南京市降水化学特征及其来源研究

为了解南京江北地区降水化学特征,分析了2011年3—6月共25个降水日的109个降水样品中的主要水溶性离子,并利用后向轨迹模式探讨了降水气团来源.结果表明:1)南京地区3—6月降水主要受南、北2种气团影响,北方气团降水的主要离子浓度高于南方气团降水.2)海盐示踪法和相关性分析显示,降水中NO₃^-和SO₄^2-主要来自燃煤、工业排放和汽车尾气;Ca²⁺主要来自地壳源;Cl^-主要来自海洋;海洋源和陆源对Mg²⁺和K⁺都有贡献,Mg²⁺的陆源贡献大于海洋源贡献,K⁺受海洋源的影响程度要低于Mg²⁺.3)南、北气团初期降水的各离子浓度高于总降水的各离子浓度,且初期降水的主要离子的富集系数高于总降水.这说明在降水初始阶段,雨水对南京大气中污染物(气态污染物和颗粒物)的云下冲刷去除作用较强,降水的离子浓度最高,局地源对降水离子的贡献较明显.     

广州白云山风景区酸雨梯度分布

对1999年白云山风景区1~10月的降水pH 值、化学成分以及1月、6月大气低层的气溶胶进行了监测.分析结果表明(1)白云山3个测点降水的平均pH值最低为4.83,最高为5.29;酸雨频率最低58 %,最高91 %;强酸雨频率最低19 %,最高39 %.降水酸度和酸雨频率呈梯度变化,pH值随高度增高而减小,酸雨和强酸雨频率增加.(2)冬季近地层大气中偏碱性气溶胶在白云山的组成比较稳定,山上和山下测点气溶胶水溶性离子成分基本一致;而夏季山上、山下的成分有所不同,山上的SO42-比例明显增大.另外,尽管气溶胶中NO3-的含量极少,但降水中NO3-有明显的富集现象.(3)白云山降水离子成分中SO42-占阴离子的比例最大、NO3-次之;Ca2+占阳离子的比例最大、NH4+稍低.随高度上升SO42-和Ca2+在降水中的比例有所下降,而NO3-和NH4+比例明显增加,NO3-和NH4+对山上降水酸度的影响是相对增大的.(4)受附近公路交通的直接影响,白云山降水中的NO3-比例较大,NO3-/SO42-当量浓度比值平均达到0.4;NO3-对白云山降水酸度有较大的贡献,而且这一贡献随高度而增大.     

福建三明市春季PM2.5中有机碳、元素碳和水溶性离子特征分析

2014年3月13日至4月20日在福建三明市利用PM_2.5中流量采样器采集大气中PM_2.5膜样品,测定了PM_2.5的质量浓度,并用热/光碳分析仪和离子色谱分析了其组分变化特征.结果表明,三明市观测期间PM_2.5的平均质量浓度为73.61±0.73 μg/m³,有机碳(OC)和元素碳(EC)的平均质量浓度分别为7.26±1.00和5.63±0.27 μg/m³,水溶性离子中SO₄^2-、NH₄⁺、NO₃^-和Na⁺的质量浓度分别为18.08±12.19、4.18±3.56、2.77±1.16和2.73±0.23 μg/m³,总和占总水溶性离子的87.76%.结合后向轨迹分析了福建三明市的污染物来源特征.该地区OC/EC的平均比值小于2,SOC(二次有机碳)生成量很少,主要以一次有机污染物为主,OC、EC与K⁺的相关性分析表明OC、EC与K⁺的来源相近,可以判断OC、EC绝大部分来源是生物质燃烧产生的污染物.在水溶性离子分析中,观测期间NO₃^-/SO₄^2-为0.159±0.02,表明三明市主要以固定源为主,机动车辆等移动源贡献较少.     

