天然水体腐殖质对双酚A光降解影响的研究

以中压汞灯模拟太阳光光源,研究了双酚A(BPA)在水体腐殖质中的光降解过程,探讨了不同来源的腐殖质、腐殖质浓度、BPA初始浓度、溶解氧等因素对BPA光解速率的影响.实验结果表明,BPA在纯水体系中直接光解很慢,但在腐殖质溶液中光解迅速,符合拟一级动力学反应.改变BPA初始浓度对BPA光解速率的影响不明显,增大溶解氧浓度会抑制BPA光解.通过活性氧分子探针鉴定了腐殖质吸收光辐射产生的羟基与单线态氧.利用GC-MS鉴定了双酚A在Nordic湖富里酸(NOFA)中的光敏化降解产物,推测出BPA敏化降解的可能历程为能量转移导致的直接光解、羟基加成和羟基氧化.     

双酚A在Suwannee富里酸溶液中的光解

以Suwannee河富里酸(SRFA)为光敏化剂,采用中压汞灯模拟阳光,研究了双酚A(BPA)在SRFA溶液(1.0mg·L^-1～50.0mg·L^-1)中的光解动力学.结果表明BPA的光解符合一级反应动力学,并且随着SRFA浓度的增加,BPA的光解速率从0.93×10^-3min^-1迅速增大到16.54×10^-3min^-1.采用分子探针方法和电子自旋共振技术(ESR)证实了SRFA在光照过程中能够产生羟基自由基和单重态氧,同时通过不同的曝气条件研究了激发三重态富里酸的电子能量转移.研究结果表明BPA在SRFA溶液中的光解历程可能与激发三重态富里酸的能量转移密切相关.最后采用GC/MS鉴定了BPA在SRFA体系中的光解产物,探讨了BPA在SRFA体系中可能的反应历程.     

Determination of photochemically-generated reactive oxygen species (ROS) in natural water

Reactive oxygen species (ROS) can be produced by interactions between sunlight and light-absorbing substances in natural water environment. ROS may participate in the indirect photolysis of trace organic pollutants, therefore resulting in the changing of their environmental fates and ecological risks in natural water system. Bisphenol A (BPA), an endocrine-disrupting chemical, exits widely in natural water. The photodegradation of BPA promoted by ROS (·OH, 1O2, HO2·/O2·-) which were produced on the excitation of ubiquitous constituents (such as nitrate ion, humic substances and Fe(III)-oxalate complexes) in natural water under simulated solar radiation was investigated. Both molecular probe method and electron spin resonance (ESR) test were used for the determine the characterization of generated ROS. It was found that ·OH was photochemically produced with the presence of nitrate ion, humic substances and Fe(III)-oxalate complexes and 1O2 was produced with the presence of humic substances. The steady-state concentrations of ·OH was 1.27×10-14 mol/L in nitrate ion, and the second-order rate constant of BPA with ·OH was 1.01×1010L/( mol·s).     

不同源胡敏酸对磺胺嘧啶紫外光降解的影响及作用机制

研究了紫外光照条件下不同来源的胡敏酸（HA）,包括标准品胡敏酸（SPHA）、水稻土胡敏酸（SDHA）、泥炭土胡敏酸（NTHA）和落叶覆盖地胡敏酸（LYHA）对抗生素磺胺嘧啶（SDZ）光降解的影响以及主要活性物种对其光降解效能的贡献.结果表明：SDZ在纯水中及与HA共存条件下,其光降解过程均符合一级动力学模型,且HA对SDZ的光降解具有促进作用,其促进效果从大到小为SPHA > SDHA > NTHA > LYHA.通过羟基自由基（·OH）和单线态氧（¹O₂）淬灭实验发现,不同来源HA产生·OH和¹O₂的能力具有一定差异性.同等背景条件下,SPHA产生的·OH量相对较多,其对SDZ光降解的贡献率（26.97%）最大,而LYHA贡献相对较小（9.33%）.同时,¹O₂对SDZ光降解起主导作用,其降解贡献率为41.33%~51.95%.     

