Degradation of diclofenac sodium using Fenton-like technology based on nano-calcium peroxide.

A nano-calcium peroxide (nCaO2) powder with a purity of 89.1% was prepared using an improved traditional method. Then, the as-prepared nCaO2 was used as the source of hydrogen peroxide (H2O2) for the Fenton-like degradation of diclofenac sodium (DCF). The results showed that nCaO2 performed better for DCF removal when compared to nCaO2 prepared by a conventional method and commercial calcium peroxide (CaO2). Further experimental results indicated that 97.5% of DCF could be removed in 180 min at a nCaO2/Fe2+-EDTA/DCF molar ratio of 16/8-8/1, which was more efficient than in the H2O2/EDTA-Fe2+/DCF and nCaO2/Fe2+/DCF systems. The best removal rate of DCF was at pH 6.0, unlike previous claims that stated that the lower the pH in the buffer system, the better the degradation of DCF. In addition, the influence of water quality parameters, such as Cl-, NO3-, SO42-, HCO3-, and humic acid (HA), on DCF removal were evaluated. A free radical masking experiment revealed the existence of hydroxyl radical (OH), superoxide radical (O2-) and singlet oxygen (1O2), and indicated that the degradation of DCF was mainly due to oxidation caused by OH. Electron paramagnetic resonance (EPR) studies for different systems and different active oxygen species were carried out, and it was further confirmed that OH radicals have high intensity in the Fenton-like system based on nCaO2. EPR results also showed that the addition of EDTA can promote the production of OH. According to the identification of the dominant reactive species and GC-MS, the possible theoretical DCF degradation pathways were proposed.

Characterization of algal organic matter as precursors for carbonaceous and nitrogenous disinfection byproducts formation: Comparison with natural organic matter.

Algal organic matter (AOM) and natural organic matter (NOM) from a typical eutrophic lake were comprehensively investigated in terms of their physico-chemical property, components and disinfection byproduct formation potentials (DBPFPs). The relationships between specific chemical properties of AOM and NOM with their corresponding DBPFPs were further evaluated during chlorination. Results indicated that AOM had lower specific UV absorbance (SUVA) but richer organic nitrogen contents than NOM. Fluorescence excitation emission matrix spectroscopy further demonstrated that AOM were chiefly composed of aromatic protein-like and soluble microbial byproduct-like matters, while NOM were mainly contributed from humic acid-like and soluble microbial byproduct-like substances. Although the molecular weight (MW) distribution of AOM and NOM showed no significant difference, size-exclusion chromatography with organic carbon as well as organic nitrogen detection (LC-OCD-OND) revealed that AOM were concentrated with the fraction of building blocks and NOM had higher concentrations of biopolymers and humics (HS). Moreover, AOM displayed higher DBPFPs than NOM, especially for nitrogenous DBPFP (N-DBPFP). MW < 1 kDa fractions both in AOM and NOM contributed the largest proportion to the formation of carbonaceous disinfection byproducts (C-DBPs). In addition, Pearson correlation analysis showed that bulk parameter SUVA was significantly relevant to the formation potentials of trihalomethane both in AOM and NOM, but was ineffective for carbonaceous DBPFP (C-DBPFP) prediction. Dissolved organic nitrogen contents in biopolymer and HS characterized by LC-OCD-OND had strong correlations with N-DBPFPs from AOM and NOM, indicating that LC-OCD-OND quantitative analysis could improve the prediction accuracy of the DBP formation than bulk parameters during NOM and AOM chlorination.

[Restoration of River Sediment by Calcium Peroxide(CaO2) Combined with Biochar].

