An efficient resin for solid-phase extraction and determination by UPLCMS/MS of 44 pharmaceutical personal care products in environmental waters

• A hydrophilic resin (GCHM) was facile synthesis and characterized. • Average absolute recovery of GCHM (75.6%) performs better than Oasis^® HLB. • Detection limits of method (SPE-UPLC-MS/MS) ranged between 0.03 and 0.6 ng/L. • 22 PPCPs were determined in environmental waters ranging from 0.5 to 1590 ng/L. In this study, a hydrophilic resin named GCHM was fabricated based on poly(N-vinyl pyrrolidone-co-divinylbenzene), characterized, and applied as a solid-phase extraction (SPE) material. Up to 44 pharmaceuticals and personal care products (PPCPs) belonging to 10 classes were recovered in environmental water samples. Different variables affecting extraction, such as adsorbent amount, sample pH, and loading speed, were optimized. Under optimal conditions, the average absolute recovery of 44 PPCPs was 75.6% using GCHM, indicating a better performance than the commercial Oasis^® HLB. SPE with home-made hydrophilic polymeric sorbent followed by ultra-performance liquid chromatography and tandem mass spectrometry was validated, and the method achieved good linearity (r²>0.991, for all analytes). In addition, the method detection limits of target compounds ranged from 0.03 to 0.6 ng/L. The developed method was applied to determine PPCPs in 10 environmental water samples taken from the Yangtze River, Huaihe River, and Taihu Lake, 1 groundwater sample from Changzhou in Jiangsu Province, 1 wastewater sample from Xiamen and 2 seawater samples from the Jiulong River in Fujian Province, China. In these samples, 22 compounds were determined at levels ranging from 0.5 to 1590 ng/L.     

Performance of activated carbon coated graphite bipolar electrodes on capacitive deionization method for salinity reduction

• Graphite bipolar electrodes act as an appropriate bed for the CDI process. • Activated carbon Coating improves the application of the electrodes. • CDI is an environmentally friendly method to apply for brackish water. • Initial concentration is the most important parameter in the CDI method. • CDI process in a batch-mode setup needs more development. This research investigates a capacitive deionization method for salinity reduction in a batch reactor as a new approach for desalination. Reductions of cost and energy compared with conventional desalination methods are the significant advantages of this approach. In this research, experiments were performed with a pair of graphite bipolar electrodes that were coated with a one-gram activated carbon solution. After completing preliminary tests, the impacts of four parameters on electrical conductivity reduction, including (1) the initial concentration of feed solution, (2) the duration of the tests, (3) the applied voltage, and (4) the pH of the solution, were examined. The results show that the maximum efficiency of electrical conductivity reduction in this laboratory-scale reactor is about 55%. Furthermore, the effects of the initial concentration of feed solution are more significant than the other parameters. Thus, using the capacitive deionization method for water desalination with low and moderate salt concentrations (i.e., brackish water) is proposed as an affordable method. Compared with conventional desalination methods, capacitive deionization is not only more efficient but also potentially more environmentally friendly.     

PPCPs in a drinking water treatment plant in the Yangtze River Delta of China: Occurrence,removal and risk assessment

• 39 PPCPs were investigated at a DWTP using the Yangtze River as its water source. • Grab and continuous sampling were conducted for the comparison of data consistency. • Ketoprofen & carbamazepine can be risk management indicators because of the high RQ. The occurrence and removal of 39 targeted pharmaceuticals and personal care products (PPCPs) from source water, through a drinking water treatment plant (DWTP) to the water supply station, were investigated around the central part of Yangtze River Delta in China using both grab sampling and continuous sampling. Totally 24 of the 39 targeted PPCPs were detected in raw water, and 12 PPCPs were detected in the finished water. The highest observed concentration was enrofloxacin (85.623 ng/L) in raw water. Removal efficiencies were remarkably negative correlated with log K_ow (r = -0.777, p<0.01) after calibration control of concentration, indicating that more soluble PPCPs are easier to remove by the combined process (prechlorination and flocculation/precipitation), the concentration level also had a great impact on the removal efficiency. The normal process in the pilot DWTP seems to be ineffective for PPCPs control, with the limited removal efficiency of less than 30% for each step: pre-chlorination, flocculation and precipitation, post-chlorination and filter. There were notable differences between the data from continuous sampling and grab sampling, which should be considered for different monitoring purposes. The chlorination and the hydrolytic decomposition of PPCPs in the water supply pipe may attenuate PPCPs concentration in the pipeline network. The PPCPs examined in the effluent of DWTP do not impose a potential health risk to the local consumers due to their RQ value lower than 0.00067.     