武汉市一次霾污染过程不同发展阶段下水溶性离子来源解析

本文利用气体组分及大气气溶胶在线监测系统(MARGA ADI 2080)观测武汉市2018年1月9—26日大气气溶胶中的8种水溶性离子(NH⁺₄、NO^-₃、SO^2-₄、Cl^-、K⁺、Ca²⁺、Na⁺和Mg²⁺),结合气象要素数据,使用主成分分析(PCA)、正定矩阵因子分析法(PMF)、HYSPLIT后向轨迹模式、潜在源区贡献(PSCF)和浓度权重轨迹(CWT),对霾污染过程中水溶性离子进行了全面的来源解析,探究了霾不同阶段下来源差异和空间分布特征。结果表明:(1)本次霾污染中的8种水溶性离子和4种污染气体,PCA解析出的源和占比分别为二次源和燃煤源的混合源(41.28%)、工业排放和土壤扬尘混合源(27.73%)和机动车排放源(9.63%),PMF解析出的源和占比分别为燃煤与土壤扬尘混合源(18.57%)、机动车排放源(20.74%)、二次源(18.30%)、光化学污染源(22.24%)和燃煤源(20.15%)。(2)霾在不同阶段下水溶性离子和4种污染气体的来源存在差异,在清洁天和霾消散阶段,光化学的贡献最高,占比分别为31.42%和36.07%;在霾发生阶段燃煤与土壤扬尘源的贡献最高,其贡献为40.94%;在霾发展阶段,最大的控制源为二次源,贡献占比为37.51%。(3)此次武汉市霾污染中PM_2.5浓度和NH⁺₄、NO^-₃和SO^2-₄的潜在源区为皖豫鄂三省和赣湘鄂三省交界处。霾污染中PM_2.5的主要影响范围是武汉市南部和北部省份,NO^-₃、NH⁺₄和SO^2-₄的主要影响区域为武汉市东北方向的城市、湖南省和江西省。     

合肥市不同天气条件下大气气溶胶粒子理化特征分析

为探讨合肥市霾天气大气气溶胶粒子的组成及来源,在2012-2013年代表性月份用安德森分级采样器在合肥市区进行大气气溶胶粒子采样,并分析各样本中水溶性无机离子成分(NH4+、Mg2+、Ca2+、Na+、 K+、NO2-、NO3-、Cl-、SO42-)。根据同期气象资料把采样背景天气分为晴空、雾、霾、轻雾等4类,详细分析了这4种天气下大气细粒子(指PM2.1)和粗粒子(粒径大于2.1 μm部分)的浓度、组成以及主要离子组分的异同。结果表明:(1)观测期间晴空天多对应空气质量优良,雾、霾天对应轻度到重度污染,从晴空天到雾、霾天,PM2.1浓度大幅度上升,且其占总悬浮颗粒物(TSP)的比例显著上升。(2)从晴空天到雾、霾天,水溶性无机离子质量占PM2.1质量浓度的比例上升,分别为46%(晴空)、67%(霾)、61%(雾)、80%(轻雾)。PM2.1中水溶性无机离子浓度居前3位的雾、霾天是SO42-、NO3-和NH4+,晴空天为SO42-、Ca2+、NO3-。(3)与晴空天相比,霾天PM2.1中水溶性无机离子浓度变化倍数最大的是NO3-(为晴空的6.1倍,下同)、其次是NH4+(3.6倍)和SO42-(3.0倍);雾和轻雾天PM2.1中水溶性无机离子浓度变化最大的是NO3-(>10倍)、其次是NH4+(>5倍)和Cl-(>4.0倍)。(4)4种天气下,与人为污染有关的离子(SO42-、NO3-、Cl-、NH4+)尺度谱存在显著差异,呈双峰型、单峰型、三峰型等;而Ca2+的尺度谱无明显变化,基本上都呈双峰型。(5)在粒径3.3 μm以下,阳、阴离子平衡较好,随着尺度增大变差,且晴空天比雾、霾天差。主要阴离子浓度间、Cl-和Na+间的比值和相关性,在晴空天和雾、霾天差异较大。      