The internal source pollution of sediment is the main factor leading to the repetition of black-odorous river channels. In order to prevent this situation, a river channel in the Binhu District of Wuxi City was used as an experimental site. In-situ CaO2 combined with a biochar covering technology was used to repair the black odorous river sediment in this channel. The effects of this technology on the quality of mud water, sedimentary volatile sulfide (AVS) and phosphorus forms, microorganisms, and restoration of black odorous sediment were investigated. The results showed that CaO2 combined with biochar coverage could significantly increase the dissolved oxygen (DO) concentration and redox potential (ORP) of the muddy water system. The DO concentration and ORP in the overlying water were maintained above 2 mg·L-1 and 50 mV, respectively. The removal rates of interstitial water ammonia-nitrogen (NH4+-N), chemical oxygen demand (COD), and total phosphorus (TP) reached 43.40%, 41.18%, and 50.97%, respectively. The removal rate of AVS in the sediment reached 37.03%. The high-throughput sequencing showed that the relative abundance of anaerobic microorganisms in the sediment was significantly reduced, and that nitrogen and sulfur removal microorganisms appeared (e.g., Thermomonas, Dechloromonas, Proteus hauser, Desulfomicrobium, and Thiobacillus). Phosphorus in the sediment was converted into Fe/Al-P and Ca-P. Therefore, in-situ CaO2 combined with biochar coverage had a good repairing effect on black odorous sediment.

A study into the species sensitivity of green algae towards imidazolium-based ionic liquids using flow cytometry.

The sensitivity of individual organisms towards toxic agents is an important indicator of environmental pollution. However, organism-specific quantification of sensitivity towards pollutants remains a challenge. In this study, we determined the sensitivity of Chlorella vulgaris (C. vulgaris) and Scenedesmus quadricauda (S. quadricauda) towards three ionic liquids (ILs), 1-alkyl-3-methyl-imidazolium chlorides [Cnmim][Cl] (n = 4,6,8). We kept all external parameters constant to identify the biotic parameters responsible for discrepancies in species sensitivity, and used flow cytometry to determine four conventional endpoints to characterise cell viability and cell vitality. Our results demonstrate that after exposure to the ILs, cell proliferation was inhibited in both species. At the same time, the cell size, complexity and membrane permeability of both algae also increased. However, while Chl a synthesis by S. quadricauda was inhibited, that of C. vulgaris was enhanced. S. quadricauda has evolved a metabolic defense that can counteract the decreased esterase activity that has been shown to occur in the presence of ILs. While it is likely that S. quadricauda was less sensitive than C. vulgaris to the ILs because of this metabolic defense, this alga may also exhibit better membrane resistance towards ILs.

[Effect of Ozonation on Microorganism in the Biological Activated Carbon and Disinfection By-Products in the Effluent].

This study was carried out in the ozone (O3) and biological activated carbon (BAC) section of a drinking water plant to investigate the effects of O3 on microbial and effluent disinfection by-products (DBPs) in BAC during drinking water treatment. The water quality, dissolved organic matter (DOM) characteristics, microbial activity, and DBPs formation at different O3 concentrations were analyzed. Results showed that the effect of O3 on microorganisms is mainly that it increased the utilization efficiency of DOM. However, excessive O3 increased the amount of organic matter such as protein and microbial metabolites (SMPs) in the effluent. When the O3 concentration increased from 0 mg·L-1 to 2.0 mg·L-1, the survival rate of microorganisms in the BAC decreased from 95.10% to 62.60%. However, since O3 transforms organic matter into a biodegradable substance, we found that microbial activity increased by 62.52% and that the biofiltration of the BAC was enhanced. When the O3 concentration was further increased to 4.0 mg·L-1, the microbial survival rate decreased to 49.9% and the protein and SMPs produced by the microorganisms increased. This resulted in an increased formation of carbon-containing DBPs (C-DBPs) and nitrogen-containing DBPs (N-DBPs) by 41.93% and 7.18%, respectively. In summary, an appropriate dosage of O3 was beneficial for removing DOM by O3-BAC, but we found that an excessive O3 concentration caused the formation of new DBPs precursors.

[Transformation of Protein in Sludge During High Solids Anaerobic Digestion].

