成都市冬季重污染过程中挥发性有机物污染特征及来源解析

采用大气挥发性有机物(VOCs)在线监测系统对成都市冬季重污染过程的VOCs进行了连续在线观测,用正交矩阵因子分解(PMF)模型开展了VOCs源解析工作,并对重污染成因进行了分析。结果表明:观测期间成都市总VOCs(TVOCs)体积分数为21.83×10~(-9)～183.59×10~(-9),平均值为54.17×10~(-9),TVOCs中烷烃浓度最高,其次为炔烃、烯烃、芳香烃和卤代烃;成都市主要VOCs污染源为机动车排放源、液化石油气燃烧排放源、工业源、生物质燃烧源和溶剂使用源,贡献率分别为34.15%、21.57%、19.08%、15.19%、10.02%;边界层压缩和静风条件可能是导致VOCs和PM2.5浓度增加的主要原因。     

基于二次有机气溶胶和臭氧生成潜势的河北挥发性有机物优控物种研究

为研究河北大气中挥发性有机物(VOCs)对臭氧(O₃)及二次有机气溶胶(SOA)生成的影响，利用2021年4—10月河北11个地市VOCs的监测数据，对河北VOCs污染特征及其关键活性组分进行分析研究。结果表明，观测期间河北VOCs平均体积分数为36.16×10^-9,低碳的醛酮类和低碳的烷烃是河北VOCs的主要构成物种。VOCs高值区主要集中在河北中南部沧州、衡水、邯郸、石家庄等地，北部城市秦皇岛、张家口VOCs浓度较低。监测期间，河北O₃生成潜势(OFP)为259.67μg/m³,SOA生成潜势为0.61μg/m³,其中衡水OFP最高，达302.96μg/m³,石家庄SOA生成潜势最高，达0.92μg/m³。甲苯、间/对二甲苯和邻二甲苯对OFP及SOA生成潜势的贡献均较大，是O₃和大气颗粒物协同控制的优控VOCs物种。     

北京与伦敦空气中气态污染物的比对研究

城市空气质量问题已经引起广泛关注.通过对中英2个大城市北京与伦敦 2004 年 8 月～2005 年12 月空气中气态污染物 O3、NOx、SO2 和 CO 浓度变化的分析与对比发现:参照世界卫生组织空气质最准则、欧盟空气质量标准、美国国家空气质量标准或国家空气质量二级标准,北京O3、NO2、SO2和 CO 浓度的超标天数或时数明显高于伦敦.观测期内,北京 O3、NOx、SO2 和 CO 浓度明显高于伦敦,平均值分别是 17.9±22.1×10-9、72.4±76.1×10-9、19.5±21.8×10-9、2 004.6±1 509.8×10-9与10.8±9.9×10-9、54,6±38.9×10-9、1.8±2.2×10-9、372.3±235.0×10-9.两城市 O3 统计日变化形式均表现为白天高、夜晚低,峰值出现在午后 14:00 左右,日较差分别为 31.5±30.9×10-9与 11.1±7.7×10-9;NO、NO2、SO2 和 CO 呈双峰态日变化,峰值出现在交通的早高峰与晚高峰附近.北京 O3 最高值出现在夏季,而伦敦出现在春季;但两城市NOx、SO2 和 CO 最高值均出现在冬季.北京与伦敦的NO2与 NO 呈显著线性相关,且斜率与截距十分相似,分别是 1.25 和 1.28 与 28.1 和 23.2;同时两城市 CO/NOx 比率明显高于 SO2/NO 分别为 14.0、4.5 与 0.13、0.03.由此可以判断:对于两城市空气污染问题,交通源的贡献要远大于点源;但点源也对两城市空气质量造成影响.此外,连续逆温的天气是造成重污染事件的原因.     

