全球二维大气化学模式和大气化学成分的数值模拟

建立了一个全球二维纬向平均化学模式,模式包括了从90°S到90°N,从地面到20 km高度的大气.模式中应用的流场来自根据加热率计算得到的剩余环流.模式化学部分包括34种大气成分、104个化学反应和光化学反应.其中,甲烷、一氧化碳和氮氧化物排放分为季节性和非季节性排放源,并将其参数化为时间和纬度的函数再应用到模式中去.按1990年的甲烷、一氧化碳和氮氧化物的的排放水平模拟得到了多种大气组成的分布,模拟结果与观测有较好的一致性.由于模式考虑了一氧化碳的季节变化,模拟得到的OH自由基分布更为合理.模式的建立为今后进一步研究大气微量成分的全球循环过程及其长期变化提供了有效的手段.     

对流层大气氧化性研究进展

对流层大气氧化性是对流层大气自我清洁能力的一个重要指标,对流层中大多数痕量气体都是通过氧化过程清除的.回顾近半个世纪以来对流层大气氧化性的研究历史,对流层大气氧化性的研究无论是从测量技术还是模式研究方面都已取得了一定的进展.工业革命以来,由于人类活动的影响,CO、NOx和碳氢化合物等大气污染物排放增多,使得全球对流层大气OH浓度呈下降趋势,未来对流层大气氧化性的变化很大程度上也取决于这些气体的排放情况.利用全球三维大气化学传输模式MOZART研究中国地区对流层大气OH自由基的分布和变化趋势表明,与全球OH自由基变化趋势不同,近10年来中国东部地区OH自由基浓度趋于增加.未来对流层大气氧化性研究的关键问题仍是OH自由基测量技术的提高问题,OH自由基观测结果是完善对流层光化学机制和改进大气化学模式的先决条件.     

羟基对赤潮生物的光合色素作用实验

羟基药剂具有氧化力极强、杀灭微生物的生化反应速度极快的特性。在容积1.8m3的水槽里进行了羟基对微藻的光合色素影响的中宇宙规模实验。羟基质量浓度达到0.55mg/L时,微生物的叶绿素a、b含量均低于检测方法的最低限值,其衰减率为100%,类胡萝卜素衰减率为92.3%,脱镁叶绿素增加了15.05倍。实验数据表明,羟基药剂将是治理赤潮的绿色有效方法。     

Relative-rate study of the gas-phase reaction of hydroxy radicals with difunctional organic nitrates at 298 K and atmospheric pressure

Rate coefficients for the reactions of difunctional nitrates with atmospherically important OH radicals are not currently available in the literature. This study represents the first determination of rate coefficients for a number of C(3) and C(4) carbonyl nitrates and dinitrates with OH radicals in a 38 l glass reaction chamber at 1000 mbar total pressure of synthetic air by 298±2 K using a relative kinetic technique.The following rate coefficients (in units of 10^-12 cm³ molecule^-1 s^-1) were obtained: 1,2-propandiol dinitrate, <0.31; 1,2-butandiol dinitrate, 1.70±0.32; 2,3-butandiol dinitrate, 1.07±0.26; -nitrooxyacetone, <0.43; 1-nitrooxy-2-butanone, 0.91±0.16; 3-nitrooxy-2-butanone, 1.27±0.14; 1,4-dinitrooxy-2-butene, 15.10±1.45; 3,4-dinitrooxy-1-butene, 10.10±0.50.The possible importance of reaction of OH as an atmospheric sink for the compounds compared to other loss processes is considered.     

范各庄井田奥灰水NO^—3离子形成机理及在水源判别中的应用

在分析范各庄井田水文地质特征的基础上,利用水文地球化学理论初步探讨了奥陶系灰岩含水层地下水中赋存高含量ＮＯ－３离子的形成机理,介绍了应用这一水化学特征分析矿井充水条件的方法。     

Urban Atmospheric Chemistry During the PUMA Campaign 1: Comparison of Modelled OH and HO<Subscript>2</Subscript> Concentrations with Measurements