Effects of Cu（Ⅱ） and humic acid on atrazine photodegradation

This work was designed to explore the characteristics of photodegradation of herbicides in the copper-polluted water body. Theresults showed that Cu(II) alone could induce a photo Fenton-like reaction to enhance the degradation of atrazine, in which hydroxylradical ( OH) was a main active species. Humic acids restrained atrazine degradation, nevertheless, when introducing Cu(II), thephotodegradation was accelerated, in which singlet oxygen (1O2) replaced OH acting as the prevailing species. A feasible mechanismfor the photochemical process was also proposed, which is helpful for better understanding the environmental photochemistry ofatrazine in the copper-polluted water.     

负载磁性废茶生物炭活化过一硫酸盐高效降解水中腐殖酸和富里酸

城市污水厂二级处理出水中含有大量的溶解性有机物(Dissolved organic matters,DOM)会对生物和受纳水体构成潜在的危害,因此有必要对二级处理出水进行深度处理.本研究以农业废弃物茶叶渣为原料,通过对废弃茶叶改性和负磁制备一种磁性废茶生物炭(Fe-tea biochar,Fe-TB),用于活化过一硫酸...     

Photodegradation of bisphenol A in Fe(Ⅲ)-oxalate complexes solution

The aqueous photodegradation of bisphenol A (BPA) in the presence of Fe(Ⅲ)-oxalate complexes (Fe(Ⅲ)-Ox), which are common compositions of natural water, was investigated in this study. BPA underwent rapid indirect photolysis in Fe(Ⅲ)-Ox solution under simulated solar irradiation, proceeding pseudo-first-order kinetics. The photolysis rate increased with decreasing pH or initial processes of Fe(Ⅲ)-Ox complexes and contributed to the photooxidation of BPA, were determined by molecular probe and electron spin resonance (ESR) methods with the steady-state concentration of 2.56 × 10-14 mol/L. Superoxide anion radical (O2.-) was consistructural analysis of the intermediate photoproducts of BPA in Fe(Ⅲ)-Ox complexes solution, the possible degradation pathways of of Fe(Ⅲ) may affect the environmental fate of BPA in natural water significantly.     

镉铅在粘土上的吸附及受腐殖酸的影响

试验研究了镉和铅2种重金属在蒙脱土和高岭土上的吸附,以及外加腐殖酸的3种组分（富里酸、棕色胡敏酸和灰色胡敏酸）的影响。镉铅在粘土上的吸附随着介质pH的升高而增加。在pH4-8范围内的任意pH点,镉在高岭土上的吸附量因富里酸而降低,因2种胡敏酸而升高;当pH值高于6时,吸附量急剧增加。外加富里酸使得铅在粘土上的吸附在pH＞6时意外出现随着介质pH而降低的趋势。     

DOM结构特征及其对17β-雌二醇光降解的影响

参照国际腐殖酸协会(IHSS)推荐的方法从滇池底泥提取出胡敏酸(HA)和富里酸(FA),以Sigma Aldrich胡敏酸(SAHA)为参照,利用元素分析、13C核磁共振和紫外-可见光谱对HA和FA的来源和结构进行了表征,并探讨了3种溶解性有机质(DOM)对17β-雌二醇(E2)光降解的影响.结果表明:HA、FA和SAHA具有相似的元素组成,3种腐殖酸的(N+O)/C值分别为0.50、0.82和0.55,与核磁共振13C谱分析的极性指数(0.32、0.42和0.33)一致.HA和FA来自于内源,具有较高的N含量和较多的缔合芳香结构,而SAHA是外源性有机质,具有更高的芳香度.低浓度的3种腐殖酸均能促进E2发生服从准一级动力学规律的光化学降解过程.E2在纯水中光降解速率为0.0071h-1,而在5mgC/L的HA、FA和SAHA作用下,E2光降解速率分别为0.0597、0.1178和0.2048h-1.3种腐殖酸促进E2光降解能力的差异主要是由含氧能团和芳香结构含量差异所致.活性氧分子探针鉴定显示HO?是腐殖酸体系受光照后产生的一种重要活性氧,其氧化降解E2的量占到了E2降解总量的70%左右.与低浓度腐殖酸相比,高浓度的3种腐殖酸均会对E2光降解产生抑制作用.     