中山市大气挥发性有机物污染特征及来源解析

为深入了解中山市挥发性有机物(VOCs)来源及对臭氧的影响，基于2021年1—12月VOCs在线监测数据，对大气VOCs体积分数、组分特征、臭氧生成潜势(OFP)和来源情况进行了研究。结果表明：中山市大气VOCs体积分数日均值为2.61×10^-9～1.14×10^-7,年均值为2.18×10^-8,其中，烷烃是占比最大的组分，占60.0%,其次是芳香烃和烯烃，分别占25.9%和9.3%。除乙烯外，臭氧污染日前十物种体积分数较非污染日上升6%～49%。中山市OFP平均值为228.43μg/m³,其中，芳香烃和烯烃是贡献率较高的组分，间/对二甲苯、甲苯、邻二甲苯和异戊二烯等是关键活性物种。VOCs主要来源有机动车排放源、油气挥发源、工业源、燃烧源、溶剂使用源、天然源。溶剂使用源和工业源是OFP贡献率最高的污染源，贡献率分别为25.5%和24.0%,燃烧源、油气挥发源、天然源和机动车排放源贡献率分别为14.1%、13.3%、11.6%和11.5%。     

上海城郊大气挥发性有机物污染特征、活性组分及风险评估

为了解上海城郊大气中挥发性有机物(VOCs)的时空污染特征及其对人体潜在健康风险,选取上海某城郊10个点位进行连续6年(2012—2017年)的采样分析。结果表明,上海该城郊大气VOCs平均质量浓度为(243.80±151.52)μg/m3,其中烷烃、卤代烃、芳香烃、含氧VOCs和不饱和脂肪烃依次占VOCs总浓度的45.72%、20.04%、18.84%、11.19%、4.21%。上海郊区不同功能区VOCs总浓度年际变化趋势较为一致,总体呈下降趋势;在空间上,化工区主干道路附近的两采样点VOCs质量浓度最高,分别为307.81、340.97μg/m~3。O3生成潜势和等效丙烯浓度计算结果显示,芳香烃为上海城郊大气中最主要的活性物种,且关键活性组分为甲苯、间/对-二甲苯和异丁烷等。上海城郊大气中27种风险VOCs的总致癌风险值为3.02×10~(-4),高于可接受限值(1.00×10~(-4)),长期暴露可能有致癌风险。     

西安市PM2.5污染特征及其估测模型

为了研究大气中PM25污染特征以及其随时间变化规律,基于西安市2013年1月-2014年4月间SO2、NO2、CO、03、日最高温度(Tmax)、日最低温度(Tmin)、PM2.5、PM10等因素的监测数据.运用统计学原理和多元回归分析方法,分析了PM25的污染特征及相关因素对其产生的贡献度,进一步建立了四季的最优多元回归模型.研究结果表明,西安市年平均质量浓度124.9 μg/m3,四季的平均污染浓度从大到小依次为冬、春、秋、夏;春夏两季贡献较大的为SO2、CO;秋冬两季贡献较大的为NO2、CO;最终建立的模型的相关系数较高,模型很好地拟合了冬春两季PM2.5变化趋势,能较准确地反映了西安市PM2.5的污染特征,具有一定的理论和实用价值.     

山西省典型炼焦企业化产工段挥发性有机物排放特征及臭氧生成潜势

选取山西省某典型焦化企业化产工段的冷鼓工序、洗脱苯工序、脱硫工序、压滤车间4个工序,采样监测其挥发性有机物(VOCs)排放特征,并运用等效丙烯浓度法和最大增量反应活性(MIR)法综合评价其VOCs的化学反应活性和臭氧生成潜势。结果表明:(1)冷鼓工序、洗脱苯工序、脱硫工序、压滤车间4个工序共检测出32种VOCs,各工序的总VOCs分别为64 809.50、4 933.80、4 610.20、6 346.90μg/m~3。(2)4个工序检出的VOCs物种均以芳香烃和卤代烃为主,其中芳香烃以苯、甲苯、二甲苯为主,卤代烃以1,2-二氯乙烷为主。(3)芳香烃为4个工序中化学反应活性最大的污染物质,且各工序中1,2,4-三甲苯和1,3,5-三甲苯均有较高的化学反应活性和臭氧生成潜势。(4)在排放浓度和臭氧生成潜势方面,冷鼓工序的贡献均为最大,是化产工段需要进行VOCs治理的重点工序。     

微量NO2对氨氧化过程中产物的影响

在无O2条件下,氨氧化速率越高,氨氧化过程中产生的NO-2-N、NO-3-N浓度和氮损失越大;NO2为25×10-6 mg/L时氮损失率最大,约为20.93%.在相同浓度的O2条件下,氮损失与氨氧化速率相关,氨氧化速率增加时,氮损失增大.在O2的体积分数为2%时,50×10-6 mg/L NO2时的氮损失率最大,为27.57%;在O2的体积分数为21%时,100×10-6 mg/L NO2时的氮损失率最大,为34.19%.     