山东暖区暴雨对流特性和环境参量的统计分析

利用2014-2018年5-9月间山东大监站逐日降水资料、Micaps常规资料以及NCEP再分析资料等,将山东暖区暴雨分为锋前型、暖切变型、副高边缘型和急流型4大类,并对山东暖区暴雨的垂直结构、对流特性以及环境参量特征进行统计。主要结论为：(1)山东暖区暴雨的低空风场主要以西南风或东南风为主,且整层风场随高度顺转。高湿区主要集中在对流层中低层。大气的自由对流高度和云底高度较低,湿层和暖云层深厚,其中急流型湿层和暖云层最为深厚。(2)山东暖区暴雨发生时,K≥30.5℃, 0.72≥SI≥-6.87,假相当位温≥334K,垂直锋区的北界位于37-39°N之间,暴雨落区位于锋区北界南侧2-3个纬距范围内。(3)暖区暴雨上空辐合中心平均值为-3×10^-5 s^-1,辐合中心均出现在700hPa以下；垂直速度中心的平均值为-1.1×10^-5 hPa.s^-1,大值中心出现在对流层中低层；涡度中心的平均值为5×10^-5 s^-1,正涡度主要在低层,且随高度的增加而减小；q925≥16g.kg^-1,q850≥12g.kg^-1,q700≥9g.kg^-1,暖区暴雨的水汽输送主要集中在低层,水汽通量散度平均值,850 hPa是-2.3×10^-6 g.cm^-2.hPa^-1.s^-1, 700 hPa 为-1.2×10^-6 g.cm^-2.hPa^-1.s^-1。     

Indirect radiative forcing and climatic effect of the anthropogenic nitrate aerosol on regional climate of China

The regional climate model (RegCM3) and a tropospheric atmosphere chemistry model (TACM) were coupled, thus a regional climate chemistry modeling system (RegCCMS) was constructed, which was applied to investigate the spatial distribution of anthropogenic nitrate aerosols, indirect radiative forcing, as well as its climatic effect over China. TACM includes the thermodynamic equilibrium model ISORROPIA and a condensed gas-phase chemistry model. Investigations show that the concentration of nitrate aerosols is relatively high over North and East China with a maximum of 29 μg m^-3 in January and 8 μg m^-3 in July. Due to the influence of air temperature on thermodynamic equilibrium, wet scavenging of precipitation and the monsoon climate, there are obvious seasonal differences in nitrate concentrations. The average indirect radiative forcing at the tropopause due to nitrate aerosols is -1.63 W m^-2 in January and -2.65 W m^-2 in July, respectively. In some areas, indirect radiative forcing reaches $-$10 W m^-2. Sensitivity tests show that nitrate aerosols make the surface air temperature drop and the precipitation reduce on the national level. The mean changes in surface air temperature and precipitation are -0.13 K and -0.01 mm d^-1 in January and -0.09 K and -0.11 mm d^-1 in July, respectively, showing significant differences in different regions.     

乌鲁木齐降水化学成分及来源分析

降水是大气中主要和次要污染物的重要收集器,是清除大气中颗粒物和气态污染物最好的清除剂。为了了解乌鲁木齐降水特征,本文利用离子色谱分析了2010年降水样品,研究表明,该区降水pH值在5.6~7.77之间,年均值为6.19,电导率变化范围为18.7~172.5μs·cm~(-1),年均值为57.73μs·cm~(-1)。降水中主要离子浓度排序为Ca~(2+)SO_4~(2-)NH_4~+Na~+Mg~(2+)Cl~-NO_3~-K~+F~-,Ca~(2+)是最主要的阳离子,SO2-4是最主要的阴离子,表明乌鲁木齐降水中的致酸物质主要是硫酸盐。总离子浓度季节变化特征表现为秋季高,冬季低。FA平均值为0.001,表明99.9%的降水酸度被碱性成分中和,NF计算结果表明Ca~(2+)具有很强的中和能力。从相关分析、富集因子来看,SO_4~(2-)和NO_3~-主要受人为源的控制,K+主要存在于土壤扬尘或生物质燃烧产生的细颗粒物中;Mg~(2+)主要来自陆源的土壤扬尘等;Cl~-主要来自海相输入,生物质燃烧、人类生活污水排放以及化工厂排放对Cl-也有很大贡献。     

