Photodegradation of bisphenol Z by UV irradiation in the presence of beta-cyclodextrin

In this work, the formation of the inclusion complex of bisphenol Z (1,1-bis(4-hydroxyphenyl)cyclohexane, abbreviated as BPCH) with beta-cyclodextrin (beta-CD) has been studied, 1:1 inclusion complex can be obtained, the formation constant of the beta-CD/BPCH complex is 5.94x10(3)M(-1). The photodegradation behavior of BPCH was investigated under monochromatic UV irradiation (lambda=254 nm). The photodegradation rate constant of BPCH in aqueous solutions with beta-CD showed a 9.0-fold increase, and simultaneously the mineralization of BPCH can be enhanced by beta-CD. The influence factors on photodegradation of BPCH were also studied and described in details, such as concentration of beta-CD, initial concentration of BPCH, organic solvent and pH. The photodegradation of BPCH in the presence of beta-CD includes the direct photolysis and the photooxidation of BPCH during the photochemical process. Some predominant photodegradation products are 4-(2,4,5-trihydroxy-phenyl)-4-(4-hydroxyphenyl) butanoic acid, 5,5-bis(4-hydroxyphenyl)pentanoic acid, meta-hydroxylated BPCH, ortho-hydroxylated BPCH and 4-(1-(4-hydroxyphenyl)pentyl)phenol respectively. The enhancement of photodegradation of BPCH mainly results from moderate inclusion depth of BPCH molecule in the beta-CD cavity. This kind of inclusion structure allows BPCH molecule sufficient proximity to secondary hydroxyl groups of the beta-CD cavity, and these hydroxyl groups could be activated and converted to hydroxyl radicals under UV irradiation, which can enhance the photooxidation of BPCH.     

紫外光降解气态氯苯的影响因素及其动力学研究

紫外光降解挥发性有机物(VOCs)是一种新型的废气处理技术.采用主波长为365 nm的500 W高压汞灯为光源,重点考察了空塔停留时间、氯苯初始浓度、反应介质等对氯苯光降解效果的影响.结果表明,在氯苯初始浓度较低时.氯苯去除率随着空塔停留时间的延长而呈线性升高.最大去除率达87%;而氯苯初始浓度过高时会使单位分子接受的光子和活性基团数量下降,引起氯苯去除率降低,空气介质中的O2和H2O在光照下可转化为活性基团.进而增强了光降解效果;而在氮气介质下光降解氯苯的效率大大降低,最大去除率仅为61%.在氯苯为0.36～8.64 mg/L时,紫外光降解氯苯遵循二级反应动力学方程.     

Destruction of phenol aqueous solution by photocatalysis or direct photolysis

The photodegradation of phenol has been investigated under a high-pressure mercury lamp with a kind of jacket (glass or quartz) depending on used UV light range and a variety of experimental conditions: UV (lambda > 200 nm) with oxygen or with TiO2 and oxygen or with N2; UV (lambda > 330 nm) with oxygen or with TiO2 and oxygen or with N2. Photocatalysis and direct photolysis of phenol have different reaction pathways. Direct photolysis of phenol yielded a brown-yellow complex organic polymer in both aerobic and anaerobic environments. The polymer cannot be mineralized in an anaerobic environment. The effects of catalyst amount and oxygen concentration in the reaction atmosphere on the destruction of phenol were studied. The results prove that an appropriate catalyst amount can avoid direct photolysis and increase the mineralization rate of phenol.     

Electrospray Ionization Mass Spectrometry (ESI-MS) monitoring of the photolysis of diazinon in aqueous solution: Degradation route and toxicity of by-products against Artemia salina

The photolytic degradation of diazinon, an organophosphorus pesticide, in aqueous medium under assorted pH values was continuously monitored by direct infusion electrospray ionization mass spectrometry (ESI-MS). The results indicated that the UV radiation was quite efficient in promoting the pesticide degradation at the three pH levels evaluated (5, 7 and 8). The m/z of the most abundant ions observed in the mass spectra (MS), in conjunction with the fragmentation patterns of such ionic species (MS/MS data), made possible the proposition of chemical structures for the main by-products formed. As a result, routes for the photodegradation of diazinon in aqueous solution could thus be suggested. In the assays using Artemia salina (brine shrimp) it was verified that the photodegradation products exhibited much lower toxicity than the primary substrate. Aiming at mimicking the conditions ordinarily found in water treatment plants, an additional series of tests was conducted with a solution containing sodium hypochlorite and diazinon. This solution, when not exposed to UV radiation, exhibited high toxicity against the microorganisms. Under the influence of UV radiation, however, the toxicity rates decreased dramatically. This result is relevant because it points toward the confident application of UV radiation to neutralize the deleterious effects caused by diazinon (and perhaps other organophosphorus pesticides) as well as sodium hypochlorite to the environment.     