珠三角城市近地面臭氧污染分布特征及变化趋势

利用2013—2017年珠三角城市空气质量监测站的大气常规污染物逐时监测数据,探究珠三角区域臭氧(O3)污染年际变化、季节变化、日变化特征。结果表明,珠三角O3浓度秋季高冬春低,在一年之内呈现2月、5月、9—11月从低到高3个峰值;在一天之内呈现昼高夜低的单峰结构,峰值大多出现在午后15:00时。珠三角中部城市超标天数较多,沿海城市超标天数较少,大部分城市每年O3超标天数逐渐增多。O3月变化和日变化与NO2呈现负相关。总体而言,NO2平均浓度越高的城市,O3昼夜爬升值越高。     

西安城郊PM_(10)和PM_(2.5)化学组分特征研究——以户县草堂寺为例

为研究西安城郊农村大气PM_(10)和PM_(2.5)中主要化学组分特征,于2014年12月至2015年10月在西安户县草堂寺采集颗粒物样品,分析了每组样品中的16种无机元素、8种水溶性离子、有机碳(OC)和元素碳(EC),对颗粒物和化学组分的浓度水平、时间变化特征进行了讨论。结果表明:(1)PM_(2.5)、PM_(10)年平均值分别为(79.78±59.12)、(118.09±79.27)μg/m~3。(2)PM_(2.5)及PM10中地壳元素浓度总体表现为春季高、秋季低;微量元素浓度表现为冬季高、夏季低。(3)PM_(2.5)和PM_(10)中SO_4~(2-)、NH_4~+、NO_3~-浓度总体表现为冬季秋季春季夏季。(4)冬、春季OC、EC明显高于夏、秋季;由OC/EC的最小值估算得到PM_(2.5)、PM_(10)中二次有机碳(SOC)年平均值分别为(7.90±8.89)、(8.55±8.50)μg/m~3,冬、春季SOC明显高于夏、秋季;秋、冬季OC、EC相关性较强,而春、夏季较弱。     

Major air pollutants in Bursa,Turkey: their levels,temporal changes,interactions, and sources

Bursa is one of the largest cities of Turkey and it hosts 17 organized industrial zones. Parallel to the increase in population, rapidly growing energy consumption, and increased numbers of transport vehicles have impacts on the air quality of the city. In this study, regularly calibrated automatic samplers were employed to get the levels of air pollution in Bursa. The concentrations of CH₄ and N-CH₄ as well as the major air pollutants including PM₁₀, PM_2.5, NO, NO₂, NO_x, SO₂, CO, and O₃, were determined for 2016 and 2017 calendar years. Their levels were 1641.62?±?718.25, 33.11?±?5.45, 42.10?±?10.09, 26.41?±?9.01, 19.47?±?16.51, 46.73?±?16.56, 66.23?±?32.265, 7.60?±?3.43, 659.397?±?192.73, and 51.92?±?25.63 µg/m³ for 2016, respectively. Except for O₃, seasonal concentrations were higher in winter and autumn for both years. O₃, CO, and SO₂ had never exceeded the limit values specified in the regulations yet PM₁₀, PM_2.5, and NO₂ had violated the limits in some days. The ratios of CO/NO_x, SO₂/NO_x, and PM_2.5/PM₁₀ were examined to characterize the emission sources. Generally, domestic and industrial emissions were dominated in the fall and winter seasons, yet traffic emissions were effective in spring and summer seasons. As a result of the correlation process between O_x and NO_x, it was concluded that the most important source of O_x concentrations in winter was NO_x and O₃ was in summer.     

