长光路傅立叶变换红外光谱技术研究氯氟烃替代物与氢氧自由基反应速率常数

利用长光路傅立叶变换红外光谱技术（LP－FTIR）,用相对速率方法研究大气中氯氟烃替代物HFC152a（CHF₂CH₃）和HCFC22（CHClF₂）与OH自由基反应速率常数,用紫外光照射O₃和H₂O的方法产生OH自由基。实验测定了700Tor大气压力和常温（298±2k）下的反应速率常数值：k（HFCl52a＋OH）＝（2.90±0.09）×10^－14cm₃·molecule^－1．S^－1,k（HCFC22＋OH）＝（3.80±0.24）×10^－15cm3．Molecule^－1．S^－1,统计误差为2σ     

相对速率法测OH自由基与几种低碳醇的反应速率常数

在 2 99± 2K温度下 ,以甲醇为参照物 ,采用相对速率方法得到了几种醇与OH自由基在气相中的反应速率常数 ,这些速率常数分别为 (单位为 :10 5m3·mol-1·s-1) :乙醇k1=17 6 ,正丙醇k2 =35 2 ,2 丙醇k3=31 2 ,正丁醇k4 =48 2 ,2 甲基—1 丙醇k5=6 2 0 ,2 甲基— 2 丙醇k6=5 36 ,正戊醇k7=5 1 4,3 甲基— 1 丁醇k8=6 8 6 .其中 2 甲基— 1 丙醇的速率常数在本文中是首次报道 .根据各自的反应速率常数计算得到它们在大气中的平均寿命分别为 :τ1=95 1h ,τ2 =47 5h ,τ3=5 3 6h ,τ4 =34 7h ,τ5=2 7 0h ,τ6=312h ,τ7=32 6h ,τ8=2 4 4h .     

苯甲酸类光催化降解和羟基自由基反应的关系

研究了13种苯甲酸类化合物在固定膜平板反应器中的光催化降解,探讨了光降解速率与化合物结构之间的定量关系（QSAR）,同时分析了苯甲酸类化合物和羟基自由基反应的速率常数与结构的关系结果表明,Hammett常数（σ）和摩尔对数溶解度（lgS）是影响本甲酸类光降解速率lgK的重要因素,其定量关系式为：lgK＝-0．309σ＋0.125lgS－2.612,苯甲酸类与羟基自由基反应的定量关系式为lgK_OH＝－0.414σ＋9．816,证实了羟基自由基在本甲酸类光催化过程中的重要作用.     

复合垂直流湿地反应动力学及水流流态的研究

 提出一种新型的复合垂直流湿地系统(IVCW),并对其反应动力学和系统的实际流态进行了研究.经过中试的运行试验,得到了系统对COD去除的反应速率方程,由示踪剂试验确定了系统中水流的停留时间分布(RTD),提出RTD的不同是湿地处理效率差异的主要原因,进而运用串联反应器模型和离散流模型两种非理想流态模型,模拟IVCW的实际水流流态,经过比较发现离散流模型模拟的效果较好.     

OH自由基与溴乙烷反应动力学和大气中存留寿命

溴代烷烃是破坏臭氧层的重要物质,用放电流动－共振荧光技术,测定ＯＨ自由基与Ｃ２Ｈ５Ｂｒ在２９７－３６９Ｋ温度范围的反应速率常数,求得其阿仑尼乌斯公式,并根据对流层的平均温度２２７Ｋ下求是ＯＨ自由基与溴乙烷反应速率常数（Ｋ）值,算出共在对流层的寿命为０．１６８ａ这将提供这类化合物使用否的重要科学根据。     

综合评定苯并（a）芘低浓度污染有毒危险性的研究

在细胞遗传损伤和免疫功能综合指标中,观察对苯并（a）芘（BaP）敏感并适用于人群检测的指标。结果显示外周血淋巴细胞姐妹染色单体交换（SCE）率与尿中BaP含量呈正相关;并在BP低于10μg/100M³的接触人群中观察到SCE率增高;血清IgG和补体C³与血中BaP含量呈负相关。以SCE率增高、IgG降低和尿中BaP负荷量增高综合评定BaP污染的有危毒险性有应用前景,饮用中华猕猴桃饮料,有助于SCE率增高的恢复和体内BaP的排出。     