Liquid chromatographic aqueous product characterization of high-energy electron beam irradiated 2-chlorobiphenyl solutions

Polychlorinated biphenyls (PCBs) are of environmental concern due to their toxic nature. Ionizing radiation has been suggested as a means to remediate PCB-contaminated samples in complex matrices. A set of experiments was performed to qualitatively and quantitatively determine the aromatic degradation products of 2-monochlorobiphenyl (2-MCB) in an aqueous system exposed to ionizing radiation. The degradation of 2-MCB was observed in aqueous samples that were exposed to radiation from a linear accelerator electron beam source. Analytical measurements performed by liquid chromatography (LC) equipped with an ultraviolet (UV) detector revealed that biphenyl, o-hydroxybiphenyl, p-hydroxybiphenyl, phenol, chlorobenzene, and other unidentified products were created after 2-MCB irradiation. These results suggest that sensitive and selective analytical methods will be required to account for all degradation products during ionizing radiation of aqueous PCB-contaminated samples.     

Biological and photochemical degradation rates of diethylenetriaminepentaacetic acid (DTPA) in the presence and absence of Fe(III)

The environmental fate of ethylenediaminetetraacetic acid (EDTA) has been extensively studied, while much less is known about the environmental behaviour of diethylenetriaminepentaacetic acid (DTPA). In this study, it was confirmed that DTPA is persistent toward biodegradation. The biodegradability of DTPA was investigated in the absence and in the presence of Fe(III) by using CO2 evolution test and Manometric respirometry test. The CO2 evolution and oxygen uptake of iron-free (DTPA was added as free acid) and Fe(III)DTPA were less than in inoculum blank. Possible inhibitor effect was analysed by testing biodegradation of sodium benzoate with and without iron-free or Fe(III)DTPA in the Manometric respirometry test. Only slight inhibition was observed when DTPA was added as free acid. Photodegradation of iron-free DTPA and Fe(III)-DTPA complex was studied by using sunlight and UV radiation at the range 315-400 nm emitted by black light lamps. The results indicate that DTPA added as free acid degrades photochemically in humic lake water. Fe(III)DTPA was shown to be very photolabile in humic lake water in the summer; the photochemical half-life was below one hour. Photodegradation products were identified by the mass spectrometric technique (GC-MS). It was shown that photodegradation of Fe(III)DTPA does not result in total mineralization of the compound. Diethylenetriaminetetraacetic acid, diethylenetriaminetriacetic acid, ethylenediaminetriacetic acid, N,N'- and/or N,N-ethylenediaminediacetic acid, iminodiacetate, ethylenediaminemonoacetic acid and glycine were identified as photodegradation products of Fe(III)DTPA. Based on these observations, we propose a photodegradation pathway for Fe(III)DTPA.     

The role of ferrous ion in Fenton and photo-Fenton processes for the degradation of phenol

The efficiency of different Fenton-related oxidative processes such as Fenton, solar-Fenton and UV-Fenton were examined using phenol as a model compound in simulated and industrial wastewater. A batch study was conducted to optimize parameters like pH, hydrogen peroxide concentration and ferrous ion concentration governing the Fenton process. At optimum conditions, different Fenton-related processes were compared for the degradation of phenol. Increased degradation and mineralisation efficiency were observed in photo-Fenton processes as compared to conventional Fenton process. The maximum mineralising efficiency for phenol with Fenton, solar and UV-Fenton processes were 41%, 96% and 97% respectively. In Fenton process, carboxylic acids like acetic acid and oxalic acid were formed as end products during the degradation of phenol while in photo-Fenton processes, both these ions were identified during the early stages of phenol degradation and were oxidized almost completely at 120 min of the reaction time. In photo-Fenton processes (solar and UV light) complete degradation were observed with 0.4 mM of Fe2+ catalyst as compared to 0.8 mM of Fe2+ in conventional Fenton process. In Fenton and solar-Fenton processes, an iron reusability study was performed to minimize the amount of iron used in treatment process. The efficacy of Fenton and solar-Fenton processes was applied to effluent from phenol resin-manufacturing unit for the removal and mineralisation of phenol.     