Degradation kinetics of anthracene by ozone on mineral oxides

To further understand the role of substrates on the heterogeneous reactions of polycyclic aromatic hydrocarbons, the reactions of ozone with anthracene adsorbed on different mineral oxides (SiO₂, α-Al₂O₃ and α-Fe₂O₃) and on Teflon disc were investigated in dark at 20 °C. No reaction between ozone and anthracene on Teflon disc was observed when the ozone concentration was ～1.18 × 10¹⁴ molecules cm^?3. The reactions on mineral oxides exhibited pseudo-first-order kinetics for anthracene loss, and the pseudo-first-order rate constant (k_1,obs) displayed a Langmuir–Hinshelwood dependence on the gas-phase ozone concentration. The adsorption equilibrium constants for ozone (K_O3) on SiO₂-1, SiO₂-2, α-Al₂O₃ and α-Fe₂O₃ were (0.81 ± 0.26) × 10^?15 cm³, (2.83 ± 1.17) × 10^?15 cm³, (2.48 ± 0.77) × 10^?15 cm³ and (1.66 ± 0.45) × 10^?15 cm³, respectively; and the maximum pseudo-first-order rate constant (k_1,max) on these oxides were (0.385 ± 0.058) s^?1, (0.101 ± 0.0138) s^?1, (0.0676 ± 0.0086) s^?1 and (0.0457 ± 0.004) s^?1, respectively. Anthraquinone was identified as the main surface product of anthracene reacted with ozone. Comparison with previous research and the results obtained in this study suggest that the reactivity of anthracene with ozone and the lifetimes of anthracene adsorbed on mineral dust in the atmosphere are determined by the nature of the substrate.     

Differences in airborne particle and gaseous concentrations in urban air between weekdays and weekends

Airborne particle number concentrations and size distributions as well as CO and NO_x concentrations monitored at a site within the central business district of Brisbane, Australia were correlated with the traffic flow rate on a nearby freeway with the aim of investigating differences between weekday and weekend pollutant characteristics. Observations over a 5-year monitoring period showed that the mean number particle concentration on weekdays was (8.8±0.1)×10³ cm⁻³ and on weekends (5.9±0.2)×10³ cm⁻³—a difference of 47%. The corresponding mean particle number median diameters during weekdays and weekends were 44.2±0.3 and 50.2±0.2 nm, respectively. The differences in mean particle number concentration and size between weekdays and weekends were found to be statistically significant at confidence levels of over 99%. During a 1-year period of observation, the mean traffic flow rate on the freeway was 14.2×10⁴ and 9.6×10⁴ vehicles per weekday and weekend day, respectively—a difference of 48%. The mean diurnal variations of the particle number and the gaseous concentrations closely followed the traffic flow rate on both weekdays and weekends (correlation coefficient of 0.86 for particles). The overall conclusion, as to the effect of traffic on concentration levels of pollutant concentration in the vicinity of a major road (about 100 m) carrying traffic of the order of 10⁵ vehicles per day, is that about a 50% increase in traffic flow rate results in similar increases of CO and NO_x concentrations and a higher increase of about 70% in particle number concentration.     

Heterogeneous reactions of ozone with pyrene, 1-hydroxypyrene and 1-nitropyrene adsorbed on particles

This work deals with the kinetic study of the reactions of ozone with pyrene, 1-hydroxypyrene and 1-nitropyrene, adsorbed on model particles. Experiments were performed at room temperature and atmospheric pressure, using a quasi-static flow reactor in the absence of light. Compounds were extracted from particles using pressurized fluid extraction (PFE) and concentration measurements were performed using gas chromatography/mass spectrometry (GC/MS). The pseudo-first order rate constants were obtained from the fit of the experimental decay of particulate polycyclic compound concentrations versus reaction time. Experiments were performed at three different O₃ concentrations from which second order rate constants were calculated. The following rate constant values were obtained at 293 K: k(O₃ + Pyrene) = (3.2 ± 0.7) × 10^?16 cm³ molecule^?1 s^?1; k(O₃ + 1OHP) = (7.7 ± 1.4) ×10 ^?16 cm³ molecule^?1 s^?1; and k(O₃ + 1NP) = (2.2 ± 0.5) × 10^?17 cm³ molecule^?1 s^?1, for pyrene, 1-hydroxypyrene and 1-nitropyrene adsorbed on silica particles. The variation in the rate constants demonstrates the strong influence of the substituent (OH or NO₂) on the heterogeneous reactivity of pyrene. The pyrene particulate concentration was also varied in order to check how this parameter may influence the experiments. Finally, oxidation products were investigated for all reactions and some were detected and identified for the first time for ozone heterogeneous reaction with pyrene adsorbed on particles.     

