超声波光催化协同降解对甲基苯磺酸水溶液的机理研究

采用超声波与光催化联合法对模拟废水中难生物降解的对甲基苯磺酸(4-TSA)进行降解实验研究,借助紫外光谱、红外光谱、质谱、气相色谱、高效液相色谱、化学需氧量和总有机碳的检测结果对反应机理进行了初步探讨.实验结果表明:超声波和光催化之间存在着协同效应;当溶液初始质量浓度30 mg/L,光催化剂TiO2投加量为100 mg...     

Appendix

Abstract

An atrazine‐degrading bacterial isolate (M91–3) was able to utilize simazine and cyanazine as N sources for glucose‐dependent growth. The degradation of these three 5‐triazine herbicides was also investigated in binary and ternary mixtures. The organism used atrazine and simazine indiscriminately, whereas cyanazine degradation was slow and delayed until the depletion of the two other herbicides. There was no apparent effect of other commonly used herbicides on the rate of atrazine degradation by M91–3.     

Photodegradation of Diquat and Paraquat in aqueous solutions by titanium dioxide: evolution of degradation reactions and characterisation of intermediates

The titanium dioxide assisted photodegradation of Diquat and Paraquat herbicides solutions has been the subject of the present investigation, considering its direct application in the treatment of contaminated waters and soils. To have a better understanding of the photodegradation process, different types of TiO2, commercial and 'home prepared' Ti(1-x)FexO2 (x = 0% and 4%), were used as catalysts, using an UV light as radiation source. The degradation reactions were followed by UV spectroscopy and the intermediates and reaction products were characterised by electrospray ionisation mass spectrometry (ESIMS) combined with collision-induced dissociation (CID) and tandem mass spectrometry (MS/MS). The present study shows that, for photocatalytic degradation of Diquat and Paraquat solutions, a basic pH can be determinant, as well as the type of catalyst. The type of catalyst can also strongly influence the degradation pattern of the herbicide. Regarding complete degradation, we were able to show that Diquat is more persistent than Paraquat. During the photocatalytic processes, several intermediate and reaction products are sequentially formed, to which structures are proposed.     

Non-degradable triazine substrates of atrazine and cyanuric acid hydrothermally and in supercritical water under the UV-illuminated photocatalytic cooperation

Strong oxidation by titanium dioxide photocatalysis can occur by photodegradation of organic contaminants in air and water. Some endocrine disruptors such as 2,4-dichlorophenoxy acetic acid (;;; ), 2,4-dichlorophenol (;;; ), nonylphenol (; ), bisphenol A (), diethyl phthalate (; ), etc. which can be neither biodegraded by bacteria nor degraded thermally can be degraded by TiO(2) photocatalytic treatment. However, incomplete photomineralization partly occurred, when TiO(2) photocatalytic degradation is employed for the treatment of certain endocrine disruptors. For example, no atrazine pesticide having triazine skeleton can be completely mineralized even by a photocatalytic procedure; the photodegradation of atrazine ultimately stops at the intermediate step of cyanuric acid, which cannot be photodegraded even after long illumination times ().In this study, the decomposition of atrazine and cyanuric acid was carried out with a device combining photocatalytic degradation in supercritical water (scH(2)O) or hydrothermal water (hyH(2)O). Atrazine and cyanuric acid can be degraded by the cooperation of either scH(2)O or hyH(2)O and UV illuminated TiO(2)-photocatalytic dispersed system under the fixed pressure of 23 MPa at 623 K or 683 K in a 120-ml Hastelloy batch reactor. The photocatalytic degradation method under high temperature and pressure has found appropriate for the photocatalytic oxidation of acetic acid and 2-chlorobiphenyl under continuous flow conditions at 160 degrees C and 20 atm (). In addition, the wet peroxide oxidation of PCBs by high temperature and pressure has been reported (). The main aims of this research are following. (i): the degradation of atrazine and cyanuric acid within the scH(2)O or hyH(2)O, (ii) the decomposition of atrazine and cyanuric acid catalyzed by TiO(2) particles under scH(2)O or hyH(2)O, and the synergistic effect for several reactions with TiO(2) and scH(2)O or hyH(2)O, and (iii) the mineralization yield of nitrogen and chlorine atoms concerning the chemical structures of atrazine or cyanuric acid (only nitrogen).     

