Nitrous and nitric acid measurements at sites in South-East England

Measurements of HONO and HNO₃ have been made using annular denuder samplers at sites in south-east England. Whilst concentrations of HNO₃ exhibited a diurnal variation, with a maximum in mid-afternoon nitrous acid shows the opposite diurnal cycle with maximum levels at night due to daytime photolysis. Concentrations of HONO increase with those of NO₂, and elevated nighttime HONO level appear to be followed by high levels of HNO₃ the following day. Average concentrations of HONO (0.45± 0.26 ppb in 24 h samples are comparable to those of HNO₃ (0.56±0.36 ppb in 24 h samples), each representing about 5–10% of the concentration of NO₂. Although NO₂ oxidation provides the source of HNO₃ concentrations of the two compounds are not related, presumably since the formation of NH₄NO₃ aerosol limits HNO₃ concentrations at out site.     

Nitrate formation on sea-salt and mineral particles—A single particle approach

Heterogeneous reactions of NO₂ and HNO₃ at sub-ppm levels with individual sea-salt and mineral particles were investigated. Particles deposited on filters and on electron microscope grids placed in a Teflon reaction chamber, were exposed to NO₂ or HNO₃ under controlled conditions. Experiments were carried out under dark conditions and were repeated under u.v. radiation (solar simulation). Nitrates formed on the particles were determined by bulk and individual particle analyses. Individual sea-salt and mineral particles were observed in a transmission electron microscope for the presence of nitrate on the particle surface.The formation of nitrates on sea-salt particles under dark conditions, was in the range of 0.1–3.3 mg NO₃⁻ g⁻¹ NaCl. Higher values were obtained for mineral particles: 0.2–8.2 mg NO₃⁻ g⁻¹ aerosol ([NO₂] =0.18 and 0.54 ppm; [HNO₃] = 0.04 ppm; exposure time 1–7 days; relative humidity = 70%). The formation of nitrates on sea-salt particles increased from 3.0 to 16.1 mg NO₃⁻ g⁻ NaCl when u.v. radiation was added. Mineral particles did not show a significant increase in nitrate formation under u.v. radiation.Microscopy showed that about 50% of the soil particles reacted with NO₂ and HNO₃ to form mixed nitrate particles. Almost all sea-salt particles (above 95%) reacted with both gases, although the reaction was not complete and took place only on the particle surface.Application of electron microscopy and a specific microspot technique provided direct evidence for the formation of nitrate on sea-salt and mineral particles exposed to NO₂ and HNO₃.     

聊城市冬季PM2.5中水溶性化合物的昼夜变化特征及来源解析

为探究聊城市冬季PM_(2.5)中水溶性物质的昼夜变化特征及其来源,于2017年1～2月进行PM_(2.5)样品采集,对其水溶性无机离子、乙二酸和左旋葡聚糖等水溶性化合物进行分析,并采用主成分分析-多元线性回归模型(PCA-MLR)对其来源进行解析.结果表明,采样期间聊城市PM_(2.5)平均质量浓度为(132. 6±65. 4)μg·m-3,是国家二级标准的1. 8倍,且夜晚PM_(2.5)的污染程度略高于白天. SNA(SO24-、NO3-和NH4+)是聊城市PM_(2.5)中最主要的水溶性离子,在白天与夜晚占总离子的质量分数为73. 4%和77. 1%,说明聊城市冬季二次污染较严重.白天与夜晚阴阳离子平衡当量比值(AE/CE)都小于1,说明PM_(2.5)呈碱性,且夜晚PM_(2.5)的酸性比白天强.无论在白天还是晚上,NH4+的主要存在形态均为NH4HSO4和NH4NO3.通过相关性分析,证实了乙二酸是在液相中经酸催化的二次氧化反应形成的,且受生物质燃烧的影响很强.通过PCA-MLR模型分析可知,聊城市冬季PM_(2.5)中的水溶性化合物主要来自机动车尾气及其二次氧化、生物质燃烧,而受矿物粉尘与煤炭燃烧的影响较小.     

