Variability of tropospheric hydroperoxides at a coastal surface site in Antarctica

The annual cycles of hydrogen peroxide (H₂O₂) and methylhydroperoxide (MHP) have been investigated at a remote site in Antarctica in order to study seasonal variations as well as chemical processes in the troposphere. The measurements have been performed from March 1997 to January 1998 and in February 1999 at the German Antarctic research station Neumayer which is located at 70°39′S, 8°15′W. The obtained time series for hydrogen peroxide and methylhydroperoxide in near-surface air represents the first all-year measurements in Antarctica and indicates clearly the occurrence of seasonal variations. During polar night mean values of 0.054±0.046 ppbv (range<0.03–0.11 ppbv) for hydrogen peroxide and 0.089±0.052 ppbv (range<0.05–0.14 ppbv) for methylhydroperoxide were detected. At the sunlit period higher Mixing ratios were found, 0.20±0.13 ppbv (range<0.03–0.91 ppbv) for hydrogen peroxide and 0.19±0.10 ppbv (range<0.05–0.89 ppbv) for methylhydroperoxide. Occasional long-range transport of air masses from mid-latitudes caused enhanced peroxide concentrations at polar night. During the period of stratospheric ozone depletion we observed peroxide mixing ratios comparable to typical winter levels.     

Effect of methylmercury on LPO levels, SH groups and activities of GSH-Px, SOD, XOD in liver of rats

ｉｔｈｔｈｅｉｎｔｒｏｄｕｃｔｉｏｎｏｆａｇｒｉｃｕｌｔｕｒａｌａｎｄｉｎｄｕｓｔｒｉａｌｄｅｖｅｌｏｐｍｅｎｔａｎｄｉｍｐｒｏｖｅｍｅｎｔｏｆｈｕｍａｎｌｉｆｅ ,ｅｎｖｉｒｏｎｍｅｎｔａｌｐｏｌｌｕｔｉｏｎｂｅｃｏｍｅｓｍｏｒｅａｎｄｍｏｒｅｏｆｃｏｎｃｅｒｎｆｏｒｐｅｏｐｌｅ.ＭｅＨｇｉｓｏｎｅｏｆｏｒｇａｎｉｃｌｉｐｉｄｓｏｌｕｂｌｅ ,ｈｅａｖｙｍｅｔａｌｌｉｃｐｏｌｌｕｔａｎｔｓ.Ａｌｔｈｏｕｇｈｉｔｓｂｉｏｌｏｇｉｃａｌｅｆｆｅｃｔｓｗｅｒｅｓｔｕｄｉｅｄｉｎｍａｎｙｆｉｅｌｄｓｂｙｒｅ…     

有机过氧化物在生产、储运过程中的危险与可操作性分析

有机过氧化物的易燃、受热分解等特殊性质和生产、储运过程要求严格的低温条件与操作程序,使得有机过氧化物潜在的危险性很高。通过基于有机过氧化物危险特性及其在生产、储运过程中物质、能量与信息的分析,依据物-能量-信息的安全要素体系,应用危险与可操作分析方法,研究了有机过氧化物的安全理论,在某种程度上是延伸了HAZOP分析的内容。     

过氧化氢对铜绿微囊藻的损伤效应研究

采用室内培养的方法研究了不同浓度H2O2对铜绿微囊藻(Microcystic aeruginosa)藻细胞的损伤效应.结果表明,H2O2浓度越大,对藻细胞的毒害作用越大.24 h之后,铜绿微囊藻藻细胞数、叶绿素a、类胡萝卜素和蛋白质含量及总抗氧化能力(T-AOC)都快速下降,而MDA含量显著增加,同时培养基中的H2O2含量也迅速降低;随着处理时间的增加,毒性效应逐渐增强;72 h之后,藻细胞各指标值都降得很低,MDA含量也增加到最大,培养基中H2O2也逐渐被消耗和分解,藻细胞的损伤效应也达到最大.其中,H2O2浓度为50 mg·L-1时,能够有效的去除藻细胞,并且对藻细胞的生理指标及抗氧化能力都有很强的损伤效应.     

Effects of typical additives on the thermal stability of ammonium peroxydisulfate

Ammonium peroxydisulfate (APS), one of the most widely used inorganic peroxides in the process industries, is a thermally unstable peroxide and potent oxidizer due to the presence of peroxy bond in the molecule and is incompatible with most substances. To investigate the effect of typical additives on the thermal decomposition of APS, in this paper, diamine phosphate (DAP), monoamine phosphate (MAP), and aluminum hydroxide (AH) were selected as additives; pure APS and samples with 10 wt% and 20 wt% of additives were first tested by differential scanning calorimetry (DSC). The experiments and analysis showed that the samples with 10 wt% of additive had better thermal stability than those with 20 wt% of additive. After screening, the three groups of 10 wt% AH, 10 wt% MAP, and 20 wt% MAP additive conditions could be considered to have a better thermal stability effect on the thermal decomposition of APS. Four groups of samples were, in turn, tested by Phi-Tec II. The adiabatic results showed two discontinuous exothermic processes; 10 wt% AH promoted the weak exothermic effect in the first stage. In contrast, the three groups of additives in the main exothermic stage showed different degrees of inhibition, and the inhibiting effect was ranked as 10 wt% AH, 10 wt% MAP, and 20 wt% MAP in order. Finally, the self-accelerated decomposition temperature (SADT) was calculated under the 25 kg standard package. The adiabatic results, including SADT, were combined to render feasible recommendations for the use of additives, which provides references for the packaging and transportation of additives and their applications.     

