Nitrogen Trioxide: Key Intermediate in the Chemistry of Polluted Air?

It is proposed that peroxyacetyl nitrate and its homologues are formed in polluted air via hydrogen abstraction from the corresponding aldehyde by nitrogen trioxide, followed by (a relatively fast) combination of the resulting acyl radical with oxygen and NO₂. This mechanism provides a simple explanation for the formation of nitric acid, HNO3, as well. Nitrogen trioxide should be able to abstract hydrogen atoms from hydrocarbons, since the H-ONO₂ bond strength is about 100 kcal/mole.     

Simulation of Sulfate and Nitrate Chemistry in Power Plant Plumes

ABSTRACT

The rate of formation of secondary particulate matter (PM) in power plant plumes varies as the plume material mixes with the background air. Consequently, the rate of oxidation of sulfur dioxide (SO₂) and nitrogen dioxide (NO₂) to sulfate and nitric acid, respectively, can be very different in plumes and in the background air (i.e., air outside the plume). In addition, the formation of sulfate and nitric acid in a power plant plume is a strong function of the chemical composition of the background air and the prevailing meteorological conditions.

We describe the use of a reactive plume model, the Reactive and Optics Model of Emissions, to simulate sulfate and nitrate formation in a power plant plume for a variety of background conditions. We show that SO₂ and NO₂ oxidation rates are maximum in the background air for volatile organic compound (VOC)-limited airsheds but are maximum at some downwind distance in the plume when the background air is nitrogen oxide (NO_x)-limited. Our analysis also shows that it is essential to obtain measurements of background concentrations of ozone, aldehydes, peroxyacetyl nitrate, and other VOCs to properly describe plume chemistry.     

A Combustion Method for the Determination of Solvent Vapors at Low Concentrations in Air

The nitrogen-containing products of smog chamber reactions have been the subject of much controversy. Concern has arisen over nitrogen products because of the almost universally poor nitrogen balance reported for irradiated mixtures of hydrocarbons and nitrogen oxides. Some possible nitrogen-containing products, such as molecular nitrogen, nitrous oxide, and nitroolefins have been investigated and shown to be unimportant. The nitrogen products most often measured are peroxyacetyl nitrate and residual nitrogen dioxide. These two products rarely comprise more than 70% of the initial nitrogen at the end of an experiment, and often account for less than 50%. Previous experiments in which total nitrate was determined in the gas phase and on the vessel walls at the end of irradiation have shown very good nitrogen balances. The assumption has been made that the nitrate arises from nitric acid formed on the walls by adsorbed N₂O₅.

In the work reported here, all major nitrogen-containing compounds have been monitored continuously for the first time. Nitric oxide and nitrogen dioxide have been monitored by chemilumines-cence and automated Saltzman techniques. Methyl, ethyl, and peroxyacetyl nitrate have been determined by gas chromatogra-phy. Two methods, one continuous and one integrated, have been specially developed to measure nitric acid both in the smog chambers and in the atmosphere. Continuous determination of these compounds yields good nitrogen balances throughout the irradiations.

Profiles of the nitrogen-containing species from irradiated HC/ NO_x mixtures are discussed in terms of nitrogen products and nitrogen balance. Differences in product distribution for different hydrocarbon systems are also considered. Using rate information from the nitrogen compound profiles, important reactions leading to nitrogen-containing products are identified. Interference with the chemiluminescent technique by HON0₂, PAN, and C₂H₅ONO₂ is discussed.     