Photochemical box modelling was undertaken to investigate OH and HO₂ radical chemistry during summer and winter field campaigns in the urban city-centre of Birmingham in the UK. The model employed the most recent version of the Master Chemical Mechanism (v3.1) and was constrained to 15-minute average measurements of long-lived species determined in situ at the site. The model was used to predict OH and HO₂ concentrations for comparison with measurements made by the fluorescence assay by gas expansion technique. Whilst there was generally good agreement between the modelled and measured OH concentrations, particularly during summer, there was sometimes a significant model under-prediction during daylight hours, which significantly skews the overall model: measured agreement. There were less measured data available for HO₂, but the agreement between model and measurement for the days where measurements existed were less good than for OH, with one or two exceptions. The modelled:measured ratios between the hours of 11:00–15:00 h for OH were 0.58 and 0.50 for summer and winter respectively. For HO₂, the same ratios were 0.56 in the summer and 0.49 in the winter. Sensitivity studies were conducted to attempt to understand the model-measurement discrepancy. The predicted radical concentrations were particularly sensitive to changes in NO_X concentrations. Constraining the model to the observed HO₂ concentrations made the OH predictions worse. These results highlight the fact that there are many complexities in urban areas and that more highly-instrumented campaigns are required in the future to further our understanding.     

Effects of Monochromatic UV-Visible Light and Sunlight on Fe(III)-Catalyzed Oxidation of Dissolved Sulfur Dioxide

The effect of UV-visible light and natural sunlight on the Fe(III)-catalyzed oxidation of dissolved sulfur dioxide has been studied under the conditions representative for those of acidified atmospheric liquids. The experimental results have shown that both sunlight and UV-visible light enhance the rate of Fe(III)-catalyzed oxidation of aqueous sulfite with wavelength ranging from 300 to 575 nm. The light enhanced oxidation is mainly due to photochemical formation of OH radicals from Fe(OH)²⁺ complexes in the wavelength region below 420 nm and SO₃^•− free radicals from Fe(III) sulfite complexes above 420 nm in the absence of organic ligands. Like the Fe(III)-catalyzed thermal chemical oxidation, the Fe(III)-catalyzed photochemical oxidation is also first order with respect to sulfite ion concentration. The sunlight irradiation can increase the Fe(III)-catalyzed oxidation of S(IV) over 45%. The presence of organic complex ligands, such as oxalate, can completely inhibit the Fe-catalyzed oxidation of S(IV) in the dark. However, the photolysis of Fe(III)-oxalato complexes generates oxalate free radicals, leading to the formation of H₂O₂ and OH radicals and the oxidation of S(IV). The rate of Fe(III)-catalyzed oxidation of S(IV) species is found to increase with increasing light intensity. The effects of sunlight on the Fe(III)-catalyzed oxidation of S(IV) should be taken into account when predicting the daytime rates of sulfuric acid formation in atmospheric water droplets.     

羟基自由基杀灭压载水中有害赤潮物种的生物有效性研究

本研究采用大气压下强电离放电协同气液混溶技术,高效制备羟基自由基(·OH)杀灭3个门的典型有害赤潮物种,使用荧光染色、测定光合作用潜能等生物学检测方法确定·OH致死阈值。结果表明,5.05×104 cells/mL的赤潮异弯藻(Heterosigma akashiwo)、5.28×104 cells/mL的亚历山大藻(Alexandrium tamarense)和5.02×104 cells/mL的中肋骨条藻(Skeletonema costatum),其致死阈值分别为1.24 mg/L、2.01 mg/L、1.12 mg/L,此时其叶绿素a分解率分别为77%、85%和74%。利用光学显微镜观察,处理前后藻细胞结构有明显的改变。因此,·OH致死方法可有效地杀灭压载水中的有害赤潮藻。     

应用遥感技术提取含稀土矿花岗岩信息

通过分析花岗岩风化壳离子吸附型稀土矿的成矿特征及地质地貌图,利用遥感手段总结出五个步骤确定该类稀土矿表面积,经过去除水系、第四系、高坡度区以及高植被覆盖区后,利用主成分分析法提取羟基异常信息,进一步确定其分布范围,经过与已知稀土矿矿床、矿（化）点分布资料验证,效果良好。     

Megamasers: Molecular Diagnostics of the Nuclear Ism

Molecular emissions are powerful tracers of intense heating and star-formation processes in galactic nuclei. In this paper we consider the characteristics of molecular Megamaser emission among the population of (Ultra-) Luminous Infrared Galaxies that are powered by intense star-formation or accretion onto a massive compact object. In addition, we consider the systematic behavior of the line emission of high-density tracer molecules. An evolutionary scenario is presented for ULIRGs that may explain the molecular line ratios observed in the population of FIR galaxies.