Disinfection is vital in ensuring water safety. However, the traditional chlorine disinfection process is prone to producing toxic and harmful disinfection by-products (DBPs). The combination of quaternary ammonium polymer and the chlorine disinfection process can solve this shortcoming. Currently, research on the control of DBPs through the combined process is not systematic and the control effect between reducing the dosage of disinfectants and DBPs remains to be studied. Quaternized cyclodextrin polymers have attracted increasing attention due to their excellent adsorption and antibacterial properties, but their synergistic effect with chlorine disinfection is still unclear. In this study, a magnetic quaternized cyclodextrin polymer (MQCDP) is synthesized in an ionic liquid green system, and a combined process of MQCDP treatment and chlorine disinfection is established. The disinfection performance of the combined process on the actual water body along with its reducing effect on the amount of chlorine disinfectant as well as the trihalomethanes (THMs) and haloacetic acids (HAAs) DBPs are explored. MQCDP has a porous structure with a specific surface area of 825 m2 g-1 and is easily magnetically separated. MQCDP can remove most of the natural organic matter (UV254 absorbance decreased by 97 %) in the water at the dosage of 1 g L-1 and kill bacteria with a sterilization rate of 85 %. Compared with disinfection using chlorine alone, the combined process has higher disinfection efficiency and significantly reduces the amount of disinfectant used. A concentration of 5 mg/L of NaClO was needed to meet the standard by chlorine disinfectant alone, while only 2 mg/L of NaClO can meet the standard for the combined process, indicating 60 % of the chlorine demand was reduced. More importantly, the combined process can significantly reduce the generation potential of DBPs. When 10 mg/L of NaClO is added, the THMs and HAAs generated by the combined process decreased by 65 % and 34 %, respectively, compared with the levels produced by single chlorine disinfection. The combined process can reduce the dosage of chlorine disinfectant and MQCDP can adsorb humic acid DBP precursors in raw water, thus lowering the generation of DBPs during disinfection. In summary, MQCDP has excellent separation and antibacterial ability, and its synergistic effects combined with the chlorine disinfection process are of great significance for controlling the amount of disin-fectant and the formation potential of DBPs, which has potential applications in actual water treatment.

Organic-inorganic hybrid coagulants combine the advantages of organic and inorganic components. In this study, magnetic loading-enhanced coagulation was employed to further enhance the coagulation efficiency of covalently bound organic silicon-ferrum hybrid coagulant. The performance of magnetic flocculation was improved as compared to the conventional coagulation procedure and the turbidity and UV254 removal by magnetic flocculation reached 99.26% and 84.03%, respectively. The optimization resulted in the best dosing sequence is magnetic powder followed by coagulant. Surprisingly, after this method, total phosphorus was able to meet the environmental quality standards for surface water Class I standard value of China (<= 0.02 mg L-1) very quickly after this method. In addition, the optimal magnetic seed size was 20-30 mu m and the dosage was 300 mg L-1. Compared with the traditional coagulation method, the settling time of magnetic coagulation was reduced to 2 min, which is 1/15 of that of the traditional coagulation method. The magnetic coagulation efficiency did not diminish even with the magnetic seeds recycled 4 times, showing excellent recovery performance (all above 90%). This provides a new reference path for the combination of organic and inorganic covalent hybrid coagulants with magnetic separation technology.

