Photosensitized degradation of bisphenol A involving reactive oxygen species in the presence of humic substances

The photodegradation of endocrine disrupter bisphenol A (BPA) in the presence of natural humic substances (HS) under simulated solar irradiation was studied. BPA underwent slow direct photolysis in neutral pure water, but rapid photosensitized degradation in four kinds of HS, following pseudo-first-order reaction. Reactive oxygen species (ROS) formed from HS were determined, including OH, (1)O(2) and H(2)O(2). The enhancement of BPA degradation by adding Fe(III) was primarily attributed to the oxidation of OH produced from photo-Fenton-like reaction. And the joint effects of HS and nitrate ions coexisting on BPA degradation appeared to depend on respective concentration levels. The effects of dissolved oxygen suggested that the energy transfer between excited state of SRFA and NOFA likely occurred, while the abstraction of phenolic hydrogen atom to reactive triplet state of NOHA possibly took place. Based on the structural analyses of main intermediates and degradation products of BPA detected by GC-MS, the possible photodegradation pathways were proposed, involving the alky cleavage, alkyl oxidation and OH addition. This study gave a better understanding for the photochemical transformation of BPA induced by ROS generated from natural water composition under sunlight irradiation.     

Photodegradation of ethylenediaminetetraacetic acid (EDTA) and ethylenediamine disuccinic acid (EDDS) within natural UV radiation range.

The rate of photodegradation of two chelating agents, ethylenediaminetetraacetic acid (EDTA) and an isomeric mixture of ethylenediamine disuccinic acid (EDDS), was analysed in humic lake water and in distilled water using exposure to sunlight, and in the laboratory using lamps emitting UV radiation in the range 315-400 nm. Degradation was studied using Fe(III) complexes and sodium salts of chelates. Fe(III) complexes were illuminated at pH 3.1 and 6.5. The results demonstrated that the rate of photodegradation of Fe(III)-EDTA and Fe(III)-EDDS complexes seems to be pH dependent. In the laboratory experiments degradation occurred much faster when the original pH was 3.1 rather than 6.5. The photodegradation of the isomeric mixture of EDDS was markedly faster than the degradation of EDTA both in the laboratory and field experiments, and both in humic and distilled water. The results indicated that in natural waters photodegradation of EDDS is independent of initial speciation of EDDS, while degradation of EDTA is dependent on its existence as Fe(III)-EDTA species.     

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.     

腐殖酸和铁对阿特拉津光降解影响的研究

为考察除草剂在水体中的自净性能，对模拟太阳光(λ> 290 nm)下腐殖酸和铁元素对阿特拉津的光化学降解进行了研究。结果表明，单独辐照阿特拉津几乎不降解。在分别加入3、5和10 mg/L的腐殖酸时，阿特拉津的降解率分别为34.36 %、40.74%和15.66 %；在Fe(Ⅲ)投加量从0.01 mmol/L增加到0.2 mmol/L时，阿特拉津的降解率从24.36 %增加到34.97 %。而在当腐殖酸与铁共存时，阿特拉津降解率则进一步提高。紫外可见光谱和荧光光谱均表明，腐殖酸-铁络合物的形成及其光化学作用，促进了阿特拉津的降解。     

Effect of metal ions and humic acid on the dechlorination of tetrachloroethylene by zerovalent iron

The dechlorination of tetrachloroethylene (PCE) by zerovalent iron (Fe(0)) in the presence of metal ions and humic acid was investigated. In the absence of metal ion and humic acid, 64% of the initial PCE was dechlorinated after 125 h with the production of ethane and ethene as the major end products. The dechlorination followed pseudo-first-order kinetics and the normalized surface rate constant (k(SA)) for PCE dechlorination was (3.43+/-0.61)x10(-3)lm(-2)h(-1). Addition of metal ions enhanced the dechlorination efficiency and rate of PCE, and the enhancement effect followed the order Ni(II)>Cu(II)>Co(II). The k(SA) for PCE dechlorination in the presence of metal ions were 2-84 times higher than that in the absence of metal ions. X-ray photoelectron spectroscopy (XPS) showed that Cu(II) and Ni(II) were reduced by Fe(0) to zerovalent metals, and resulted in the formation of bimetallic system to accelerate the dechlorination reaction. On the contrary, humic acid out-competed the reactive sites on iron surface with PCE, and subsequently decreased the dechlorination efficiency and rate of PCE by Fe(0). However, the reactivity of Fe(0) for PCE dechlorination in the presence of metal ions and humic acid increased by a factor of 3-161 when compared to the iron system containing humic acid alone. Since humic acid and metal ions are the most often found co-existing compounds in the contaminated aquifers with chlorinated hydrocarbons, results obtained in this study is useful to better understand the feasibility of using Fe(0) for long-term application to the remediation of contaminated sites.     