An experimental and numerical study of the thermal oxidation of chlorobenzene

A combustion-driven flow reactor was used to examine the formation of chlorinated and non-chlorinated species from the thermal oxidation of chlorobenzene under post-flame conditions. Temperature varied from 725 to 1000 K, while the equivalence ratio was held constant at 0.5. Significant quantities of chlorinated intermediates, vinyl chloride and chlorophenol, were measured. A dominant C-Cl scission destruction pathway seen in pyrolytic studies was not observed. Instead, hydrogen-abstraction reactions prevailed, leading to high concentrations of chlorinated byproducts. The thermal oxidation of benzene was also investigated for comparison. Chemical kinetic modeling of benzene and chlorobenzene was used to explore reaction pathways. Two chlorobenzene models were developed to test the hypothesis that chlorobenzene oxidation follows a CO-expulsion breakdown pathway similar to that of benzene. For the temperatures and equivalence ratio studied, hydrogen abstraction by hydroxyl radicals dominates the initial destruction of both benzene and chlorobenzene. Chlorinated byproducts (i.e., chlorophenol and vinyl chloride) were formed from chlorobenzene oxidation in similar quantities and at similar temperatures to their respective analogue formed during benzene oxidation (i.e., phenol and ethylene).     

Efficient mineralization of gaseous benzyl chloride by VUV/UV photodegradation in humid air

Environmental Science and Pollution Research - VUV/UV photodegradation technology, which is free of catalysts or oxidants, has been regarded as an efficient method to decompose gaseous VOCs....     

Toxicity of fenamiphos and its metabolites to the cladoceran Daphnia carinata: the influence of microbial degradation in natural waters

The acute toxicity of an organophosphorous pesticide, fenamiphos and its metabolites, fenamiphos sulfoxide, fenamiphos sulfone, fenamiphos phenol, fenamiphos sulfoxide phenol and fenamiphos sulfone phenol, to a cladoceran, Daphnia carinata was studied in both cladoceran culture medium and natural water collected from a local river. The toxicity followed the order: fenamiphos>fenamiphos sulfone>fenamiphos sulfoxide. The hydrolysis products of fenamiphos, F. sulfoxide (FSO) and F. sulfone (FSO(2)) (F. phenol, FSO phenol and FSO(2) phenol) were not toxic to D. carinata up to 500microgl(-1) water, suggesting hydrolysis reaction leads to detoxification. Also the toxicity was reduced in natural water compared to the cladoceran culture medium due to microbial mediated degradation of toxicants in the natural water. Fenamiphos and its metabolites were stable in both cladoceran water and filter-sterilised natural water while these compounds showed degradation in unfiltered natural water implicating the microbial role in degradation of these compounds. To our knowledge this is the first study on acute toxicity of fenamiphos metabolites to cladoceran and this study suggests that the organophosphate pesticides are highly toxic to fresh water invertebrates and therefore pollution with these compounds may adversely affect the natural ecosystems.     

大型蚤标志酶用于城市二级出水毒性的评价

大型蚤是一种国际公认的标准实验生物,广泛应用于污水、地表水等水质毒性检测。毒性水平较低的城市二级出水,对大型蚤往往无急性毒性效应,而具有慢性毒性效应,但慢性毒性检测周期过长,因此探索一种更灵敏的指标,实现快速检测,对于控制二级出水的水质风险具有重要意义。本研究考察了大型蚤在短期暴露于城市二级出水条件下,其体内乙酰胆碱酯酶、超氧化物歧化酶、过氧化氢酶、ATP酶、羧酸酯酶和碱性磷酸酯酶的酶活变化特征,从中筛选出对二级出水毒性响应灵敏的标志酶指标。实验结果表明,碱性磷酸酯酶、过氧化氢酶对二级出水毒性响应相对较灵敏,具有成为标志酶的潜力,研究结果为城市二级出水生物毒性评价方法优化提供新的思路。     