丁二烯过氧化物的生成、危害及安全性研究

综述了国内外丁二烯过氧化物研究进展，主要包括丁二烯过氧化物的危害性、成因、危险评价和热稳定性，并对今后的研究方向进行了展望。     

Fe(VI)/CaO2双氧化体系降解水环境中的DMP

研究了高铁酸盐（Fe（VI））/过氧化钙（CaO₂）联合处理对邻苯二甲酸二甲酯（DMP）的降解性能及机理,分析了共存离子的影响.基于响应面方法中的Box-Behnken实验设计进行了多因素实验,采用二次多项式和逐步回归法拟合了DMP去除率与Fe（VI）投加量、CaO₂投加量和反应时间之间的关系,对实验条件进行了优化分析.结果表明,在初始pH值为中性条件下,Fe（VI）/CaO₂可以有效去除DMP,降解过程符合准一级动力学模型.当Fe（VI）/CaO₂/DMP物质的量比为1.1/4.4/1时,模型预测DMP最大降解率为95.57%,和验证实验得出的降解率90.14%相近,表明该响应面模型具有较好的模拟和预测能力.HCO₃^-和Mg²⁺对DMP的降解有一定抑制作用.自由基清除实验结果显示,羟基自由基（HO·）和超氧自由基（O₂^-·）对DMP的降解具有重要贡献,表明Fe（VI）和CaO₂可形成类芬顿试剂协同降解污染物.DMP的主要降解途径包括酯基水解、侧链氧化和苯环的羟基化;主要降解产物为邻苯二甲酸单甲酯,2,5-二羟基苯甲酸,间苯二甲酸,草酸等.     

The influence of ClO− and acidity in the reaction between H2O2 and CuCl2

The potentially explosive reaction of hydrogen peroxide (H₂O₂) and copper chloride (CuCl₂) was investigated. Pressure tests revealed that the reaction was strongly temperature - dependent and can easily undergo runaway reaction. Nevertheless, there was only a slight pressure increase at the low temperatures studied or when using low concentrations of CuCl₂. Under the conditions generating the slight pressure increase, hypochlorite anions (ClO⁻) are generated and the acidity increases. As the reaction reaches completion, ClO⁻ disappears, and the acidity decreases. Interestingly, the addition of phosphate buffer to maintain the weakly acid conditions led to a runaway reaction, and the use of basic ClO⁻ promoted the exothermic reaction. Based on the results, acidity has a strong impact on the reaction behaviour.     

Thermal hazard accident investigation of hydrogen peroxide mixing with propanone employing calorimetric approaches

Hydrogen peroxide (H₂O₂), historically, due to its broad applications in the chemical industries, has caused many serious fires and explosions around the world. Its thermal hazards may also be incurred by an incompatible reaction with other chemicals, and a runaway reaction may be induced in the last stage. This study applied thermal analytical methods to explore the H₂O₂ leading to these accidents by incompatibility and to discuss what might be formed by the upset situations. Thermal hazard analysis contained a solvent, propanone (CH₃COCH₃, so-called acetone), which was deliberately selected to mix with H₂O₂ for investigating the degree of thermal hazard. Differential scanning calorimetry (DSC) and vent sizing package 2 (VSP2) were employed to evaluate the thermal hazard of H₂O₂. The results indicated that H₂O₂ is highly hazardous while mixed with propanone, as a potential contaminant. The time to maximum rate (TMR) was used as emergency response time in the chemical industries. Therefore, TMR of H₂O₂ was calculated to be 70 min for runaway reaction (after T₀) and TMR of H₂O₂/propanone was discovered to be 27 min only. Fire and explosion hazards could be successfully lessened if the safety-related data are properly imbedded into manufacturing processes.     

Na_2CO_3/H_2O_2“稳定”的CO_2的型体研究(Ⅱ)——“稳定性二氧化氯”溶液的UV吸收光谱、纸层析特性、微观结构和离子色谱分析

本文对以稳定剂H_2O_2和Na_2CO_3与ClO_2制备的所谓"稳定性二氧化氯"溶液的UV吸收光谱、纸层析特性、微观结构及离子色谱进行了分析,并与纯NaClO_2及ClO_2溶液做了对比.结果表明,“稳定性二氧化氯” 与NaClO_2在UV吸收光谱、层析比移值、微观结构、离子色谱这几方面都具有很好或极其相似的一致性 表明“稳定性二氧化氮’与NaClO_2溶液中氯氧化物存在型体的一致性.因此,认为“稳定性二氧化氯“溶液中ClO_2是以亚氯酸盐ClO_2~-的型体存在的.