra, molecular weight (MW) fractionation was simultaneously applied to elucidate the mechanisms of chlorination and PAC adsorption on AOM-based DBPs. The fluorescence regional integration (FRI) EEM results showed a clear correlation between the fluorescent properties and MW distribution of AOM. A decreasing trend was observed after a rapid increase in fluorescence intensity during the chlorination and PAC treatment of water samples in the simulation experiments in deionized (DI) water and source water. The DBP formation potential (FP) in the source water was consistent with the change in AOM during chlorination and PAC adsorption. In addition, EEM showed decent predictability of AOM-based trihalomethanes (THM) FPs (R2 = 0.77-0.99) invoking a combination with MW fractionation. Macromolecular protein compounds were highly correlated with the formation of dichloroacetonitrile (DCAN) (R2 = 0.89-0.98). These post-mortems results imply that EEM spectra are a useful tool for identifying AOM-based precursors to reveal the accurate environmental fate and risk assessments of AOM.

Inactivation mechanism of E. coli in water by enhanced photocatalysis under visible light irradiation.

Developing efficient and economical technologies for drinking water disinfection remains a challenge. We synthesized Ag/AgBr/LDH doped with various silver mass concentrations and explored its ability to inactivate E. coli under visible light irradiation (λ ≥ 400 nm). Our results indicated a total inactivation of E. coli (107 CFU·mL-1) within 80 min using 2 % Ag/AgBr/LDH in a laboratory-scale test. The method was evaluated for disinfecting three effluent samples collected from one drinking water treatment plant, covering representative water treatment processes. After five consecutive runs, the inactivation efficiency decreased slightly to 89 % in CFU·mL-1, indicating that the photocatalysts had excellent stability and reusability. The mechanisms were analyzed by combining chemical and biological methods. It was verified that singlet oxygen (1O2), hydrogen peroxide (H2O2), and photo-generated electrons (e-) were significant contributors to the inactivation process. Scanning electron microscopy images analysis showed the disruption of the membrane integrity of E. coli by photocatalytic oxidation. Internal component leakage and reduced enzyme activity were also observed in terms of K+ leakage, ß-galactosidase activity, and antioxidant enzyme activity. The results by the transcriptomic analysis implied that Ag/AgBr/LDH regulating the oxidative stress response and cell membrane damage related genes was the main inactivation mechanism.

Molecular characterization of disinfection byproduct precursors in filter backwash water from 10 drinking water treatment plants.

Organic matter reacts with chlorine forming disinfection byproducts (DBPs) including trihalomethanes (THMs), haloacetamides (HAMs), haloacetic acids (HAAs), and haloacetonitriles (HANs). Filter backwash water (FBW) is either released back to the environment or recycled to the head of the treatment plant after solids settling and the remaining dissolved organic matter is a significant pool of DBP precursors that are not well understood. We characterized dissolved organic matter in FBW from 10 treatment plants and low molecular weight (MW < 1 kDa) organic matter contributed the most to DBP formation. We demonstrated overall similarity of the molecular composition (e.g., elemental ratios, m/z, DBE) of the 10 samples of FBW by Fourier transform ion cyclotron resonance mass spectrometry. Aromatic and more highly oxidized compounds preferentially reacted with chlorine, forming DBPs. Low MW (<450 Da) aliphatic compounds, and highly unsaturated and phenolic compounds were the primary precursors of THMs, HANs, and HAMs, and the formation potentials (FPs) of these groups of DBPs were correlated with multiple individual molecular formulae. HAA FPs were correlated with low MW, highly unsaturated and phenolic compounds. These advances in the understanding of the molecular composition of DBP precursors in FBW may develop the effective strategies to control DBP formation and limit impacts on the quality of finished water, and can be expanded to understanding DBP precursors in drinking water sources.

Degradation pathways and kinetics of chloroacetonitriles by UV/persulfate in the presence of bromide.