Toxicity and biodegradability of sulfonamides and products of their photocatalytic degradation in aqueous solutions

The photocatalytic degradation of sulfacetamide, sulfathiazole, sulfamethoxazole and sulfadiazine in water solutions during their illumination of UV radiation (lambda(max) 366 nm) with TiO2 catalyst was examined. The growth-inhibition effect of sulfonamides and intermediate products theirs photodegradation was investigated in aqueous solution with the green alga Chlorella vulgaris. The biodegradability of the investigated compounds was determined in the illuminated solutions and is expressed as Biochemical Oxygen Demand. It was found that all of the investigated sulfonamides in the initial solutions were resistant to biodegradation and were toxic relative to C. vulgaris. The toxicity (EC50 values) relative to C. vulgaris increased in the following order sulfacetamide, sulfathiazole, sulfamethoxazole, sulfadiazine. All of the investigated sulfonamides undergo photocatalytic degradation. The toxicity of intermediate products of the sulfonamides degradation was significantly lower than the toxicity of sulfonamides in the initial solutions and was dependent on illumination time and degradation rate. The intermediate products of photocatalysis in contrast to the initial sulfonamides, might be mineralized using biological methods.     

Direct VUV photodegradation of gaseous α-pinene in a spiral quartz reactor: intermediates, mechanism, and toxicity/biodegradability assessment

Photodegradation of gaseous α-pinene by a vacuum ultraviolet (VUV) in a spiral reactor was investigated under various gaseous reaction media and residence time, and their respective effects on types and biodegradability of the intermediates were studied. Analysis of carbon amounts showed that about 33% and 43% of total carbon were converted to soluble organic carbon in the air medium with a relative humidity (RH) of 35-40% at empty bed residence times (EBRTs) of 18 and 45 s. Based on the identified intermediates by GC/MS and IC, a photodegradation pathway was proposed by the combined roles of photolysis, OH. photooxidation and O? photooxidation. Biodegradability to active sludge, toxicity to Chlorella vulgaris and 96-well microplates showed that α-pinene could be largely converted to more biodegradable and less toxic compounds through photodegradation in the air reaction medium with a RH of 35-40% at an EBRT of 18s, in which the initial concentration was 600 mg m?3. Therefore, VUV photodegradation could be applied as an effective pre-treatment method for detoxification and biodegradability improvement under the optimized photodegradation conditions. Such results supported the potential use of VUV photodegradation to improve the removal capacity of conventional biological treatments for hydrophobic and poorly biodegradable compounds.     

Photodegradation of organophosphorus insecticides - investigations of products and their toxicity using gas chromatography-mass spectrometry and AChE-thermal lens spectrometric bioassay

Four organophosphorus compounds: azinphos-methyl, chlorpyrifos, malathion and malaoxon in aqueous solution were degraded by using a 125 W xenon parabolic lamp. Gas chromatography-mass spectrometry (GC-MS) was used to monitor the disappearance of starting compounds and formation of degradation products as a function of time. AChE-thermal lens spectrometric bioassay was employed to assess the toxicity of photoproducts. The photodegradation kinetics can be described by a first-order degradation curve C=C0e(-kt), resulting in the following half lives: 2.5min for azinphos-methyl, 11.6 min for malathion, 13.3 min for chlorpyrifos and 45.5 min for malaoxon, under given experimental conditions. During the photoprocess several intermediates were identified by GC-MS suggesting the pathway of OP degradation. The oxidation of chlorpyrifos results in the formation of chlorpyrifos-oxon as the main identified photoproduct. In case of malathion and azinphos-methyl the corresponding oxon analogues were not detected. The formation of diethyl (dimethoxy-phosphoryl) succinate in traces was observed during photodegradation of malaoxon and malathion. Several other photoproducts including trimethyl phosphate esters, which are known to be AChE inhibitors and 1,2,3-benzotriazin-4(3H)-one as a member of triazine compounds were identified in photodegraded samples of malathion, malaoxon, and azinphos-methyl. Based on this, two main degradation pathways can be proposed, both result of the (P-S-C) bond cleavage taking place at the side of leaving group. The enhanced inhibition of AChE observed with the TLS bioassay during the initial 30 min of photodegradation in case of all four OPs, confirmed the formation of toxic intermediates. With the continuation of irradiation, the AChE inhibition decreased, indicating that the formed toxic compounds were further degraded to AChE non-inhibiting products. The presented results demonstrate the importance of toxicity monitoring during the degradation of OPs in processes of waste water remediation, before releasing it into the environment.     