低温弱光对设施番茄苗期营养物质和干物质分配的影响

本试验以PAR （光合有效辐射）800 μmol·m^-2·s^-1，温度25℃为对照（CK），设置6个处理[L1T1（PAR 200 μmol·m^-2·s^-1，4℃）、L1T2（PAR 200 μmol·m^-2·s^-1，6℃）、L1T3（PAR 200 μmol·m^-2·s^-1，8℃）、L2T1（PAR 400 μmol·m^-2·s^-1，4℃）、L2T2（PAR 400 μmol·m^-2·s^-1，6℃）和L2T3（PAR 400 μmol·m^-2·s^-1，8℃）]，分别处理6、12、24、48和72 h，以研究低温弱光双重胁迫对番茄苗期干物质分配以及不同器官的可溶性糖、可溶性蛋白和游离氨基酸含量的影响.结果表明：低温弱光双重胁迫使地下部分干物质分配比例减小，而对地上部分干物质分配比例无显著影响，地下部分的干物质分配比例随时间的变化与地上部分相反；低温弱光胁迫显著降低了番茄茎和叶片的可溶性糖、可溶性蛋白和游离氨基酸的含量；根的可溶性糖含量随胁迫时间的变化趋势与地上部分不一致，但根、茎、叶片的可溶性糖含量均以L2T3处理72 h含量最高，分别为94.88、77.09和41.62 mg·g^-1；根的可溶性蛋白含量随胁迫时间的变化趋势与地上部分不一致，茎和叶片的可溶性蛋白含量均以L2T3处理12 h最高，以L1T1处理72 h最低；不同器官的游离氨基酸含量随胁迫时间的变化趋势与可溶性蛋白相反；弱光对番茄干物质和营养物质含量的影响小于低温.研究证实苗期番茄在低温弱光胁迫前期，干物质和营养物质先向地上部分分配，胁迫24 h后则更多地向根系积累.     

伊宁市降水化学成分及来源分析

降水是大气中主要和次要污染物的重要收集器,是大气中颗粒物和气态污染物最好的清除剂。本文利用离子色谱分析了2011年伊宁市90个降水样品,结果表明,该区降水pH月均值在5.27—7.1之间,年均值为6.26,电导率变化范围为34.64~63μs·cm~(-1),年均值为45.7μs·cm~(-1)。降水中主要离子浓度排序为Ca~(2+)SO_4~(2-)NH_4~+Mg~(2+)Cl~-NO_3~-Na~+F~-K~+,Ca~(2+)是最主要的阳离子,年均值为421.76μeq·L~(-1),SO_4~(2-)是最主要的阴离子,年均值为149.09μeq·L~(-1),表明伊宁降水中的致酸物质主要是硫酸盐。总离子浓度季节变化特征表现为春夏季高,秋冬季低,总离子浓度明显低于乌鲁木齐和沈阳,与北京类似,远高于杭州、广州,表明伊宁降水污染比北方城市轻,但是陆源贡献远大于南方城市。FA平均值为0.003,表明99.7%的降水酸度被碱性成分中和,NF计算结果表明Ca~(2+)的中和能力最强,其次是NH_4~+。从相关分析和因子分析来看,F~-、SO_4~(2-)、NO_3~-、Cl~-、NH_4~+主要受人为源的控制,Ca~(2+)、K~+主要来源于土壤和浮尘,Na~+、Mg~(2+)主要来源为土壤盐碱化、风化、干旱浮尘等自然源。     

OH in the tropical upper troposphere and its relationships to solar radiation and reactive nitrogen

In situ measurements of [OH], [HO₂] (square brackets denote species concentrations), and other chemical species were made in the tropical upper troposphere (TUT). [OH] showed a robust correlation with solar zenith angle. Beyond this dependence, however, [OH] did not correlate to its primary source, the product of [O₃] and [H₂O] ([O₃]?[H₂O]), or its sink [NO_y]. This suggests that [OH] is heavily buffered in the TUT. One important exception to this result is found in regions with very low [O₃], [NO], and [NO_y]. Under these conditions, [OH] is highly suppressed, pointing to the critical role of NO in sustaining OH in the TUT and the possibility of low [OH] over the western Pacific warm pool due to strong marine convections bringing NO-poor air to the TUT. In contrast to [OH], [HO_x] ([OH] + [HO₂]) correlated reasonably well with [O₃]?[H₂O]/[NO_y], suggesting that [O₃]?[H₂O] and [NO_y] are the significant source and sink, respectively, of [HO_x].     

Atmospheric chemistry of the monoterpene reaction products nopinone,camphenilone, and 4-acetyl-1-methylcyclohexene

Rate constants for the gas-phase reactions of OH radicals with nopinone (6,6-dimethylbicyclo[3.1.1]heptan-2-one) and camphenilone (3,3-dimethylbicyclo[2.2.1]heptan-2-one) and for the reactions of 4-acetyl-1-methylcyclohexene with OH and NO₃ radicals and O₃ have been measured at 296±2 K. The rate constants (cm³ molecule^–1 s^–1 units) obtained were, for reaction with the OH radical: nopinone, (1.43±0.37)×10^–11; camphenilone, (5.15±1.44)×10^–12; and 4-acetyl-1-methylcyclohexene, (1.29±0.33)×10^–10; for reaction with the NO₃ radical: 4-acetyl-1-methylcyclohexene, (1.05±0.38)×10^–11; and for reaction with O₃: 4-acetyl-1-methylcyclohexene, (1.50±0.53)×10^–16. These data are used to calculate the tropospheric lifetimes of these monoterpene atmospheric reaction products.     

