2007和2008年夏季北京奥运馆大气PM10与PM2.5质量浓度变化特征

为了监测北京奥运主场馆附近大气颗粒物的污染状况以及评估奥运污染源减排措施对北京大气颗粒物质量浓度变化的影响,利用颗粒物在线监测仪器TEOM于2007年和2008年夏季,在奥运主场馆附近的中国科学院遥感应用研究所办公楼楼顶对大气颗粒物PM₁₀和PM_2.5进行了连续同步观测。结果表明,2007年夏季监测点附近大气PM₁₀与PM_2.5质量浓度的平均值分别为153.9和71.2μg·m^-3,而2008年夏季PM₁₀与PM_2.5质量浓度的平均值分别为85.2和52.8μg·m^-3。与奥运前一年同时段相比,奥运时段大气PM₁₀和PM_2.5的质量浓度分别下降44.5%和25.1%。对比分析奥运前后的2次典型污染过程发现,空气相对湿度的增加和偏南气流输送的共同影响易造成大气颗粒物的累积增长,而降雨的湿清除作用和偏北气流则会使大气颗粒物浓度迅速降低。在相近的气象条件下,奥运前后的污染过程中,大气细粒子的日均增长速率分别为25.1和13.9μg·m^-3·d^-1,而大气粗粒子的日均增长速率分别为20.8和2.2μg·m^-3·d^-1,奥运时段污染累积过程中大气粗、细粒子的增长速率分别显著低于和略低于奥运前同时段污染过程中颗粒物的增长速率。污染源减排措施的实施是奥运期间大气颗粒物质量浓度降低的主要原因,从控制效果来看,奥运期间实施的污染源减排措施对大气粗粒子的控制效果明显好于大气细粒子。     

三亚地区冬春季大气污染特征观测研究

为了研究海南省三亚地区冬春季大气污染状况,于2011年12月—2013年4月的冬春季节在三亚鹿回头村(监测点位于三亚市郊,三面临海,周围没有工业污染源)开展了大气主要污染物(NO_x、O₃、PM_2.5)的连续监测,利用观测数据对三亚地区冬春季大气污染变化特征进行分析.结果表明:三亚地区大气污染物浓度均低于国家一级标准的浓度值,NO、NO₂、NO_x、O₃、PM_2.5质量浓度的日平均值(平均值±标准差)分别为(2.1±2.2)、(5.2±3.4)、(7.3±3.8)、(59.8±28.4)和(17.5±14.3)μg·m^-3.在污染物的日变化方面,NO_x、PM_2.5呈现典型的双峰型,其峰值分别出现在08:00和17:00,峰谷在13:00;O₃的日变化为单峰型,峰值出现在13:00.通过后向轨迹分析发现,三亚地区大气污染物受局地源排放和外源输送的共同影响,来自陆地的气流易造成污染物的积累,而来自海上的气流则有利于污染物的清除.     

青岛市秋冬季霾期PM1及其含碳组分理化特征及来源研究

对2017年11月1日—2018年1月31日与2018年11月1日—2019年1月31日连续两年青岛市大气PM₁进行监测,获取了PM₁中含碳组分的变化趋势,结合国控站点监测数据和气象条件,分析了秋冬季PM₁来源.结果表明：2017、2018年秋冬季观测期间PM₁日均质量浓度分别为40.58±25.98、42.55±25.05 μg/m³;霾日质量浓度分别为84.71±16.70、81.52±18.39 μg/m³.与2017年相比,2018年同期PM₁质量浓度增长4.85%,霾日下降3.76%.2017年霾日PM₁中OC、EC质量浓度分别为13.67±3.95、3.95±1.02 μg/m³,2018年分别为16.48±6.34、3.34±1.16 μg/m³.与2017年相比,2018年霾日OC质量浓度增长20.56%,EC下降15.44%.2017、2018年霾日SOC质量浓度分别是非霾日的1.28和2.15倍,表明霾污染发生时易发生有机碳二次转化.含碳组分主成分分析均解析出3个因子.因子1解释变量均最大,分别为58.98%、67.14%,其表征含碳组分主要源于生物质燃烧、燃煤、道路扬尘及汽油车尾气等排放源.由后向气流轨迹分析得出,2017、2018年秋冬季气团轨迹多起源于内蒙古,经河北、天津、山东等省市抵达青岛.     