Chloroacetonitriles (CANs) are highly toxic nitrogenous disinfection by-products (N-DBPs), which frequently appear in water supply systems and have attracted widespread attention. UV/persulfate (PS) is an effective method to degrade CANs. Bromide (Br-) is widespread in aquatic environments and reacts with oxidative radicals to produce secondary reactive bromine species (RBS), which affects the degradation of CANs by UV/PS. It was found that the degradation of CANs was highly inhibited by Br-. The apparent first-order reaction rate constants of monochloroacetonitrile (MCAN), dichloroacetonitrile (DCAN) and trichloroacetonitrile (TCAN) decreased from 2.63 × 10-3, 2.00 × 10-3 and 8.66 × 10-4 s-1 to 2.58 × 10-4, 1.61 × 10-4 and 1.59 × 10-4 s-1, respectively after adding 20 µM of Br-. HO• was the main radicals contributing to the degradation of CANs when the concentration of Br- was less than 10 µM, compared with SO4•- and direct photolysis. When the concentration of Br- was up to 20 µM, the contributions of RBS accounted for 85.7%, 90.7% and 89.9% of the apparent degradation rate constants of CANs, respectively. During the reaction, about 65% of nitrogen atoms were transformed into NO3- by the CC bond cleavage and oxidation. The yields of Cl- by dechlorination reaction accounted for 83.5%, 71.0% and 41.2% of the chlorine contents in MCAN, DCAN and TCAN, respectively. It was verified that CANs react with free bromine (HOBr) to produce bromochloroacetonitrile (BCAN). DCAN and TCAN are hydrolyzed to produce corresponding haloacetamides (HAMs), which are further reacted with HOBr to produce bromodichloroacetic acid (BDCAA). Furthermore, the generation of bromate was also worth noting via the oxidation of Br- in the UV/PS system.

Accumulation of chiral pharmaceuticals (ofloxacin or levofloxacin) onto polyethylene microplastics from aqueous solutions.

Drug chirality is attracting increasing attention because the enantiomers of the same chiral pharmaceutical usually exhibit different biological activities, metabolic pathways, and toxicities. The ubiquitous presence of microplastics (MPs) can enrich organic pollutants commonly found in the environment. However, knowledge about the enrichment of pharmaceutical enantiomers to MPs is relatively limited. We investigated the occurrence of enantioselectivity of ofloxacin (OFL) and levofloxacin (LEV) in the adsorption processes on polyethylene (PE) and the interactions influenced by environmental factors. The results showed that the adsorption efficiency of OFL was generally 3-5% (p < 0.05) higher than that of LEV, indicating the different affinities of the enantiomers to PE, but the adsorption process of OFL and LEV on PE was both well described by pseudo-first-order kinetics and liner isotherm models. The chirality of OFL and LEV was not affected by sizes of PE particles and solution salinity due to the identical physicochemical properties. An examination of pH effect indicated that OFL showed better acid-base adaptability than LEV. Moreover, the differences in enantiomeric enrichment between OFL and LEV on PE were promoted with increasing UV light exposure time and natural organic matter (NOM) concentrations. Using Fourier transform infrared spectroscopy (FTIR), we demonstrated that the constituents of the functional groups in chiral NOM were greatly related to the enantiomer stereoselectivity of OFL, subsequently affecting their adsorption in a chiral environment. The excitation-emission matrix (EEM) spectra confirmed the enantioselective behaviors of chiral pharmaceuticals under UV light due to the different optical activity and humic acid-like and fulvic acid-like molecular structure of the enantiomers. These findings imply that the enantioselectivity of drug enantiomers should be considered in presence of microplastics, leading to a more accurate environmental fate and risks assessments of chiral pharmaceuticals.

New insights into the cooperative adsorption behavior of Cr(VI) and humic acid in water by powdered activated carbon.