Gaseous and particulate water-soluble organic and inorganic nitrogen in rural air in southern Scotland

Simultaneous daily measurements of water-soluble organic nitrogen (WSON), ammonium and nitrate were made between July and November 2008 at a rural location in south-east Scotland, using a ‘Cofer’ nebulizing sampler for the gas phase and collection on an open-face PTFE membrane for the particle phase. Average concentrations of NH₃ were 82 ± 17 nmol N m^?3 (error is s.d. of triplicate samples), while oxidised N concentrations in the gas phase (from trapping NO₂ and HNO₃) were smaller, at 2.6 ± 2.2 nmol N m^?3, and gas-phase WSON concentrations were 18 ± 11 nmol N m^?3. The estimated collection efficiency of the nebulizing samplers for the gas phase was 88 (±8) % for NH₃, 37 (±16) % for NO₂ and 57 (±7) % for WSON; reported average concentrations have not been corrected for sampling efficiency. Concentrations in the particle phase were smaller, except for nitrate, at 21 ± 9, 10 ± 6 and 8 ± 9 nmol N m^?3, respectively. The absence of correlation in either phase between WSON and either (NH₃ + NH₄⁺) or NO₃^? concentrations suggests atmospheric WSON has diverse sources. During wet days, concentrations of gas and particle-phase inorganic N were lower than on dry days, whereas the converse was true for WSON. These data represent the first reports of simultaneous measurements of gas and particle phase water-soluble nitrogen compounds in rural air on a daily basis, and show that WSON occurs in both phases, contributing 20–25% of the total water-soluble nitrogen in air, in good agreement with earlier data on the contribution of WSON to total dissolved N in rainfall in the UK.     

Environmental photochemical fate of pesticides ametryn and imidacloprid in surface water (Paranapanema River,São Paulo,Brazil)

In addition to direct photolysis studies, in this work the second-order reaction rate constants of pesticides imidacloprid (IMD) and ametryn (AMT) with hydroxyl radicals (HO^●), singlet oxygen (¹O₂), and triplet excited states of chromophoric dissolved organic matter (³CDOM^*) were determined by kinetic competition under sunlight. IMD and AMT exhibited low photolysis quantum yields: (1.23?±?0.07)?×?10^–2 and (7.99?±?1.61)?×?10^–3 mol Einstein^?1, respectively. In contrast, reactions with HO^● radicals and ³CDOM* dominate their degradation, with ¹O₂ exhibiting rates three to five orders of magnitude lower. The values of k_IMD,HO● and k_AMT,HO● were (3.51?±?0.06)?×?10⁹ and (4.97?±?0.37)?×?10⁹ L mol^?1 s^?1, respectively, while different rate constants were obtained using anthraquinone-2-sulfonate (AQ2S) or 4-carboxybenzophenone (CBBP) as CDOM proxies. For IMD this difference was significant, with k_IMD,3AQ2S*?=?(1.02?±?0.08)?×?10⁹ L mol^?1 s^?1 and k_IMD,3CBBP*?=?(3.17?±?0.14)?×?10⁸ L mol^?1 s^?1; on the contrary, the values found for AMT are close, k_AMT,3AQ2S*?=?(8.13?±?0.35)?×?10⁸ L mol^?1 s^?1 and k_AMT,3CBBP*?=?(7.75?±?0.80)?×?10⁸ L mol^?1 s^?1. Based on these results, mathematical simulations performed with the APEX model for typical levels of water constituents (NO₃^?, NO₂^?, CO₃^2?, TOC, pH) indicate that the half-lives of these pesticides should vary between 24.1 and 18.8 days in the waters of the Paranapanema River (São Paulo, Brazil), which can therefore be impacted by intensive agricultural activity in the region.

     

NOX fluxes from several typical agricultural fields during summer-autumn in the Yangtze Delta,China

NO_X fluxes from three kinds of vegetable lands and a rice field were measured during summer–autumn in the Yangtze Delta, China. The average NO fluxes from the rice fields (RF), celery field (CE), maize field (MA) and cowpea field (CP) were 4.1, 30.8, 54 and 32.2 ng N m^?2 s^?1, respectively; and the average NO₂ fluxes were ?2.12, 0.68, 1.33 and 0.5 ng N m^?2 s^?1, respectively. The liquid N fertilizer (the mixture of swine excrement and urine) which is widely applied to vegetable lands by Chinese farmers was found to quickly stimulate NO emission, and have significant contribution to NO emission from the investigated vegetable lands. Apparent linearity correlations were found between NO₂ fluxes and the ambient concentrations of the rice fields, with a compensation point of about 2.84 μg m^?3. Total emissions of NO during summer–autumn time from this area were roughly estimated to be 4.1 and 8.4 Gg N for rice field and vegetable lands, respectively.     