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.     

2014—2019年北京和南京地区PM2.5和臭氧质量浓度相关性研究

自2014年以来,中国细颗粒物（PM_2.5）浓度大幅度下降,但臭氧（O₃）浓度逐年缓慢上升,厘清PM_2.5和O₃（P-O）相关性尤为关键.在本研究中,2014—2019年北京和南京PM_2.5年均质量浓度下降幅度分别为-6.86和-6.15 μg·m^-3·a^-1;而日最大8小时平均O₃质量浓度（MDA8 O₃）年均增长幅度为1.50和1.75 μg·m^-3·a^-1.研究期间,北京地区MDA8 O₃质量浓度小于100 μg·m^-3,P-O呈负相关;而当质量浓度大于100 μg·m^-3时,P-O为正相关.通过Pearson相关系数研究P-O两者相关性.在两个城市每月相关性分析中,在每日时间尺度5—9月为强的正相关;而小时时间尺度11月至次年2月趋于负相关.在北京,P-O每月和季节相关性变化大于南京.在日变化中,夏季在16时为强的正相关,春秋两季在13—17时为弱的正相关,而在春、秋和冬季8时,却为强的负相关.     

武汉市冬季灰霾期PM2.5中水溶性无机离子的特征

2018年1月,利用颗粒物采样器采集武汉市大气PM_2.5样品并进行水溶性无机离子（F^-、Cl^-、NO₃^-、SO₄^2-、Na⁺、NH₄⁺、K⁺、Mg²⁺、Ca²⁺）的分析.结果表明,NO₃^-、SO₄^2-、NH₄⁺是PM_2.5中最主要的3种水溶性无机离子,除Mg²⁺与Ca²⁺外,PM_2.5与WSⅡs （水溶性无机离子）之间的相关性显著,且移动源贡献占主导地位.阴阳离子平衡表明武汉市冬季灰霾期PM_2.5呈中性或弱酸性.通过混合单粒子拉格朗日综合轨迹模式模拟并采用分层聚类得出了4种主要的后向气流轨迹及相应的PM_2.5和水溶性离子浓度,结果表明区域传输对此次灰霾期影响较大.     

武汉大气能见度与PM2.5浓度及相对湿度关系的非线性分析及能见度预报

武汉作为中部地区高湿度代表城市,大气污染严重,霾天气多发,但有关该地区大气能见度与PM_2.5浓度及相对湿度(RH)的定量关系尚不明确。利用2014年9月—2015年3月武汉地区逐时能见度、相对湿度及颗粒物质量浓度观测数据,研究分析了武汉大气能见度与PM_2.5浓度及相对湿度的关系,并进行能见度非线性预报初探,得到以下结论:武汉霾时数发生比例高,霾的发生和加重是能见度降低的主要原因;能见度降低伴随大量细粒子产生和累积,这是武汉大气能见度恶化的重要诱因。细颗粒物浓度与相对湿度共同影响和制约大气能见度变化,高湿高浓度时能见度显著下降,湿情景下(RH≥40%),能见度恶化主要是由湿度增高诱使细颗粒物粒径吸湿增长导致其散射效率增大造成的。当RH >90%时,能见度随湿度升高成线性递减,相对湿度每升高1%,武汉平均能见度降低0.568 km。而干情景下(RH<40%),能见度迅速降低的关键因素是PM_2.5质量浓度升高。在城市大气细粒子污染背景下,能见度与相对湿度成非线性关系,这主要与PM_2.5对能见度的影响及吸湿性颗粒物的散射效率变化有关。PM_2.5浓度与能见度成幂函数非线性关系,80%≤RH<90%湿度区段下相关性最强。PM_2.5浓度对能见度的影响敏感阈值是随着湿度升高而减小的,干情景下能见度10 km对应的PM_2.5浓度阈值为70 μg/m³,湿情景下该阈值为18—55 μg/m³。当PM_2.5质量浓度低于约40 μg/m³时,继续降低PM_2.5可显著提高武汉大气能见度。预报试验表明,基于神经网络方法建立大气能见度非线性预报模型是可行的,预报能见度相关系数为0.86,均方根误差为1.9 km,能见度≤10 km的TS评分为0.92。网络模型具有较高预报性能,对霾的判别有较高准确性,为衔接区域环境气象数值预报模式,建立大气能见度精细化动力统计模型提供参考依据。     