Significant increase of assimilable organic carbon (AOC) levels in MBR effluents followed by coagulation,ozonation and combined treatments: Implications for biostability control of reclaimed water

• Annual AOCs in MBR effluents were stable with small increase in warmer seasons. • Significant increase in AOC levels of tertiary effluents were observed. • Coagulation in prior to ozonation can reduce AOC formation in tertiary treatment. • ∆UV₂₅₄ and SUVA can be surrogates to predict the AOC changes during ozonation. As water reuse development has increased, biological stability issues associated with reclaimed water have gained attention. This study evaluated assimilable organic carbon (AOC) in effluents from a full-scale membrane biological reactor (MBR) plant and found that they were generally stable over one year (125–216 µg/L), with slight increases in warmer seasons. After additional tertiary treatments, the largest increases in absolute and specific AOCs were detected during ozonation, followed by coagulation-ozonation and coagulation. Moreover, UV₂₅₄ absorbance is known to be an effective surrogate to predict the AOC changes during ozonation. Applying coagulation prior to ozonation of MBR effluents for removal of large molecules was found to reduce the AOC formation compared with ozonation treatment alone. Finally, the results revealed that attention should be paid to seasonal variations in influent and organic fraction changes during treatment to enable sustainable water reuse.     

Mechanism of dichloromethane disproportionation over mesoporous TiO2 under low temperature

• Mechanism of DCM disproportionation over mesoporous TiO₂ was studied. • DCM was completely eliminated at 350℃ under 1 vol.% humidity. • Anatase (001) was the key for disproportionation. • A competitive oxidation route co-existed with disproportionation. • Disproportionation was favored at low temperature. Mesoporous TiO₂ was synthesized via nonhydrolytic template-mediated sol-gel route. Catalytic degradation performance upon dichloromethane over as-prepared mesoporous TiO₂, pure anatase and rutile were investigated respectively. Disproportionation took place over as-made mesoporous TiO₂ and pure anatase under the presence of water. The mechanism of disproportionation was studied by in situ FTIR. The interaction between chloromethoxy species and bridge coordinated methylenes was the key step of disproportionation. Formate species and methoxy groups would be formed and further turned into carbon monoxide and methyl chloride. Anatase (001) played an important role for disproportionation in that water could be dissociated into surface hydroxyl groups on such structure. As a result, the consumed hydroxyl groups would be replenished. In addition, there was another competitive oxidation route governed by free hydroxyl radicals. In this route, chloromethoxy groups would be oxidized into formate species by hydroxyl radicals transfering from the surface of TiO₂. The latter route would be more favorable at higher temperature.     

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

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

Using loose nanofiltration membrane for lake water treatment: A pilot study

• A pilot study was conducted for drinking water treatment using loose NF membranes. • The membranes had very high rejection of NOM and medium rejection of Ca²⁺/Mg²⁺. • Organic fouling was dominant and contribution of inorganic fouling was substantial. • Both organic and inorganic fouling had spatial non-uniformity on membrane surface. • Applying EDTA at basic conditions was effective in removing membrane fouling. Nanofiltration (NF) using loose membranes has a high application potential for advanced treatment of drinking water by selectively removing contaminants from the water, while membrane fouling remains one of the biggest problems of the process. This paper reported a seven-month pilot study of using a loose NF membrane to treat a sand filtration effluent which had a relatively high turbidity (~0.4 NTU) and high concentrations of organic matter (up to 5 mg/L as TOC), hardness and sulfate. Results showed that the membrane demonstrated a high rejection of TOC (by>90%) and a moderately high rejection of two pesticides (54%–82%) while a moderate rejection of both calcium and magnesium (~45%) and a low rejection of total dissolved solids (~27%). The membrane elements suffered from severe membrane fouling, with the membrane permeance decreased by 70% after 85 days operation. The membrane fouling was dominated by organic fouling, while biological fouling was moderate. Inorganic fouling was mainly caused by deposition of aluminum-bearing substances. Though inorganic foulants were minor contents on membrane, their contribution to overall membrane fouling was substantial. Membrane fouling was not uniform on membrane. While contents of organic and inorganic foulants were the highest at the inlet and outlet region, respectively, the severity of membrane fouling increased from the inlet to the outlet region of membrane element with a difference higher than 30%. While alkaline cleaning was not effective in removing the membrane foulants, the use of ethylenediamine tetraacetate (EDTA) at alkaline conditions could effectively restore the membrane permeance.     