Determination of the Tropospheric Hydroxyl Radical by Liquidphase Scrubbing and HPLC: Preliminary Results

A preliminary study was carried out toexamine the feasibility of measuring tropospherichydroxyl radicals (OH) by liquidphase scrubbing andhigh performance liquid chromatography (HPLC). Thepotential advantages of this approach are itssimplicity, portability, and low expense. Thesampling system employs glass bubblers to trapatmospheric OH into a buffered solution of salicylicacid (o-hydroxybenzoic acid, OHBA). Rapidreaction of OH with OHBA produces a stable fluorescentproduct, 2,5-dihydroxybenzoic acid (2,5-DHBA), whichis determined by reverse-phase HPLC and fluorescencedetection. Our preliminary field results indicatethat this method is most suitable for OH measurementsin clean tropospheric air, where interferences fromother atmospheric species appear to be negligible orminor relative to polluted air. In clean air, thesampling period is about 45–90 minutes, which yieldsa detection limit of approximately 3–6 ×10⁵ radicalscm^-3. During an OHintercomparison experiment at the Caribou samplingsite in Colorado, our liquidphase scrubber method wascompared with the ion-assisted mass spectrometry (MS)method. Our results were within the same range asthose of the ion-assisted MS method (1–5 ×10⁶ radicals cm^-3) within our precision atthat time (about ±30–50%). Preliminary testsin Pullman, WA indicated that the method might alsofunction in moderately polluted air by acidifying thescrubbing solution or by adding a scavenger tosuppress interferences. In Pullman, mid-day OHconcentrations were usually in the range of 2–20 ×10⁶ radicals cm^-3. Nighttime OHconcentrations were always low, either at or slightlyabove the detection limit.     

Simulation Chamber Studies of the Atmospheric Oxidation of 2-Methyl-3-Buten-2-ol: Reaction with Hydroxyl Radicals and Ozone Under a Variety of Conditions

This article presents a complete study of the diurnal chemical reactivity of the biogenic volatile organic compound (BVOC), 2-methyl-3-buten-2-ol (MBO) in the troposphere. Reactions of MBO with OH and with ozone were studied to analyse the respective parts of both processes in the global budget of MBO atmospheric reactivity. They were investigated under controlled conditions for pressure (atmospheric pressure) and temperature (298 ± 2 K) using three complementary European simulation chambers. Reaction with OH radicals was studied in the presence of and in the absence of NO _x . The kinetic study was carried out by relative rate study using isoprene as a reference. The rate constant found for this reaction was molecule⁻¹ cm³ s⁻¹. FTIR spectroscopy, DNPH- and PFBHA-derivatisation analyses were performed for reactions with both OH radicals and ozone. In both reactions, the hydroxycarbonyl compound, 2-hydroxy-2-methylpropanal (HMPr) was positively identified and quantified, with a yield of in the reaction with OH, and a yield of and 0.84 ± 0.08 in the reaction with ozone under dry (HR < 1%) and humid conditions (HR = 20%–30%). A primary production of two other carbonyl compounds, acetone , and formaldehyde was found in the case of the dry ozonolysis experiments. Under humid conditions, only formaldehyde was co-produced with HMPr as a primary carbonyl compound, with a yield of . For the reaction with OH, three other carbonyl compounds were detected, acetone , formaldehyde and glycolaldehyde . In addition some realistic photo-oxidation experiments were performed to understand in an overall way the transformations of MBO in the atmosphere. The realistic photo-oxidation experiments were conducted in the EUPHORE outdoor simulation chamber. It was found that this compound is a weak secondary aerosol producer (less than 1% of the carbon balance). But it was confirmed that it is a potentially significant source of acetone, Δ[Acetone]/Δ[MBO] = 0.45. With our experimental conditions ([MBO]₀ = 200 ppb, [NO]o = 50 ppb), an ozone yield of Δ[O₃]/Δ[MBO] = 1.05 was found.     

