区域性光化学模式与LLA-C机制的模拟性能比较

以 Ｌ Ｌ Ａ－ Ｃ 机制为基准,在［ Ｎ Ｍ Ｈ Ｃ］／［ Ｎ Ｏ＃ － ｘ］ 比率分别为１７９ 、７１４ 、２８６ 条件下测试了区域性光化学模式（ Ｒ Ｏ Ｓ） 的模拟性能。结果表明 Ｒ Ｏ Ｓ 模式在上述三种初值条件下均能从总体趋势上给出与 Ｌ Ｌ Ａ － Ｃ 机制相似的结果, 但只有当非甲烷烃浓度较高（［ Ｎ Ｍ Ｈ Ｃ］／［ Ｎ Ｏｘ］ ＞ １２） 时 Ｒ Ｏ Ｓ 模式模拟值与 Ｌ Ｌ Ａ－ Ｃ 机制预测值比较接近。在这种条件下, Ｒ Ｏ Ｓ 模型对 Ｏ Ｈ 的预测值有待改进。我国大气中相当高的［ Ｎ Ｍ Ｈ Ｃ］／［ Ｎ Ｏｘ］ 比率说明 Ｒ Ｏ Ｓ 模式用于全国范围内的空气质量趋势模拟是可行的。     

大城市气溶胶对光化辐射通量及臭氧的影响研究(Ⅱ)——数值试验分析

城市化已引起大量痕量气态污染物、气溶胶以及臭氧前体物的人为排放,从而引起区域大气化学循环的扰动变化。在分析国内外研究现状与观测实例的基础上,进一步用辐射模式与化学模式研究了气溶胶对到达地面的光化辐射通量以及臭氧形成的影响,表明气溶胶可显著减小到达地面的光化学辐射通量,减缓光化学反应进程,并进一步抑制臭氧的形成;在目前广州等大城市的污染过程中,高浓度的气溶胶可造成光化学辐射通量衰减高达70%~80%,紫外线的衰减比可见光更明显,在可见光波段随波长增大衰减幅度减小,气溶胶层的存在对短波长激发的光化学过程的影响更加显著。分析说明城市污染大气中光化学反应的生成物与反应物之间存在自抑制过程,在目前的城市群复合污染情况下,气溶胶与臭氧之间的非线性相互作用值得关注。     

The Effect of Temperature and Humidity on the Reaction of Ozone with Combustion Soot: Implications for Reactivity near the Tropopause

The effect of temperature (296–238 K) on the reaction of combustion soot (n-hexane) with ozone at low concentration (6–8 ppm) has been measured. Long optical path FTIR spectroscopy has revealed the rate law for ozone loss beyond initial stages, second order in O₃, to be the same over this range of conditions. The reaction rate is 3.5 times lower at 238 K than at 296 K, and reveals an activation energy of 12.9 ± 0.5 kJ mol^–1. The effect of humidity on the reaction has been estimated using its recently determined rate law dependence (p^0.2). These data, differing from O₃ reaction kinetics obtained from other types of carbonaceous particles used as surrogates for atmospheric soot, have implications for the role of combustion soot in atmospheric chemistry. Any involvement of aircraft soot in ozone depletion near the tropopause, for example, should be estimated using these temperature and humidity dependences.     

负载型纳米Pd/Fe对挥发性氯代烃的去除

氯代烃的污染治理已成为当今世界最热门的研究领域之一。以水体中最常见的氯代烃污染物1,1-二氯乙烯（1,1-DCE）、林丹（γ-HCH）为主要目标污染物,探讨了不同条件下负载型纳米Pd/Fe对氯代烃的去除效果。负载型纳米Pd/Fe采用浸渍→液相还原→还原沉淀的方法制备,透射电镜显示采用该方法制备的负载型金属钯和铁的平均粒径均在纳米级范围内。负载型纳米Pd/Fe具有较高的表面反应活性,当负载型纳米Pd/Fe 用量为40 g/L、反应时间达2 h时,1.1-二氯乙烯和林丹的去除率分别达到85%和100%。脱氯率与Pd/Fe投加量、钯含量、初始pH值、反应温度等因素有关,与溶液的初始浓度关系不大。负载型纳米Pd/Fe对11-DCE和γ-HCH去除均符合一级反应动力学方程,速率常数分别为0-528 3 h^-1及2-012 9 h^-1,反应的半衰期t1/2分别为1.31 h和0.34 h。推断在反应过程中,Fe腐蚀产生的H2为主要还原剂,Pd是良好的加氢催化剂,在金属颗粒表面形成高浓度反应相,使反应短时间内完成。     

流动条件下斜长石与NaCl热液相互作用的实验研究

利用金袋热设备，于３００℃，５０ＭＰａ和流动条件下（流速：７ｍｌ／ｈ和１ｍｌ／ｈ研究了斜长石与１ｍｏｌ／ｋｇＮａＣｌ溶液的相互作用，还在同一温度压力下进行了静态实验，着重考察反应后溶液化学和长石表面化学成分的变化，以探讨钠交代作用的机理，结果表明，反应反溶液的ＰＨ值升高，Ｎａ含量降低；Ｓｉ，Ｃａ，Ｋ和Ａｌ转入溶液的特征与反应状态以及溶液流速有关；斜长石的钠交代作用涉及及钙长石组分溶解和钠长石组分结     