Review of heterogeneous photochemical reactions of NOy on aerosol－A possible daytime source of nitrous acid (HONO) in the atmosphere

As an important precursor of hydroxyl radical, nitrous acid (HONO) plays a key role in the chemistry of the lower atmosphere. Recent atmospheric measurements and model calculations show strong enhancement for HONO formation during daytime, while they are inconsistent with the known sources in the atmosphere, suggesting that current models are lacking important sources for HONO. In this article, heterogeneous photochemical reactions of nitric acid/nitrate anion and nitrogen oxide on various aerosols were reviewed and their potential contribution to HONO formation was also discussed. It is demonstrated that HONO can be formed by photochemical reaction on surfaces with deposited HNO3 , by photocatalytic reaction of NO2 on TiO2 or TiO2 -containing materials, and by photochemical reaction of NO2 on soot, humic acids or other photosensitized organic surfaces. Although significant uncertainties still exist in the exact mechanisms and the yield of HONO, these additional sources might explain daytime observations in the atmosphere.     

Field tests of a passive sampler for atmospheric ozone at California mountain forest locations

Field tests of a colorant-based ozone passive sampler have been carried out during the 1990 smog season at five mountain forest locations in California. Co-located measurements of ambient ozone were made at all field sites using the passive sampler and a reference method, ultraviolet (u.v.) photometry. The sampling duration ranged from 3 to 30 days. Nitrogen dioxide, aldehydes and the phytotoxic oxidants peroxyacetyl nitrate (PAN) and peroxypropionyl nitrate (PPN) were measured at one location to assess possible interferences. The average precision of the measurements, calculated from data for 42 sets of colocated passive samplers, was 12%. Data for all field locations could be reduced to a single equation relating color change (ΔE units) to ozone dose (units: ppb-days). This polynomial equation could be reduced to a linear equation for color changes not exceeding 8 ΔE units (equivalent to sampling durations of up to 15 days), with good agreement between field data and earlier calibration results obtained in the laboratory. Both polynomial and linear equations can be used to obtain quantitative, time-integrated measurements of ambient ozone. The performance of the passive sampler showed no dependence on changes in ambient temperature and humidity. Interferences from air pollutants other than ozone contributed a total positive bias of less than 5% to the measured ozone concentrations: 3% for NO₂, 1.3% for PAN, 0.2% for PPN, and 0.% or less for formaldehyde and acetaldehyde.     

Seasonal and diurnal variations of atmospheric peroxyacetyl nitrate, peroxypropionyl nitrate, and carbon tetrachloride in Beijing

Atmospheric peroxyacetyl nitrate(PAN), peroxypropionyl nitrate(PPN), and carbon tetrachloride(CCl4) were measured from September 2010 to August 2011 in Beijing. PAN exhibited low values from mid-autumn to early spring(October to March) with monthly average concentrations ranging from 0.28 to 0.73 ppbV, and increased from early spring to summer(March to August), ranging from 1.37–3.79 ppbV. The monthly variation of PPN was similar to PAN, with low values(below detection limit to 0.18 ppbV) from mid-autumn to early spring, and a monthly maximum in September(1.14 ppbV). The monthly variation of CCl4was tightly related to the variation of temperature, exhibiting a minimum in winter(69.3 pptV) and a maximum of 180.6 pptV in summer. Due to weak solar intensity and short duration, PAN and O3showed no distinct diurnal patterns from morning to night during winter, whereas for other seasons, they both exhibited maximal values in the late afternoon(ca. 15:00 to 16:00 local time) and minimal values during early morning and midnight. Good linear correlations between PAN and PPN were found in autumn(R = 0.91), spring(R = 0.94), and summer(R = 0.81), with slopes of 0.130, 0.222, and 0.133, respectively, suggesting that anthropogenic hydrocarbons dominated the photochemical formation of PANs in Beijing. Positive correlation between PAN and O3 in summer with the low slopes( O3 / PAN) ranging from 9.92 to 18.0 indicated serious air pollution in Beijing, and strong negative correlation in winter reflected strong O3consumption by NO titration and less thermal decompositin of PAN.     