Nanoscale zerovalent iron (nZVI) has garnered significant attention as an efficient advanced oxidation activator, but its practical application is hindered by aggregation and oxidation. Coating nZVI with carbon can effectively addresses these issues. A simple and scalable production method for carbon-coated nZVI composite is highly desirable. The anti-oxidation and catalytic performance of carbon-coated nZVI composite merit in-depth research. In this study, a highly stable carbon-coated core-shell nZVI composite (Fe0@RF-C) was successfully prepared using a simple method combining phenolic resin embedding and carbothermal reduction. Fe0@RF-C was employed as a heterogeneous persulfate (PS) activator for degrading 2,4-dihydroxybenzophenone (BP-1), an emerging contaminant. Compared to commercial nZVI, Fe0@RF-C exhibited superior PS activation performance and oxidation resistance. Nearly 95% of BP-1 was removed within 10 min in the Fe0@RF-C/PS system. The carbon layer promotes the enrichment of BP-1 and accelerates its degradation through singlet oxygen oxidation and direct electron transfer processes. This study provides a straightforward approach for designing highly stable carbon-coated nZVI composite and elucidates the enhanced catalytic performance mechanism by carbon layers.

Pillararene polymers have been widely used as excellent adsorbents for water treatment, but pillararene polymers with ultra-high specific surface area and versatility are still rarely reported. Herein, a quaternary ammonium salt modified pillar [5] arene polymer, QPBP [5], with specific surface area of 1844 m2 g-1 was successfully synthesized. Since QPBP [5] has abundant different adsorption sites, it exhibits excellent performance for the simultaneously removal of organic pollutants with different charges from water. The selected three model pollutants, Rhodamine B (RhB, positively charged), Sulfamethazine (SMT, electrically neutral) and Fulvic acid (FA, negatively charged), could be rapidly and efficiently removed from water by QPBP [5] within 10 min, which are much faster than them by most of the reported adsorbents. RhB and SMT are mainly adsorbed through hydrophobic interactions with the QPBP [5] surface, while FA is mainly removed through ion exchange. In addition, QPBP [5] also showed excellent reusability and adsorption performance for the environmentally relevant concentration of pollutants. Furthermore, the quaternary ammonium groups on QPBP [5] makes it a solid disinfectant with excellent antibacterial properties. In conclusion, QPBP [5] is a promising multifunctional adsorbent for the treatment of complex pollutants in water.

The complex composition of water bodies often complicates the water treatment process. Coagulation is an important part of water treatment, subsequent water treatment can be simplified by maximally removing sus-pended particles, natural organic matter, and pathogenic microorganisms during coagulation. Here, we devel-oped a novel silicon-ferrum hybrid coagulant (SFHC). The morphology and structure were described by scanning electron microscopy (SEM), transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FTIR), elemental analysis (EA) and X-ray diffraction (XRD). The Fe-ferron reaction kinetics were used to evaluate the morphological distribution of Fe species in SFHC. It was finally determined that the SFHC with Si/Fe of 0.1 and B value of 1.0 showed the best coagulation efficiency. At the optimum dose, SFHC achieved 95.83% removal of 20 mg L-1 humic acid wastewater, and turbidity was almost completely removed in kaolin waste-water. SFHC maintained high coagulation efficiency over a wide range of pH values (pH 5-9), which was su-perior to conventional coagulants. Furthermore, SFHC has excellent coagulation performance to the soluble small-molecular pollutants as nitrate (NO3-), phosphate (PO43-) and diclofenac (DCF) in water, and has good bacteriostatic ability to pathogenic microorganisms (96.94% bacteriostatic rate at 40 x 10-5 mol L-1 dosage). Regarding actual water bodies, SFHC also showed excellent performance. Therefore, SFHC has great potential as a multifunctional and effective coagulant.