Direct and indirect photolysis of cyhalofop in aqueous systems

The photodegradation of the aryloxyphenoxy propionic herbicide cyhalofop-butyl (2R)-2-[4-(4-cyano-2-fluorophenoxy)phenoxy]butylpropanoate (CyB), and of its primary metabolite (2R)-2-[4-(4-cyano-2-fluorophenoxy)phenoxy]propanoic acid (CyA) was studied in water at different irradiation wavelengths. The sunlight irradiation was investigated also in the presence of humic acid (HA), Fe oxide, titanium dioxide (TiO₂) and zinc oxide (ZnO) as photocatalysts.CyB and CyA were rapidly degraded by UV irradiation. CyB afforded the butyl ester of 2-[3-(4-cyano-2-fluorophenyl)-4-hydroxy-phenoxy]propanoic acid (CyI), a metabolite arising from a photo-Fries rearrangement. Instead, CyA yielded (R)-2-4-(4-carboxyl-2-fluorophenoxy)phenoxypropanoic acid (CyD), a dicarboxylic acid arising from the photo-hydrolysis of cyano group via amide. CyB was stable in simulated sunlight also in the presence of the catalysts tested.The irradiation of a CyA solution, in the presence of HA or Fe oxide, with simulated sunlight did not produce any significant degradation. In the same experimental conditions, CyA was totally mineralized in the presence of TiO₂ and ZnO.     

Photolysis of 14C-sulfadiazine in water and manure

Photolysis of 14C-sulfadiazine in aqueous solution under simulated sunlight followed first-order kinetics. The impact of H2O2, humic acid, fulvic acid and acetone to enhance the photodegradation of sulfadiazine (SDZ) was studied. Six photoproducts, 4-OH-SDZ, 5-OH-SDZ, N-formyl-SDZ, 4-[2-iminopyrimidine-1(2H)-yl] aniline, 2-aminopyrimidine, and aniline were identified. Extrusion of SO2 was found to be the main degradation process during irradiation. These photoproducts can occur in water and soil upon sunlight exposure, when soil is treated with SDZ contained in manure. Due to photodegradation the experimental half-life of the SDZ in water was 32h and in the presence of photosensitizers the half-life values were 19.3-31.4h, 17.2-31.4h, 12.6-29.8h, and 3.8-30.7h for H2O2, humic acid, fulvic acid, and acetone, respectively depending on the concentration of the photosensitizers. The presence of photosensitizers markedly reduced SDZ persistence, indicating that indirect photolytic processes are important factors governing the photodegradation of SDZ in aqueous environments. Investigation revealed further persistence behavior of SDZ in manure. The half-life value of SDZ in manure was 158h.     

UV-light induced mineralization of organic matter bound chlorine in Lake Bjän,Sweden--a laboratory study

Surface water and aqueous solutions of isolated organic matter from a humic rich lake in southern Sweden were exposed to artificial UV radiation to investigate the UV light induced influence on organic matter bound chlorine in natural systems. It was found that the photodegradation of organic matter bound chlorine was more pronounced than the photodegradation of organic carbon. After 120 h of irradiation of the isolated organic matter, only 35% of the initial organochlorine was still in the solution compared to about 70% of the dissolved organic carbon (DOC). A similar result was obtained for unfractionated surface water. Furthermore, our results indicate that the loss of organic chlorine was mainly due to a mineralization of organic chlorine into chloride ions. The total decrease of organic chlorine after 120 h was 32 microg Cl(org) l(-1), of which the major part disappeared in the initial irradiation phase. A similar increase was observed in the chloride concentration (34 microg Cl(-) l(-1)).     