广州番禺大气成分站一次典型光化学污染过程PAN和O3分析

通过对广州番禺大气成分站（GPACS）的光化学相关污染物（O₃、PAN、VOCs、NO₂、NO）以及气象要素进行观测,分析2010~2016年期间发生在广州地区一次典型光化学污染过程.结果表明,该光化学污染过程期间,O₃和PAN总体体积分数比较高,最大O₃小时体积分数为140.6×10^-9,而最大PAN小时体积分数为4.7×10^-9.NO整体体积分数较低,对O₃的化学滴定和PAN的去除影响较小.NO₂整体体积分数较高、辐射较强和风速较低则有利于O₃和PAN的形成和积累.PAN和O₃具有一定的线性关系（R²=0.55）,而形成PAN和O₃前体物VOCs物种不完全相同影响着它们的线性关系,在生成PAN的VOCs物种中,乙烯、丙烷、异戊二烯和甲苯所占的比例较大,而对臭氧生成潜势较大的物种有异戊二烯、1,3,5-三甲苯、丙烯、间,对-二甲苯以及甲苯.对PA自由基体积分数进行估算,发现它的日均值体积分数在0.11×10^-12~0.16×10^-12范围变化,远高于其它地区,表明此次发生的光化学反应较为强烈.     

天津夏季边界层低层大气中PAN和O3的输送特征分析

采用在线仪器监测分析2017年夏季天津气象铁塔220 m观测平台大气中过氧乙酰硝酸酯(PAN)和O_3的体积分数,并结合气象观测资料和后向轨迹分析PAN和O_3的输送特征.观测期间PAN和O_3体积分数平均值分别为(0.73±0.56)×10~(-9)和(53±25)×10~(-9),最大小时体积分数分别为3.49×10~(-9)和137×10~(-9),PAN和O_3体积分数具有相似的日变化特征,白昼PAN和O_3浓度高于夜间,且PAN和O_3浓度相关系数(R2=0.52)显著高于夜间(R2=0.21).观测期间偏南风下PAN和O_3浓度最高,偏东风下最低,风玫瑰图和后向轨迹聚类分析都表明,来源于西南方向的气流轨迹对应的污染物浓度最高,途经渤海和河北、辽宁沿海地区的偏东气流对应的PAN和O_3体积分数最低,边界层内输送对PAN和O_3的体积分数分布起到了重要作用.     

A captive-air irradiation study of the response of nitric acid and peroxyacetyl nitrate to ozone control strategies in Los Angeles

Outdoor smog chamber experiments were used to study the sensitivity of the yields of two important nitrogen-containing pollutants, nitric acid (HNO₃) and peroxyacetyl nitrate (PAN) to changes in nonmethane hydrocarbon (HC) and nitrogen oxide (NO_x) concentrations in Los Angeles. The experiments were conducted at two sites in the Los Angeles Basin using eight chambers filled with morning Los Angeles air on 33 days. At least one chamber was unchanged and served as a control, while the initial HC and/or NO_x concentrations were changed by 25–50% in up to seven chambers to simulate O₃ control strategies and to broaden the range of HC - NO_x conditions studied. Empirical models that predict the maximum yields of HNO₃ and PAN were used to determine the response of these pollutants to three possible ozone control strategies. All three strategies (reductions in HC, NO_x or both HC and NO_x) reduced PAN while only NO_x reductions decreased HNO₃. However, reducing NO_x increased the HC reductions required to attain lower O₃ levels. Thus, there is a conflict between the O₃ and HNO₃ control strategies.     