苏南三市秋冬季PM2.5中水溶性离子和元素特征及源解析

2010年11月16日至12月17日在南京、常州、苏州三城市设置采样点,24 h采集大气PM_2.5样品,并测定其水溶性无机离子和元素的浓度,在此基础上讨论PM_2.5及无机组分的时空分布特征。结果表明,采样期间,PM_2.5污染较严重,且苏州最重,常州次之,南京最轻,南京、苏州、常州日均浓度分别是国家二级标准(75 μg/m³)的1.44、2.32、1.53倍;三市PM_2.5离子组分中,阴离子均以SO₄^2-和NO₃^-为主,阳离子以Ca²⁺和Mg²⁺为主;苏州Na⁺和Cl^-之间的相关性较高,其受到海盐输送影响较大;三城市PM_2.5中Ca是最主要元素,Al次之。运用主成分法分析南京、常州和苏州PM_2.5的来源可知,三城市PM_2.5受多个污染源影响,包括生物质燃烧、地表扬尘、五金工业及汽车尾气排放等。     

南京北郊2011年春季气溶胶粒子的散射特征

利用南京北郊2011年春季积分浊度仪的观测资料,结合PM_2.5质量浓度、能见度和常规气象资料,分析了南京北郊春季气溶胶散射系数的变化特征、散射系数与PM_2.5质量浓度和能见度的关系。结果表明,观测期间气溶胶散射系数平均值为311.5±173.3 Mm^-1,小时平均值出现频率最高的区间为100~200 Mm^-1;散射系数的日变化特征明显,总体为早晚大,中午及午后小。散射系数与PM_2.5质量浓度的变化趋势基本一致,但与能见度呈负相关关系。霾天气期间散射系数日平均值为700.5±341.4 Mm^-1,最高值达到近1 900 Mm^-1;结合地面观测资料、NCEP/NCAR再分析资料和后向轨迹模式分析显示,霾期间气块主要来自南京南部和东南方向。     

城市下垫面影响空气污染的机制分析

本文采用RBLM-chem模式,利用杭州市高分辨率城市建筑等资料,定量分析城市动力效应、热力效应以及城市植被、人为热对SO₂、NO₂、O₃、PM_2.5等主要污染物浓度的影响。结果表明,城市化过程使得大部分城区温度上升约1℃,相对湿度下降约6%,风速下降约0.8 m·s^-1,湍流动能增强约0.03 m²·s^-2。城市动力效应主要通过降低城市风速,使得城区污染物浓度升高,SO₂浓度有近5 μg·m^-3的上升,PM_2.5、O₃浓度也有近15 μg·m^-3的上升。城市热力效应主要通过热岛环流使城区污染物向上输送,令地面污染物浓度降低,在城市大部分区域PM_2.5都有大约10 μg·m^-3的浓度下降。城市动力效应大于热力效应,城市的总体作用是使污染物浓度升高。城市下垫面使污染物浓度上升的另外一个机制是代替了自然有植被的下垫面,使污染物干沉降速度下降,但这一作用小于动力学效应。另一方面,人为热对城市主要污染物浓度都起着减小的作用,其中SO₂、NO₂、O₃、PM_2.5浓度降幅分别在2.5、3.0、6.0、10.0 μg·m^-3左右。城市植被可以显著增加污染物干沉降速度,使主要污染物SO₂、NO₂、O₃和PM_2.5的干沉降速度分别上升0.1、0.1、0.03、0.06 m·s^-1左右,相应地使上述污染物浓度分别下降2.5、6.0、4.0、6.0 μg·m^-3左右。     

Products and mechanisms of the gas phase reactions of NO3 with CH3SCH3, CD3SCD3, CH3SH and CH3SSCH3