Study of chlorothalonil photodegradation in natural waters and in the presence of humic substances

Photodegradation of chlorothalonil was studied in different natural waters (sea, river and lake) as well as in distilled water under natural and simulated solar irradiation. The effect of dissolved organic matter (DOM) such as humic and fulvic substances on the photodegradation rate of chlorothalonil was also studied in simulated sunlight. The presence of DOM enhanced the photodegradation of chlorothalonil with the exception of seawater. The kinetics were determined through gas chromatography electron capture detection (GC/ECD) and the photodegradation proceeds via pseudo-first-order reaction in all cases. Half-life ranged from 1 to 48 h. In natural and humic water chlorothalonil photodegradation gave rise to two different intermediates compared to distilled water demonstrating that the transformation of chlorothalonil depend on the constitution of the irradiated media and especially from DOM. The byproducts identified by GC/MS techniques were: chloro-1,3-dicyanobenzene, dichloro-1,3-dicyanobenzene, trichloro-1,3-dicyanobenzene and benzamide.     

溶液中阴离子和腐殖酸对UV/H2O2降解2,4-二氯酚的影响

研究了UV/H2O2工艺对2,4-二氯酚(2,4-DCP)的去除效果和水中阴离子、腐殖酸对该工艺降解2,4-DCP的影响.结果表明:UV/H2O2工艺可以有效地去除水中2,4-DCP,光降解过程符合一级反应动力学模型;在H2O2投加量为8 mg/L、1个30 W低压汞灯照射下,2,4-DCP在蒸馏水和自来水中反应速率常数分别为0.023 2、0.016 2 min-1;NO-3、Cl-、HCO-3对2,4-DCP光降解有抑制作用,当3种阴离子摩尔浓度为0.5、10.0、20.0 mmol/L时,对2,4-DCP光降解的抑制程度为HCO-3＞NO-3＞Cl-;腐殖酸在低浓度时,促进光降解反应进行,在高浓度时,2,4-DCP的光降解受到抑制.自来水中的反应速率常数低于蒸馏水中的反应速率常数是由于水中多种阴离子和腐殖酸影响的结果.     

Photodegradation of 17alpha-ethynylestradiol in aqueous solution exposed to a high-pressure mercury lamp (250 W)

The photodegradation of 17alpha-ethynylestradiol (EE(2)) induced by high-pressure mercury lamp (lambda> or =313, 250 W) in aqueous solution of EE(2) was investigated initially. The affecting factors on the photodegradation were studied and described in details, such as EE(2) initial concentration, Fe(3+), algae, exposure time, and so on. The concentration of EE(2) in distilled water was mainly determined using fluorescence spectrophotometer. The photodegradation of EE(2) in aqueous solution exposed to high-pressure mercury lamp was evident and could be accelerated by Fe(3+) or algae (e.g. Anabaena cylindrica) in general. With the algae concentration increasing, photodegradation rate increased. In this paper, the mechanism of photocatalytic degradation of EE(2) by Fe(3+) or algae is discussed primarily.     

Solar light induced and TiO2 assisted degradation of textile dye reactive blue 4

Aqueous solutions of reactive blue 4 textile dye are totally mineralised when irradiated with TiO2 photocatalyst. A solution containing 4 x 10(-4) M dye was completely degraded in 24 h irradiation time. The intensity of the solar light was measured using Lux meter. The results showed that the dye molecules were completely degraded to CO2, SO4(2-), NO3-, NH4+ and H2O under solar irradiation. The addition of hydrogen peroxide and potassium persulphate influenced the photodegradation efficiency. The rapidity of photodegradation of dye intermediates were observed in the presence of hydrogen peroxide than in its absence. The auxiliary chemicals such as sodium carbonate and sodium chloride substantially affected the photodegradation efficiency. High performance liquid chromatography and chemical oxygen demand were used to study the mineralisation and degradation of the dye respectively. It is concluded that solar light induced degradation of textile dye in wastewater is a viable technique for wastewater treatment.     

Abiotic degradation of imazethapyr in aqueous solution

The photodegradation of imazethapyr [2-(4,5-dihydro-4-méthyl-4-(1-méthylethyl)-5-oxo-1H-imidazol-2-yl)-5-ethyl-3-pyridinecarboxylic acid] in aqueous solution in the presence of titranium dioxide (TiO2) and humic acids (HA) at different ratios of herbicide/TiO2 and herbicide/humic acids was studied at pH 7.0. Irradiation was carried out with polychromatic light using Heraeus apparatus equipped with xenon lamp to simulate sunlight having a spectral energy distribution similar to solar irradiation (>290 nm). The concentration of remaining herbicide was followed using a High Pressure Liquid Chromatograph (HPLC) equipped with UV detector at 230 nm. In pure aqueous solution imazethapyr degrades slowly and the photodegradation leads to the formation of two metabolites labelled A and B. The presence of TiO2 caused enhancement of the degradation rate. The presence of HA induced an increase of the photodegradation of the pesticide with respect to pure aqueous solution.     