Photodegradation of quinestrol in waters and the transformation products by UV irradiation

Quinestrol is synthetic estrogen used in contraceptive and hormone replacement therapy and occasionally for treating breast cancer and prostate cancer. It can make its way into the environment through sewage discharge and waste disposal produced by human excretions. In this study, the photodegradation kinetics of quinestrol in various conditions was investigated by UV and solar irradiation. The affecting factors were studied including concentration of hydrogen peroxide, different water types, and the initial concentrations of quinestrol. Concurrently, the transformation products and presumed pathways of quinestrol in distilled water by UV irradiation were identified and proposed. The results showed that the degradation of quinestrol in both irradiation conditions followed the pseudo-first-order kinetics. More rapid degradation was observed by UV irradiation (k = 0.018 min⁻¹) than solar irradiation (k = 0.004 h⁻¹), and the photodegradation rate of quinestrol depended on the concentration of hydrogen peroxide, the initial concentration of quinestrol and water types. The transformation products of quinestrol in distilled water were identified by gas chromatography/mass spectrometry. When exposed to UV irradiation, quinestrol in aqueous solution was rapidly degraded, giving at least ten photodegradation products. The chemical structures of ten degradation products were identified on the basis of mass spectrum interpretation and literature data.     

Transformation and Ecotoxicity of Carbamic Pesticides in Water (5 pp)

Background N-methylcarbamate insecticides are widely used chemicals for crop protection. This study examines the hydrolytic and photolytic cleavage of benfuracarb, carbosulfan and carbofuran under natural conditions. Their toxicity and that of the corresponding main degradation products toward aquatic organisms were evaluated. Methods Suspensions of benfuracarb, carbosulfan and carbofuran in water were exposed to sunlight, with one set of dark controls, for 6 days, and analyzed by 1H-NMR and HPLC. Acute toxicity tests were performed on Brachionus calyciflorus, Daphnia magna, and Thamnocefalus platyurus. Chronic tests were performed on Pseudokirchneriella subcapitata, and Ceriodaphnia dubia. Results and Discussion Under sunlight irradiation, benfuracarb and carbosulfan gave off carbofuran and carbofuran-phenol, while only carbofuran was detected in the dark experiments. The latter was degraded to phenol by exposure to sunlight. Effects of pH, humic acid and KNO3 were evaluated by kinetics on dilute solutions in the dark and by UV irradiation, which evidenced the lability of the pesticide at pH 9. All three pesticides and phenol exhibited acute and higher chronic toxicity towards the aquatic organisms tested. Conclusion Investigation on the hydrolysis and photolysis of benfuracarb and carbosulfan under natural conditions provides evidence concerning the selective decay to carbofuran and/or phenol. Carbofuran is found to be more persistent and toxic. Recommendations and Outlook The decay of benfuracarb and carbosulfan to carbofuran and the relative stability of this latter pesticide account for many papers that report the detection of carbofuran in water, fruits and vegetables.     

Photochemical and photocatalytic degradation of gaseous toluene using short-wavelength UV irradiation with TiO2 catalyst: comparison of three UV sources

The feasibility of the use of short-wavelength UV (254+185 nm) irradiation and TiO2 catalyst for photodegradation of gaseous toluene was evaluated. It was clear that the use of TiO2 under 254+185 nm light irradiation significantly enhanced the photodegradation of toluene relative to UV alone, owed to the combined effect of photochemical oxidation in the gas phase and photocatalytic oxidation on TiO2. The photodegradation with 254+185 nm light irradiation was compared with other UV wavelengths (365 nm (black light blue lamp) and 254 nm (germicidal UV lamp)). The highest conversion and mineralization were obtained with the 254+185 nm light. Moreover, high conversions were achieved even at high initial concentrations of toluene. Catalyst deactivation was also prevented with the 254+185 nm light. Regeneration experiments with the deactivated catalyst under different conditions revealed that reactive oxygen species played an important role in preventing catalyst deactivation by decomposing effectively the less reactive carbon deposits on the TiO2 catalyst. Simultaneous elimination of photogenerated excess ozone and residual organic compounds was accomplished by using a MnO2 ozone-decomposition catalyst to form reactive species for destruction of the organic compounds.     