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

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

Mechanisms for simultaneous ozonation of sulfamethoxazole and natural organic matters in secondary effluent from sewage treatment plant

• SMX was mainly degraded by hydrolysis, isoxazole oxidation and double-bond addition. • Isoxazole oxidation and bond addition products were formed by direct ozonation. • Hydroxylated products were produced by indirect oxidation. • NOM mainly affected the degradation of SMX by consuming ^•OH rather than O₃. • Inhibitory effect of NOM on SMX removal was related to the components’ aromaticity. Sulfamethoxazole (SMX) is commonly detected in wastewater and cannot be completely decomposed during conventional treatment processes. Ozone (O₃) is often used in water treatment. This study explored the influence of natural organic matters (NOM) in secondary effluent of a sewage treatment plant on the ozonation pathways of SMX. The changes in NOM components during ozonation were also analyzed. SMX was primarily degraded by hydrolysis, isoxazole-ring opening, and double-bond addition, whereas hydroxylation was not the principal route given the low maximum abundances of the hydroxylated products, with m/z of 269 and 287. The hydroxylation process occurred mainly through indirect oxidation because the maximum abundances of the products reduced by about 70% after the radical quencher was added, whereas isoxazole-ring opening and double-bond addition processes mainly depended on direct oxidation, which was unaffected by the quencher. NOM mainly affected the degradation of micropollutants by consuming ^•OH rather than O₃ molecules, resulting in the 63%–85% decrease in indirect oxidation products. The NOM in the effluent were also degraded simultaneously during ozonation, and the components with larger aromaticity were more likely degraded through direct oxidation. The dependences of the three main components of NOM in the effluent on indirect oxidation followed the sequence: humic-like substances>fluvic-like substances>protein-like substances. This study reveals the ozonation mechanism of SMX in secondary effluent and provides a theoretical basis for the control of SMX and its degradation products in actual water treatment.     

Effect of gastric fluid on adsorption and desorption of endocrine disrupting chemicals on microplastics

• Effect of gastric fluid on EDCs adsorption-desorption to microplastics was evaluated. • The gastric fluid enhanced desorption of EDCs on the surface of microplastics. • Adsorption and desorption isotherms fitted the Freundlich model well. • Desorption ratios of EE2 (55%–59%) on PVC were larger than that of E2 (49%–55%). • Decrease in pH and increase in ionic strength in gastric fluid strengthen desorption. Microplastics and endocrine disrupting chemicals are emerging pollutants in the marine environment because of their potential hazards. The effect of gastric fluid on the adsorption and desorption of 17β-estradiol (E2) and 17α-ethynylestradiol (EE2) to microplastics was investigated. The adsorption and desorption isotherms of E2/EE2 on microplastics could be well fitted by the Freundlich model while the Gibbs free energy of these processes were negative, proving that the reaction occurred spontaneously on the heterogeneous surface of the microplastics. Desorption ratios of EE2 (55%–59%) on PVC were larger than that of E2 (49%–55%) to indicate that EE2 was less stable in gastric fluid, which could be explained by the fact that the hydrophobicity of EE2 was greater than E2. E2/EE2 were more easily desorbed from PVC in the gastric fluid and the desorption amount (5.25–12.91/7.19–17.86 μg/g) increased by 2.51 times in comparison with that in saline solution (2.22–7.81/2.87–10.80 μg/g). The decrease of pH and the increase of ionic strength in gastric fluid could further strengthen desorption of E2/EE2 from PVC. The promotion of gastric juice on desorption of PVC was achieved by reducing the hydrophobicity of the PVC surface. The desorption rate of E2/EE2 at 18°C and 38°C was respectively 44%–47%/46%–50% and 49%–55%/56%–59%, indicating that PVC loaded with E2/EE2 had a relatively greater risk of releasing pollutants in the gastric fluid of constant temperature marine organisms while higher temperatures exposed higher hazards for variable temperature animals. The interaction between microplastics and pollutants might be mainly hydrophobic interaction.     