TiO_2膜光催化降解4,4’-二溴联苯的研究

研究了负载于玻璃上的同定化催化剂TiO2膜光催化降解水中4,4'-二溴联苯(4,4'-DBB)的效果,考察了溶液pH值和4,4'-DBB初始浓度等对TiO2膜光催化降解4,4'-DBB的影响,探讨了降解机理.结果表明.TiO2膜光催化降解水中4,4'-DBB的效果良好,紫外光照射8 b,初始浓度为4 mg/L的4,4'-DBB的降解率高达94%,降解速率随着4,4'-DBB初始浓度的增大而下降.在溶液pH=1时,4,4'-DBB的降解效率最高.超声的加入使降解反应的速率加快.经拟合发现4,4'-DBB的降解符合拟一级反应规律,并推导出动力学方程.     

Effect of inorganic and organic solutes on zero-valent aluminum-activated hydrogen peroxide and persulfate oxidation of bisphenol A

The effect of varying inorganic (chloride, nitrate, sulfate, and phosphate) and organic (represented by humic acid) solutes on the removal of aqueous micropollutant bisphenol A (BPA; 8.8 μM; 2 mg/L) with the oxidizing agents hydrogen peroxide (HP; 0.25 mM) and persulfate (PS; 0.25 mM) activated using zero-valent aluminum (ZVA) nanoparticles (1 g/L) was investigated at a pH of 3. In the absence of the solutes, the PS/ZVA treatment system was superior to the HP/ZVA system in terms of BPA removal rates and kinetics. Further, the HP/ZVA process was not affected by nitrate (50 mg/L) addition, whereas chloride (250 mg/L) exhibited no effect on the PS/ZVA process. The negative effect of inorganic anions on BPA removal generally speaking increased with increasing charge in the following order: NO₃^? (no inhibition)?<?Cl^? (250 mg/L)?=?SO₄^2??<?PO₄^3? for HP/ZVA and Cl^? (250 mg/L; no inhibition)?<?NO₃^??<?SO₄^2??<?PO₄^3? for PS/ZVA. Upon addition of 20 mg/L humic acid representing natural organic matter, BPA removals decreased from 72 and 100% in the absence of solutes to 24 and 57% for HP/ZVA and PS/ZVA treatments, respectively. The solute mixture containing all inorganic and organic solutes together partly suppressed the inhibitory effects of phosphate and humic acid on BPA removals decreasing to 46 and 43% after HP/ZVA and PS/ZVA treatments, respectively. Dissolved organic carbon removals were obtained in the range of 30 and 47% (the HP/ZVA process), as well as 47 and 57% (the PS/ZVA process) for the experiments in the presence of 20 mg/L humic acid and solute mixture, respectively. The relative Vibrio fischeri photoluminescence inhibition decreased particularly for the PS/ZVA treatment system, which exhibited a higher treatment performance than the HP/ZVA treatment system.     

Ferric citrate-induced photodegradation of dyes in aqueous solutions

The photooxidation of dye solutions containing Fe(III)-citrate complexes was studied. The photodegradation under near-UV light of the five dyes, C. I. reactive red 2, C. I. reactive blue 4, C. I. reactive black 8, C. I. basic red 13 and C. I. basic yellow 2, in aqueous solutions at pH2.0 containing Fe(III)-citrate complexes was found to follow pseudo-first order kinetics. The photodegradation rates of the dye, C. I. reactive red 2, decreased with increasing the initial dye concentration in range of 20 – 60 mg/L . A comparatively higher photodegradation efficiency of the dye was gained under the condition of pH2.0 and the Fe(III) to citrate ratio 1:2.     