Effects of humic acid fractions with different polarities on photodegradation of 2, 4-D in aqueous environments

Four fractions (A, B, C, and D) of humic acids (HAs) were separated based on the polarity from weak to strong. UV-vis absorption and Fourier transform infrared spectroscopy (FTIR) analysis show that the fractions C and Dpossessedmore aromatic C=C content. The influences of HAs and their fractions on the photolysis were investigated by the photodegradation of 2,4-D solutions under simulated solar light irradiation. The degradation rate of 2,4-D was found to decrease in the presence of bulk HAs or their fractions especially at high HAs concentration. The fractions of strong polarity C and D retarded the degradation rate more than the fractions of weak polarity A and B. This could be attributed to the different absorption intensity of the four HAs fractions in the order of D ⩾ C > A > B, and the stronger π-π electron donor-acceptor interactions between the strong polar fractions and 2,4-D.     

Effects of methyl-CD and humic acid on hydrolytic degradation of the herbicide

IntroductionDiclofopmethylhasbeenintroducedbyFarbwerkeHoechstAGforthecontrolofabroadspectrumofwildoatsandotherannualgrassweedsinavarietyofcrops.Theherbicidehaslowsolubility,strongadsorptionandlowvaporpressure,indicatingthatitwouldbeimmobileunderfieldconditions(Smith,1986).Laboratoryandfieldstudieshaveshownitunderwentarapidhydrolysistodiclofopinplantandsoil,thecorrespondingpropionicacidthatislessherbicidalthantheparentcompounddiclofopmethyl(Smith,1977;1986;Martens,1978).Cyclodextrinsarecycli…     

羟基致死船舶压载水微生物的生化影响研究

试验表明羟基比值浓度达到0．63mg／L左右时，足以杀死压载水微生物。在此浓度下也会引起微生物的糖、脂质、蛋白质、核酸、酶等发生强烈的化学反应。脂质过氧化物含量上升为原来的3倍；总蛋白质减少了33．4％；核酸中RNA、DNA分别减少了46．9％、77．0％；葡萄糖却增加了1倍，羟基破坏了多糖，使之降解为单糖；过氧化物酶含量减少了21．9％；超氧化物歧化酶减少了54．2％；分离微生物后海水中过氧化氢酶、超氧化物歧化酶分别减少了83．1％、33．2％，上述生化试验资料清楚表明了羟基对微生物三大基本分子(核酸、蛋白质、葡萄糖)、抗氧化酶系(过氧化酶、过氧化氢酶、超氧化物歧化酶)以及脂质均有强烈的破坏作用，这也是致死压载水微生物的主要原因。     

羟基对海水水质影响的研究

低浓度羟基溶液能100％致死浮游动植物、细菌、弧菌、孢子，同时又大幅度改善了压载水水质。在每小时处理2t压载水的模拟试验中取得如下改善水质数据：对生物有害的亚硝酸盐、氨盐的下降率高达98．35％、99．5％；浊度下降50％，水的透明度有明显的改善；C0T从0．54mg／L减少到未检出；由于羟基对细胞残骸的氧化分解，使TOC含量上升了1倍；Cu、Pb、Fe下降幅度分别达到38．1％、70．8％、40．3％，对生物无害的Zn增加近2倍，这是因Zn是许多酶和蛋白质分子的活性中心原子，羟基分解细胞后，溢出溶入水中所致。保证了排放地域水生生物的安全。     