Gaseous Pollutants in St. Louis and Other Cities

During the fall of 1972, a study was undertaken to characterize gaseous air pollutants in the St. Louis metropolitan area. Information obtained in this study will be used in planning air pollution modeling studies to be carried out over the next 4 or 5 years under the Regional Air Pollution Study (RAPS) of the Environmental Protection Agency. From analyses of roadway samples, it was found that certain compounds in automotive emissions such as acetylene, carbon monoxide, o-xylene, ethylene, and 2-methylpentane occur in consistent proportions to other compounds. The concentrations of these indicator compounds in atmospheric samples were used to estimate the amounts of other hydrocarbons present that are attributable to automotive related emissions. Methane, ethane, and propane were found to originate principally from nonautomotive sources, both at St. Louis University and the St. Louis CAMP station. Similar concentrations were found in urban and non-urban areas. A comparison of ethylene-CO and propyl-ene-CO ratios in urban and non-urban areas indicates that CO can serve as an indicator of transport of urban pollutants. Sunlight irradiations of captured air samples showed increasing ozone production with increasing initial concentrations of hydrocarbons and nitrogen oxides. Substantial ozone and peroxyacetyl nitrate were formed from a total non-methane hydrocarbon concentration of only ¹/₄ ppm C.     

Objections to the use of polyvinyl fluoride in smogchamber experiments

The interference of low molecular weight additives in polyvinyl fluoride film (PVF; “Tedlar”) used for the construction of smogchambers has been investigated by means of irradiation experiments, chemical modelling and analytical techniques. The results indicate that PVF is unsuitable as a wall material for smogchambers, owing to interference in hydrocarbon measurements, possibly NO_x-measurements, and in the formation of ozone and peroxyacetyl nitrate. This information is thought to be of interest to present and future workers in air pollution research.     

Photochemical Pollution at Two Southern California Smog Receptor Sites

A one-year survey of air quality has been carried out at two southern California inland locations, Perris and Palm Springs (90 km E-SE and 120 km E of Los Angeles) to evaluate transport of photochemical smog from the Los Angeles area and to assess population exposure to toxic air pollutants in the Coachella Valley and eastern Riverside County. Air pollutants measured included formaldehyde, acetaldehyde, nitric acid, and peroxyacetyl nitrate (PAN). Acetic acid was also measured as part of the time-integrated method employed to measure PAN. In addition, intensive studies were carried out at both locations and included measurements of aldehydes, nitric acid, PAN, peroxypropionyl nitrate (PPN), methylchloroform and tetrachloroethylene.

Maximum concentrations of HCHO, CH₃CHO, HNO₃, PAN, PPN, CH₃COOH and C₂CI₄ were 26, 21, 4.5, 7.6, 0.42, 6.6 and 0.29 ppb in Palm Springs and 15, 30, 6.3, 9.1, 0.73, 7.8 and 0.43 ppb in Perris. Pollutant concentrations measured in Palm Springs and Perris are compared to those measured in the Los Angeles area, and are discussed in terms of formation and removal during transport.     

Vegetation: A Sink for Atmospheric Pollutants

The possibility of vegetation being an important sink for gaseous air pollutants was investigated. Plant pollutant uptake measurements were made utilizing a typical vegetation canopy and chambers that were designed specifically for gaseous exchange studies. The data indicate that an alfalfa canopy removed gases from the atmosphere in the following order: hydrogen fluoride (HF) > sulfur dioxide (SO₂) > chlorine (Cl₂) > nitrogen dioxide (NO₂) > ozone (O₃) > peroxyacetyl nitrate (PAN) > nitric oxide (NO) > carbon monoxide (CO). The absorption rate of NO was low, and no absorption of CO could be detected with the methods used. In the typical ambient concentration range uptake increased linearly with increasing concentration except for O₃ and Cl₂ which caused partial stomatal closure at the higher concentrations. Wind velocity above the plants, height of the canopy, and light intensity were shown to affect the pollutant removal rate. A relationship between the absorption rate and solubility of the pollutant in water was also shown. It was concluded that vegetation may be an important sink for many gaseous air pollutants.     