Summertime photochemical ozone formation in Santiago,Chile

The city of Santiago, Chile experiences frequent high pollution episodes and as a consequence very high ozone concentrations, which are associated with health problems including increasing daily mortality and hospital admissions for respiratory illnesses. The development of ozone abatement strategies requires the determination of the potential of each pollutant to produce ozone, taking into account known mechanisms and chemical kinetics in addition to ambient atmospheric conditions. In this study, the photochemical formation of ozone during a summer campaign carried out from March 8–20, 2005 has been investigated using an urban photochemical box model based on the Master Chemical Mechanism (MCMv3.1). The MCM box model has been constrained with 10 min averages of simultaneous measurements of HONO, HCHO, CO, NO, j(O¹D), j(NO₂), 31 volatile organic compounds (VOCs) and meteorological parameters. The O₃–NO_x–VOC sensitivities have been determined by simulating ozone formation at different VOC and NO_x concentrations. Ozone sensitivity analyses showed that photochemical ozone formation is VOC-limited under average summertime conditions in Santiago. The results of the model simulations have been compared with a set of potential empirical indicator relationships including H₂O₂/HNO₃, HCHO/NO_y and O₃/NO_z. The ozone forming potential of each measured VOC has been determined using the MCM box model. The impacts of the above study on possible summertime ozone control strategies in Santiago are discussed.     

Heterogeneous reaction of NO2 with soot at different relative humidity

The influences of relative humidity (RH) on the heterogeneous reaction of NO₂ with soot were investigated by a coated wall flow tube reactor at ambient pressure. The initial uptake coefficient (γ _initial) of NO₂ showed a significant decrease with increasing RH from 7 to 70%. The γ _initial on “fuel-rich” and “fuel-lean” soot at RH = 7% was (2.59 ± 0.20) × 10^?5 and (5.92 ± 0.34) × 10^?6, respectively, and it decreased to (5.49 ± 0.83) × 10^?6 and (7.16 ± 0.73) × 10^?7 at RH = 70%, respectively. Nevertheless, the HONO yields were almost independent of RH, with average values of (72 ± 3)% for the fuel-rich soot and (60 ± 2)% for the fuel-lean soot. The Langmuir-Hinshelwood mechanism was used to demonstrate the negative role of RH in the heterogeneous uptake of NO₂ on soot. The species containing nitrogen formed on soot can undergo hydrolysis to produce carboxylic species or alcohols at high RH, accompanied by the release of little gas-phase HONO and NO.

     

Atmospheric chemistry of 1-methyl-2-pyrrolidinone

Rate constants for the atmospheric reactions of 1-methyl-2-pyrrolidinone with OH radicals, NO₃ radicals and O₃ have been measured at 296±2 K and atmospheric pressure of air, and the products of the OH radical and NO₃ radical reactions investigated. Using relative rate techniques, rate constants for the gas-phase reactions of OH and NO₃ radicals with 1-methyl-2-pyrrolidinone of (2.15±0.36)×10^-11 cm³ molecule^-1 s^-1 and (1.26±0.40)×10^-13 cm³ molecule^-1 s^-1, respectively, were measured, where the indicated errors include the estimated overall uncertainties in the rate constants for the reference compounds. An upper limit to the rate constant for the O₃ reaction of <1×10^-19 cm³ molecule^-1 s^-1 was also determined. These kinetic data lead to a calculated tropospheric lifetime of 1-methyl-2-pyrrolidinone of a few hours, with both the daytime OH radical reaction and the nighttime NO₃ radical reaction being important loss processes. Products of the OH radical and NO₃ radical reactions were analyzed by gas chromatography with flame ionization detection and combined gas chromatography–mass spectrometry. N-methylsuccinimide and (tentatively) 1-formyl-2-pyrrolidinone were identified as products of both of these reactions. The measured formation yields of N-methylsuccinimide and 1-formyl-2-pyrrolidinone were 44±12% and 41±12%, respectively, from the OH radical reaction and 59±16% and ∼4%, respectively, from the NO₃ radical reaction. Reaction mechanisms consistent with formation of these products are presented.