Organic micropollutant in the aquatic environment has become a worldwide problem. In this study, a new DMpillar[5]arene-based porous organic polymer (DMPBP[5]) with the highest surface area of 1347.4 & PLUSMN; 39.3 m(2) g(-1) is developed through Friedel-Crafts alkylation reaction between DMpillar[5]arene (DMP5) and 4,4 & PRIME;-bis (chloromethyl)-1,1 & PRIME;-biphenyl (BCMBP) to remove a wide range of organic micropollutants with fast removal rate and large uptake amounts. The synthesized DMPBP[5] can capture many types of organic pollutants in water including positively charged, negatively charged and neutral ones and those with different hydrophilicity, through host-guest interaction, hydrophobic interaction, electrostatic interaction and 7C-7C interaction. For some pollutants, the adsorption kinetic constants of DMPBP[5] are thousands of times larger than that of activated carbon (AC) and even 104-105 times larger than that of resin (XAD-4), and the adsorption capacities of DMPBP[5] are about 3 and 4 times higher than that of AC and XAD-4, respectively. The superior adsorption performance of DMPBP[5] is attributed to permanent porosity and accessible binding sites because of the introduction of rigid structure. Even at environmentally relevant concentrations, DMPBP[5] can quickly remove the pollutants simultaneously and can be easily regenerated with methanol under ambient conditions. In short, due to the wide adsorption range, excellent adsorption performance, and easy recyclability, DMPBP[5] is an excellent adsorbent for wastewater treatment with great application potential.

Keeping water clean is of vital significance for human health and environmental protection. In order to remove organic micro-pollutants and natural organic substances in water bodies and kill pathogenic microorganisms simultaneously, this study synthesized a multifunctional porous β-cyclodextrin polymer with a high specific surface area by introducing quaternary ammonium groups and rigid benzene rings, respectively, which was then polymerized with crosslinking agent-4,4'-bis (chloromethyl)-1,1'-biphenyl (BCMBP) in an ionic liquid system. The grafting of quaternary ammonium groups was beneficial for the removal of negative-charged humic acid (HA) and sterilization. The introduction of numerous rigid structures during benzylation and Friedel-Crafts alkylation reaction could significantly improve the porosity and specific surface area of the polymer, conducive to the exposure of cyclodextrin binding sites and contaminant adsorption. By changing the proportions of quaternization and benzylation, the structure and surface properties of the polymer could be adjusted, thus further regulating the adsorption performance. Compared with activated carbon, the polymer named BQCD-BP with a huge surface area of 1133 m2 g-1 prepared under optimized conditions showed outstanding adsorption performance and sterilization ability. The pseudo-second-order kinetic constant of BQCD-BP reached 1.2058 g·mg-1·min-1, which was approximately 50 times greater than that of activated carbon (0.0256 g·mg-1·min-1) under the same experimental condition. The adsorption capacity of BQCD-BP to HA was twice as high as that to AC, and the antibacterial ability of BQCD-BP was significant, achieving 90% at the dosage of 1g L-1. Moreover, the adsorption process was hardly affected by the hydrochemical conditions, and the polymer was easy to regenerate. In addition, the excellent adsorption and antibacterial performance of the polymer were also identified by natural water treatment. COD was almost completely removed, and the removal efficiency of TP reached 92% after contact with BQCD-BP. The sterilization rate of BQCD-BP to viable bacteria in complex water bodies reached 82%. Undoubtedly, BQCD-BP is a potential multifunctional water treatment material with reasonable design in the actual water purification.

Porous thienyl cyclodextrin polymer was synthesized in a green recyclable ionic liquid system for the first time to remove PPCPs.

The combination of adsorption-photocatalysis and advanced oxidation processes (AOP) based on sulfate (SO4 center dot-) for the treatment of organic pollution has the advantages of a high degradation rate, affordability, and an absence of secondary pollution. This study combined amphiphilic super-crosslinked porous cyclodextrin resin (PBCD-B-D), bismuth oxybromide (BiOBr), a composite material with dual functions of adsorption and photocatalysis, and AOP based on SO4 center dot- for the treatment of Acid Orange 7 (AO7) in water. The combination of BiOBr/PBCD-B-D (BOP-24) with peroxymonosulfate (PMS) showed an optimal adsorption-photocatalytic effect. Compared to the 24% PBCD-B-D (BOP-24)/visible light system, the degradation efficiency of BOP-24/PMS system for AO7 is increased from 64.1% to 99.2% within shorter time (similar to 60 min). Moreover, the BOP-24/PMS system showed a wide range of pH application (pH = 3-11). The addition of Cl-, SO42-, and NO3 promoted the photodegradation of AO7, whereas the addition of CO32- did not. The free radical capture experiments of the BOP-24/PMS AO7 degradation system showed that center dot O-2, h(+), center dot OH, and SO4 center dot- are reactive species. The proposed BOP-24 system used adsorption and a unique cavity structure to enrich AO7 near the active site, thereby reducing the path for PMS activation. PMS also acted as an electron (e(-)) acceptor to promote the transfer of part of e(-) to PMS, thereby further improving the efficiency of carrier separation. The proposed system is an effective method to improve the degradation of pollutants and broadens the range of application of SO4 center dot--based AOP technology.