Vertical distributions of COS,CS2, DMS and other sulfur compounds in a loblolly pine forest

Measurements of atmospheric COS, CS₂, DMS, SO₂ and aerosol sulfate and methanesulfonate (MSA) concentrations were conducted in a loblolly pine forest in central Georgia between July and September 1990. The daytime profiles obtained for the reduced sulfur gases (COS, CS₂, DMS) often showed significantly higher concentrations at the canopy level than above the forest canopy, indicating a net emission of these gases from the tree tops. No evidence was found for a net uptake of COS by the canopy during daytime. With one exception, all COS concentrations measured during the day were significantly higher than corresponding nighttime values. These results appear to be in conflict with recent studies suggesting a net uptake of atmospheric COS by plants during photosynthetic activity. Possible explanations for these different findings are discussed. Nighttime profiles indicated no major biosphere-atmosphere exchange of COS, CS₂ or DMS. Nighttime DMS concentrations were significantly higher than corresponding daytime values. A clear inverse relationship between the diel variations of DMS and MSA was observed, consistent with rapid photochemical oxidation of DMS under the given conditions.     

Studying high ozone concentrations by using the Danish Eulerian model

The long-range transport of air pollutants (LRTAP) over Europe is studied by a mathematical model based on a system of partial differential equations (PDEs). The number of PDEs is equal to the number of species studied and the model contains 35 species at present. Among the species are NO, NO₂, NO₃⁻, HNO₃, NH₃, NH₄⁺, O₃, PAN, SO₂, SO₄²⁻ and may hydrocarbons. Most of the 70 chemical reactions involved in the model are nonlinear (including here many photochemical reactions).The model requires large sets of input data. Emissions of SO₂, NO_x, NH₃ and both natural and anthropogenic volatile organic compounds (VOC) are needed in the model. The meteorological data consist of fields of wind velocities, precipitation, surface temperatures, temperatures of the boundary layer, relative humidities and cloud cover, which are read in the beginning of every 6-h interval. Both daytime and nighttime mixing heights are used in the model.Many of the species in the model vary on a diurnal basis. An investigation of the main mechanisms that determine the diurnal variation of the ozone concentrations is performed. One of the important conditions that is necessary if one wants to represent correctly the diurnal variations of the concentrations is to have access to meteorological data that vary diurnally. This is especially true for the temperature and the mixing height.The use of modern numerical algorithms (which are combined with vectorization of the most time-consuming numerical procedures) allows one to perform long-term runs with the model on several high-speed computers. Results obtained in runs with meteorological data for July 1985 and August–October 1989 are discussed. The computed concentrations and depositions are compared with measurements taken at stations located in different European countries. The agreement between calculated concentrations and measurements is reasonably good.Results obtained with several scenarios, in which the NO_x emission and/or the anthropogenic VOC emissions are varied, are presented. Several main conclusions are drawn by studying the results obtained during the comparisons. Some plans for future development of the models are discussed.     

Sulfur dioxide,hydrogen sulfide,total reduced sulfur,chlorinated hydrocarbons and photochemical oxidants in southern California museums

Indoor and outdoor concentrations of the air pollutants ozone, NO₂, SO₂, H₂S, total reduced sulfur (TRS), peroxyacetyl nitrate (PAN), methyl chloroform and tetrachloroethylene, have been measured at three southern California museums. Indoor maxima were 175 ppb for NO₂, 77 ppb for O₃, 0.7 ppb for PAN, 1.2 ppb for C₂Cl₄, >6.3 ppb for CH₃CCl₃, 2.5 ppb for SO₂, 1.4 ppb for TRS, and 46 ppt for H₂S. Indoor levels and indoor/outdoor (I/O) ratios for the chlorinated hydrocarbons pointed out to indoor sources. Outdoor and indoor levels of SO₂ and TRS were low at all three museums, but I/O ratios for SO₂ were high and averaged 0.89. H₂S concentrations were low, 16–46 ppt at one museum and less than 6 ppt at the other two museums. I/O ratios for the air pollutants with outdoor sources (ozone, PAN and NO₂) showed substantial variations, from low values of 0.02–0.33 at locations without influx of outdoor air to high values of 0.85–0.88 at locations experiencing high influx of outdoor air. Of the 10 institutions we have surveyed in southern California to date, eight exhibit high I/O ratios, e.g. 0.60–1.00 for PAN. Of the four museums surveyed that were equipped with HVAC and chemical filtration, only two yielded the expected low I/O ratios.     