气相色谱-脉冲氦离子化检测法(GC-PDHID)分析大气中分子氢(H2)浓度

在商用Agilent7890A型气相色谱的基础上,通过自组装、集成及调试,建成了基于气相色谱-脉冲氦离子化检测器(GCPDHID,gas chromatography-pulsed discharge helium ionization detector)观测大气中H2浓度的高精度分析系统.系统采用保留时间定性,峰高定量,最低检测限约为1×10-9(摩尔分数,下同).对浓度约为600×10-9的标气重复进样140次用峰高定量的标准偏差优于0.3×10-9.系统对409.30×10-9~867.74×10-9浓度范围的大气H2具有较好的线性响应.系统使用2瓶标气定量,满足世界气象组织/全球大气观测计划(WMO/GAW)对本底大气H2观测的比对目标.2013年1~11月在广州城区开展大气H2采样观测,采集的样品运回北京实验室利用所建系统进行浓度分析,结果表明该城区大气H2浓度在450×10-9~700×10-9之间波动,观测到最低值出现在每日14:00(北京时,下同),最高值在20:00,其大气H2季节变化趋势与北半球同纬度站点情况类似.     

Changes in the quality of river water before, during and after a major flood event associated with a La Niña cycle and treatment for drinking purposes

The treatment of organics present in the lower reaches of a major river system（the Murray–Darling Basin, Australia） before（March–July 2010）, during（December 2010–May 2011） and after（April–December 2012） a major flood period was investigated. The flood period（over 6 months）occurred during an intense La Nia cycle, leading to rapid and high increases in river flows and organic loads in the river water. Dissolved organic carbon（DOC） increased（2–3 times） to high concentrations（up to 16 mg/L） and was found to correlate with river flow rates. The treatability of organics was studied using conventional jar tests with alum and an enhanced coagulation model（mEnCo）. Predicted mean alum dose rates（per mg DOC） were higher before（9.1 mg alum/mg DOC） and after（8.5 mg alum/mg DOC） than during the flood event（8.0 mg alum/mg DOC）,indicating differences in the character of the organics in raw waters. To assess the character of natural organic matter present in raw and treated waters, high performance size exclusion chromatography with UV and fluorescence detectors were used. During the flood period, high molecular weight UV absorbing compounds（〉2 kDa） were mostly detected in waters collected,but were not evident in waters collected before and afterwards. The relative abundances of humic-like and protein-like compounds during and following the flood period were also investigated and found to be of a higher molecular weight during the flood period. The treatability of the organics was found to vary over the three climate conditions investigated.     

Temperature dependence of the absolute rate constant for the reaction of ozone with dimethyl sulfide

Absolute rate constants for the reaction of ozone with dimethyl sulfide (DMS) were measured in a 200-L Teflon chamber over the temperature range of 283-353 K. Measurements were carried out using DMS in large excess over ozone of 10 to 1 or greater. Over the indicated temperature range,the data could be fit to the simple Arrhenius expression as KDMS = (9.96±3.61)×10-11exp(-(7309.7±1098.2)/T)cm3/(molecule·s). A compared investigation of the reaction between ozone and ethene had a kc2H4 value of(1.35±0.11)×10-18 cm3/(molecule·s) at room temperature.     

Evidence for a Neoproterozoic carbonate ramp on the northern edge of the Central African craton: relations with late Proterozoic intracratonic troughs

During Late Proterozoic times, the Archaean Central African craton was affected by trough faulting which led to the formation of grabens, the Sangha aulacogen being the main structure of this type in the studied area. This transverse basin connects with other basins on the northern and south-western borders of the craton. During the Cryogenian, this network of basins was filled with fluvio-deltaic and lacustrine periglacial deposits. The glacio-eustatic transgression in Neoproterozoic III (end-Proterozoic) times flooded extensive areas of shelf on the northern edge of the craton, leading to the development of carbonate sedimentation in a broad outer shelf environment associated with nearshore barriers and evaporitic lagoons. These facies are similar to those developed in the West Congolian Schisto-calcaire (shale-limestone) ramp succession. The North-Central African ramp succession (sediment slope) contains an example of tidal rhythmites in vertical accretion, which occurs beneath the barrier deposits on the subtidal outer shelf. Mathematical analysis of the bedding pattern yields a period of 29–30 days for the lunar month, a result which is in agreement with astrophysical evidence for this epoch (i.e. 650 Ma ago). Major subsidence and seismic activity on this gently sloping platform, associated with the proximity of the Sangha aulacogen, caused the triggering of carbonate turbidites and mass flow deposits. The proliferation of microbial mats under euphotic conditions on an extensive shelf led to the build-up of a carbonate platform. During early Neoproterozoic III times, the West Congolian and North-Central African ramps prograded northwards and southwards, respectively, into the Sangha aulacogen. The sea at that time was restricted to a long graben-like basin, while a remaining area of marine sedimentation persisted into the Palaeozoic. Thus the pattern of end-Proterozoic carbonate sedimentation on the borders of the Central African craton can be interpreted in terms of an overall gently sloping ramp model with progradation converging towards the Sangha aulacogen.