Products and mechanisms of the reaction between the nitrate radical (NO₃) and three of the most abundant reduced organic sulphur compounds in the atmosphere (CH₃SCH₃, CH₃SH and CH₃SSCH₃), have been studied in a 480 L reaction chamber using in situ FT-IR and ion chromatography as analytical techniques. In the three reactions, methanesulphonic acid was found to be the most abundant sulphur containing product. In addition the stable products SO₂, H₂SO₄, CH₂O, and CH₃ONO₂ were identified and quantified and thionitric acid-S-methyl ester (CH₃SNO₂) was observed in the i.r. spectrum from all of the three reactions. Deuterated dimethylsulphide (CD₃SCD₃) showed an isotope effect on the reaction Deuterated dimethylsulphide (CD₃SCD₃) showed an isotope effect on the reaction rate constant (k_H/k_D) of 3.8±0.6, indicating that hydrogen abstraction is the first step in the NO₃+CH₃SCH₃ reaction, probably after the formation of an inital adduct.Based on the products and intermediates identified, reaction mechanisms are proposed for the three reactions.     

Aqueous Phase Reaction of HNO4: The Impact on Tropospheric Chemistry

We use a global atmospheric chemistry transport model to study the possible influence of aqueous phase reactions of peroxynitric acid (HNO₄) on the concentrations and budgets of NO_x, SO_x, O₃ and H₂O₂. Laboratory studies have shown that the aqueous reaction of HNO_4aq withHSO^– _3aq, and the uni-molecular decomposition of the NO₄ ^– anion to form NO₂ ^– (nitrite) occur on a time scale of about a second. Despite a substantial contribution of the reaction of HSO^– _3aq with HNO_4aq to the overall in-cloud conversion of SO₂ to SO₄ ^2–, a simultaneous decrease of other oxidants (most notably H₂O₂) more than compensated the increase in SO₄ ^2– production. The strongest influence of heterogeneous HNO₄ chemistry was found in the boundary layer, where calculated monthly average ozone concentrations were reduced between 2% to 10% andchanges of H₂O₂ between –20% to +10%compared to a simulation which ignores this reaction. Furthermore, SO₂ was increased by 10% to 20% and SO₄ ^2–depleted by up to 10%. Since the resolution of our global model does not enable a detailed comparison with measurements in polluted regions, it is not possible to verify whether considering heterogeneous HNO₄ reactions results in a substantial improvement of atmospheric chemistry transport models. However, the conversion of HNO₄ in the aqueous phase seems to be efficient enough to warrant further laboratory investigations and more detailed model studies on this topic.     

闪电产生氮氧化物对青藏高原臭氧低谷形成的影响

为了进一步了解青藏高原闪电的产生氮氧化物（LNO_x）经由光化学反应对O₃浓度变化及夏季O₃低谷形成的可能影响,本文利用2005~2013年由OMI卫星得到的对流层NO₂垂直浓度柱（NO₂ VCD）、O₃总浓度柱（TOC）和O₃廓线以及星载光学瞬变探测器OTD和闪电成像仪LIS获取的总闪电数资料,对青藏高原和同纬度长江中下游地区的TOC和NO₂ VCD月均值时空分布特征、闪电与NO₂ VCD的相关性和O₃的垂直分布特征及其与LNO_x的关系进行了对比分析。结果表明,青藏高原的O₃低谷主要出现在夏季和秋季,其TOC值比同纬度长江中下游地区低约10~15 DU（Dobson unit）。青藏高原NO₂VCD总体较小,表现为夏高冬低的分布特征。青藏高原夏季O₃浓度受南亚高压的影响总体呈减小趋势,但因强雷暴天气导致对流层中上部LNO_x浓度升高,并随强上升气流向对流层顶输送,同时通过光化学反应使O₃浓度增加,缩小了青藏高原和同纬度地区的O₃浓度差,减缓了O₃总浓度的下降,抑制了夏季O₃低谷的进一步深化。     

