Zhaofu Qiu

Identification of priority pharmaceuticals in the water environment of China

In recent years, increasing attention has been paid to the trace-level contamination of pharmaceuticals in the water environment all over the world. Considering a large number of pharmaceuticals used, it is crucial to establish a priority list of pharmaceuticals that should be monitored and/or treated first. In the present study, we developed a ranking system based on the pharmaceutical consumption, removal performance in the wastewater treatment plants (WWTPs) and potential ecological effects, and applied to the situation of China. 39 pharmaceuticals, which had available consumption data and also been reported previously in the WWTPs of China, were selected as candidate pharmaceuticals. Among them, seventeen pharmaceuticals were considered as priority pharmaceuticals, out of which, erythromycin, diclofenac acid and ibuprofen, had the high priority. Compared with other literatures, we found that some pharmaceuticals given concerns to globally should also be included in the priority list in China; while some pharmaceuticals, not mentioned in other literatures, such as cefalexin, ketoconazole, should be also given prior consideration in China. Among all the therapeutic classes, antibiotics, which were grossly abused in China, contributed the most to the priority pharmaceuticals. However, priority antibiotics accounted for only 32% of candidate antibiotics, while 71% and 100% of the candidate anti-inflammatory and antilipidemic respectively were identified as the priority pharmaceuticals, indicating that antibiotics might be overanxiously considered in the previous studies on their behaviors in the WWTPs of China.

Occurrence and removal of six pharmaceuticals and personal care products in a wastewater treatment plant employing anaerobic/anoxic/aerobic and UV processes in Shanghai, China.

The occurrence and removal of six pharmaceuticals and personal care products (PPCPs) including caffeine (CF), N, N-diethyl-meta-toluamide (DEET), carbamazepine, metoprolol, trimethoprim (TMP), and sulpiride in a municipal wastewater treatment plant (WWTP) in Shanghai, China were studied in January 2013; besides, grab samples of the influent were also taken every 6xa0h, to investigate the daily fluctuation of the wastewater influent. The results showed the concentrations of the investigated PPCPs ranged from 17 to 11,400xa0ng/L in the WWTP. A low variability of the PPCP concentrations in the wastewater influent throughout the day was observed, with the relative standard deviations less than 25xa0% for most samples. However, for TMP and CF, the slight daily fluctuation still reflected their consumption patterns. All the target compounds except CF and DEET, exhibited poor removal efficiencies (<40xa0%) by biological treatment process, probably due to the low temperature in the bioreactor, which was unfavorable for activated sludge. While for the two biodegradable PPCPs, CF, and DEET, the anaerobic and oxic tank made contributions to their removal while the anoxic tank had a negative effect to their elimination. The tertiary UV treatment removed the investigated PPCPs by 5–38xa0%, representing a crucial polishing step to compensate for the poor removal by the biologic treatment process in winter.

Pharmaceuticals and personal care products in the leachates from a typical landfill reservoir of municipal solid waste in Shanghai, China: Occurrence and removal by a full-scale membrane bioreactor

Knowledge on the pharmaceuticals and personal care products (PPCPs) in landfill leachates, which are an important source of PPCPs in the environment, was very limited. Hence, four sampling campaigns were conducted to determine eighteen PPCPs in the landfill leachates from a landfill reservoir in Shanghai. Five of the target PPCPs were first included in a landfill leachate study. Additionally, their removal from landfill leachates by a full-scale membrane bioreactor (MBR) was illustrated. The results showed fourteen out of eighteen PPCPs were detectable in at least one sampling campaign and achieved individual concentrations ranging from 0.39 to 349μg/L in the landfill leachates. Some PPCPs exhibited higher contamination levels than those reported in other countries. Good removal of PPCPs by MBR led to a largely reduced contamination level (<LOQ to 10.6μg/L) in the treated landfill leachates, which was, however, still much higher than those in municipal wastewaters in Shanghai. To the best of our knowledge, this is the first report on the removal of PPCPs in landfill leachates. The findings emphasized the necessity to further study the PPCPs in the landfill leachates in China and the requirement to enhance their removal in the landfill leachates.

