An FTIR product study of the photooxidation of dimethyl disulfide

The products of the 254 nm photolysis of ppm levels of DMDS have been studied as a function of the O₂ partial pressure at 760 Torr (N₂ + O₂) and 298±2 K. The major sulfur containing compounds detected were SO₂ and CH₃SO₃H (methane sulfonic acid, MSA) and the major carbon containing compounds were CO, HCHO, CH₃OH and CH₃OOH (methyl hydroperoxide). Within the experimental error limits the observed sulfur and carbon balances were approximately 100%. CH₃OOH has been observed for the first time in such a photooxidation system. Its observation provides evidence for the formation of CH₃ radicals by the further oxidation of the CH₃S radicals formed in the primary photolysis step.From the behavior of the DMDS photolysis products as a function of the O₂ partial pressure, O₃ concentration and added OH radical source it is postulated that the further reactions of CH₃SOH (methyl sulfenic acid), formed in the reaction OH + CH₃SCCH₃ CH₃SOH + CH₃S, are the main source of MSA in the 254 nm photolysis of DMDS.Some of the possible implications of the results of this study for the degradation mechanisms of other atmospherically important organic sulfur compounds, in particular DMS, are briefly considered.     

Ground Based FTIR Measurements of Stratospheric Species from Harestua, Norway During Sesame and Comparison with Models

Vertical columns of HF, HCl, HNO3, ClONO2, N2O, ClO and COF2 were measured at Harestua, Norway (60.22° N, 10.75° E, Elevation 600 a.s.l.) beginning on 24 November 1994 and concluding on 1 May 1995 during Phase-III of the SESAME (Second European Stratospheric Arctic and Mid-latitude Experiment) measurement campaign. The vertical columns of HCl, HNO3 and ClONO2 measured on 81 days were compared with columns calculated by the 3-D Cambridge model SLIMCAT. In addition the results were also interpreted by comparison with a photochemical trajectory model. Good agreement was seen for HCl while the nitrogen compounds showed larger discrepancies, especially for ClONO2. Evidence for chlorine activation was seen with 65% reduction of the chlorine reservoirs (HCl + ClONO2) while the levels of ClO were greatly enhanced. Interpretation of the loss with the trajectory model indicated condensation of chlorine on PSCs. The vertical column ratio of COF2 and HF was measured to 0.21 outside the vortex and a factor of two lower inside. The recovery of ClONO2 was seen to be much faster than that of HCl in the early spring.     

太湖藻源溶解性有机质光化学降解研究

蓝藻水华暴发过程会产生大量的溶解性有机质——藻源溶解性有机质(A-DOM);A-DOM的光化学降解影响其迁移转化和在湖泊中的功能.本研究从太湖藻华中提取A-DOM,利用三维荧光光谱-平行因子分析法(EEMsPARAFAC),研究A-DOM中各组分的光化学降解;再研究不同光照强度、溶解氧浓度、A-DOM浓度、波长对A-DOM的降解的影响.结果显示,A-DOM中含有4种EEMs-PARAFAC组分:C1(UVC类腐殖质)、C2(UVA类腐殖质)、C3(类色氨酸)和C4(类络氨酸),对总荧光强度的贡献比例分别为22.2%、8.6%、68.1%和1.1%.当DOC初始浓度为10 mg/L、反应温度为28℃、pH=8.0时,经500 W汞灯(391.7 W/m~2)光照12 h,A-DOM的总光化学降解率(以a_(355)计)为70.4%;荧光组分C1、C2和C3的降解率分别为96.1%、85.4%和99.2%,三者的光反应性为C3C1C2.条件控制实验显示溶解氧的增加和光强的增强均有助于A-DOM的降解;A-DOM光化学降解主要发生在紫外区,可见光不能使C1和C2得到降解.结果表明A-DOM的光化学降解速度较快,且能通过控制光强、照射光波长和引入溶解氧等条件控制降解速度.实验结果可为湖泊蓝藻水华暴发时的应急处理和保障饮用水安全提供理论依据.     

Kinetics of the reactions of hydroxyl radicals with alkyl nitrates and with some oxygen-containing organic compounds studied under simulated atmospheric conditions

Rate constants have been measured for the reactions of hydroxyl radicals with alkyl nitrates and with some oxygen-containing organic compounds by a competitive technique. Mixtures of synthetic air containing a few ppm of nitrous acid, ethylene and the organic substrate were photolysed in a Teflon bag smog chamber. Based on the value k _HO+C2H₄}=8.1×10^-12 cm³ molecule^-1 s^-1 the following rate constants were obtained for the hydroxyl radical reactions at 750 Torr and at 303 K in units of 10^-12 cm³ molecule^-1: CH₃ONO₂, 0.37±0.09; C₂H₅ONO₂, 0.48±0.20; n-C₃H₇ONO₂, 0.70±0.22; C₂H₅OH, 3.6±0.4; CH₃COCH₃, 0.26±0.08; CH₃CO₂ i-C₃H₇, 3.0±0.8; CH₃CO₂ n-C₃H₇, 2.4±0.2. The results are discussed in relation to the available literature data and the implications of the results are considered in terms of the smog reactivity of these molecules.     