Dewatered waste sludge with a total solid (TS) concentration of 12% was used for mesophilic (37℃) anaerobic digestion (AD). The biotransformation mechanism of protein and the reason for the low conversion efficiency of protein under high solids AD was investigated by analyzing the variation of protein composition in the sludge before and after AD. The results showed that the conversion rate of protein in the sludge was 34.26% after 45 days of AD. The reason for the low efficiency of protein conversion was the poor mass transfer efficiency under the condition of high solids content and the large amount of ammonia nitrogen produced with the hydrolysis. After 45 days of AD, the total ammonia nitrogen (TAN) concentration reached 1201 mg·L-1, which resulted in the inhibition of the AD process, especially the decomposition of protein. Some of the protein converted to humic acid-like and fulvic acid-like substances, which are more difficult to decompose based on the three-dimensional fluorescence spectroscopy (3D-EEM) analysis. Two-dimensional electrophoresis (2-DE)- mass spectrometry (MS) was adopted for identifying the composition of protein in sludge before and after AD. It showed that the relative molecular weight and the isoelectric point (pI) of the protein in the sludge decreased after AD and most of the proteins left in the digested sludge came from the micro-organisms. These proteins cannot be further decomposed by the microbes because of the decreased microbial metabolic capacity at the end of the AD process or lack of specific enzymes for the hydrolysis of these proteins. This ultimately resulted in the low decomposition efficiency of the total protein in the sludge.

Insights into influencing factor, degradation mechanism and potential toxicity involved in aqueous ozonation of oxcarbazepine (CHEM46939R1).

Oxcarbazepine (OXC), as a potent antiepileptic drug, is widely used in recent years, but its residue is potentially harmful to the environment. Although ozonation is a high-efficient technology for chemical oxidation during water treatment, it cannot completely mineralize organic matters, but partially transforms them into some unidentified by-products. In order to provide more insight into OXC ozonation process, the influencing factor, transformation mechanism and potential toxicity were comprehensively investigated in this study. The results showed that the optimal ozonation temperature was 20 °C with a pseudo-first-order reaction rate constant of 0.161 min-1. The increase of pH significantly enhanced OXC degradation, while the presence of bicarbonate caused a remarkable negative effect, manifesting that hydroxyl radical (OH) oxidation should play an important role in OXC ozonation. Moreover, transformation mechanism was further elucidated based on the identification of ten OXC-related by-products using UPLC-Q-TOF-MSn, which mainly consisted of electrophilic substitution, N-heterocyclic ring cleavage and re-arrangement, hydroxylation, carbonylation, demethoxylation and deamidation, etc. The toxicity evaluation, using US Environmental Protection Agency Toxicity Estimation Software Tool (US-EPA TEST), suggested that most identified by-products were probably more toxic than OXC itself. Besides, further experiments, by measuring inhibitory effect of ozonated mixture on Vibrio fischeri bioluminescence, demonstrated that by-products with higher toxicity tended to be accumulated under a short reaction time. Taken together, the present investigation provided valuable information for further understanding OXC ozonation process, and suggested that special attention should be paid to the control and elimination of toxic transformation by-products in future studies.

[Transformation of Disinfection Byproduct Precursors During the Wastewater Regeneration Processes].

Disinfection byproduct(DBP) precursors during the wastewater regeneration processes were separated into hydrophilic fraction(HPI), hydrophobic fraction(HPO) and transphilic fraction(TPI) with macroporous resin. DBP precursors in these water samples were characterized with fluorescence excitation emission matrix, Fourier transformation infrared and nuclear magnetic resonance, and were further tested for their DBP formation potential(DBPFP) after chlorination. The results indicated that main DBP precursors in sewage were humic acid and aliphatic hydrocarbons, and were mainly dominated by HPI. Primary treatment(sedimentation) could effectively remove hydrophobic humic acid through the mutual exclusion between HPO and water. The removal of humic acid would lead to the obvious reduction of carbonaceous disinfection byproduct formation potential(C-DBPFP). In addition, nitrogenous disinfection byproduct formation potential(N-DBPFP) was found to be increased due to the increase of DON/DOC value. Although secondary treatment(biotreatment) was effective in removing humic acid and aliphatic hydrocarbons, it could produce a large amount of soluble microbial products(SMP), which led to the enhancement of HPO percentage. And the accumulation of SMP resulted in the significant increase of C-DBPFP and N-DBPFP. Humic acid and hydrophobic SMP could be removed by the advanced treatment(cloth filtration), leading to the reduction of HPO percentage and the increase of HPI percentage. The decrease of humic acid and hydrophobic SMP would cause the reduction of C-DBPFP and N-DBPFP in the advanced treatment.

[Construction of a High Efficiency Anaerobic Digestion System for Vinegar Residue].