Chromium and humic acid often co-exist in wastewater and source waters, and the removal of chromium through sorption by activated carbon may be greatly influenced by humic acid. In this study, we systematically evaluated concurrent adsorption of humic acid (HA) and hexavalent chromium (Cr(VI)) in water by powdered activated carbon (PAC) and further, the effect on conversion to trivalent chromium (Cr(III)). Adsorption of both HA and Cr(VI) was significantly enhanced in the dual adsorbate system as compared to treatments with HA or Cr(VI) alone. The removal of HA increased by 16.0% in the presence of 80 mg/L Cr(VI), while the removal of Cr(VI) similarly increased with increasing levels of HA. However, the promotion effect of HA was found to decrease with increasing pH. With HA at 20 mg/L, removal of Cr(VI) increased from 40.09% to 70.12% at pH 3, which was about twice the increase at pH 10. The cooperative adsorption mechanism was explored using scanning electron microscopy coupled with energy dispersive spectroscopy (SEM-EDS), Raman spectroscopy, Fourier transform infrared spectrometer (FTIR), and X-ray photoelectron spectroscopy (XPS). Comprehensive analysis of spectra suggested that the mutual promotion between HA and Cr(VI) adsorption was attributable to the formation of Cr(VI)-HA and Cr(III)-HA complexes that were readily adsorbed on the PAC surfaces. The higher HA concentrations increased the reduction of Cr(VI) to Cr(III), which was likely due to the electron transfer provided by the functional groups such as -CO, -OH and -COOH in both PAC and HA. At pH 3, 99.1% of Cr adsorbed on the PAC surface was in the form of Cr(III). These findings imply that the interactions between Cr(VI) and HA in the process of water treatment by PAC provides additional and synergistic benefits, leading to a greater removal of chromium.

Recent progress of silver-containing photocatalysts for water disinfection under visible light irradiation: A review.

Photocatalysis has emerged as an environmentally friendly approach for microbial disinfection. The development of visible-light-driven (VLD) photocatalysts for water pollution remediation is imperative, considering that visible light constitutes a substantial fraction of the solar spectrum. The modification of photocatalysts by Ag/AgX (X = Cl, Br, I) deposition can be used to improve photocatalytic efficiencies. This is achieved by preventing photogenerated electron-hole pairs recombination through electron trapping mechanisms. With the introduction of silver NPs, visible light absorption can also be increased through its SPR enhancement. Silver also possesses excellent antimicrobial properties. Consequently, a novel class of Ag/AgX-containing hybrid materials has recently emerged as a promising candidate for water disinfection. This review summarizes the latest advances in the synthesis of Ag/AgX-containing photocatalysts using various synthetic methods. The microbial disinfection efficiencies of the as-prepared materials, the main reactive oxygen species and disinfection mechanisms are also reviewed in detail. Finally, some areas that need to be improved are discussed along with new insights as perspectives for future developments in this field.

Formation and control of C- and N-DBPs during disinfection of filter backwash and sedimentation sludge water in drinking water treatment.

Drinking water treatment plants (DWTPs) produce filter backwash water (FBW) and sedimentation sludge water (SSW) that may be partially recycled to the head of DWTPs. The impacts of key disinfection conditions, water quality parameters (e.g., disinfection times, disinfectant types and doses, and pH values), and bromide concentration on controlling the formation of trihalomethanes (THMs), haloacetic acids (HAAs), haloacetonitriles (HANs), and haloacetamides (HAMs) during disinfection of FBW and SSW were investigated. Concentrations of most disinfection byproducts (DBPs) and associated calculated toxicity increased with extended chlorination for both FBW and SSW. During chlorination of both FBW and SSW, elevated chlorine doses significantly increased THM yields per unit dissolved organic carbon (DOC), but decreased HAN and HAM yields, with minimum effect on HAA yields. Chloramine disinfection effectively inhibited C-DBP formation but promoted N-DBPs yields, which increased with chloramine dose. Calculated toxicities after chloramination increased with chloramine dose, which was opposite to the trend found after free chlorine addition. An examination of pH effects demonstrated that C-DBPs were more readily generated at alkaline pH (pH=8), while acidic conditions (pH=6) favored N-DBP formation. Total DBP concentrations increased at higher pH levels, but calculated DBP toxicity deceased due to lower HAN and HAM concentrations. Addition of bromide markedly increased bromo-THM and bromo-HAN formation, which are more cytotoxic than chlorinated analogues, but had little impact on the formation of HAAs and HAMs. Bromide incorporation factors (BIFs) for THMs and HANs from both water samples all significantly increased as bromide concentrations increased. Overall, high bromide concentrations increased the calculated toxicity values in FBW and SSW after chlorination. Therefore, while currently challenging, technologies capable of removing bromide should be explored as part of a strategy towards controlling cumulative toxicity burden (i.e., hazard) while simultaneously lowering individual DBP concentrations (i.e., exposure) to manage DBP risks in drinking water.