The destruction of benzene by calcium peroxide activated with Fe(II) in water

The ability of Fe(II)-activated calcium peroxide (CaO2) to remove benzene is examined with a series of batch experiments. The results showed that benzene concentrations were reduced by 20 to 100% within 30 min. The magnitude of removal was dependent on the CaO2/Fe(II)/Benzene molar ratio, with much greater destruction observed for ratios of 4/4/1 or greater. An empirical equation was developed to quantify the destruction rate dependence on reagent composition. The presence of oxidative hydroxyl radicals (HO•) and reductive radicals (primarily O2•-) was identified by probe compound testing and electron paramagnetic resonance (EPR) tests. The results of the EPR tests indicated that the application of CaO2/Fe(II) enabled the radical intensity to remain steady for a relatively long time. The effect of initial solution pH was also investigated, and CaO2/Fe(II) enabled benzene removal over a wide pH range of 3.0~9.0. The results of radical scavenging tests showed that benzene removal occurred primarily by HO• oxidation in the CaO2/Fe(II) system, although reductive radicals also contributed. The intermediates in benzene destruction were identified to be phenol and biphenyl. The results indicate that Fe(II)-activated CaO2 is a feasible approach for treatment of benzene in contaminated groundwater remediation.

Supramolecular polymer assembly in aqueous solution arising from cyclodextrin host–guest complexation

Summary The employment of cyclodextrin host–guest complexation to construct supramolecular assemblies with an emphasis on polymer networks is reviewed. The main driving force for this supramolecular assembly is host–guest complexation between cyclodextrin hosts and guest groups either of which may be discrete molecular species or substituents on a polymer backbone. The effects of such complexation on properties at the molecular and macroscopic levels are discussed. It is shown that cyclodextrin complexation may be used to design functional polymer materials with tailorable properties, especially for photo-, pH-, thermo- and redox-responsiveness and self-healing.

Benzene oxidation by Fe(III)-activated percarbonate: matrix-constituent effects and degradation pathways

Complete degradation of benzene by the Fe(III)-activated sodium percarbonate (SPC) system is demonstrated. Removal of benzene at 1.0 mM was seen within 160 min, depending on the molar ratios of SPC to Fe(III). A mechanism of benzene degradation was elaborated by free-radical probe-compound tests, free-radical scavengers tests, electron paramagnetic resonance (EPR) analysis, and determination of Fe(II) and H2O2 concentrations. The degradation products were also identified using gas chromatography-mass spectrometry method. The hydroxyl radical (HO.) was the leading species in charge of benzene degradation. The formation of HO. was strongly dependent on the generation of the organic compound radical (R.) and superoxide anion radical (O.). Benzene degradation products included hydroxylated derivatives of benzene (phenol, hydroquinone, benzoquinone, and catechol) and aliphatic acids (oxalic and fumaric acids). The proposed degradation pathways are consistent with radical formation and identified products. The investigation of selected matrix constituents showed that the Cl and HCO3 had inhibitory effects on benzene degradation. Natural organic matter (NOM) had accelerating influence in degrading benzene. The developed system was tested with groundwater samples and it was found that the Fe(III)-activated SPC has a great potential in effective remediation of benzene-contaminated groundwater while more further studies should be done for its practical application in the future because of the complex subsurface environment.

Removal of pharmaceutical and personal care products by sequential ultraviolet and ozonation process in a full-scale wastewater treatment plant

The application of appropriate advanced treatment process in the municipal wastewater treatment plants (WWTPs) has become an important issue considering the elimination of emerging contaminants, such as pharmaceutical and personal care products (PPCPs). In the present study, the removal of 13 PPCPs belonging to different therapeutic classes by the sequential ultraviolet (UV) and ozonation process in a full-scale WWTP in Beijing was investigated over the course of ten months. Most of the target PPCPs were effectively removed, and the median removal efficiencies of individual PPCPs, ranging from − 13% to 89%, were dependent on their reaction rate constants with molecular ozone. Noticeable fluctuation in the removal efficiencies of the same PPCPs was observed in different sampling campaigns. Nevertheless, the sequential UV and ozonation process still made a significant contribution to the total elimination of most PPCPs in the full-scale WWTP, by compensating for the poor or fluctuant removal performance of PPCPs by biologic treatment process.