Theoretical studies on OH and Cl initiated hydrogen atom abstraction of HFE-227pc (CF3OCF2CHF2)

The kinetics of hydrogen atom abstraction reactions of HFE-227pc by OH and Cl was studied by ab initio method. The structural optimization and frequency calculation of the titled compound and the species formed during the abstraction reactions were performed with density functional theory using hybrid meta density functional MPWB1K with 6–31?+?G(d,p) basis set. The energy of the species was further refined by making a single point energy calculation at G3B3 level of theory. The standard enthalpies of formation of reactant and the radical formed after H-atom abstraction was calculated using isodesmic method. The rate constants of abstraction reactions were calculated using Conventional Transition State Theory (CTST) and were found to be 1.5?×?10^?15 and 0.53?×?10^?16 cm³molecule^?1 s^?1 for OH and Cl respectively. The calculated value for the abstraction by OH is close to the experimental value of 2.26?×?10^?15 cm³molecule^?1 s^?1 whereas the same for Cl is found to be about five times lower than that of 2.70?×?10^?16 cm³molecule^?1 s^?1. The theoretical studies yielded the enthalpies of formation and the rate constants that are vital in determining the lifetime of HFE-227pc.     

Oxidation of sulphur compounds in the atmosphere: I. Rate constants of OH radical reactions with sulphur dioxide,hydrogen sulphide,aliphatic thiols and thiophenol

The reactions of OH radicals with SO₂, H₂S, thiophenol, and a series of aliphatic thiols (1–5 C-atoms) have been investigated in 201 and 381 reaction chambers at 1 atm total pressure and 300 K using a competitive kinetic technique. Initially, OH radicals were produced by photolysis of CH₃ONO/NO mixtures in air. Applying this OH source rate constants for OH with SO₂, H₂S, and thiophenol in synthetic air were determined to be (1.1±0.2)×10^-12, (5.5±0.8)×10^-12 and (1.1±0.2)×10^-11 cm³ s^-1, respectively. However, when this method was applied to the aliphatic thiols the rate constants obtained were found to be dependent on the partial pressures of O₂ and NO. These effects have been attributed to the built-up of a radical species, not yet identified, which leads to uncontrolled chain reactions in the system. Using the photolysis of H₂O₂ at wavelengths greater than 260 nm as the OH source in 1 atm N₂, rate constants for the 1–5 aliphatic thiols in the range 2.9 to 5.6×10^-11 cm³ s^-1 were obtained. The rate constants obtained in the present study are compared with recent literature values.     

The acid catalyzed nitration of methanol: formation of methyl nitrate via aerosol chemistry

The aqueous phase acid-catalyzed reaction of methanol (CH₃OH) with nitric acid (HNO₃) to yield methyl nitrate (CH₃ONO₂) under atmospheric conditions has been investigated using gas-phase infrared spectroscopy. Reactions were conducted in aqueous sulfuric acid solutions (50.5–63.6 wt.%) with [CH₃OH] = 0.00005–0.005 M and [HNO₃] = 0.02–0.21 M, at 278.2–328.6 K. Methyl nitrate production rates increased linearly with CH₃OH and HNO₃ concentrations and exponentially with sulfuric acid weight percent within the regime studied. Rates increased linearly with nitronium ion concentration, indicating that the reaction involves as the nitrating agent under these conditions. At 298 K, the rate of methyl nitrate production can be calculated from k _obs [CH₃OH][HNO₃], where k _obs  = 2.337 × 10⁻¹³(exp(0.3198*wt.% H₂SO₄)) when the solubility of CH₃ONO₂ in acidic solution is approximated by H* for pure water. The temperature dependence of the rate coefficient is related to solution composition, with activation energies of 59 and 49 kJ/mol at 51.1 and 63.6 wt.% H₂SO₄, respectively, when k is calculated from rate. The temperature dependence has also been parameterized for application to the atmosphere, but the small quantities of present in aerosol particles will result in methyl nitrate production rates too small to be of significance under most atmospheric conditions. An erratum to this article can be found at     

Gas phase reactions of alkyl nitrates with hydroxyl radicals under tropospheric conditions in comparison with photolysis