Degradation of propyl paraben by activated persulfate using iron-containing magnetic carbon xerogels: investigation of water matrix and process synergy effects

An advanced oxidation process comprising an iron-containing magnetic carbon xerogel (CX/Fe) and persulfate was tested for the degradation of propyl paraben (PP), a contaminant of emerging concern, in various water matrices. Moreover, the effect of 20 kHz ultrasound or light irradiation on process performance was evaluated. The pseudo-first order degradation rate of PP was found to increase with increasing SPS concentration (25–500 mg/L) and decreasing PP concentration (1690–420 μg/L) and solution pH (9–3). Furthermore, the effect of water matrix on kinetics was detrimental depending on the complexity (i.e., wastewater, river water, bottled water) and the concentration of matrix constituents (i.e., humic acid, chloride, bicarbonate). The simultaneous use of CX/Fe and ultrasound as persulfate activators resulted in a synergistic effect, with the level of synergy (between 35 and 50%) depending on the water matrix. Conversely, coupling CX/Fe with simulated solar or UVA irradiation resulted in a cumulative effect in experiments performed in ultrapure water.     

Leaching of bisphenol A (BPA) to seawater from polycarbonate plastic and its degradation by reactive oxygen species

In this study, (1) change in the concentration of bisphenol A (BPA) leached from polycarbonate (PC) tube to control water (BPA free), seawater and river water at 20 and 37 degrees C as a function of time, (2) the fate of BPA caused by addition of H(2)O(2) and Fe(3+) to seawater containing BPA leached from PC tube were assessed. BPA leached from PC tube to all water samples increased with the ascendant of temperature and with the passage of time. The BPA leaching velocity in seawater was the fastest in three samples (11 ng/day for seawater, 4.8 ng/day for river water 0.8 ng/day for control water at 37 degrees C).BPA leaching velocity from PC tube was significantly high at pH 8 (50 mM Na(2)HPO(4)) and increased dose-dependently. There was no difference in the velocity of BPA among the 50 mM phosphate-buffers at pH 6.5, 7.0 and 7.5. BPA was leached three times higher by addition of Na(+) than K(+). However, the higher the K(+) concentration, the larger the BPA leached from PC tube. Na(+) mixed with PO(4)(-) was effective on BPA leaching from PC tube, but not with SO(4)(-) or Cl(-). The results suggested that BPA leaching from PC tube would be attributed to the concentration of bibasic phosphate such as Na(2)HPO(4) and K(2)HPO(4) in water samples. BPA was degraded in both control water and seawater in the presence of radical oxygen species, but the degradation rate was lower in seawater than in control water, suggesting that anti-oxidative system exists in seawater. Neo-synthesized substance in both control water and seawater in the presence of reactive oxygen species was identified as BPA-quinone by LC-MS.     

Ultraviolet degradation of methyltins: elucidating the mechanism by identification of a detected new intermediary product and investigating the kinetics at various environmental conditions

The photodegradation of methyltins, as environmental pollutants, has scarcely been studied so far because of the shortage of rapid and sensitive speciation methods, even though they have very simple structures. The photodegradation of monomethyltin trichloride (MMT), dimethyltin dichloride (DMT) and trimethyltin chloride (TMT) was studied with our new developed HPLC-FPD hyphenated system, which enables rapid and sensitive detection of methyltins. The half-life times and kinetic rate constants of their degradation at different pH were calculated. The results suggest that MMT, DMT and TMT can be degraded under the UV irradiation rapidly at different pH, with a degradation rate sequence of TMT相似文献   

Synchronous-scan fluorescence spectra of Chlorella vulgaris solution

The characterization of the Chlorella vulgaris solution was carried out using synchronous-scan spectroscopy. The range of concentration of algae and Fe(III) in aqueous solutions were 5 × 10⁸–8 × 10⁹ cells l⁻¹ and 10–60 μM, respectively. Effective characterization method used was synchronous-scan fluorescence spectroscopy. The wavelength difference (Δλ) of 90 nm was maintained between excitation and emission wavelengths; 90 nm was found to be the best Δλ for effective characterization of Chlorella vulgaris solution with or without quencher species (e.g., Fe(III), humic acid (HA)) for the first time. The peak was observed at about EX 236.6 nm/EM 326.6 nm for synchronous-scan fluorescence spectra. The fluorescence quenching of algae in system of algae–Fe(III)–HA was studied using synchronous-scan spectroscopy for the first time. Fe(III) was clearly the effective quencher. The relationship between I₀/I (quenching efficiency) and c (concentration of Fe(III) added) was a linear correlation for the algae solution with Fe(III). Also, Aldrich humic acid was found to be an effective quencher. pH effect on synchronous-scan fluorescence intensity of algal solution with Fe(III) and/or HA was evident.