Interaction of nitrogen dioxide (NO2) with a monolayer of oleic acid at the air–water interface – A simple proxy for atmospheric aerosol

The reactions between atmospheric oxidants and organic amphiphiles at the air–water interface of an aerosol droplet may affect the size and critical supersaturation required for cloud droplet formation. We demonstrate that no reaction occurs between gaseous nitrogen dioxide (1000 ppm in air) and a monolayer of an insoluble amphiphile, oleic acid (cis-9-octadecenoic acid), at the air–water interface which removes material from the air–water interface. We present evidence that the NO₂ isomerises the cis-9-octadecenoic (oleic) acid to trans-9-octadecenoic (elaidic) acid. The study presented here is important for future and previous studies of (1) the reaction between the nitrate radical, NO₃, and thin organic films as NO₂ is usually present in high concentrations in these experimental systems and (2) the effect of NO₂ air pollution on the unsaturated fatty acids and lipids found at the air–liquid surface of human lung lining fluid.     

Photochemical Reactivities of Paraffinic Hydrocarbon-Nitrogen Oxide Mixtures Upon Addition of Propylene or Toluene

Effects associated with photochemical air pollution were measured during irradiation of n-butane-nitrogen oxide or n-butane-ethane-nitrogen oxide mixtures, with small amounts of propylene or toluene added. The effects measured including nitrogen dioxide and oxidant dosages, yields of formaldehyde and peroxy-acetyl nitrate, and eye irritation response. The results obtained clearly show that beneficial effects result from selective changes in hydrocarbon composition as well as from reduction of total hydrocarbon concenfration. Exclusion of olefins and alkylbenzenes was highly effective in reducing oxidant dosage, formaldehyde and peroxyacetyl nitrate concentrations, and eye irritation response. The only penalty was a modest increase in nitrogen dioxide dosage. A large reduction in nitrogen oxide concentration reduced nitrogen dioxide dosage and eye irritation response, but with the penalty of a large increase in oxidant dosage. The desirability of preferentially reducing olefins and alkylbenzenes rather than paraffinic hydrocarbons, acetylene, and benzene is strongly supported by this study. Research and development efforts should be directed toward preferential hydrocarbon control by mechanical or catalytic control     

Processes Influencing Secondary Aerosol Formation in the San Joaquin Valley during Winter

Abstract

Air quality data collected in the California Regional PM₁₀/PM_2.5 Air Quality Study (CRPAQS) are analyzed to qualitatively assess the processes affecting secondary aerosol formation in the San Joaquin Valley (SJV). This region experiences some of the highest fine particulate matter (PM_2.5) mass concentrations in California (≤188 μg/m³ 24-hr average), and secondary aerosol components (as a group) frequently constitute over half of the fine aerosol mass in winter. The analyses are based on 15 days of high-frequency filter and canister measurements and several months of wintertime continuous gas and aerosol measurements. The phase-partitioning of nitrogen oxide (NO_x)-related nitrogen species and carbonaceous species shows that concentrations of gaseous precursor species are far more abundant than measured secondary aerosol nitrate or estimated secondary organic aerosols. Comparisons of ammonia and nitric acid concentrations indicate that ammonium nitrate formation is limited by the availability of nitric acid rather than ammonia. Time-resolved aerosol nitrate data collected at the surface and on a 90-m tower suggest that both the daytime and nighttime nitric acid formation pathways are active, and entrainment of aerosol nitrate formed aloft at night may explain the spatial homogeneity of nitrate in the SJV. NO_x and volatile organic compound (VOC) emissions plus background O₃ levels are expected to determine NO_x oxidation and nitric acid production rates, which currently control the ammonium nitrate levels in the SJV. Secondary organic aerosol formation is significant in winter, especially in the Fresno urban area. Formation of secondary organic aerosol is more likely limited by the rate of VOC oxidation than the availability of VOC precursors in winter.     

Interpretation of Meteorological Pollutant Roses in Areas Subject to Nocturnal Drainage Winds

