Ozonation of the 5-fluorouracil anticancer drug and its prodrug capecitabine: Reaction kinetics,oxidation mechanisms,and residual toxicity

Specific second-order rate constants were determined for 5-FU and CAP with ozone. Reaction sites were confirmed by kinetics, Fukui analysis, and products. The olefin moiety was the main ozone reaction site for 5-FU and CAP. Carboxylic acids comprised most of the residual TOC for 5-FU. Ozonation removed the toxicity associated with 5-FU and products but not CAP. Anticancer drugs (ADs) have been detected in the environment and represent a risk to aquatic organisms, necessitating AD removal in drinking water and wastewater treatment. In this study, ozonation of the most commonly used antimetabolite ADs, namely 5-fluorouracil (5-FU) and its prodrug capecitabine (CAP), was investigated to determine reaction kinetics, oxidation mechanisms, and residual toxicity. The specific second-order rate constants between aqueous ozone and 5-FU, 5-FU⁻, 5-FU²⁻, CAP, and CAP⁻ were determined to be 7.07(±0.11)×10⁴ M⁻¹·s⁻¹, 1.36(±0.06)×10⁶ M⁻¹·s⁻¹, 2.62(±0.17)×10⁷ M⁻¹·s⁻¹, 9.69(±0.08)×10³ M⁻¹·s⁻¹, and 4.28(±0.07)×10⁵ M⁻¹·s⁻¹, respectively; furthermore, the second-order rate constants for ^•OH reaction with 5-FU and CAP at pH 7 were determined to be 1.85(±0.20)×10⁹ M⁻¹·s⁻¹ and 9.95(±0.26)×10⁹ M⁻¹·s⁻¹, respectively. Density functional theory was used to predict the main ozone reaction sites of 5-FU (olefin) and CAP (olefin and deprotonated secondary amine), and these mechanisms were supported by the identified transformation products. Carboxylic acids constituted a majority of the residual organic matter for 5-FU ozonation; however, carboxylic acids and aldehydes were important components of the residual organic matter generated by CAP. Ozone removed the toxicity of 5-FU to Vibrio fischeri, but the residual toxicity of ozonated CAP solutions exhibited an initial increase before subsequent removal. Ultimately, these results suggest that ozone is a suitable technology for treatment of 5-FU and CAP, although the residual toxicity of transformation products must be carefully considered.     

不同底物条件下金属离子螯合剂对厌氧消化的影响

借助气相色谱分析,研究了金属离子螯合剂在不同有机酸存在时对厌氧消化的影响.结果表明,螯合剂A的添加可以有 效提高不同有机酸的甲烷产量和产甲烷速率,促进有机酸向甲烷的转化. 当螯合剂A的添加量为10μmoI/L时,丁酸、丙酸和乙酸的甲烷产量分别增加了19.8%、133.0%和45.2%.产甲烷的延滞期也明显缩短,最高产甲烷速率提高了4倍多.丁酸厌氧氧消化的4～8d间,丁酸降解率达56%,同时,气相色谱未检测到乙酸的累积,说明丁酸转化为乙酸后,乙酸很快被产甲烷菌利用.螯合剂A对有机酸产甲烷的促进作用可从酶学上得到支持,以乙酸为例,添加10μmoI/L螯合剂A时,污泥(vss)中辅酶F₄₂₀含量由空白实验的1.20μmoI/g提高到1.52μmoI/g.     

Oxidation of diesel soot on binary oxide CuCr(Co)-based monoliths

Binary oxide systems (CuCr₂O₄, CuCo₂O₄), deposited onto cordierite monoliths of honeycomb structure with a second support (finely dispersed Al₂O₃), were prepared as filters for catalytic combustion of diesel soot using internal combustion engine's gas exhausts (O₂, NO_x, H₂O, CO₂) and O³ as oxidizing agents. It is shown that the second support increases soot capacity of aforementioned filters, and causes dispersion of the particles of spinel phases as active components enhancing thereby catalyst activity and selectivity of soot combustion to CO₂. Oxidants used can be arranged with reference to decreasing their activity in a following series: O₃ >> NO₂ > H₂O > NO > O₂ > CO₂. Ozone proved to be the most efficient oxidizing agent: the diesel soot combustion by O₃ occurs intensively (in the presence of copper chromite based catalyst) even at closing to ambient temperatures. Results obtained give a basis for the conclusion that using a catalytic coating on soot filters in the form of aforementioned binary oxide systems and ozone as the initiator of the oxidation processes is a promising approach in solving the problem of comprehensive purification of automotive exhaust gases at relatively low temperatures, known as the "cold start" problem.     