The model of high solid anaerobic digestion was used by improving the degree of homogeneity of the reaction system and biogas slurry reflux to gradually increase the material load. The vinegar residue-efficient anaerobic digestion system was successfully constructed without pretreatment.The optimum anaerobic digestibility was observed when the material loading of the reaction system reached 6.15 g·(L·d)-1, when the amount of biogas produced per unit of dry material was 396 mL·g-1, and the amount of methane produced per unit of dry material was 211 mL·g-1. The degradation rate of hemicellulose reached 63.66%, which was the main reason for the improvement of anaerobic digestion performance. The degradation rates of cellulose and lignin were 21.46% and 24.43%, respectively. The lower degradation efficiency was mainly due to the complicated degradation of the benzene ring structure in lignin and hindered hydrolysis of cellulose, which had a shielding effect on cellulose degradation.

[Treatment of Urban Runoff Pollutants by a Multilayer Biofiltration System].

In order to control the non-point source pollution from road runoff in Wuxi City effectively, a multilayer biofiltration system was designed to remove a variety of pollutants according to the characteristics of road runoff in Wuxi, and the experimental research was carried out to study the effect on rainwater pollution purification. The results show that the system has a good performance on removing suspended solids (SS), organic pollutant (COD), nitrogen and phosphorus: all types of multilayer biofiltration systems have a high removal rate for SS, which can reach 90%. The system with activated carbon (GAC) has higher removal rates for COD and phosphorus. The system with zeolite (ZFM) has a relatively better removal efficiency for nitrogen. The addition of wood chips in the system can significantly improve the system efficiency for nitrogen removal. Between the two configurations of layered and distributed wood chips, configurations of distributed wood chips reach higher COD, phosphorus and nitrogen pollutants removal efficiencies since they can reduce the release of wood chips dissolution.

Degradation of phenazone in aqueous solution with ozone: influencing factors and degradation pathways.

Oxidation kinetics and degradation pathways of phenazone (an analgesic and antipyretic drug) upon reaction with O3 were investigated. Kinetic studies on degradation of phenazone were carried out under different operating conditions such as temperature, pH, anions and H2O2 addition. Results showed that the degradation followed the pseudo-first-order kinetic model. The reaction rate constant (kobs) of phenazone reached the maximum at 20 °C (9.653×10(-3) s(-1)). The presence of NO3(-) could enhance the degradation rate, while the addition of HCO3(-), SO4(2)(-), Cl(-) and the rise of pH showed negative effects on the ozonation of phenazone. H2O2 addition increased the phenazone degradation efficiency by 45.9% with the optimal concentration of 0.135 mM. Reaction by-products were evaluated by UPLC-Q-TOF-MS, which allowed the identification of a total of 10 by-products. The transformation pathways of phenazone ozonation consisted mainly of electrophilic addition and substitution, pyrazole ring opening, hydroxylation, dephenylization and coupling. The toxicity of these intermediate products showed that they are expected not to be more toxic than phenazone, with the exception of P7 (aniline) and P10 (1,5-dimethyl-4-((1-methyl-2-phenylhydrazinyl)methoxy)-2-phenyl-1H-pyrazol-3(2H)-one).

Performance and dynamic characteristics of microbial communities in an internal circulation reactor for treating brewery wastewater.

A laboratory-scale internal circulation (IC) anaerobic reactor fed with brewery wastewater was operated at 35 degrees C + 1 degrees C. The influent was pumped into the bottom of the IC reactor by a pulse pump, whereas the effluent was drawn from the upper outlet and allowed to flow into the effluent tank. The biogas volume was recorded using a gas container connected to a biogas metre. The results indicated that the maximum organic loading rate (OLR) of the IC reactor was 19.5 kg chemical oxygen demand (COD)/m3/day; at which point, the dominant archaeal populations found in the sludge using the polymerase chain reaction with denaturing gradient gel electrophoresis were Methanosaeta species. The COD removal efficiencies of the reactor exceeded 85%, with a maximum specific methane production rate of 210 mL CH4/g volatile suspended solids (VSS)/day and a coenzyme F420 content of 0.16 micromol/g VSS, respectively. The main archaeal species in the sludge samples at different OLRs varied greatly, as compared with the organisms in the inoculated sludge. The dominant archaeal species in the treated sludge at low OLRs were Methanosarcina species, whereas those at high OLRs were Methanosaeta species.