The solubility of SO2 and the dissociation of H2SO3 in NaCl solutions

The pK ₁ ^* and pK ₂ ^* of H₂SO₃ have been determined in NaCl solutions as a function of ionic strength (0.1 to 6 m) and temperature (5 and 25 °C). The extrapolated values in water were found to be in good agreement with literature data. The experimental results have been used to determine the Pitzer interaction parameters for SO₂, HSO ₃ ^- and SO ₃ ^- in NaCl solutions. The resultant parameters for NaHSO₃ and Na₂SO₃ were found to be in reasonable agreement with the values for NaHSO₄ and Na₂SO₄. It, thus, seems reasonable to assume that the interactions of Mg²⁺ and Ca²⁺ with HSO ₃ ^- and SO ₃ ^- can be estimated from the values with HSO ₄ ^- and SO ₄ ^- until experimental values are available. Measurements of pK ₁ ^* and pK ₂ ^* in artificial seawater were found to be in good agreement with the calculated values using the derived Pitzer parameters. It is, thus, possible to make reasonable estimates of the activity coefficients of HSO ₃ ^- and SO ₃ ^- ions and pK ₁ ^* and pK ₂ ^* for the ionization of H₂SO₃ in marine aerosols.     

武汉市源成分谱特征研究

通过采集武汉市土壤风沙尘、建筑水泥尘、城市扬尘、餐饮源、生物质燃烧源、工业煤烟尘和电厂煤烟尘等7类源样品,并分析其碳组分、水溶性离子组分和无机元素组分,建立PM₁₀和PM_2.5源成分谱.研究表明,地壳元素Si、Ca、Al以及Fe等是土壤风沙尘的主要特征组分,其中Si是含量最高的成分,也是土壤风沙尘的标识组分.无组织建筑水泥尘中Si和Ca元素含量较高,将Ca元素作为无组织建筑水泥尘区别其他源类的重要元素,而有组织建筑水泥尘中OC、SO₄^2-含量比无组织建筑水泥尘高.城市扬尘中Ca的含量相对较高,表明城市扬尘受到建筑水泥尘影响较多.生物质燃烧源成分谱中OC的含量远高于成分谱中其他组分,另外Cl^-和K的平均含量也较高,K一般为生物质源的特征元素.     

The heterogeneous formation of N2O in air containing NO2, O3 and NH3

In a nighttime system and under relatively dry conditions (about 15 ppm H₂O), the reaction mixture of NO₂, O₃, and NH₃ in purified air turns out to result in the formation of nitrous oxide (N₂O). The experiments were performed in a continuous stirred flow reactor, in the concentration region of 0.02–2 ppm.N₂O is thought to arise through the heterogeneous reaction of gaseous N₂O₅ and absorbed NH₃ at the wall of the reaction vessel % MathType!MTEF!2!1!+-% feaafeart1ev1aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn% hiov2DGi1BTfMBaeXatLxBI9gBaerbd9wDYLwzYbItLDharqqtubsr% 4rNCHbGeaGqiVu0Je9sqqrpepC0xbbL8F4rqaqpepeea0xe9qqVa0l% b9peea0lb9sq-JfrVkFHe9peea0dXdarVe0Fb9pgea0xa9pue9Fve9% Ffc8meGabaqaciGacaGaaeqabaWaaeaaeaaakeaatCvAUfKttLeary% qr1ngBPrgaiuaacqWFOaakcqWFobGtcqWFibasdaWgaaWcbaGae83m% amdabeaakiab-LcaPmaaBaaaleaacqWFHbqyaeqaaOGaey4kaSIaai% ikaiab-5eaonaaBaaaleaacqWFYaGmaeqaaOGae83ta80aaSbaaSqa% aiab-vda1aqabaGccaGGPaWaaSbaaSqaaiaadEgaaeqaaOGaeyOKH4% Qae8Nta40aaSbaaSqaaiab-jdaYaqabaGccqWFpbWtcqGHRaWkcqWF% ibascqWFobGtcqWFpbWtdaWgaaWcbaGae83mamdabeaakiabgUcaRi% ab-HeainaaBaaaleaacqWFYaGmaeqaaOGae83ta8eaaa!59AC!\[(NH_3 )_a + (N_2 O_5 )_g \to N_2 O + HNO_3 + H_2 O\]In principle, there is competition between this reaction and that of adsorbed H₂O with N₂O₅, resulting in the formation of HNO₃. At high water concentrations (RH>75%), no formation of N₂O was found. Although the rate constant of adsorbed NH₃ with gaseous N₂O₅ is much larger than that of the reaction of adsorbed H₂O with gaseous N₂O₅, the significance of the observed N₂O formation for the outside atmosphere is thought to be dependent on the adsorption properties of H₂O and NH₃ on a surface. A number of NH₃ and H₂O adsorption measurements on several materials are discussed.     

