Synergistic disinfection effects and reduction of disinfection by-products in water treatment using magnetic quaternized cyclodextrin polymer combined with chorine disinfection process.

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 disinfectant and the formation potential of DBPs, which has potential applications in actual water treatment.

Porous pillararene-based polymer as adsorbent and solid disinfectant for water treatment.

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.

Multifunctional porous ß-cyclodextrin polymer for water purification.

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 ß-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.

Insights into the photocatalytic activation of peroxymonosulfate by visible light over BiOBr-cyclodextrin polymer complexes for efficient degradation of dye pollutants in water.

The combination of adsorption-photocatalysis and advanced oxidation processes (AOP) based on sulfate (SO4•-) 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•- 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 (∼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 •O2-, h+, •OH, and SO4•- 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•--based AOP technology.

In situ monitoring of phthalate esters (PAEs) pollution and environmental risk assessment in Poyang Lake Basin by DGT Technology using cyclodextrin polymer as binding phase.

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.

Multifunctional ß-Cyclodextrin Polymer for Simultaneous Removal of Natural Organic Matter and Organic Micropollutants and Detrimental Microorganisms from Water.

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 ß-cyclodextrin polymer (ß-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 ß-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, ß-CDP can simultaneously remove these pollutants without competitive adsorption. The maximum adsorption capacity of ß-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, ß-CDP also showed excellent bactericidal properties due to the quaternary ammonium groups. At a concentration of 15 g L-1, ß-CDP can remove 98% of the tested Escherichia coli. Moreover, the synthesis of ß-CDP is simple, green, and easy to industrialize. All of these findings indicate that ß-CDP, as an ideal multifunctional material, presents potential for practical applications for water treatment and disinfection.

Green synthesis of a magnetic ß-cyclodextrin polymer for rapid removal of organic micro-pollutants and heavy metals from dyeing wastewater.

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 ß-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 m2 g-1 and 153 m2 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.

Biological treatment of fracturing waste liquid in a membrane-coupled internal circulation aerobic biological fluidized bed with the assistance of coagulation.

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.

[Effects of Salinity on the Operation of EGSB Reactors and the Anaerobic Granular Sludge].

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.