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

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

Sludge fermentation liquid addition attained advanced nitrogen removal in low C/N ratio municipal wastewater through short-cut nitrification-denitrification and partial anammox

• Sludge fermentation liquid addition resulted in a high NAR of 97.4%. • Extra NH₄⁺-N from SFL was removed by anammox in anoxic phase. • Nitrogen removal efficiency of 92.51% was achieved in municipal wastewater. • The novel system could efficiently treat low COD/N municipal wastewater. Biological nitrogen removal of wastewater with low COD/N ratio could be enhanced by the addition of wasted sludge fermentation liquid (SFL), but the performance is usually limited by the introducing ammonium. In this study, the process of using SFL was successfully improved by involving anammox process. Real municipal wastewater with a low C/N ratio of 2.8–3.4 was treated in a sequencing batch reactor (SBR). The SBR was operated under anaerobic-aerobic-anoxic (AOA) mode and excess SFL was added into the anoxic phase. Stable short-cut nitrification was achieved after 46d and then anammox sludge was inoculated. In the stable period, effluent total inorganic nitrogen (TIN) was less than 4.3 mg/L with removal efficiency of 92.3%. Further analysis suggests that anammox bacteria, mainly affiliated with Candidatus_Kuenenia, successfully reduced the external ammonia from the SFL and contributed approximately 28%–43% to TIN removal. Overall, this study suggests anammox could be combined with SFL addition, resulting in a stable enhanced nitrogen biological removal.     

Sorption mechanisms of diphenylarsinic acid on natural magnetite and siderite: Evidence from sorption kinetics,sequential extraction and extended X-ray absorption fine-structure spectroscopy analysis

• DPAA sorption followed pseudo-secondary and intra-particle diffusion models. • Chemical bonding and intra-particle diffusion were dominant rate-limiting steps. • DPAA simultaneously formed inner- and outer-sphere complexes on siderite. • DPAA predominantly formed occluded inner-sphere complexes on magnetite. • Bidentate binuclear bond was identified for DPAA on siderite and magnetite. Diphenylarsinic acid (DPAA) is both the prime starting material and major metabolite of chemical weapons (CWs). Because of its toxicity and the widespread distribution of abandoned CWs in burial site, DPAA sorption by natural Fe minerals is of considerable interest. Here we report the first study on DPAA sorption by natural magnetite and siderite using macroscopic sorption kinetics, sequential extraction procedure (SEP) and microscopic extended X-ray absorption fine-structure spectroscopy (EXAFS). Our results show that the sorption pseudo-equilibrated in 60 minutes and that close to 50% and 20%–30% removal can be achieved for magnetite and siderite, respectively, at the initial DPAA concentrations of 4–100 mg/L. DPAA sorption followed pseudo-secondary and intra-particle diffusion kinetics models, and the whole process was mainly governed by intra-particle diffusion and chemical bonding. SEP and EXAFS results revealed that DPAA mainly formed inner-sphere complexes on magnetite (>80%), while on siderite it simultaneously resulted in outer-sphere and inner-sphere complexes. EXAFS analysis further confirmed the formation of inner-sphere bidentate binuclear corner-sharing complexes (²C) for DPAA. Comparison of these results with previous studies suggests that phenyl groups are likely to impact the sorption capacity and structure of DPAA by increasing steric hindrance or affecting the way the central arsenic (As) atom maintains charge balance. These results improve our knowledge of DPAA interactions with Fe minerals, which will help to develop remediation technology and predict the fate of DPAA in soil-water environments.     