Thermal decomposition pathways for peroxyacetyl nitrate (PAN): Implications for atmospheric methyl nitrate levels

The unimolecular decomposition pathways of peroxyacetyl nitrate (PAN) have been investigated in the presence of added NO₂ over the temperature range 298–345 K. The major products of the PAN decomposition were CO₂ and, depending on the ratio of O₂ to NO₂ in the experiment, either CH₂O or methyl nitrate. From the observed PAN decay rates and product yields, upper limits for the direct formation of either NO₃ or methyl nitrate from the unimolecular decay of PAN were obtained. The results indicate that these channels occur with rate constants that are thousands of times slower than dissociation of PAN into peroxyacetyl and NO₂, and that PAN decomposition is not a significant source of atmospheric methyl nitrate.     

Southern California air quality study: Peroxyacetyl nitrate

Information on the spatial and seasonal variations of ambient peroxyacetyl nitrate (PAN) has been obtained from simulataneous measurements made at five, seven or nine Southern California locations in June-September and November-December, 1987. Summertime (smog season) levels of PAN were consistent with photochemical formation during transport, and increased substantially from coastal to inland locations. Daily maxima (up to 30 ppb) coincided with those of ozone at all locations and shifted from midday at coastal sites to late afternoon inland.Elevated levels of PAN, e.g. up to 19 ppb on 3 December 1987, were observed during the fall at all coastal and central locations, where they consistently exceeded summertime levels.     

Laboratory tests of KI and alkaline annular denuders

Annular denuders coated with KI and with alkaline solutions have been tested for their ability to remove atmospheric pollutants including ozone, NO₂, SO₂, formaldehyde, methyl nitrate and peroxyacetyl nitrate. Tests were carried out at flow rates of 0.4–2.0 ℓ min⁻¹, using particle-free ambient air as well as purified air to study the effect of atmospheric CO₂ on alkaline denuder performance. Denuders coated with KI were efficient in removing O₃, NO₂, SO₂ (> 95%) and PAN (84±3%) but not methyl nitrate (44%) and formaldehyde (<5%). Selective removal of PAN from NO₂, and vice versa, could be obtained with annular denuders coated with NaOH, which removed 100% PAN and ⩽15% NO₂, and with alkaline guaiacol, which removed ⩾99% NO₂ and ⩽6% PAN.     

An estimate of the conversion rates of SO2 to SO2-4 and NO2 to HNO3+ NO3- for the evaluation air pollution in Beijing

The conversion rates of SO₂ to SO^2-₄ and NO₂ to HNO₃₊NO₃- are estimated from the field-data obtained in Beijing in summer, 1988. The results show that the conversion rate of NO₂ is about four times as much as that of SO₂; The conversion rates have a diurnal variation in a day. On the average, the rate of SO₂ is estimated to be 4.7% h^-1 during the daytime and 3.4% h^-1 during the nighttime. Similarly, the rate of NO₂ is estimated to be 17.2% h^-1 and 12% h^-1 respectively.     

Nitrogen budget for eastern Canada

A Lagrangian model incorporating S and N chemistry has been developed by the Atmospheric Environment Service. It was used to produce an annual nitrogen budget including annual nitrogen transboundary flux estimates for 1980 for eastern Canada.The model used trajectories computed from the analyzed winds produced at the Canadian Meteorological Centre (CMC) in addition to the temperature and precipitation analyses. The model parameterized the dry and wet deposition and chemical transformation of NO₂, nitrate (including HNO₃) and PAN using monthly, time-dependent dry deposition velocities, scavenging ratios and transformation rates. The model was integrated throughout eastern Canada on a 6-h basis for 1980. The boundary point concentrations were used to compute input and output fluxes which were summed over several boundary segments to give annual transboundary flux estimates.The total annual N deposition was about 0.6 TgN with high deposition in August and December and the lowest in February. Wet NO₃⁻ deposition (0.2 TgN) was higher than the dry deposition of any single N species (NO₂, nitrate or PAN) but lower than all dry N deposition combined. The annual N input (output) flux was about 1.0 (0.5) TgN. The highest input and output fluxes occurred in December and the lowest input and output fluxes occurred in May.     

