TiO2薄膜光催化降解双酚A的研究

采用sol-gel法制备TiO2薄膜。以该薄膜为催化剂，研究了在H2O2存在的条件下，对内分泌干扰物质双酚A的光催化降解反应。分别讨论了pH值、H2O2的加入量、双酚A的初始浓度以及光照时间对降解反应的影响。结果表明，在pH=4，30mg／L的H2O2中对初始浓度为50mg／L的双酚A溶液光照180min有较好的降解效果。     

Fenton氧化-混凝联合工艺处理络合铜镍废水的研究

采用Fenton试剂氧化-混凝联合工艺对难处理络合铜镍电镀废水进行了研究,考察了废水初始pH值、H2O2初始浓度、[Fe2 ]/[H2O2]、反应时间和温度、混凝液pH、混凝剂质量浓度对处理过程的影响,探讨了废水的降解途径和机理.结果表明,在体系初始pH=4,温度30℃,H2O2投加量为800mg/L,[Fe2 ]/[H2O2]=0.1,反应时间60 min,混凝液pH=8及混凝剂质量浓度为500mg/L的条件下,废水的COD去除率为96.98%,Cu2 为99.91%,Ni2 为99.92%,处理水完全达到国家一级排放标准.同时依据GC/MS对X-GN降解最终产物的分析结果,推导出废水的基本降解机理和途径.     

UV/H2O2工艺降解水中双酚A影响因素的研究

研究了UV/H2O2工艺对双酚A(BPA)的降解效果及影响田素.结果表明,UV/H2O2工艺可以有效降解水体中BPA,降解过程符合一级反应动力学模型;紫外光强对BPA的降解速度影响较小;H2O2浓度对BPA的降解具有促进和抑制的双重作用;BPA初始浓度对BPA降解没有影响;在酸性条件下,有利于BPA降解;NO-3、Cl-、HCO-3对BPA降解有抑制作用;当HCO-3、NO-3、Cl-摩尔浓度均为5mmol/L时,对BPA降解的抑制程度为HCO-3>NO-3>Cl-.腐殖酸在低浓度时,促进BPA降解反应进行;在高浓度时,BPA的降解受到抑制.     

Fenton试剂处理选矿废水机理研究

研究了用Fenton试剂处理选矿废水中残余的黄药,分别考查了氧化时间、反应初始pH值、Fe2+浓度及H2O2用量对黄药降解效果的影响,用正交试验确定了4个因素的最好条件。结果表明:初始pH值和H2O2用量是影响去除效果的主要因素;氧化时间为60 m in,反应初始pH=4,[Fe2+]=20 mg/L,[H2O2]=20 mg/L,黄药的浓度为125 mg/L时,黄药的去除率达到99.5%;初步探讨了Fenton试剂净化废水中黄药的机理是.OH自由基先将黄药氧化为过氧化黄原酸盐,再将其氧化为CO2,黄药得到去除。     

Fenton氧化-混凝联合工艺处理络合铜镍废水的研究

采用Fenton试剂氧化-混凝联合工艺对难处理络合铜镍电镀废水进行了研究,考察了废水初始pH值、H2O2初始浓度、[Fe^2＋]/[H2O2]、反应时间和温度、混凝液pH、混凝剂质量浓度对处理过程的影响,探讨了废水的降解途径和机理.结果表明,在体系初始pH=4,温度30℃,H2O2投加量为800mg/L,[Fe^2＋]/[H2O2]=0.1,反应时间60 min,混凝液pH=8及混凝剂质量浓度为500mg/L的条件下,废水的COD去除率为96.98%,Cu^2＋为99.91%,Ni^2＋为99.92%,处理水完全达到国家一级排放标准.同时依据GC/MS对X-GN降解最终产物的分析结果,推导出废水的基本降解机理和途径.     

光助Ce-Fe/Al2O3催化H2O2降解阳离子红GTL模拟废水

利用Ce-Fe/Al2O3为催化剂的非均相光Fenton体系降解阳离子红GTL模拟废水,考察了H2O2浓度、催化剂用量、初始pH值及不同工艺过程对降解效果的影响,通过紫外-可见漫反射光谱、红外光谱、XPS手段研究铁在反应中的价态变化.结果表明,在11 W低压汞灯照射下,非均相光Fenton体系能够有效地降解结构稳定的阳离子红GTL,在pH 6,反应温度20℃,时间90 min,Ce-Fe/Al2O3 2 g/L,H2O2浓度340 mg/L,含50 mg/L阳离子红GTL模拟废水TOC去除率为92.40%;光Fenton反应中Fe(Ⅲ)转化为Fe(Ⅱ).     