氮配位的磁性高分子复合微球P（GMA—MMA—AA）／Fe3O4负载钯催化水相Suzuki反应的研究

以可控自由基聚合技术制备的磁性高分子复合微球P（GMA—MMA．AA）／Fe3O4为载体,三乙烯四胺为配体制备了一种新型的负载型钯催化剂。采用透射电镜、振动样品磁强计、x射线光电子能谱仪和x射线衍射分析仪等手段对催化剂进行了表征,并评价了催化剂对水相Suzuki反应的催化活性。结果表明,催化剂的平均粒径为800nm左右,钯在载体表面呈高度分散状态,整个催化剂呈超顺磁性。该催化剂在空气氛围中就能较好的催化水相中芳基卤代物与苯硼酸的Suzuki反应,较高产率且立体选择性地生成取代的联苯产物,反应过程中催化剂可稳定分散于反应体系中,并可在外磁场作用下快速与从体系分离。催化剂重复使用5次后,仍具有较高的活性。     

A Study on the Dissolution Kinetics of Basalt—Water Interaction under Different pH Conditions I：Release of Elements and pH Neutralization Effect

Experimental research on the chemical weathering of alkaline-olivine basalt from Huangyi Mountain,Kuandain County,Liaoning.Province and olivine basalt from Dayangke,Mingxi County,Fujian Province has shown that the acidity of the solution tends to become neutral regardless of what the acidity of the starting solution would be during basalt0-water interaction.We call this phenome-non“pH neutralized Effect”.The dissolved species in the solution were determined and unreacted and reacted sample-surface chemical components involved or uninvolved in reaction were analyzed using X-ray photoelectron spectroscopy(XPS).The results revealed two different mechanisms of dissolution of basalt in acidic and basic solutions.     

Experimental Study Assessing the Role of Sedimentary Organic Materials to Control the Redox State of Ground Materials to Control the Redox State of Groundwater: Consumption of Dissolved Oxygen by Humic Acid

Abstract: A total of 189 runs were completed to determine the rate of dissolved oxygen consumption in water by the reaction humic acid at 25°, 45°, and 65°C. Glass vial bottles were used as reaction vessels, and humic aicd and pure water of different intitial O₂ concentration was loaded with humic acid/water weight of 0.008 and 0.009. Vials were opened periodically to measure O₂ concentrations. The pH of the solution fluctuated in the early stages of the experiments and gradually decreased to a constant value. Dissolved oxygen concentration decreased, for example, from initial value of 12 mg/l to 9 mg/l at 25°C, to 5 mg/l at 45°C, and to 2 mg/l at 65°C after the reaction of 500 hours. Analyses of rates suggest that the reaction is first order, and rate constants are 8.42 × 10^-9 at 25°C, 2.22 × 10^-8 at 45°C, and 1.28 × 10^-7 moles m^-2 s^-1 at 65°C.     

Petrology and geochemistry of peridotites from IODP Site U1309 at Atlantis Massif, MAR 30°N: micro- and macro-scale melt penetrations into peridotites

Peridotite samples recovered from IODP Site U1309 at the Atlantis Massif in the Mid-Atlantic Ridge were examined to understand magmatic processes for the oceanic core complex formation. Original peridotite was fragmented, and the limited short peridotite intervals are now surrounded by a huge gabbro body probably formed by late-stage melt injections. Each peridotite interval has various petrographical and geochemical features. A spinel harzburgite in contact with gabbro shows evidence of limited melt penetrations causing gradual compositional change, in terms of trace-element compositions of pyroxenes, as well as modal change near the boundary. Geochemistry of clinopyroxenes with least melt effects indicates that the harzburgite is originally mantle residue formed by partial melting under polybaric conditions, and that such a depleted peridotite is one of the components of the oceanic core complex. Some of plagioclase-bearing peridotites, on the other hand, have more complicated origin. Although their original features were partly overprinted by the injected melt, the original peridotites, both residual and non-residual materials, were possibly derived from the upper mantle. This suggests that the melt injected around an upper mantle region or into mantle material fragments. The injected melt was possibly generated at the ridge-segment center and, then, moved and evolved toward the segment end beneath the oceanic core complex.     

咸阳城区地下热水地球化学演化模拟

应用水文地球化学模拟(PHREEQC软件)对咸阳城区地下热水进行了水文地球化学演化和路径模拟.模拟路径分别为西、西北两个补给方向.模拟结果表明,,地下水流向发生了一系列的水-岩反应,,线R5→SP2,SP2水化学类型由Na-HCO2-Cl转化为Na-Cl型,而西北线R6→SP2水化学类型由Na-Ca-HCO3 -el转化为Na-Cl型,在水流路径上SiO2(玉髓)、方解石、白云石和高岭石发生了沉淀,而岩盐、石膏、天青石、钠长石、云母和萤石发生了溶解作用.对研究区地下热水地球化学反应路径模拟,描述了研究区地下热水补给到排泄的演化特征,表明水-岩作用模拟对于揭示研究区地下水化学演化环境具有重要的指示意义.