Removal of arsenic by pilot-scale vertical flow constructed wetland

• VFCWs are effective for the treatment of arsenic-containing wastewater. • Arsenic removal did not affect the removal of nutrients, except for TP in CW500. • Arsenic removal was highest when the temperature peaked and the reed was in bloom. • Substrate accumulation contributed more to arsenic removal than plant absorption. Four pilot-scale Vertical Flow Constructed Wetlands (VFCWs) filled with gravel and planted with Phragmites australis were operated for seven months in the field to study the efficiency of arsenic removal in contaminated wastewater. The average arsenic removal efficiency by the VFCWs was 52.0%±20.2%, 52.9%±21.3%, and 40.3%±19.4% at the theoretical concentrations of 50 μg/L (CW50), 100 μg/L (CW100), and 500 μg/L (CW500) arsenic in the wastewater, respectively. The results also showed no significant differences in the removal efficiency for conventional contaminants (nitrogen, phosphorus, or chemical oxygen demand) between wastewater treatments that did or did not contain arsenic (P>0.05), except for phosphorus in CW500. The highest average monthly removal rate of arsenic occurred in August (55.9%–74.5%) and the lowest in November (7.8%–15.5%). The arsenic removal efficiency of each VFCW was positively correlated with temperature (P<0.05). Arsenic accumulated in both substrates and plants, with greater accumulation associated with increased arsenic concentrations in the influent. The maximum accumulated arsenic concentrations in the substrates and plants at the end of the experiment were 4.47 mg/kg and 281.9 mg/kg, respectively, both present in CW500. The translocation factor (TF) of arsenic in the reeds was less than 1, with most of the arsenic accumulating in the roots. The arsenic mass balance indicated that substrate accumulation contributed most to arsenic removal (19.9%–30.4%), with lower levels in plants (3.8%–9.5%). In summary, VFCWs are effective for the treatment of arsenic-containing wastewater.     

Comparative genotoxicity of water processed by three drinking water treatment plants with different water treatment procedures

• Genotoxicity of substances is unknown in the water after treatment processes. • Genotoxicity decreased by activated carbon treatment but increased by chlorination. • Halogenated hydrocarbons and aromatic compounds contribute to genotoxicity. • Genotoxicity was assessed by umu test; acute and chronic toxicity by ECOSAR. • Inconsistent results confirmed that genotoxicity cannot be assessed by ECOSAR. Advanced water treatment is commonly used to remove micropollutants such as pesticides, endocrine disrupting chemicals, and disinfection byproducts in modern drinking water treatment plants. However, little attention has been paid to the changes in the genotoxicity of substances remaining in the water following the different water treatment processes. In this study, samples were collected from three drinking water treatment plants with different treatment processes. The treated water from each process was analyzed and compared for genotoxicity and the formation of organic compounds. The genotoxicity was evaluated by an umu test, and the acute and chronic toxicity was analyzed through Ecological Structure- Activity Relationship (ECOSAR). The results of the umu test indicated that biological activated carbon reduced the genotoxicity by 38%, 77%, and 46% in the three drinking water treatment plants, respectively, while chlorination increased the genotoxicity. Gas chromatograph-mass spectrometry analysis revealed that halogenated hydrocarbons and aromatic compounds were major contributors to genotoxicity. The results of ECOSAR were not consistent with those of the umu test. Therefore, we conclude that genotoxicity cannot be determined using ECOSAR .     

TiO2@palygorskite composite for the efficient remediation of oil spills via a dispersion-photodegradation synergy

• A novel and multi-functional clay-based oil spill remediation system was constructed. • TiO₂@PAL functions as a particulate dispersant to break oil slick into tiny droplets. • Effective dispersion leads to the direct contact of TiO₂ with oil pollutes directly. • TiO₂ loaded on PAL exhibits efficient photodegradation for oil pollutants. • TiO₂@PAL shows a typical dispersion-photocatalysis synergistic remediation. Removing spilled oil from the water surface is critically important given that oil spill accidents are a common occurrence. In this study, TiO₂@Palygorskite composite prepared by a simple coprecipitation method was used for oil spill remediation via a dispersion-photodegradation synergy. Diesel could be efficiently dispersed into small oil droplets by TiO₂@Palygorskite. These dispersed droplets had an average diameter of 20–30 mm and exhibited good time stability. The tight adsorption of TiO₂@Palygorskite on the surface of the droplets was observed in fluorescence and SEM images. As a particulate dispersant, the direct contact of TiO₂@Palygorskite with oil pollutants effectively enhanced the photodegradation efficiency of TiO₂ for oil. During the photodegradation process, •O₂⁻and •OH were detected by ESR and radical trapping experiments. The photodegradation efficiency of diesel by TiO₂@Palygorskite was enhanced by about 5 times compared with pure TiO₂ under simulated sunlight irradiation. The establishment of this new dispersion-photodegradation synergistic remediation system provides a new direction for the development of marine oil spill remediation.     