赤泥协同Fenton法处理焦化废水的研究

采用赤泥吸附协同Fenton法处理焦化废水,两者协同处理对COD的去除率高于其单独处理之和.考察了赤泥投加量、初始pH值、反应温度、H2O2浓度和Fe2+浓度等因素对降解效果的影响,实验结果表明,在20 g/L的赤泥、初始pH=3、80 mmol/L的H2O2、224 mg/L的Fe2+的最佳条件下,经过120 min...     

光催化降解内分泌干扰物双酚A的响应面分析与优化

对光催化降解内分泌干扰物双酚A进行了研究,使用响应面方法(RSM)结合中心组合设计(CCD),对光催化过程中的影响因素(光强、Ti O2浓度、初始双酚A浓度)进行了探讨和分析,构建响应面模型,并对反应条件进行了优化。此响应面模型能够较好地模拟实验结果,可以用于探索设计空间。优化的最佳反应条件为:Ti O2浓度1.80 g/L、初始双酚A浓度41.08 mg/L、UV光强6.61 m W/cm2,预测和实验最大双酚A去除率分别为81.5%和82.3%,数值比较接近,说明此响应面模型能够有效描述光催化反应过程,优化光催化反应条件,为光催化技术工程应用和光反应器设计提供技术参考。     

涡流空化/Fenton协同降解溶液中活性艳红K-2BP

采用涡流空化(SC)/Fenton协同降解溶液中活性艳红K-2BP,探讨了H2O2、Fe2+、pH、涡流压力以及活性艳红K-2BP初始浓度对SC/Fenton降解效果的影响。结果表明,H2O2和Fe2+的浓度过高或过低都会降低活性艳红K-2BP的降解率,低pH环境有助于活性艳红K-2BP的降解,活性艳红K-2BP的降解率随涡流压力的增大而升高,随其初始浓度的增加而降低。当活性艳红K-2BP初始质量浓度为10mg/L,H2O2质量浓度为165mg/L,Fe2+摩尔浓度为1.5×10-4mol/L,pH为4.0,涡流压力为0.8MPa时,活性艳红K-2BP降解率可达91.81%。     

UV/H_2O_2-NaOH沉淀法处理铜-酒石酸络合体系模拟电镀废水的研究

含铜电镀废水中酒石酸等络合剂的存在,使得采用普通氢氧化物或硫化物沉淀法难以满足达标排放的要求。采用UV/H2O2-NaOH沉淀法处理铜-酒石酸络合体系模拟电镀废水,考察了光照时间、初始pH、H2O2投加量等因素对处理过程的影响。结果表明,对于铜-酒石酸络合体系(酒石酸质量浓度为418mg/L,CuSO4·5H2O质量浓度为196mg/L),得出的最佳处理条件为:光照时间70min,H2O2投加量1.07g/L,初始pH 3.0,出水中铜质量浓度可以低于0.3mg/L的排放标准,为后续工业化应用奠定了基础。     

Interaction of bisphenol A with rat hepatic cytochrome P450 enzymes

The effect of bisphenol A (BPA) on the kinetics of cytochrome P450 (P450)-dependent monooxygenases in rat liver microsomes was studied. Testosterone 16beta-hydroxylase (TS16BH) and testosterone 2alpha-hydroxylase (TS2AH) activities were extensively inhibited by BPA at 100 microM (69% and 74%, respectively). The inhibition type was mixed for both P450-dependent monooxyganases. The Ki of TS16BH and TS2AH from Lineweaver-Burk plots were 25.9 and 24.9 microM, respectively. The activities of acetanilide 4-hydroxylase (AA4H), 7-ethoxycoumarin O-deethylase (ECOD), bufuralol 1'-hydroxylase (BF1'H), chlorzoxazone 6-hydroxylase (CZ6H) and testosterone 6beta-hydroxylase (TS6BH) were also effectively inhibited by BPA at 100 microM (43-52%). The inhibition type of these P450-dependent monooxygenases was mixed or uncompetitive, and the K(i)s (50.5-88.5 microM) were higher than those of TS16BH and TS2AH. By contrast, the values of IC50 and Ki of testosterone 7alpha-hydroxylase (TS7AH) and lauric acid omega-hydroxylase (LAOH) for BPA were >1000 microM. These results suggest that BPA interacts with rat hepatic CYP1A2, CYP2A2, CYP2B2, CYP2C11, CYP2D1, CYP2E1 and CYP3A2 in vitro.     