DNA氧化损伤在太阳光致M13mp2噬菌体突变中的作用

以野生型大肠菌ＣＳＨ５０及ｍｕｔＭ缺陷的大肠菌ＭＦ６７为宿主，观察了太阳光对Ｍ１３ｍｐ~２噬菌体单链ＤＮＡ ｌａｃＺα基因区域的致突变性．结果显示，太阳光照射引起噬菌体ｌａｃＺα基因区域的突变，在ｍｕｔＭ缺陷的宿主中更为明显；０．２５ｍｏｌ／Ｌ的甘露醇可以部分拮抗太阳光的致突变作用．以ＥＳＲ自旋捕捉法检测了太阳光、长波紫外线（ＵＶＡ）及中波紫外线（ＵＶＢ）照射Ｍ１３ｍｐ~２噬菌体样品中的自由基，结果还显示，太阳光和ＵＶＡ照射可引起羟自由基的产生，而ＵＴＢ照射则没有明显的自由基信号产生说明太阳光致突变作用与ＤＮＡ氧化损伤有关，羟自由基在其中发挥一定的作用     

UV-B辐射对亚历山大藻生长及其生理生化特征的影响

通过生物化学的方法,研究了UV-B辐射对亚历山大藻(Alexandrium tamarense)生长及其可溶性蛋白、叶绿素a、H2O2、丙二醛(MDA)含量和超氧化物歧化酶(SOD)活力的影响.结果表明:UV-B辐射会抑制亚历山大藻的生长并对其生理生化特征产生明显的影响;经过UV-B辐射后,可溶性蛋白和叶绿素a含量呈现降低的趋势;H2O2、丙二醛含量和超氧化物歧化酶活力呈现升高的趋势;UV-B辐射产生过量的活性氧自由基是导致亚历山大藻受损伤的主要原因.     

Redox potential E_H [Se(VI)/Se(IV)] of aqueous extractof soils from Yongshou Kaschin-Beck diseaseregion and the influence by humic acid

The relation between EH [Se(VI)/Se(IV)] and pH of soil aqueous extract in Kaschin-Beck disease region and the effects of natural redox agents, namely humic substances, MnO2 and Fe2+, on the redox property of the system were studied. The results indicated that both humic acid and Fe2+ could enhance the reducibility of Se(VI) and MnO2, a limited oxidizability for Se(IV). Fe2+ showed a weak reducibility only at low pH value. The reducibilities of three sulfur-containing compounds for Se(VI) were in following order:thioglycollic acid > L-cysteine > sulfide     

Degradation of endocrine disruptor bisphenol A in drinking water by ozone oxidation

The ozone oxidation of endocrine disruptor bisphenol A in drinking water was investigated. A stainless completely mixed reactor was employed to carry out the degradation experiments by means of a batch model. With an initial concentration of 11.0 mg/L, the removal efficiencies of BPA (bisphenol A) could be measured up to 70%, 82%, and 90% when the dosages of ozone were 1, 1.5, and 2 mg/L, respectively. The impacts on BPA degradation under the conditions of different ozone dosages, water background values, BPA initial concentrations, and ozone adding time were analyzed. The results showed that ozone dosage plays a dominant role during the process of BPA degradation, while the impact of the contact time could be ignored. UV wavelength scanning was used to confirm that the by-products were produced, which could be absorbed at UV254. The value of UV254 was observed to have changed during the ozonation process. Based on the change of UV254, it could be concluded that BPA is not completely degraded at low ozone dosage, while shorter adding time of total ozone dosage, high ozone dosage, and improvement of dissolved ozone concentration greatly contribute to the extent of BPA degradation. The effects of applied H₂O₂ dose in ozone oxidation of BPA were also examined in this study. The O₃-H₂O₂ processes proved to have similar effects on the degradation of BPA by ozone oxidation. Translated from Environmental Science, 2006, 27(2): 294–299 [译自: 环境科学]     

腐殖酸钠对钙、镁离子吸附效果的研究

实验研究了腐殖酸钠混合液对钙、镁离子的吸附性能。高温条件下由草炭和NaOH制取的腐殖酸钠混合液,吸附水中的钙镁离子,结果发现：随着混合液用量的增加,其对钙镁离子的去除效率增加。当混合液用量为8ml时,二者的吸附效率均在88％以上,其中对镁离子的去除率可达100％,而且由于钙镁离子具有相同的核外电子层结构及类似的化学性质,因此混合液对钙镁离子的去除效果类似,表明腐殖酸钠混合液对钙镁离子具有极好的去除效果,可广泛应用于处理含钙镁离子的污水。