The fabrication of a dual-function material is an effective strategy to promote the degradation of pollutants through the synergy of adsorption and photocatalysis. Herein, we introduce an amphiphilic hyper-crosslinked porous cyclodextrin polymer (PBCD-B-D) into bismuth oxide bromide (BiOBr) via a one-pot solvothermal method to construct three-dimensional (3D) spherical flower-shaped BiOBr/PBCD-B-D (BOP) composites for removing the organic dye Acid Orange 7 (AO7). The prepared BiOBr composite loaded with 24% PBCD-B-D (BOP-24) displayed an optimal adsorption-photocatalytic effect. Under different concentration gradients, the pseudo first-order reaction rate constant of BOP-24 was 2-5 times that of BiOBr after visible-light irradiation. The unique cavity structure of PBCD-B-D resulted in a strong inclusion ability, which could concentrate organic pollutants and shorten the mass transfer distance. The introduction of PBCD-B-D to BiOBr led to an increase in the specific surface area and pore volume, which not only provided a large number of adsorption sites and active centers but also produced oxygen vacancies to improve charge separation. In addition, a possible degradation pathway was proposed for AO7 based on 3D excitation-emission matrix fluorescence spectra and analysis by liquid chromatography-mass spectrometry. This work combines the advantages of both adsorption and photo catalytic technologies for environmental remediation, and opens an avenue for dual-function high-surface-area adsorbent/photocatalysts via a one-pot in situ method.

Poyang Lake is the first freshwater lake in China, which is an important drinking water source. In recent years, industrial pollution has led to the increased phthalate acid esters (PAEs) in Poyang Lake. PAEs are a class of typical endocrine disruptors that can accumulate in organisms and interfere with their secretion systems. Thus, the accurate determination of PAEs in Poyang Lake is important for health risk prediction and the development of corresponding control means. Monitoring organic pollutants in water using the diffusive gradient in thin films technique (DGT) has attracted much attention due to more accuracy and convenience than the traditional methods. This study used an inexpensive amphiphilic cyclodextrin polymer (PBCD) as the sorbent for the binding gel. This new binding gel has an ultra-high specific surface area and excellent adsorption performance. Diffusion coefficients of the five PAEs were determined, and the performance of DGT such as adsorption capacity and deployment time (1-4 days) was tested using five PAEs as models. The assembled PBCD-DGT was used to examine the performance in a complex simulated water environment. The sampling capability of PBCD-DGT was verified in Yangshan Lake, and a large-scale field application was conducted in Poyang Lake basin. The results of 11 sampling points showed that the concentration ranges of dimethyl phthalate, diethyl phthalate, diallyl phthalate, dipropyl phthalate, and dibutyl phthalate were 434-2594 ng/L, 40-314 ng/L, 80-527 ng/L, 45-308 ng/L, and ND-182 ng/L, respectively. The health risk index (HI) and ecological risk quotient (RQ) values of PAEs in the Poyang Lake watershed were far below 1, indictating a lower health and ecological risk. Considering that PAEs are bioaccumulative and persistent, it is very necessary to continue to pay attention to its pollution status and health and ecological risk changes in Poyang Lake Basin in the future.