Using polymer mats to biodegrade atrazine in groundwater: laboratory column experiments

Large-scale column experiments were undertaken to evaluate the potential of in situ polymer mats to deliver oxygen into groundwater to induce biodegradation of the pesticides atrazine, terbutryn and fenamiphos contaminating groundwater in Perth, Western Australia. The polymer mats, composed of woven silicone (dimethylsiloxane) tubes and purged with air, were installed in 2-m-long flow-through soil columns. The polymer mats proved efficient in delivering dissolved oxygen to anaerobic groundwater. Dissolved oxygen concentrations increased from <0.2 mg l(-1) to approximately 4 mg l(-1). Degradation rates of atrazine in oxygenated groundwater were relatively high with a zero-order rate of 240-380 microg l(-1) or a first-order half-life of 0.35 days. Amendment with an additional carbon source showed no significant improvement in biodegradation rates, suggesting that organic carbon was not limiting biodegradation. Atrazine degradation rates estimated in the column experiments were similar to rates determined in laboratory culture experiments, using pure cultures of atrazine-mineralising bacteria. No significant degradation of terbutryn or fenamiphos was observed under the experimental conditions within the time frames of the study. Results from these experiments indicate that remediation of atrazine in a contaminated aquifer may be achievable by delivery of oxygen using an in situ polymer mat system.     

Degradation of the drug diclofenac in water by sonolysis in presence of catalysts

Diclofenac, as one of the most popular antiphlogistics, is produced in great quantities. Nowadays this drug is ubiquitously present in the aquatic environment due to its resistance to biodegradation. Degradation by ultrasonic irradiation is a possibility to eliminate diclofenac from water without the addition of chemicals. The sonolysis of diclofenac in water was investigated at ultrasound frequencies of 24 kHz, 216 kHz, 617 kHz, and 850 kHz and in the presence of various catalysts (TiO2, SiO2, SnO2, and titanosilicate). The degradation of diclofenac by sonolysis of an aqueous solution at 617 kHz followed first-order kinetics. Catalysts, especially TiO2 increased the rate of degradation. Within 30 min of irradiation, the relative concentration of diclofenac decreased from 100% to 16%. By HPLC and GC-MS methods, chlorinated anilines, phenols and carboxylic acid derivatives were detected as a result of the sonolysis. About 35% of organic chlorine was transformed into inorganic chloride. Most of the identified degradation products in the sonolysis of diclofenac were the same compounds that were detected during photo-oxidation experiments with this anti-inflammatory drug.     

Abiotic degradation (photodegradation and hydrolysis) of imidazolinone herbicides

The abiotic degradation of the imidazolinone herbicides imazapyr, imazethapyr and imazaquin was investigated under controlled conditions. Hydrolysis, where it occurred, and photodegradation both followed first-order kinetics for all herbicides. There was no hydrolysis of any of the herbicides in buffer solutions at pH 3 or pH 7; however, slow hydrolysis occurred at pH 9. Estimated half-lives for the three herbicides in solution in the dark were 6.5, 9.2 and 9.6 months for imazaquin, imazethapyr and imazapyr, respectively. Degradation of the herbicides in the light was considerably more rapid than in the dark with half lives for the three herbicides of 1.8, 9.8 and 9.1 days for imazaquin, imazethapyr and imazapyr, respectively. The presence of humic acids in the solution reduced the rate of photodegradation for all three herbicides, with higher concentrations of humic acids generally having greater effect. Photodegradation of imazethapyr was the least sensitive to humic acids. The enantioselectivity of photodegradation was investigated using imazaquin, with photodegradation occurring at the same rate for both enantiomers. Abiotic degradation of imidazolinone herbicides on the soil surface only occurred in the presence of light. The rate of degradation for all herbicides was slower than in solution, with half-lives of 15.3, 24.6 and 30.9 days for imazaquin, imazethapyr and imazapyr, respectively. Abiotic degradation of these herbicides is likely to be slow in the environment and is only likely to occur in clear water or on the soil surface.     