海南岛澄黄滨珊瑚共生藻对环境变化的适应性

在全球气候变暖和人类活动加剧导致珊瑚礁严重衰退的背景下,以抗逆性强的澄黄滨珊瑚（Porites lutea）为研究对象,于 2013 年 10 月―2014 年 8 月在海南岛文昌和三亚对其共生藻密度及光合效率开展了季节性调查研究。结果显示：1）澄黄滨珊瑚共生藻的密度及光合效率均存在显著的季节变化,共生藻密度在冬季最低、夏季较高,其光合效率在冬季较高,春夏季较低。2）澄黄滨珊瑚共生藻密度的空间差异远小于其季节变化的差异,但水深 1~2 m 澄黄滨珊瑚共生藻的密度普遍高于水深 4~6 m 的澄黄滨珊瑚,三亚澄黄滨珊瑚共生藻的光合效率明显高于文昌。3）进一步分析发现,在诸多环境因子中,海表温度 SST 和水体营养是驱动海南岛澄黄滨珊瑚共生藻密度及光合效率变化的主要环境因素,而光合效率的空间差异则可能是珊瑚对生存环境长期驯化的结果。由于文昌和三亚沿岸海水养殖和潜水旅游等人类活动频繁,礁区海水面临富营养化的风险,推测海南岛澄黄滨珊瑚面临 SST 上升和营养胁迫联合效应的严重威胁。     

光化学臭氧日变化特征与其前体物关系的探讨

应用大气光化学模式研究了日最大臭氧体积分数及其出现时刻与其前体物NMHC、NOx体积分数及NMHC／NOx比值的关系。结果表明，影响日最大臭氧体积分数（ψ03max）脊线位置（EKMA图，Empirical Kinetic Modeling Approach）的关键因子是NMHC成份组成比例；日臭氧体积分数达到最大值需要的时间（τ03max）与NMHC／NOx比值及NMHC成份组成比例有关，与NMHC、NOx体积分数关系不大。此外，利用该结果解释了近20a北京日最大臭氧体积分数出现时刻具有不断提前的变化趋势的原因。     

Boundary-Layer Ozone in Croatia

An analysis of ozone distribution in the atmosphericboundary layer based on monitoring data from two TORstations in Croatia is given. The levels were found tobe generally higher than expected for the continentalbackground. At the Puntijarka station, which can betaken as representative for the region, high valuesare mainly associated with transport from the west.The RBI station represents an urban site withoccasional photosmog situations. Short termmeasurements along the Adriatic coast have shown thatthere is a negative north to south gradient in ozoneconcentration as predicted by model calculations, butalso that some local photochemical production takesplace even at the remote Adriatic island far frompollution sources.     

广州夏季雨水硝酸盐δ15N变化特征

通过对广州2007年夏季雨水硝酸盐δ15的研究,讨论了广州地区雨水硝酸盐的主要来源及与之有关的大气化学演变过程。雨水硝酸盐占δ15N的变化趋势与N2O5含量的相似。暗示雨水硝酸盐δ15N与氮氧化合物的大气化学过程之间存在某种联系。白天雨水硝酸盐δ15N值偏低,与OH自由基氧化NOx生成硝酸盐的“白天反应”为主要反应相一致;18：00以后硝酸盐δ15N值呈升高趋势,则与N2O5累积的“夜间反应”成为主导反应相一致。因“白天反应”生成的HNO3的δ15N值受同位素分馏影响较小,白天雨水硝酸盐占δ15N值更能准确反映大气NOx的来源。白天雨水硝酸盐占δ15N平均值为2．5‰±2．1‰,表明除火力发电厂和机动车尾气排放来源外,雷电以及海源对大气NOx可能也有潜在贡献。     

广东省和江苏省大气甲醛时空变化对比分析

利用Aura/OMI月均甲醛对流层垂直柱浓度数据对2005年—2016年中国广东省和江苏省的大气甲醛的时空变化规律、不同排放源的前体物的潜在贡献进行了分析。甲醛在广东省主要集中在珠三角地区,在江苏省分布则相对较为均匀。2005年—2010年,随着经济发展,在两省都发现了大面积的甲醛增加趋势;相应的,在2011年—2016年,由于减排等治理措施的实施,在两省都有大面积的甲醛减少现象。广东省的甲醛主要呈现出春季、秋季高于冬季再高于夏季的特征;而江苏地区夏季甲醛浓度远高于其他季节,并与光照强度的季节性特征较为一致。此外,由于广东省甲醛分布的均一性较差,因此区域性因素(如地形等)对广东省甲醛分布可能有着较大的影响。各个排放源中,工业源、交通源对珠三角潜在贡献可能较大;自然源对梅州等林地覆盖地区可能有相对较高的影响;在江苏省,各个排放源对甲醛的贡献相对均衡,但夏季较为频繁的生物质燃烧可能对夏季高值甲醛有着相对较高的贡献。