UV-TiO_2光催化氧化降解双酚A的动力学研究

采用自制光催化氧化反应器,研究了双酚A(BPA)在纳米TiO_2悬浆体系中的光催化氧化特性.结果表明:(1)UV-TiO_2对水中BPA有较强光催化氧化降解作用.在10 W低压汞灯照射下,当纳米TiO_2用量为1.0 g/L、pH为5.5、BPA初始质量浓度为10 mg/L、曝气量为4.0 mL/min、温度为室温、反应时间为120 min时,BPA去除率可达97.1%.当pH≥9.5时,120 min后BPA已经基本光催化氧化降解完全.(2)BPA的光催化氧化降解曲线均很好地符合一级反应动力学方程.其速率常数与纳米TiO_2用量、pH、BPA初始浓度、曝气量有关;促进·OH和电子-空穴对的生成是提高光催化氧化反应速率的重要途径.     

Influence of the presence of heavy metals and surface-active compounds on the sorption of bisphenol A to sediment

The effects of different heavy metals (Cd, Pb), cationic surfactants cetyltrimethylammonium bromide (CTAB), anionic surfactant sodium dodecylbenzenesulfonate (SDBS) and the chemistry of the solution (pH and ionic strength) on the sorption of bisphenol A (BPA) to sediment were studied. Results showed that the presence of Cd and Pb caused a significant increase on the sorption of BPA to sediment and the sorption isotherms were in good agreement with Freundlich equation. The effect of surfactants on the adsorption of BPA onto sediment was found to strongly depend on the type of the surfactants. The presence of CTAB promoted BPA sorption and the amount of BPA adsorbed onto sediment increased linearly with concentration of CTAB. In contrast, the presence of anionic surfactant (SDBS) caused a slight reduction on the sorption of BPA. It was also found that the sorption behavior of BPA was affected by solution pH and ionic strength. The larger amount of BPA was absorbed with higher ionic strength and lower pH. This study may provide important insights into the understanding of the transport and fate of BPA in the environment.     

Chlorination of bisphenol A in aqueous media: formation of chlorinated bisphenol A congeners and degradation to chlorinated phenolic compounds

The chlorination of bisphenol A (BPA) in aqueous media was investigated in order to describe the degradation profile of this compound and the formation of chlorinated products. Aqueous solutions of BPA (approx. 1 mg/l) were chlorinated by sodium hypochlorite solution at room temperature and under weakly alkaline conditions. Chlorinated compounds were extracted with dichloromethane and determined by gas chromatography/mass spectrometry (GC/MS). BPA was consumed completely within 5 min of chlorination, when the initial chlorine concentration was 10.24 mg/l (molar ratio to BPA, 58.7). On the other hand, when the initial chlorine concentration was 1.03 mg/l (molar ratio, 6.56), 9.3% of BPA still remained after 60 min chlorination. Five chlorinated BPA congeners, 2-chlorobisphenol A (MCBPA), 2,6-dichlorobisphenol A (2,6-D2CBPA), 2,2'-dichlorobisphenol A (2,2'-D2CBPA), 2,2',6-trichlorobisphenol A (T3CBPA) and 2,2', 6,6'-tetrachlorobisphenol A (T4CBPA) were formed in the earlier stages of chlorination. Several chlorinated phenolic compounds, 2,4,6-trichlorophenol (T3CP), 2,6-dichloro-1,4-benzoquinone (D2CBQ), 2,6-dichloro-1,4-hydroquinone (D2CHQ), C9H10Cl2O2, C9H8Cl2O and C10H12Cl2O2, were also formed by further chlorination.     