Photosonochemical degradation of trichloroacetic acid in aqueous solution

The degradation of trichloroacetic acid (TCA) was studied with ultraviolet (UV) photolysis, ultrasound (US) sonolysis and their combination. It was found that the degradation in the combined processes was more significant than in the UV photolysis or sonolysis alone. The effects of pH and dissolved gases on the rate of photosonochemical degradation of TCA were investigated and the degradation kinetics, mechanism and possible degradation products were discussed in detail.     

Treatment of 2,4-D, mecoprop, and dicamba using membrane bioreactor technology

Phenoxyacetic and benzoic acid herbicides are widely used agricultural, commercial, and domestic pesticides. As a result of high water solubility, mobility, and persistence, 2,4-dichlorophenoxyacetic acid (2,4-D), methylchlorophenoxypropionic acid (mecoprop), and 3,6-dichloro-2-methoxybenzoic acid (dicamba) have been detected in surface and waste waters across Canada. As current municipal wastewater treatment plants do not specifically address chronic, trace levels of contaminants like pesticides, an urgent need exists for an efficient, environmentally friendly means of breaking down these toxic herbicides. A commercially available herbicide mix, WeedEx, containing 2,4-D, mecoprop, and dicamba, was subjected to treatment using membrane bioreactor (MBR) technology. The three herbicides, in simulated wastewater with a chemical oxygen demand of 745 mg/L, were introduced to the MBR at concentrations ranging from 300 μg/L to 3.5 mg/L. Herbicides and biodegradation products were extracted from MBR effluent using solid-phase extraction followed by detection using high-performance liquid chromatography coupled with mass spectrometry. 2,4-D was reduced by more than 99.0 % within 12 days. Mecoprop and dicamba were more persistent and reduced by 69.0 and 75.4 %, respectively, after 112 days of treatment. Half-lives of 2,4-D, mecoprop and dicamba during the treatment were determined to be 1.9, 10.5, and 28.3 days, respectively. Important water quality parameters of the effluent such as dissolved oxygen, pH, ammonia, chemical oxygen demand, etc. were measured daily. MBR was demonstrated to be an environmentally friendly, compact, and efficient method for the treatment of toxic phenoxyacetic and benzoic acid herbicides.     

Influence of microbial and synthetic surfactant on the biodegradation of atrazine

The present study reports the effect of surfactants (rhamnolipids and triton X-100) on biodegradation of atrazine herbicide by strain A6, belonging to the genus Acinetobacter. The strain A6 was able to degrade nearly 80 % of the 250-ppm atrazine after 6 days of growth. The bacterium degraded atrazine by de-alkylation process. Bacterial cell surface hydrophobicity as well as atrazine solubility increased in the presence of surfactant. However, addition of surfactant to the mineral salt media reduced the rate and extent of atrazine degradation by decreasing the bioavailability of herbicide. On the contrary, addition of surfactant to atrazine-contaminated soil increased the rate and extent of biodegradation by increasing the bioavailability of herbicide. As compared to triton X-100, rhamnolipids were more efficient in enhancing microbial degradation of atrazine as a significant amount of atrazine was removed from the soil by rhamnolipids. Surfactants added for the purpose of hastening microbial degradation may have an unintended inhibitory effect on herbicide degradation depending upon contiguous condition, thus highlighting the fact that surfactant must be judiciously used in bioremediation of herbicides.     

Abiotic degradation (photodegradation and hydrolysis) of imidazolinone herbicides

The abiotic degradation of the imidazolinone herbicides imazapyr, imazethapyr and imazaquin was investigated under controlled conditions. Hydrolysis, where it occurred, and photodegradation both followed first-order kinetics for all herbicides. There was no hydrolysis of any of the herbicides in buffer solutions at pH 3 or pH 7; however, slow hydrolysis occurred at pH 9. Estimated half-lives for the three herbicides in solution in the dark were 6.5, 9.2 and 9.6 months for imazaquin, imazethapyr and imazapyr, respectively. Degradation of the herbicides in the light was considerably more rapid than in the dark with half lives for the three herbicides of 1.8, 9.8 and 9.1 days for imazaquin, imazethapyr and imazapyr, respectively. The presence of humic acids in the solution reduced the rate of photodegradation for all three herbicides, with higher concentrations of humic acids generally having greater effect. Photodegradation of imazethapyr was the least sensitive to humic acids. The enantioselectivity of photodegradation was investigated using imazaquin, with photodegradation occurring at the same rate for both enantiomers. Abiotic degradation of imidazolinone herbicides on the soil surface only occurred in the presence of light. The rate of degradation for all herbicides was slower than in solution, with half-lives of 15.3, 24.6 and 30.9 days for imazaquin, imazethapyr and imazapyr, respectively. Abiotic degradation of these herbicides is likely to be slow in the environment and is only likely to occur in clear water or on the soil surface.     