The composition of aerosol particle products formed from the photochemical reaction of terpenes with NO_x and the chemical reaction of terpenes with ozone was determined using direct insertion probe/high resolution mass spectrometry. Samples of the aerosol particles generated from these gas phase reactions were collected on stainless steel disks using a specially-designed impactor. The samples were analyzed using computer-controlled high resolution mass spectrometry. The photochemical reaction of limonene with NO_x produced more than 30 reaction products in the aerosol phase. The major products identified included aldehydes, alcohols, acids, peroxides, and nitrate esters of alcohols, acids, and peroxides. In addition, there was evidence of dimeric and possibly trimeric reaction products. The composition of aerosol particle products formed from the dark reaction of ozone with limonene was determined and found similar to those products generated in the photochemical reaction, excluding the nitrated species. Aerosol concentrations were monitored using nephelometry which indicated a conversion of terpene to aerosol of 50% or greater for both the limonene and terpinolene reaction systems. The results show that direct insertion probe high resolution mass spectrometric technique has the capability for determining the composition of very polar and high molecular weight materials in aerosol particles. The composition of terpene aerosol particle products and the mass spectral data obtained from their analysis can be used in further studies to determine the importance of terpene aerosol particle formation in ambient air.     

Observations of H2O2 and PAN in a rural atmosphere

Measurements of gaseous H2O2 and peroxyacetyl nitrate (PAN) concentrations in air are given for a site in rural southern England over an approximately 4-year period. In both cases the data show both diurnal and seasonal patterns. Temperature and wind direction had clear influences on the recorded concentrations of both species. There was an indication of increasing H2O2 concentrations with time. The use of a two-dimensional global model confirmed that this would be expected to occur alongside growth in ozone formation. It is suggested that, during photochemical episodes, the sequential build-up of ozone, PAN and H2O2 could be important in influencing the ability of vegetation to resist the effects of aggressive pollutants.     

Continuous measurement of peroxyacetyl nitrate (PAN) in suburban and remote areas of western China

Knowledge on atmospheric abundance of peroxyacetyl nitrate (PAN) is important in assessing the severity of photochemical pollution, and for understanding chemical transformation of reactive odd nitrogen and its impact on the budget of tropospheric ozone (O₃). In summer 2006, continuous measurements of PAN were made using an automatic GC–ECD analyzer with an on-line calibrator at a suburban site of Lanzhou (LZ) and a remote site of Mt. Waliguan (WLG) in western China, with concurrent measurements of O₃, total reactive nitrogen (NO_y) and carbon monoxide (CO). At LZ, several photochemical episodes were observed during the study, and the average mixing ratio of PAN (plus or minus standard deviation) was 0.76 (±0.89) ppbv with the maximum value of 9.13 ppbv, compared to an average value of 0.44 (±0.16) ppbv at remote WLG. The PAN mixing ratios in LZ exhibited strong diurnal variations with a maximum at noon, while enhanced concentrations of PAN were observed in the evening and a minimum in the afternoon at WLG. The daily O₃ and PAN concentration maxima showed a strong correlation (r² = 0.91) in LZ, with a regression slope (PAN/O₃) of 0.091 ppbv ppbv^?1. At WLG, six well-identified pollution plumes (lasting 2–8 h) were observed with elevated concentrations of PAN (and other trace gases), and analysis of backward particle release simulation shows that the high-PAN events at WLG were mostly associated with the transport of air masses that had passed over LZ.     

The effect of O2 and NO2 on the ring retaining products of the reaction of toluene with hydroxyl radicals

The reaction of toluene with hydroxyl radicals produces ring retaining products either from H-atom abstraction from the methyl group: benzaldehyde and benzylalcohol or from the addition of the hydroxyl radical to the aromatic ring: o-, m+p-cresol. The yields obtained in experiments carried out in nitrogen and in air matrix were statistically not significantly different. The addition of NO₂ to the reactants had no effect on the formed o-cresol, indicating that reaction of the hydroxy-methylcyclohexadienyl radical with NO₂ is not contributing significantly to the formation of o-cresol. This is in agreement with recent studies postulating the more stable toluene oxide as the intermediate resulting from the reaction of hydroxy-methylcyclohexadienyl with oxygen rather than the peroxy radical. m-nitrotoluene was the major nitrotoluene formed in the presence of NO₂, increasing linearly with increasing the initial concentration of NO₂ with zero intercept. The observed 2-methyl 1,4 benzoquinone and traces of phenol and benzene were determined to be secondary products.     