Amphiphilic hyper-crosslinked porous cyclodextrin polymer (PBCD-B-D) with a surface area of 1445 m(2) g(-1) was synthesized for rapid removal of organic micropollutants. Partially benzylated cyclodextrin was crosslinked with 4,4'-bis(chloromethyl)-1,1'-biphenyl and alpha,alpha'-dichloro-p-xylene by the Friedel-Crafts alkylation reaction. The hydrophilicity of the PBCD-B-D surface is modulated by controlling the number of hydroxyl groups on cyclodextrin. Benzylation reaction is more likely to occur at the C-2 and C-6 positions of cyclodextrin hydroxyl groups according to Gaussian computation. Four different water-soluble pollutants (3-phenylphenol, 2-naphthol, p-nitrophenol, and 4-chlorophenol) were selected for adsorption study. The adsorption rate of PBCD-B-D is extremely high, and the removal efficiency reaches above 95% in 1 min. For the adsorption of 3-phenylphenol and 2-naphthol, the rate constants of PBCD-B-D are 827-1187 and 396-413 times larger than those of granular activated carbon (GAC) and beta-cyclodextrin polymer crosslinked with epichlorohydrin (EPI-CDP), respectively. The adsorption capacity of PBCD-B-D is 2 and 4 times higher than that of GAC and EPI-CDP, respectively. The combination of cyclodextrin inclusion mechanism, hydrophobic attraction, and hydrogen bonding allows PBCD-B-D to adsorb both hydrophobic and hydrophilic pollutants. PBCD-B-D can be easily regenerated at room temperature using methanol as eluent. In addition, PBCD-B-D showed excellent adsorption performance towards mixed pollutants at environmentally relevant concentrations. According to the thermodynamic study, the adsorption of organic compounds onto PBCD-B-D belongs to physical adsorption and is spontaneous. PBCD-B-D is a potential novel adsorbent for water treatment owing to its excellent adsorption performance, low cost, and good regenerability.

Natural organic matter (NOM), organic micropollutants (OMPs), and detrimental microorganisms are three major pollutants that affect water quality. To remove these pollutants, a quaternary ammonium-functionalized β-cyclodextrin polymer (β-CDP) is successfully synthesized in the aqueous phase. The N2 and CO2 adsorption/desorption analysis showed that the polymer mainly contains ultra-micropores (<1 nm), with a Langmuir surface area of 89 m2 g-1. Two kinds of NOM, humic acid and fulvic acid, and five OMPs, 2-naphthol (2-NO), 3-phenylphenol (3-PH), 2,4,6-trichlorophenol (2,4,6-TCP), bisphenol A (BPA), and bisphenol S (BPS), were selected as model pollutants to study the performance of β-CDP and three kinds of commercial adsorbents, including granular activated carbon, DARCO-AC, and two resins, XAD-4 and D-201, were used for comparison. The polymer shows ultrarapid adsorption kinetics for the removal of these pollutants, with pseudo-second-order rate constants two to three orders of magnitude higher than that of the commercial activated carbon and resins. Due to the different adsorption sites of NOM and OMPs, β-CDP can simultaneously remove these pollutants without competitive adsorption. The maximum adsorption capacity of β-CDP for HA, FA, 2-NO, 3-PH, 2,4,6-TCP, BPA, and BPS based on the Langmuir model is 40, 166, 74, 101, 108, 103, and 117 mg g-1, respectively. After use, the polymer can be easily regenerated at room temperature. In addition, β-CDP also showed excellent bactericidal properties due to the quaternary ammonium groups. At a concentration of 15 g L-1, β-CDP can remove 98% of the tested Escherichia coli. Moreover, the synthesis of β-CDP is simple, green, and easy to industrialize. All of these findings indicate that β-CDP, as an ideal multifunctional material, presents potential for practical applications for water treatment and disinfection.