Strategies to evaluate biodegradability: application to chlorinated herbicides

The biodegradability of nitrochlorinated (diuron and atrazine) and chlorophenoxy herbicides (2,4-D and MCPA) has been studied through several bioassays using different testing times and biomass/substrate ratios. A fast biodegradability test using unacclimated activated sludge yielded no biodegradation of the herbicides in 24 h. The inherent biodegradability test gave degradation percentages of around 20–30 % for the nitrochlorinated herbicides and almost complete removal of the chlorophenoxy compounds. Long-term biodegradability assays were performed using sequencing batch reactor (SBR) and sequencing batch membrane bioreactor (SB-MBR). Fixed concentrations of each herbicide below the corresponding EC₅₀ value for activated sludge were used (30 mg L^?1 for diuron and atrazine and 50 mg L^?1 for 2,4-D and MCPA). No signs of herbicide degradation appeared before 35 days in the case of diuron and atrazine and 21 days for 2,4-D, whereas MCPA was partially degraded since the early stages. Around 25–36 % degradation of the nitrochlorinated herbicides and 53–77 % of the chlorophenoxy ones was achieved after 180 and 135 days, respectively, in SBR, whereas complete disappearance of 2,4-D was reached after 80 days in SB-MBR.     

Comparative study of the effects of MCPA, butylate, atrazine, and cyanazine on Selenastrum capricornutum

The herbicides MCPA, butylate, atrazine and cyanazine are extensively used in Canadian agriculture and information regarding their effects on indigenous biota is scarce. Phytotoxicity assessments were conducted in the laboratory on the common green alga Selenastrum capricornutum using both the active ingredient of the herbicides and their formulated products (for MCPA and butylate). Endpoints determined after the 96 h exposure included algal population growth inhibition (IC50-cell counts), percent lethality (LC50-flow cytometry derived) and photosynthetic electron transport inhibition (EC50-fluorescence induction). Pesticide formulations had greater toxic effects than the active ingredient alone. The 96 h IC50 (50% Inhibition Concentration) and LOEC (Lowest Observable Effects Concentration) using cell counts of S. capricornutum were 18.4 and 8.9 mg l(-1) respectively for MCPA-active ingredient and for MCPA-formulated, these were 0.62 and 0.0062 mg l(-1) respectively. Those for butylateactive ingredient were 61.0 and 8.3 mg l(-1) and for butylate-formulated 1.46 and 0.17 mg l(-1), respectively. The triazines active ingredient, which are photosynthetic inhibitors, had greater effects than either the MCPA or butylate. The IC50 for cyanazine and atrazine were 0.059 and 0.026 mg l(-1), respectively. By comparing the IC50 and LC50 values for the tested active ingredients, it was found that the effects of atrazine were algicidal, whereas those of cyanazine, butylate and MCPA were algistatic.     

Treatment of atrazine by integrating photocatalytic and biological processes

This research examines the degradation of atrazine by photocatalytic oxidation (PCO) under different experimental conditions. Deisopropylatrazine, deethylatrazine and deethyldeisopropylatrazine were formed as major intermediates based on gas chromatography-mass spectrometry. The reaction mixture was found to be toxic towards two bioassays, i.e. the Microtox and amphipods survival tests even when atrazine was completely degraded by PCO within 2 h under optimized conditions. The results indicate that adding H2O2 could significantly enhance the degradation of atrazine by PCO. Ammeline, ammelide and cyanuric acid (CA) became the major intermediates/products as detected by high performance liquid chromatography from 6th to the 40th h of PCO treatment. After 72 h PCO treatment, only CA was detectable in the reaction mixture. Further degradation of CA was carried out by a newly isolated CA-degrading bacterium, Sphingomonas capsulata. The photochemical pretreatment integrated with microbial degradation lead to the complete degradation and detoxification of atrazine.     