Metabolism of the environmental estrogen bisphenol A by plant cell suspension cultures

The metabolism of the environmental estrogen bisphenol A (BPA) was studied in heterotrophic plant cell suspension cultures of soybean (Glycine max), wheat (Triticum aestivum), foxglove (Digitalis purpurea), and thorn apple (Datura stramonium), which were regarded as metabolic model systems for intact plants. Three main metabolic routes of BPA were observed in the tissues. Most of the radioactivity found in the cell extracts consisted of carbohydrate conjugates of BPA amounting to about 85% (foxglove), 80% (wheat), 7% (soybean) and 15% (thorn apple) of applied 14C. The second main route was formation of non-extractable residues. Portions detected were low in foxglove (3.9% of applied 14C), moderate in wheat (13.5%), high in thorn apple (27.4%) and soybean (49.4%). With thorn apple, BPA derived bound residues were preponderantly resistant towards acid treatment; only traces of BPA were released. The third route was the formation of a highly polar, presumably polymeric material detected in media of soybean and thorn apple (29.3% and 36.0% of applied 14C, respectively). The mechanism of its formation remained unknown. In thorn apple, this highly polar material was formed extremely rapidly, and was considerably stable. Only traces of BPA were liberated by hydrolytic treatment with cellulase or acid. During hydrolysis experiments with glycoside fractions, non-extractable residues and highly polar materials, low amounts of presumably primary metabolites of BPA (up to 6% of applied 14C) were detected besides the parent compound; their chemical structures remained unclear.     

Occurrence of bisphenol A in surface water and uptake in fish: evaluation of field measurements

In this study the actual presence of the suspected endocrine disrupter Bisphenol A (BPA) in water systems was studied in the Netherlands. BPA was shown to be present in Dutch surface water at levels up to 330 ng/l, and one occasional observation of 21 microg/l. During the three sampling periods, 60-80% of the samples, most from marine and estuarine locations, contained BPA levels below the limit of quantification (14-40 ng/l). At a selected number of locations the presence of BPA in fish was studied, which showed that BPA varied from 2 to 75 ng/g in the liver and 1 to 11 ng/g in the muscle. Based on present measured concentrations in surface water and on literature derived toxicity data it was concluded that ecotoxicological effects nor estrogenic effects are likely to occur in the field situation.     

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.     

超声波／零价铁降解水中双酚A

研究了超声波／零价铁（US／Fe^0）工艺对水中双酚A（BPA）的降解效果及影响因素。结果表明，US／Fe^0工艺可以有效降解水中的BPA，具有协同作用，且降解过程符合一级动力学规律；Fe^0具有促进和抑制的双重作用；超声功率越大，越有利于BPA的降解；初始浓度较低时，BPA的降解效果较好；弱酸性条件有利于BPA的降解；加入一定量的自由基捕获剂（正丁醇）可以抑制BPA的降解；联合作用2h后，TOC的去除率较低，说明其矿化程度不完全。     

Human UDP-glucuronosyltransferase isoforms involved in bisphenol A glucuronidation

Bisphenol A (BPA) is one of a number of potential endocrine disruptors which may affect normal hormonal function. In this study, human UDP-glucuronosyltransferase (UGT) isoforms involved in BPA glucuronidation were studied by kinetic analyses using human liver microsomes and recombinant human UGTs expressed in insect cells (UGT1A1, UGT1A3, UGT1A4, UGT1A6, UGT1A9, UGT2B4, UGT2B7, UGT2B15 and UGT2B17). BPA glucuronidation was catalyzed by UGT1A1, UGT1A3, UGT1A9, UGT2B4, UGT2B7 and UGT2B15 as well as by human liver microsomes. Among these UGTs, UGT2B15 showed the highest activity of BPA glucuronidation at low- (1.0 microM) and high- (20 microM) substrate concentrations. Kinetic analyses of BPA glucuronidation were performed by constructing Michaelis-Menten and Eadie-Hofstee plots. The kinetic profile of BPA glucuronidation by pooled human liver microsomes and UGT2B15 was monophasic, the K(m) and V(max) values were 6.39 microM and 4250 pmol min(-1)mg(-1)protein for pooled human liver microsomes, and 8.68 microM and 873 pmol min(-1)mg(-1)protein for UGT2B15, respectively. The K(m) values for BPA glucuronidation by pooled human liver microsomes and UGT2B15 were similar. These findings demonstrate that BPA is mainly glucuronidated by UGT2B15 in human liver microsomes, and suggest that this UGT isoform plays important roles in the detoxification and elimination of BPA.     

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.