Microbial diversity characteristics and the influence of environmental factors in a large drinking-water source.

Although the influence of environmental factors on the microbial community in water sources is crucial, it is seldom evaluated. The seasonal relationship between microbial diversity of bacteria and fungi and environmental factors was investigated in a large drinking-water reservoir using Illumina MiSeq sequencing. Forty-one bacterial phyla and nine fungal phyla were analyzed in the Qingcaosha Reservoir, Shanghai, China. The predominant bacterial phyla were Actinobacteria, Proteobacteria, Bacteroidetes, and Cyanobacteria, with the maximum relative abundance of 46%, 36.6%, 16.1%, and 14.9%, respectively. Actinobacteria were observed to be the predominant bacterial phylum during spring and summer. The maximum relative abundance of unclassified fungi appeared in summer (98.8%), which was higher than that of Ascomycota and Basidiomycota (11.7% and 8.2%, respectively). Principal coordinate analysis (PCoA) results showed that the structural similarity in the bacterial community was greater during summer and winter; however, the fungal community exhibited a greater similarity during spring and summer. 2-Methylisoborneol (2-MIB), an olfactory compound produced by microorganisms, was detected at a concentration of 8.97 ng/L during summer, which was slightly lower than the olfactory threshold (10 ng/L). The positive correlation between Actinobacteria and unclassified fungi and 2-MIB (p < 0.05) confirmed that Actinobacteria and unclassified fungi produced 2-MIB. The chemical oxygen demand (COD) was 1.48-1.94 mg/L, and the maximum concentrations of total nitrogen (TN) and total phosphorus (TP) were 2.1 mg/L and 0.5 mg/L, respectively. Chloroflexi were negatively correlated with COD (p < 0.05) but positively correlated with TP (p < 0.01). Nitrospirae were negatively correlated with COD (p < 0.05), but positively correlated with TN (p < 0.05). Among the classified fungi, Rozellomycota, Basidiomycota (p < 0.05), and Chytridiomycota (p < 0.01) were positively correlated with TP. Therefore, the relative abundance of predominant bacteria was affected by various environmental factors; however, fungi were mainly influenced by TP.

Haloacetonitriles and haloacetamides precursors in filter backwash and sedimentation sludge water during drinking water treatment.

Haloacetonitriles (HANs) and haloacetamides (HAMs) are nitrogenous disinfection byproducts that are present in filter backwash water (FBW) and sedimentation sludge water (SSW). In many cases FBW and SSW are recycled to the head of drinking water treatment plants. HAN and HAM concentrations in FBW and SSW, without additional oxidants, ranged from 6.8 to 11.6 nM and 2.9 to 3.6 nM of three HANs and four HAMs, respectively. Upon oxidant addition to FBW and SSW under formation potential conditions, concentrations for six HANs and six HAMs ranged from 92.2 to 190.4 nM and 42.2 to 95.5 nM, respectively. Therefore, at common FBW and SSW recycle rates (2 to 10% of treated water flows), the precursor levels in these recycle waters should not be ignored because they are comparable to levels present in finished water. Brominated HAN and chlorinated HAM were the dominant species in FBW and SSW, respectively. The lowest molecular weight ultrafiltration fraction (< 3 kDa) contributed the most to HAN and HAM formations. The hydrophilic (HPI) organic fraction contributed the greatest to HAN precursors in sand-FBW and SSW and were the most reactive HAM precursors in both sand- or carbon-FBWs. Fluorescence revealed that aromatic protein-like compounds were dominant HAN and HAM precursors. Therefore, strategies that remove low molecular weight hydrophilic organic matter and aromatic protein-like compounds will minimize HAN and HAM formations in recycled FBW and SSW.