Sorption and predicted mobility of herbicides in Baltic soils

This study was undertaken to determine sorption coefficients of eight herbicides (alachlor, amitrole, atrazine, simazine, dicamba, imazamox, imazethapyr, and pendimethalin) to seven agricultural soils from sites throughout Lithuania. The measured sorption coefficients were used to predict the susceptibility of these herbicides to leach to groundwater. Soil-water partitioning coefficients were measured in batch equilibrium studies using radiolabeled herbicides. In most soils, sorption followed the general trend pendimethalin > alachlor > atrazine approximately amitrole approximately simazine > imazethapyr > imazamox > dicamba, consistent with the trends in hydrophobicity (log K(ow)) except in the case of amitrole. For several herbicides, sorption coefficients and calculated retardation factors were lowest (predicted to be most susceptible to leaching) in a soil of intermediate organic carbon content and sand content. Calculated herbicide retardation factors were high for soils with high organic carbon contents. Estimated leaching times under saturated conditions, assuming no herbicide degradation and no preferential water flow, were more strongly affected by soil textural effects on predicted water flow than by herbicide sorption effects. All herbicides were predicted to be slowest to leach in soils with high clay and low sand contents, and fastest to leach in soils with high sand content and low organic matter content. Herbicide management is important to the continued increase in agricultural production and profitability in the Baltic region, and these results will be useful in identifying critical areas requiring improved management practices to reduce water contamination by pesticides.     

Decolorization and biodegradability of photocatalytic treated azo dyes and wool textile wastewater

The photodegradation and biodegradability have been investigated for four non-biodegradable commercial azo dyes, Reactive YellowKD-3G, Reactive Red 15, Reactive Red 24, Cationic Blue X-GRL, an indicator. Methyl Orange, and one industrial wool textile wastewater, using TiO2 suspensions irradiated with a medium pressure mercury lamp. The color removal of dyes solution and dyeing wastewater reached to above 90% within 20-30 min. of photocatalytic treatment. Biochemical oxygen demand (BOD) was found to increase, while chemical oxygen demand (COD), total organic carbon (TOC) decreased, so that the ratio of BOD5/COD of the wastewater increased from original zero up to 0.75. The result implies that photocatalytic oxidation enhanced the biodegradability of the dye-containing wastewater and therefore relationship between decolorization and biodegradability exists. When the color disappeared completely, the wastewater biodegraded normally and could be discharged for further treatment. The experimental results demonstrate that it is possible to combine photocatalysis with conventional biological treatment for the remedy of wastewater containing generally non-biodegradable azo dyes.     

Degradation of atrazine by an acclimatized soil fungal isolate

A fungal strain able to use atrazine (2-chloro-4-ethylamino-5-isopropylamino-1,3,5-triazine) as a source of nitrogen was isolated from a corn field soil that has been previously treated with the herbicide. This strain was purified and acclimatized to atrazine at a higher level in the laboratory. A supplemented N was required to trigger the reaction. Atrazine was degraded at a faster rate in inoculated mineral salt medium (MSM) than non-inoculated MSM. Within 20 days, nearly 34% of the atrazine was degraded in inoculated medium while only 2% of the herbicide was degraded in non-inoculated medium. Degradation of atrazine by the isolated fungal strain was also studied in sterile and non-sterile soil to determine the compatibility of the isolated strain with native microorganisms in soil. The degradation of atrazine was found to be more in inoculated sterile soil than in inoculated non-sterile soil. Cell free extract (CFE) of fungal mycelium degraded about 50% of the atrazine in buffer in 96 hours compared to the control. Four atrazine metabolites were isolated and characterized by LCMS. On the basis of morphological parameters the isolate was identified as Penicillium species. Results indicated that the microorganism may be useful for remediation of atrazine-contaminated soil.     