Isoprene and its degradation products as strong ozone precursors in Insubria,Northern Italy

Frequent smog episodes occur during spring, summer, and autumn in Insubria, Northern Italy. On a test site in this area the atmospheric concentration of the photo-oxidants ozone and peroxyacetyl nitrate has been monitored over a year (2000) together with ozone precursors listed in the European Union Air Quality Directive 2002/3/EC, such as nitrous oxides (NO_X) and volatile organic compounds (VOC) including hydrocarbons and carbonyls. The results of this study revealed a strong impact of biogenic isoprene on the air quality.In winter isoprene was detected at the ppt level and correlated with anthropogenic VOC. However, during the growing season isoprene exhibited a distinct diurnal variation with maximum concentrations late in the afternoon reaching up 70 ppbC attributed to strong emissions from the abundant vegetation of broad-leaf deciduous trees in this area. A new HPLC-MS method was developed for the determination of isoprene's primary atmospheric oxidation products methacrolein as its 2,4-dinitrophenylhydrazone and methyl vinyl ketone as an unusual double derivative with 2,4-dinitrophenylhydrazine. Methacrolein and methyl vinyl ketone followed the same diurnal and annual trends as isoprene. The average monthly concentration of isoprene and these products ranged from around 10 ppbC in June, July and September to 20 ppbC in August, which constitutes 15–30% of C₃–C₉ VOCs. The contribution from isoprene photo-oxidation to the ambient air formaldehyde concentrations was also found to be high during this period ranging from 30% to 60% in May, June, July and August.From the atmospheric VOC and NO_X concentrations the local photochemical ozone formation was estimated by the incremental reactivity approach. The calculations showed that in summer isoprene's contribution to the local ozone formation was as high as 50–75%.     

Photochemical oxidant pollution and vegetation: effects of mixtures of gases, fog and particles

Photochemical 'smog' contains mixtures of gases (e.g. ozone, nitrogen dioxide), and dry particles (e.g. nitrates). Intermittent fog in the same geographical area can be acidic with high concentrations of nitric acid. Results from recent field studies in the Los Angeles Basin have emphasized the relative toxicity of these components of photochemical air pollution. Studies have focused on gaseous+fog or gaseous+dry particulate effects on conifers, gaseous+fog effects on crops, and the effects of trace pollutants produced during generation of ozone on crops. Data from these studies indicate that direct alterations in growth and physiological responses were observed only with gaseous pollutants (primarily ozone), or repeated applications of highly acidic fogs (pH < 2.7). Direct particle dry deposition effects are unclear. Few interactions have been found between gaseous pollutants and acidic fog. Charcoal-filtered open-top chambers are highly effective in removing pollutants in the following order: fog (100%) > peroxyacetyl nitrate > ozone > nitrogen dioxide > sulfur dioxide > nitrate ion > ammonium ion > sulfate ion. However, nitric oxide concentrations are higher in charcoal-filtered chambers than in ambient air. The studies point out the importance of considering other components of photochemical pollution in addition to ozone, especially when investigating subtle, long-term effects on vegetation.     

Assessment of the Ozone-Nitrogen Oxide-Volatile Organic Compound Sensitivity of Mexico City through an Indicator-Based Approach: Measurements and Numerical Simulations Comparison