Rate constants for the reaction of OH radicals with some branched alkyl nitrates have been measured applying a competitive technique. Methyl nitrite photolysis in synthetic air was used as OH radical source at 295±2 K and 1000 mbar total pressure. Using a rate constant of 2.53×10^-12 cm³ s^-1 for the reaction of OH radicals with n-butane as reference, the following rate constants were obtained (units: 10^-12 cm³ s^-1): isopropyl nitrate, 0.59±0.22; isobutyl nitrate, 1.63±0.20; 3-methyl-2-butyl nitrate, 1.95±0.15; 2-methyl-1-butyl nitrate, 2.50±0.15; 3-methyl-1-butyl nitrate, 2.55±0.35. These values have been combined with the literature data to recalculate the substituent factors F(X) for the different nitrate groups which can be used to predict OH rate constants for organic nitrates for which experimental data are not available.Preliminary measurements of the photolysis frequency of isopropyl nitrate have shown that for this nitrate as a model substance, OH reactions and direct photolysis are of equal importance under tropospheric conditions.     

Measurement and calculation of OH reactivity at a United Kingdom coastal site

Measurements of OH reactivity were made at the Weybourne Atmospheric Observatory on the North Norfolk coast, UK in May 2004. A wide range of supporting species was also measured concurrently as part of the TORCH-2 field campaign, allowing a detailed study of the OH oxidation chemistry to be carried out. Measurements were made in a variety of air masses, with the 3 most prevalent being air from the Atlantic that arrived at the site from over mainland UK in a South Westerly direction, and much cleaner Northerly air that originated over the far North Sea or Arctic, passed over the North Sea and arrived at the site from a North/North Easterly direction. Direct OH reactivity measurements were made on 6 days during the campaign and with influence of 2 of the 3 air masses prevalent during the study period. The average, minimum and maximum measured OH reactivity are: 4.9, 1.3 and 9.7 respectively. The measured OH reactivity was compared to key OH sinks such as NO₂ and CO and a general positive correlation was observed. OH reactivity (k′) was then calculated using the full range of OH sinks species that were measured (including >30 NMHCs) and their pseudo first order rate constants for reaction with OH. For much of the measurement period there is a significant difference between the measured and calculated k′, with an average value of k′_meas- k′_calc?=?1.9 s^-1, indicative of unmeasured OH sinks. A zero-dimensional box model containing a subset of the Master Chemical Mechanism was used to calculate the OH reactivity more accurately. The simultaneously measured trace species were used as inputs to the model and their oxidative degradation was described by a chemical mechanism containing ~5,000 species. The extra OH sinks species produced by the model, resulted in an improvement in the agreement between k′_meas and k′_calc, however the averaged missing OH reactivity across the entire measurement period remained at 1.4 s^-1. Speculation is made as to the source of this missing reactivity, including reference to studies showing that a potentially large number of high molecular weight aromatic species could be unmeasured by standard instrumentation.     

Kinetics and Products of the Gas-Phase Reaction of OH Radicals with 5-Hydroxy-2-Pentanone at 296± 2 K

The 1,4-hydroxycarbonyl 5-hydroxy-2-pentanone is an important product of the gas-phase reaction of OH radicals with n-pentane in the presence of NO. We have used a relative rate method with 4-methyl-2-pentanone as the reference compound to measure the rate constant for the reaction of OH radicals with 5-hydroxy-2-pentanone at 296 ± 2 K. The carbonyls were sampled by on-fiber derivatization using a Solid Phase Micro Extraction (SPME) fiber coated with O> -(2,3,4,5,6-pentafluorobenzyl)hydroxylamine hydrochloride with subsequent thermal desorption of the oxime derivatives and quantification by gas chromatography with flame ionization detection. For comparison, the reference compound was also analyzed following sample collection onto a Tenax adsorbent cartridge. Products of the reaction were investigated using coated-fiber SPME sampling with gas chromatography-mass spectrometry analysis as well as by using in situ atmospheric pressure ionization mass spectrometry. A rate constant for the reaction of OH radicals with 5-hydroxy-2-pentanone of (1.6 ± 0.4) × 10^–11 cm³ molecule^–1 s^–1 was obtained at 296 ± 2 K. Two dicarbonyl products, of molecular weight 86 and 100, were observed and are attributed to CH₃C(O)CH₂CHO and CH₃C(O)CH₂CH₂CHO, respectively. Reaction schemes leading to these products are presented.