Nitrate-induced photodegradation of atenolol in aqueous solution: kinetics, toxicity and degradation pathways

The extensive utilization of β-blockers worldwide led to frequent detection in natural water. In this study the photolysis behavior of atenolol (ATL) and toxicity of its photodegradation products were investigated in the presence of nitrate ions. The results showed that ATL photodegradation followed pseudo-first-order kinetics upon simulated solar irradiation. The photodegradation was found to be dependent on nitrate concentration and increasing the nitrate from 0.5 mM L⁻¹ to 10 mM L⁻¹ led to the enhancement of rate constant from 0.00101 min⁻¹ to 0.00716 min⁻¹. Hydroxyl radical was determined to play a key role in the photolysis process by using isopropanol as molecular probe. Increasing the solution pH from 4.8 to 10.4, the photodegradation rate slightly decreased from 0.00246 min⁻¹ to 0.00195 min⁻¹, probably due to pH-dependent effect of nitrate-induced OH formation. Bicarbonate decreased the photodegradation of ATL in the presence of nitrate ions mainly through pH effect, while humic substance inhibited the photodegradation via both attenuating light and competing radicals. Upon irradiation for 240 min, only 10% reduction of total organic carbon (TOC) can be achieved in spite of 72% transformation rate of ATL, implying a majority of ATL transformed into intermediate products rather than complete mineralization. The main photoproducts of ATL were identified by using solid phase extraction-liquid chromatography-mass spectrometry (SPE-LC-MS) techniques and possible nitrate-induced photodegradation pathways were proposed. The toxicity of the phototransformation products was evaluated using aquatic species Daphnia magna, and the results revealed that photodegradation was an effective mechanism for ATL toxicity reduction in natural waters.     

The study of lag phase and rate improvement of TCE decay in UV/surfactant systems

The photodegradation of trichloroethene (TCE) in surfactant micelles was investigated. The decay of TCE was studied in the Rayonet RPR-200 merry-go-round photoreactor, at 253.7 nm monochromatic ultraviolet (UV) lamps, in the presence of surfactants. Surfactants are used as additional hydrogen sources to improve the photodegradation rates of TCE. About three times the rate increment is observed in the presence of Brij 35 surfactant micelles than in water alone. The increasing concentrations of H+ and Cl- indicate that they are the final products of TCE photodegradation (i.e. photodechlorination is the dominant mechanism in this system). A lag phase is observed at the beginning of the degradation, but the duration of the lag phase is apparently reduced as the initial pH increases. Because the overall decay of TCE is also found faster at higher pH levels, it is suggested that the free radical reaction is dominant at high pH levels, and the formation of lag phases is mainly due to the deficiency of free radicals at lower pH levels. The photodecomposition of TCE in surfactant micelles is also proven to be a clean and effective process. It generates no chlorinated by-products or intermediates during the process, and TCE is fully decomposed within a reasonable time.     

The acute toxicity of phenol and unionized ammonia, separately and together, to the ephemeropteran Baetis rhodani (Pictet)

The acute toxicity of phenol and ammonia, singly and in combination, to larvae of the ephemeropteran, Baetis rhodani, was examined using a computerized continuous flow system in the laboratory. The 24 h LC50 values (with 95% confidence intervals) were calculated to be 29.9 (17.3-51.5) mg phenol litre(-1) and 8.2 (2.0-33.0) mg un-ionized ammonia litre(-1). When phenol and ammonia were together in low concentration (< 20 mg litre(-1) and < 3 mg litre(-1) [un-ionized], respectively), they expressed their toxicity additively, but at higher concentrations they behaved in a greater-than-additive manner. When the 24 h LC50 values were used to predict the toxicity of a coking plant effluent, containing principally ammonia and phenol, it was found that the B. rhodani larvae died quicker than expected indicating the presence of other toxic chemicals. This exemplifies the value of using direct toxicity assessments to detect the presence of unknown toxicants.