Abstract

The ozone (O₃) sensitivity to nitrogen oxides (NO_x, or nitric oxide [NO] + nitrogen dioxide [NO₂]) versus volatile organic compounds (VOCs) in the Mexico City metropolitan area (MCMA) is a current issue of scientific controversy. To shed light on this issue, we compared measurements of the indicator species O₃/NO_y (where NO_y represents the sum of NO + NO₂ + nitric acid [HNO₃] + peroxyacetyl nitrate [PAN] + others), NO_y, and the semiempirically derived O₃/NO_{z surrogate} (where NO_{z surrogate} is the derived surrogate NO_z, and NO_z represents NO_x reaction products, or NO_y – NO_x) with results of numerical predictions reproducing the transition regimes between NO_x and VOC sensitivities. Ambient air concentrations of O₃, NO_x, and NO_y were measured from April 14 to 25, 2004 in one downwind receptor site of photo-chemically aged air masses within Mexico City. MCMA-derived transition values for an episode day occurring during the same monitoring period were obtained through a series of photochemical simulations using the Multiscale Climate and Chemistry Model (MCCM). The comparison between the measured indicator species and the simulated spatial distribution of the indicators O₃/NO_y, O₃/NO_{z surrogate}, and NO_y in MCMA suggest that O₃ in this megacity is likely VOC-sensitive. This is in opposition to past studies that, on the basis of the observed morning VOC/NO_x ratios, have concluded that O₃ in Mexico City is NO_x-sensitive. Simulated MCMA-derived sensitive transition values for O₃/NO_y, hydrogen peroxide (H₂O₂)/HNO₃, and NO_y were found to be in agreement with threshold criteria proposed for other regions in North America and Europe, although the transition crossover for O₃/NO_z and O₃/HNO₃ was not consistent with values reported elsewhere. An additional empirical evaluation of weekend/weekday differences in average maximum O₃ concentrations and 6:00- to 9:00-a.m. NO_x and NO levels registered at the same site in April 2004 indirectly confirmed the above results. A preliminary conclusion is that additional reductions in NO_x emissions in MCMA might cause an increase in presently high O₃ levels.     

Characterization of the major chemical species in PM2.5 in the Kaohsiung City,Taiwan

The concentrations and characteristics of the major components in ambient fine particles in the urban city of Kaohsiung, Taiwan were measured and evaluated. PM_2.5 samples were collected using a dichotomous sampler from November 1998 to April 1999 and analyzed for water-soluble ion species using ion chromatography and for carbonaceous species using an elemental analyzer. It was found that SO₄²⁻, NO₃⁻, and NH₄⁺ dominated the identifiable components, and occupied 42.2% and 90.0% of PM_2.5 mass and total dissolved ionic concentrations. Carbonaceous species (organic and elemental carbon) accounted for 20.8% of PM_2.5. The secondary aerosol formed through the NO₂/SO₂ gas-to-particle conversion was estimated based on the sulfur/nitrogen oxidation ratio (SOR/NOR), i.e., sulfate sulfur/nitrate nitrogen to total sulfur/total nitrogen. The average SOR and NOR values were 0.25 and 0.07 for PM_2.5. The high SOR and NOR values obtained in this study suggested that there existed a secondary formation of SO₄²⁻ from SO₂ along with NO₃⁻ from NO₂ in the atmosphere. The secondary organic carbon formed through the volatile organic compound gas-to-particle conversion was estimated from the minimum ratio between organic and elemental carbon obtained in this study, and was found to constitute 40.0% of the total organic carbon for PM_2.5 (6.6% of the particle mass). The results obtained in this study suggest that the formation of secondary aerosols due to conversion from gaseous precursors is significant and important in urban locations.     

Causes of the elevated nitrate aerosol levels during episodic days in Taichung urban area,Taiwan

The purpose of this study is to explore the possible reasons accounting for elevated nitrate aerosol levels during high particulate days (HPD) in Taichung urban area of central Taiwan. To achieve this goal, simultaneous measurements of particulate and gaseous pollutants were carried out from September 2004 to April 2005 using an annular denuder system (ADS). The formation rate of NO₂ to nitrate aerosol, calculated using the relevant chemical reactions, was employed to interpret enhanced nitrate aerosol concentrations during HPD. The observations showed that nitrate concentration during HPD was 14 times higher than that during low particulate days (LPD). The average formation rate during HPD was 4.0% h^?1, which was 3.1 times higher than that during LPD. The quantitative analysis showed that the formation rate was mainly influenced by temperature and relative humidity. Lower temperature and higher relative humidity led much nitrate aerosol formation in HPD. Moreover, the residence time analysis of air masses staying over the studied area showed that the slow-motion air retained high nitrate concentrations due to more nitrate aerosol converted from the precursors in NOx-rich areas.     

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.