[Performance and microbial community dynamic characteristics of an internal circulation reactor treating brewery wastewater].

A lab-scale internal circulation reactor (IC) fed by artificial brewery wastewater was operated with increasing volumetric loading rate under 35 degrees C continuously. The reactor performance and the relationship between microbial community structure and bioactivity in the anaerobic sludge were investigated during the operation. The COD removal efficiency was above 85%, furthermore, the maximum volumetric loading rate (VLR) and the maximum specific methanogenic activity (SMA) of the reactor could be up to 20 kg x (m3 x d)(-1) and 210 mL x (g x d)(-1) respectively. The results from the dehydrogenase and the bacteria DGGE experiments demonstrated that the dehydrogenase variation tendency was positively correlated to total light intensity of the whole bacteria DGGE bands for each sample. The total light intensity of the whole bacteria DGGE bands can use as a referential index for biomass liveweight in anaerobic system. Moreover, the coenzyme F420 content related to the relative abundance of Methanosaeta based on coenzyme F420 and archaebacteria DGGE analysis. As the volumetric loading rate increased, Methanomsaeta became significantly dominant, which was accompanied by the coenzyme F420 content increasing. The content could be up to 0.16 micromol x g(-1), meanwhile, the superiority of Methanosaeta became significantly obvious; UPGAMA analysis and Shannon index also confirmed the dynamic changes of microbial community structure during the operation.

[Degradation of medroxyprogesterone in drinking water by ozone oxidation].

Kinetics on degradation efficiency of medroxyprogesterone (MPA) by ozonation was investigated in this paper. And the operating parameters such as MPA initial concentration, ozone dosage, pH and radicals scavenger (HCO3-) were further discussed. Results showed that MPA could be degraded effectively by ozonation, with a first-order kinetics in continuous ozone aeration system and a second-order kinetics in semibatch ozone aeration system, when the initial concentrations of MPA were 3, 5, 10 mg x L(-1). The increases of pH and the addition of HCO3- would bring negative effects to the degradation of MPA. The degradation efficiency of MPA decreased from 89.8% to 54.8% with pH increase from 3.10 to 9.02, and the rate constant k decreased from 0.1463 L x (mg x min)(-1) to 0.049 5 L x (mg x min)(-1) and the degradation efficiency decreased 22.2 percentage points with the addition of HCO3-, in semibatch aeration system.

[Urban non-point source pollution control by runoff retention and filtration pilot system].

A runoff retention and filtration pilot system was designed and the long-term purification effect of the runoff was monitored. Runoff pollution characters in 2 typical events and treatment effect of the pilot system were analyzed. The results showed that the runoff was severely polluted. Event mean concentrations (EMCs) of SS, COD, TN and TP in the runoff were 361, 135, 7.88 and 0.62 mg/L respectively. The runoff formed by long rain presented an obvious first flush effect. The first 25% flow contributed more than 50% of the total pollutants loading of SS, TP, DTP and PO4(3-). The pilot system could reduce 100% of the non-point source pollution if the volume of the runoff was less than the retention tank. Otherwise the overflow will be purification by the filtration pilot system and the removal rates of SS, COD, TN, TP, DTP and PO4(3-) reached 97.4% , 61.8%, 22.6%, 85.1%, 72.1%, and 85.2% respectively. The system was stable and the removal rate of SS, COD, TN, and TP were 98.6%, 65.4%, 55.1% and 92.6%. The whole system could effectively remove the non-point source pollution caused by runoff.

Enhancement of substrate solubilization and hydrogen production from kitchen wastes by pH pretreatment.