Characterization of bacterial diversity in an atrazine degrading enrichment culture and degradation of atrazine,cyanuric acid and biuret in industrial wastewater

An enrichment culture was used to study atrazine degradation in mineral salt medium (MSM) (T1), MSM+soil extract (1:1, v/v) (T2) and soil extract (T3). Results suggested that enrichment culture required soil extract to degrade atrazine, as after second sequential transfer only partial atrazine degradation was observed in T1 treatment while atrazine was completely degraded in T2 and T3 treatments even after fourth transfer. Culture independent polymerase chain reaction-denaturing gradient gel electrophoresis (PCR-DGGE) technique confirmed selective enrichment of genus Bacillus along with Pseudomonas and Burkholderia. Degradation of atrazine/metabolites in the industrial wastewater was studied at different initial concentrations of the contaminants [wastewater-water (v/v) ratio: T1, 1:9; T2, 2:8; T3, 3:7; T4, 5:5 and T5, undiluted effluent]. The initial concentrations of atrazine, cyanuric acid and biuret ranged between 5.32 and 53.92 µg mL^?1, 265.6 and 1805.2 µg mL^?1 and 1.85 and 16.12 µg mL^?1, respectively. The enrichment culture was able to completely degrade atrazine, cyanuric acid and biuret up to T4 treatment, while no appreciable degradation of contaminants was observed in the undiluted effluent (T5). Inability of enrichment culture to degrade atrazine/metabolites might be due to high concentrations of cyanuric acid. Therefore, a separate study on cyanuric acid degradation suggested: (i) no appreciable cyanuric acid degradation with accumulation of an unidentified metabolite in the medium where cyanuric acid was supplemented as the sole source of carbon and nitrogen; (ii) partial cyanuric acid degradation with accumulation of unidentified metabolite in the medium containing additional nitrogen source; and (iii) complete cyanuric acid degradation in the medium supplemented with an additional carbon source. This unidentified metabolite observed during cyanuric acid degradation and also detected in the enrichment culture inoculated wastewater samples, however, was degraded up to T4 treatments and was persistent in the T5 treatment. Probably, accumulation of this metabolite inhibited atrazine/cyanuric acid degradation by the enrichment culture in undiluted wastewater.     

Performance of photocatalytic reactors using immobilized TiO2 film for the degradation of phenol and methylene blue dye present in water stream

TiO2 thin film photocatalyst was successfully synthesized and immobilized on glass reactor tube using sol-gel method. The synthesized TiO2 coating was transparent, which enabled the penetration of ultra-violet (UV) light to the catalyst surface. Two photocatalytic reactors with different operating modes were tested: (a) tubular photocatalytic reactor with re-circulation mode and (b) batch photocatalytic reactor. A new proposed TiO2 synthesized film formulation of 1 titanium isopropoxide: 8 isopropanol: 3 acetyl acetone: 1.1 H2O: 0.05 acetic acid (in molar ratio) gave excellent photocatalytic activity for degradation of phenol and methylene blue dye present in the water. The half-life time, t1/2 of photocatalytic degradation of phenol was 56 min at the initial phenol concentration of 1000 microM in the batch reactor. In the tubular photocatalytic reactor, 5 re-circulation passes with residence time of 2.2 min (single pass) degraded 50% of 40-microM methylene blue dye. Initial phenol concentration, presence of hydrogen peroxide, presence of air bubbling and stirring speed as the process variables were studied in the batch reactor. Initial methylene blue concentration, pH value, light intensity and reaction temperature were studied as the process variables in the tubular reactor. The synthesized TiO2 thin film was characterized using SEM, XRD and EDX analysis. A comparative performance between the synthesized TiO2 thin film and commercial TiO2 particles (99% anatase) was evaluated under the same experimental conditions. The TiO2 film was equally active as the TiO2 powder catalyst.     

微波辅助光催化降解阿特拉津的表观动力学

以内分泌干扰物阿特拉津为目标物,建立循环流化床微波辅助光催化体系,研究其微波辅助光催化降解规律。表观动力学研究发现,当阿特拉津初始浓度较低时,其在微波辅助光催化体系中的降解符合表观一级反应动力学特征。降解反应速率常数与阿特拉津初始浓度呈负线性相关,与紫外光强呈正线性相关,与催化剂浓度呈抛物线性相关。表观反应速率常数kobs=3.95×10-4c-0.27030I1.2224W0.3283,该模型计算值与实验值吻合较好,平均相对偏差仅为0.5%,可用于预测微波辅助光催化降解低浓度有机污染物的反应规律。