Improved membrane sequencing batch reactor: effect of carbon and nitrogen volumetric loading rate on dephosphatation.

A lab-scale anaerobic-anoxic-aerobic membrane bioreactor (A2NO-MBR) fed with synthetic wastewater was operated to investigate the impact of influent carbon and nitrogen volumetric loading rate (VLR) on dephosphatation, and the corresponding influent concentration was 100-300 mg L-1 (COD), 24-50 mg L-1 (NH4+-N) and 4.8-6.0 mg L-1 (TP), respectively. The results demonstrated that carbon VLR had a negligible effect on the COD removal with effluent below 50 mg L-1, and high and stable removal capacity for phosphorus were also obtained, regardless of carbon VLR change. Whereas TN removal efficiency was positively correlated with carbon VLR reduction, and lower carbon VLR produced a negative effect on TN removal. In addition, since nitrate served as an electron acceptor for denitrifying phosphorus removal (DPR), a significant effect on nitrogen and phosphorus removal was observed with different nitrogen VLR. The TN and TP removal efficiency was 68.30 ± 1.36%, 70.70 ± 1.23%, 45.19 ± 1.72% and 41.63 ± 3.09%, 98.14 ± 0.53%, 53.34 ± 2.68% with influent nitrogen VLR of 0.024 ± 0.001, 0.034 ± 0.001 and 0.045 ± 0.001 kg-N/(m3 d), respectively. Moreover, bacterial community structure of sludge samples in Run I and V from anaerobic-anoxic-aerobic-SBR (named A2OSBR_1 and A2OSBR_2) and membrane bioreactor (named N-MBR_1 and N-MBR_2) revealed that Candidatus_Accumulibacter was the most dominant genus in A2OSBR_1 (21.50%) and A2OSBR_2 (18.98%). The relative lower carbon VLR favoured the enrichment of Saprospiraceae, which was related with DPR, with the proportion of 9.31% and 14.61% in A2OSBR_1 and A2OSBR_2. Besides, Nitrospira and Nitrosomonas with proportions of 11.14%, 5.38% in N-MBR_1 and 10.72%, 6.77% in N-MBR_2 were observed, which were likely responsible for the nearly complete nitrification.

Nutrients removal performance of a denitrifying phosphorus removal process in alternate anaerobic/anoxic-aerobic double membrane bioreactors (A2N-DMBR).

An alternate anaerobic/anoxic-aerobic double membrane bioreactors process (A2N-DMBR) was proposed to improve denitrifying phosphorus removal efficiency. The system was operated for 70 d under different nitrogen/phosphorus (N/P) ratios with synthetic wastewater to present the performance evaluation of nutrients removal and microbial community structure in the A2N-DMBR process. The results showed that when the influent total phosphorus (TP) was 6.4 mg/L, the corresponding N/P ratio of 8.8, the high removal capacity of nitrogen and phosphorus could be achieved with the average effluent TP and total nitrogen (TN) concentration of 0.8 mg/L and 12.0 mg/L, respectively. Periodical test showed that pH and oxidation-reduction potential (ORP) could be used as control parameters for anaerobic phosphate release, and ORP was also closely related with the phosphate uptake in anoxic phase. The high-throughput sequencing analysis revealed that the Proteobacteria and Xanthomonadales-nobank related to biological nitrogen and phosphorus removal was domination bacteria at phylum and genus level in A2N-DMBR system, with the proportion of 42.5% and 39.1%, respectively. Furthermore, Dechloromonas, which was further detected as putative denitrifying phosphorus accumulating organisms (DPAOs), was enriched (9.9%) in the system.