Pretreatment at different pHs was adopted in this study to enhance the substance solubilization and hydrogen production from kitchen wastes through anaerobic digestion. After a pretreatment set at pH = 13, solubilization of kitchen wastes improved substantially as the concentration of soluble carbohydrate, soluble protein, lipids and soluble chemical oxygen demand increased by 283.1%, 203.2%, 259.1% and 108.2%, respectively, as compared with those of the control. The maximum hydrogen production potential reached 105.38 mL/g VS after the pretreatment, which was 2.66 times that of the control. Furthermore, butyric acid and acetic acid were the major components in the total metabolites after fermentation, while propionic acid had a relatively low concentration. Finally, the concentration of exoprotein and exopolysaccharide within extracellular polymeric substances (EPS) kept increasing during the initial 14 and 9 hours, respectively, then decreased afterwards. However, the concentration of DNA increased throughout the whole stage. The total EPS might indirectly indicate the anaerobic digestion process. These findings may represent a feasible method for high-quality treatment of kitchen wastes.

[Degradation of microcystin-RR by ozonation process].

Degradation of algal toxin Microcystin-RR (MC-RR) by ozonation processes was investigated. The degradation rate of MC-RR reached 83.0% at ozone/MC-RR dosage of 6, and the degradation efficiency was decreased with increase of pH or NOM contents. Ozonation byproducts of MC-RR under different ozone dosages were detected by HPLC-MS to elucidate degradation mechanisms and pathways. The results showed that MC-RR degradation by attacking of ozone and hydrogen radicals mainly involved in substitution and cleavage of the Adda conjugated diene structure, cleavage of the peptide bond between Mdha and Ala. And Adda degradation pathway exerted a dominant position during the process.

Detoxification and degradation of microcystin-LR and -RR by ozonation.

In the present study, two Microsystins (MCs) of Microcystin-LR and Microcystin-RR were degraded with different dosages of ozone (O(3)). The possible degradation pathways were elucidated by analyzing their intermediates and end-products with liquid chromatography-mass spectrometry (LC-MS) method. The toxicity of the MCs ozonation products was also evaluated by assaying the protein phosphatase inhibition in vitro and acute toxicity in vivo. Results demonstrated that ozonation was a promising technology for removal and detoxification of the cyanotoxins. The MCs destruction was mainly involved in the attack of ozone on Adda side chain. First, the conjugated diene structure of Adda moiety was attacked by hydroxyl radical (OH()) to produce dihydroxylated products, then the hydroxylated 4-5 and/or 6-7 bond of Adda was cleaved into aldehyde or ketone peptide residues, and finally the residues were oxidized into the corresponding carboxylic acids. The fragmentation of the Mdha-Ala peptide bond of MCs also contributed positively to the oxidation process. Additionally, the attack on the benzene ring of Adda side chain was exclusively observed during MC-RR degradation. The toxicity evaluation of MCs ozonation products revealed that those end-products had no adverse effects in vivo and in vitro ozonation that could completely remove the MCs' toxicity.

[Degradation of microcystin-lR by ozonation process].

Degradation and byproducts of microcystin-LR (MC-LR) under different ozone dosages were investigated, and, the pathway and mechanism for the degradation of MC-LR were also elucidated according to the molecular weight of 8 degradation byproducts during ozonation process in this paper. The results showed that there were two pathways for the degradation of MC-LR by ozone. The first one is that the diene structure in Adda side chain was attacked and cleaved, which was named as Adda degradation pathway. The second one is that the pathway of Mdha and Ala degradation, which was that the peptide bond between Mdha and Ala was attacked and cleaved. Adda degradation pathway was dominant and mainly responsible for the degradation of MC-LR byozone. The removal of MC-LR by ozone could reach 92% when O3:MC is 6.

Evaluation of the efficacy of upflow anaerobic sludge blanket reactor in removal of colour and reduction of COD in real textile wastewater.

The upflow anaerobic sludge blanket (UASB) reactor was evaluated for its efficacy in decolourization and reduction in chemical oxygen demand (COD) of real textile wastewater (RTW) under different operational conditions. The efficiency of UASB reactor in reducing COD was found to be over 90%. Over 92% of colour removal due to biodegradation was achieved. The activities of the anaerobic granules were not affected during the treatment of textile wastewater. Cocci-shaped bacteria were the dominant group over Methanothrix like bacteria in textile wastewater treatment. Alkalinity, volatile fatty acids (VFA) content and pH in effluents indicated that the anaerobic process was not inhibited by textile wastewater. It is concluded that UASB reactor system can effectively be used in the treatment of textile wastewater for the removal of colour and in the reduction of COD.