Determination of chemical warfare agents

Ethylarsine dichloride was used during WW I as a chemical warfare agent. Residues of this chemical warfare agent and its metabolites are still present today and continue to contaminate soil and water. A gas Chromatographic method for the detection and determination of ethylarsine dichloride is shown. Six dithiols were tested as possible derivatization reagents for ethylarsine dichloride. With selection of the dithiol, matrix interferences can be eliminated because of the different retention times of the derivatives.     

Destruction of diphenylarsine chloride (CLARK I) with activated ozone

The new technology of Plasmazon® uses the extremely strong oxidation of radicals to break up the compocunds of organic connections, e.g. chemical warfare agents like Clark I. In making a comparison of oxidation to normal ozone, the factor of the Plasmazon® -technology is available up to 10³. The investigation in an experimental test shows that it is possible to destroy the warfare agent character of Clark I. As the possibility of a large-lot application this technology is the method of choice for other chemical or biological warfare agents.     

提高植物修复效率的技术途径与强化措施

通过物理、化学或生物学手段,从土壤、植物及其生境3个方面着手来提高植物去除土壤重金属能力是植物修复技术应用研究的重要方向.对国内外植物修复过程中所应用的强化手段与辅助措施进行了一定的研究,分别阐述了施肥、水分管理、耕作栽培、修复剂、生物技术等方法的作用机制及应用效果.今后,植物修复技术需针对有应用前景的超富集植物进行生境特征的系统研究,并着重开发高效、低风险的土壤修复剂,注重植物修复成套技术的工程应用研究.     

Evaluation of N-acetylcysteine and glutathione as quenching agents for the analysis of halogenated disinfection by-products

Disinfection by-products(DBPs), formed from the reactions of disinfectants with natural organic matter and halides in drinking water, were considered to be cytotoxic and genotoxic, and might trigger various cancers. The relatively low concentration of DBPs in finished water(low μg/L or even ng/L levels) and the interference from water matrix inhibited in situ determination of DBPs. Moreover, the further formation and degradation of DBPs by disinfectants during the holding time(several hours to s...     

高分子螯合剂的制备,表征及性能研究

高分子量的聚丙烯酰胺,通过发生在侧基上的Ｍａｎｎｉｃｈ反应,使之带有螯合基团。高分子的结构经约外光谱和核磁共振氢谱得到确证。考察了聚合物对Ｎｉ＾２＋离子的螯合能力,比较了经胺化改性及酸化所得的螯合剂对Ｎｉ＾２＋、Ｃｕ＾２＋、Ｚｎ＾２＋的螯合能力,研究了酸度对螯合剂螯合能力的影响。结果表明,制得的具有螯合侧基的高分子能对重金属离子有效螯合,且螯合能力几乎与体系的酸度无关。     

重金属捕集剂对水中微量Hg(Ⅱ)的处理研究

针对含汞废水采用常规处理难以达标的问题,选用二硫代氨基甲酸盐类(DTCR-2)、2,4,6-三硫醇基钠硫代三嗪(TMT-18B)、硫化钠(Na2S)和氢氧化钙[Ca(OH)2]作为重金属捕集剂,对水中微量Hg2+进行深度处理研究.通过处理效果的对比,最终选用DTCR-2作为Hg2+最理想的捕集剂,重点考察了pH值、DTCR-2投加量、反应时间、Hg2+初始浓度及其他重金属离子等因素对Hg2+去除效果的影响.结果表明,在Hg2+初始浓度为100μg.L-1,pH为8.0,投加量1.0倍化学计量比,反应时间10 min时处理效果较好,Hg2+剩余浓度为41.36μg.L-1,低于国家排放标准中的限值(50μg.L-1).另外,Cd2+、Pb2+、Cu2+这3种重金属离子对DTCR-2去除Hg2+具有抑制作用,影响大小依次为Cu2+>Pb2+>Cd2+,而Zn2+具有促进作用.通过本研究,可以为DTCR-2处理低浓度含汞废水工艺设计提供理论支持.     

二段混凝沉淀-曝气氧化-砂滤处理印刷电路板废水

探讨印刷电路板废水处理工艺。针对某印刷电路板厂废水水质特点,采用“二段混凝沉淀一曝气氧化一砂滤”工艺对其进行处理。运行结果表明,废水准确分类及预处理、曝气氧化和投加重金属捕捉荆是保证出水达标的重要措施。该工艺处理效果稳定,出水水质低于《污水综合排放标准》（GB8978-1996）中一级标准。本研究为印刷电路板废水的处理提供了一条可行途径。