临安冬夏季SO2、NO2和O3体积分数特征及与气象条件的关系

对临安大气本底站2003-2004年冬、夏季二氧化氮(NO2)、二氧化硫(SO2)、臭氧(O3)进行了分析.结果表明:冬季NO2和SO2平均体积分数分别为19.48×10-9和35.74 x10-9,而夏季的平均体积分数分别为4.81×10-9和8.12×10-9,冬季高于夏季;O3在夏季的平均体积分数为33.55×10-9,略高于冬季的25.44×10-9;夜间NO2和SO2体积分数比白天高,并且NO2呈明显的单峰单谷型分布,O3也呈单峰型但峰值出现在白天.NO2、SO2体积分数存在着明显的“假日效应”,假日比非假日低,周五高于假日和非假日;但O3体积分数没有明显的假日效应.降水对SO2有明显的清除作用,但对NO2的清除作用不明显.与风向对比发现,夏季高体积分数的NO2、SO2都受到NW、WNW风的影响,冬季则分别受NE和SW、SSW风的影响;而O3受风向的影响较复杂,与局地光化学反应有关.     

Modified HNO3 seasonality in volcanic layers of a polar ice core: Snow-pack effect or photochemical perturbation?

Using the chemical composition of snow and ice of a central Greenland ice core, we have investigated changes in atmospheric HNO₃ chemistry following the large volcanic eruptions of Laki (1783), Tambora (1815) and Katmai (1912). The concentration of several cations and anions, including SO ₄ ^2– and NO ₃ ^– , were measured using ion chromatography. We found that following those eruptions, the ratio of the concentration of NO ₃ ^– deposited during winter to that deposited during summer was significantly higher than during nonvolcanic periods. Although we cannot rule out that this pattern originates from snow pack effects, we propose that increased concentrations of volcanic H₂SO₄ particles in the stratosphere may have favored condensation and removal of HNO₃ from the stratosphere during Arctic winter. In addition, this pattern might have been enhanced by slower formation of HNO₃ during summer, caused by direct consumption of OH through oxidation of volcanic SO₂.     

Measurement of the photodissociation coefficient of NO2 in the atmosphere: II,stratospheric measurements

The photodissociation coefficient of NO₂, J _{NO 2}, has been measured from a balloon platform in the stratosphere. Results from two balloon flights are reported. High Sun values of J _{NO 2} measured were 10.5±0.3 and 10.3±0.3×10^-3 s^-1 at 24 and 32 km respectively. The decrease in J _{NO 2} at sunset was monitored in both flights. The measurements are found to be in good agreement with calculations of J _{NO 2} using a simplified isotropic multiple scattering computer routine.     

Photochemistry of N2O4 Adsorbed on Ice Surfaces at 193 nm

A multi-layer deposited ice film was prepared through water vapor deposition on a Ni plate in a vacuum chamber at 90 K, and was used as it was or after annealing at 140 K. NO₂ was adsorbed as N₂O₄ approximately 90 K on the ice film prepared as above, and irradiated by 193 nm excimer laser light. The time-of-flight (TOF) spectra of the desorbed species, i.e., NO₂, NO, O₂ and O, were measured by a quadrupole mass spectrometer. The photochemical process obeyed an one-photon process. The relative yields of the products and their TOF spectra were dependent on the preparation condition of the ice film and also varied with the continuation of the laser irradiation. From the ice film annealed at 140 K, NO₂, NO and O₂ were desorbed with an approximate ratio of 1:1:0.01. From the non-annealed film, the relative yield of NO₂ was much smaller than that of NO. The TOF spectrum of NO from the non-annealed ice film consisted of distinctly different two components corresponding to the 1700 and 100 K translational temperature, respectively. The fast component was lost when additional ice was deposited on the adsorbed N₂O₄. NO was supposed to be a predissociation product from the electronically excited NO₂ prepared through the photodissociation of N₂O₄.