Simple synthesis of a swellable porous β-cyclodextrin-based polymer in the aqueous phase for the rapid removal of organic micro-pollutants from water.

Adsorption is one of the most preferred techniques in the advanced treatment of dyeing wastewater. Magnetic porous materials with good adsorption performance, excellent reusability, and a green synthesis route are highly desirable adsorbents in commerce. In this study, we synthesized a magnetic beta-cyclodextrin polymer (MNP-CM-CDP) containing many macro- and ultramicropores in aqueous phase. CO2 adsorption-desorption isotherms and a dye adsorption method provided Langmuir specific surface areas for the MNP-CM-CDP of 114.4 m(2) g(-1) and 153 m(2) g(-1), respectively. Model pollutants (BPA, MB, BO2, RhB, Cr(III), Pb(II), Zn(II), and Cu(II)) were rapidly and efficiently removed from the aqueous solution by the MNP-CM-CDP. In addition, the polymer could be easily separated from the solution under an external magnetic field. The adsorption of the contaminants was dependent on pH, while the effects of ionic strength and humic acid were slight in the concentration range studied. The polymer could be easily regenerated at room temperature and retained good adsorption performance. Moreover, the MNP-CM-CDP showed good feasibility for the removal of pollutants from actual dyeing wastewater samples.

The existence of high concentrations of salinity and organics would have a great impact on the microorganisms when using bioreactors to treat wastewater. Thus, it is necessary to find bioreactors resistant to high concentrations of salinity. The effect of salinity on an expanded granular sludge bed reactor (EGSB) was studied by increasing the Cl- concentration from 0 to 10000 mg·L-1 using simulated high salinity wastewater with a COD volume loading of 3.267 kg·(m3·d)-1. The results show no obvious inhibitory effect of Cl- on the microorganism when the concentration of Cl- was below 7500 mg·L-1. Above 1.3 m3·(m3·d)-1 volumetric gas production rate was maintained and COD removal rate could achieved 98.1% when the Cl- concentration up to 7500 mg·L-1 while the large particle size of anaerobic granular sludge occupying the majority of of the system. The anaerobic granular sludge was seriously affected when the Cl- concentration as 10000 mg·L-1. The community structure of the anaerobic granular sludge was analyzed using high-throughput sequencing when the Cl- concentration was 0 and 5000 mg·L-1. The results show that the salinity stress produced different dominant groups. The dominant species were Methanobacterium, Methanospirillum, Methanothrix, and Paludibacter when the Cl- concentration was 5000 mg·L-1, but Methanoregula and Longilinea were the dominant species when the Cl- concentration was 0.

Fracturing waste liquid (FWL) is generated during shale gas extraction and contains high concentrations of suspended solid, salinity and organic compounds, which needs proper management to prevent excessive environmental disruption. Biological treatment of the FWL was attempted in this study using a membrane-coupled internal circulation aerobic biological fluidized bed (MC-ICABFB) after being treated by coagulation. The results showed that poly aluminum chloride (PAC) of 30 g/L, polyacrylamide (PAM) of 20 mg/L and pH of 7.0 were suitable choices for coagulation. The pretreated FWL mixed with synthetic wastewater at different ratios were used as the influent wastewater for the reactor. The MC-ICABFB had relatively good performance on COD and NH4+-N removal and the main residual organic compound in the effluent was phthalates according to the analysis of GC-MC profiles. In addition, a suitable pretreatment process for the FWL to facilitate biological treatment of the wastewater needs further research.

介绍了几种高效去除工业废水中重金属离子的方法,即离子交换树脂法、膜处理、EDI,综述了这些方法的发展运用,比较了它们的优缺点,最终发现膜处理在去除重金属离子方面有明显的优势.分析并得出膜处理为核心单元结合其他几种高效的处理技术将是实现工业废水零排放的重要途径,但其膜污染以及浓水处理是影响金属离子零排放的关键,最后展望了未来工业废水重金属离子零排放的发展方向.