Surface water treatment benefits from the presence of algae: Influence of algae on the coagulation behavior of polytitanium chloride

• Emerging titanium coagulation was high-efficient for algae-laden water treatment. • Polytitanium coagulation was capable for both algae and organic matter removal. • Surface water purification was improved by around 30% due to algae inclusion. • Algae functioned as flocculant aid to assist polytitanium coagulation. • Algae could enhance charge neutralization capability of polytitanium coagulant. Titanium-based coagulation has proved to be effective for algae-laden micro-polluted water purification processes. However, the influence of algae inclusion in surface water treatment by titanium coagulation is barely reported. This study reports the influence of both Microcystis aeruginosa and Microcystis wesenbergii in surface water during polytitanium coagulation. Jar tests were performed to evaluate coagulation performance using both algae-free (controlled) and algae-laden water samples, and floc properties were studied using a laser diffraction particle size analyzer for online monitoring. Results show that polytitanium coagulation can be highly effective in algae separation, removing up to 98% from surface water. Additionally, the presence of algae enhanced organic matter removal by up to 30% compared to controlled water containing only organic matter. Polytitanium coagulation achieved significant removal of fluorescent organic materials and organic matter with a wide range of molecular weight distribution (693–4945 Da) even in the presence of algae species in surface water. The presence of algae cells and/or algal organic matter is likely to function as an additional coagulant or flocculation aid, assisting polytitanium coagulation through adsorption and bridging effects. Although the dominant coagulation mechanisms with polytitanium coagulant were influenced by the coagulant dosage and initial solution pH, algae species in surface water could enhance the charge neutralization capability of the polytitanium coagulant. Algae-rich flocs were also more prone to breakage with strength factors approximately 10% lower than those of algae-free flocs. Loose structure of the flocs will require careful handling of the flocs during coagulation-sedimentation-filtration processes.     

Enhanced hydrogen production in microbial electrolysis through strategies of carbon recovery from alkaline/thermal treated sludge

• High hydrogen yield is recovered from thermal-alkaline pretreated sludge. • Separating SFL by centrifugation is better than filtration for hydrogen recovery. • The cascaded bioconversion of complex substrates in MECs are studied. • Energy and electron efficiency related to substrate conversion are evaluated. The aim of this study was to investigate the biohydrogen production from thermal (T), alkaline (A) or thermal-alkaline (TA) pretreated sludge fermentation liquid (SFL) in a microbial electrolysis cells (MECs) without buffer addition. Highest hydrogen yield of 36.87±4.36 mgH₂/gVSS (0.026 m³/kg COD) was achieved in TA pretreated SFL separated by centrifugation, which was 5.12, 2.35 and 43.25 times higher than that of individual alkaline, thermal pretreatment and raw sludge, respectively. Separating SFL from sludge by centrifugation eliminated the negative effects of particulate matters, was more conducive for hydrogen production than filtration. The accumulated short chain fatty acid (SCFAs) after pretreatments were the main substrates for MEC hydrogen production. The maximum utilization ratio of acetic acid, propionic acid and n-butyric acid was 93.69%, 90.72% and 91.85%, respectively. These results revealed that pretreated WAS was highly efficient to stimulate the accumulation of SCFAs. And the characteristics and cascade bioconversion of complex substrates were the main factor that determined the energy efficiency and hydrogen conversion rate of MECs.     

Water-level based discrete integrated dynamic control to regulate the flow for sewer-WWTP operation

• A model-free sewer-WWTP integrated control was proposed. • A dynamic discrete control based on the water level was developed. • The approach could improve the sewer operation against flow fluctuation. • The approach could increase transport capacity and enhance pump efficiency. This study aims to propose a multi-point integrated real-time control method based on discrete dynamic water level variations, which can be realized only based on the programmable logic controller (PLC) system without using a complex mathematical model. A discretized water level control model was developed to conduct the real-time control based on data-automation. It combines the upstream pumping stations and the downstream influent pumping systems of wastewater treatment plant (WWTP). The discretized water level control method can regulate dynamic wastewater pumping flow of pumps following the dynamic water level variation in the sewer system. This control method has been successfully applied in practical integrated operations of sewer-WWTP following the sensitive flow disturbances of the sewer system. The operational results showed that the control method could provide a more stabilized regulate pumping flow for treatment process; it can also reduce the occurrence risk of combined sewer overflow (CSO) during heavy rainfall events by increasing transport capacity of pumping station and influent flow in WWTP, which takes full advantage of storage space in the sewer system.     

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

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