Enhancement effects of reducing agents on the degradation of tetrachloroethene in the Fe(II)/Fe(III) catalyzed percarbonate system.

In this study, the effects of reducing agents on the degradation of tetrachloroethene (PCE) were investigated in the Fe(II)/Fe(III) catalyzed sodium percarbonate (SPC) system. The addition of reducing agents, including hydroxylamine hydrochloride, sodium sulfite, ascorbic acid and sodium ascorbate, accelerated the Fe(III)/Fe(II) redox cycle, leading to a relatively steady Fe(II) concentration and higher production of free radicals. This, in turn, resulted in enhanced PCE oxidation by SPC, with almost complete PCE removal obtained for appropriate Fe and SPC concentrations. The chemical probe tests, using nitrobenzene and carbon tetrachloride, demonstrated that HO was the predominant radical in the system and that O2(-) played a minor role, which was further confirmed by the results of electron spin resonance measurements. PCE degradation decreased significantly with the addition of isopropanol, a HO scavenger, supporting the hypothesis that HO was primarily responsible for PCE degradation. It is noteworthy that Cl(-) release was slightly delayed in the first 20 min, indicating that intermediate products were produced. However, these intermediates were further degraded, resulting in the complete conversion of PCE to CO2. In conclusion, the use of reducing agents to enhance Fe(II)/Fe(III) catalyzed SPC oxidation appears to be a promising approach for the rapid degradation of organic contaminants in groundwater.

Enhanced degradation of trichloroethene by calcium peroxide activated with Fe(III) in the presence of citric acid

Trichloroethene (TCE) degradation by Fe(III)- activated calcium peroxide (CP) in the presence of citric acid (CA) in aqueous solution was investigated. The results demonstrated that the presence of CA enhanced TCE degradation significantly by increasing the concentration of soluble Fe(III) and promoting H2O2 generation. The generation of HO• and O2–• in both the CP/Fe(III) and CP/Fe(III)/CA systems was confirmed with chemical probes. The results of radical scavenging tests showed that TCE degradation was due predominantly to direct oxidation by HO•, while O2–• strengthened the generation of HO• by promoting Fe(III) transformation in the CP/Fe (III)/CA system. Acidic pH conditions were favorable for TCE degradation, and the TCE degradation rate decreased with increasing pH. The presence of Cl–, HCO3–, and humic acid (HA) inhibited TCE degradation to different extents for the CP/Fe(III)/CA system. Analysis of Cl–production suggested that TCE degradation in the CP/Fe (III)/CA system occurred through a dechlorination process. In summary, this study provided detailed information for the application of CA-enhanced Fe(III)-activated calcium peroxide for treating TCE contaminated groundwater.

Pharmaceuticals and consumer products in four wastewater treatment plants in urban and suburb areas of Shanghai.

Ten pharmaceuticals and two consumer products were investigated in four wastewater treatment plants (WWTPs) in Shanghai, China. The concentrations of target compounds in the wastewater influents ranged from below the limit of quantification (LOQ) to 9340xa0ng/L, with the frequency of detection of 31–100xa0%, and the removal efficiencies were observed to be −82 to 100xa0% in the four WWTPs. Concentrations of most target compounds (i.e. diclofenac, caffeine, metoprolol, sulpiride) in the wastewater influents were around three to eight times higher in urban WWTPs than in suburb ones, probably due to the different population served and lifestyles. Mean concentrations of target compounds in the wastewater influent generally decreased by 5–76xa0% after rainfall due to the dilution of raw sewage by rainwater, which infiltrated into the sewer system. In the WWTPs located in the suburb area, the increased flow of wastewater influent led to a shortened hydraulic retention time (HRT) and decreased removal efficiencies of some compounds. On the contrary, the influence of rainfall was not significant on the removal efficiencies of investigated compounds in urban WWTPs, probably due to the almost unchanged influent flow, good removal performance, or bypass system employed.