Photochemical formation of particulate dicarboxylic acids under long-range transport in central Japan

Long-range transport (LRT) of photochemical air pollution from the coastal area with large emission sources to the inland mountainous region occurs very frequently in the central Japan region on clear summer days. It is caused by local winds and the transport route is almost-fixed geographically. Along this route, behavior of dicarboxylic acids in the airborne aerosols was investigated in the cooperative field observation of meteorology and chemistry. Measurements were made every 3-h at inland sites.The concentrations of dicarboxylic acids as well as NO₃⁻ and total organic C increased in the daytime and decreased at night. The maximum are attained when the transported air mass was arrived at the sampling sites. These diurnal variations were similar to that of O₃.In the daytime, although the phthalates (di-n-butyl and dioctyl), n-alkanes (C₂₁C₃₂) and pinon aldehyde were abundant in the airborne aerosols, the dicarboxylic acids (C₂C₁₀) were the most abundant species and the total concentrations attained from 30 to 50% of the total organic particulate matter. In addition, of the dicarboxylic acids, more than 70% were estimated to be produced by photochemical reactions in the daytime. Thus, it was concluded that most of the dicarboxylic acids were produced by the photochemical oxidation of anthropogenic compounds during LRT.     

Wintertime peroxyacetyl nitrate (PAN) in the megacity Beijing: Role of photochemical and meteorological processes

Previous measurements of peroxyacetyl nitrate(PAN) in Asian megacities were scarce and mainly conducted for relative short periods in summer. Here, we present and analyze the measurements of PAN, O3, NOx, etc., made at an urban site(CMA) in Beijing from 25 January to 22 March 2010. The hourly concentration of PAN averaged 0.70 × 10 9mol/mol(0.23 × 10 9–3.51 × 10 9mol/mol) and was well correlated with that of NO2but not O3, indicating that the variations of the winter concentrations of PAN and O3in urban Beijing are decoupled with each other. Wind conditions and transport of air masses exert very significant impacts on O3, PAN, and other species. Air masses arriving at the site originated either from the boundary layer over the highly polluted N-S-W sector or from the free troposphere over the W-N sector. The descending free-tropospheric air was rich in O3, with an average PAN/O3ratio smaller than 0.031, while the boundary layer air over the polluted sector contained higher levels of PAN and primary pollutants, with an average PAN/O3ratio of 0.11. These facts related with transport conditions can well explain the observed PAN-O3decoupling. Photochemical production is important to PAN in the winter over Beijing. The concentration of the peroxyacetyl(PA) radical was estimated to be in the range of 0.0014 × 10 12–0.0042 × 10 12 mol/mol. The contributions of the formation reaction and thermal decomposition to PAN's variation were calculated and found to be significant even in the colder period in air over Beijing, with the production exceeding the decomposition.     

夏季北京市大气中PAN与PPN的监测分析

采用在线监测仪器,在2005-08对北京市中关村地区大气中的PAN和PPN浓度进行了监测.结果表明,大气中存在着高浓度的PAN和PPN,其最高体积分数分别为2 493.2×10^-12和509.2×10^-12;PPN与PAN的浓度相关性很强,相关系数R²=0.949 5;［PPN］/［PAN］为20.2%. PAN和PPN的浓度在夜间有1个峰值出现,白天高浓度的PAN和PPN出现在NO₂浓度较高而NO浓度较低的时段,PAN与O₃的浓度变化趋势基本一致并显示出一定的相关性.