Peroxypropionyl Nitrate Research Articles

Observations of ozone, acyl peroxy nitrates, and their precursors during summer 2019 at Carlsbad Caverns National Park, New Mexico

ABSTRACT Carlsbad Caverns National Park (CAVE) is located in southeastern New Mexico and is adjacent to the Permian Basin, one of the most productive oil and natural gas (O&G) production regions in the United States. Since 2018, ozone (O3) at CAVE has frequently exceeded the 70 ppbv 8-hour National Ambient Air Quality Standard. We examine the influence of regional emissions on O3 formation using observations of O3, nitrogen oxides (NOx = NO + NO2), a suite of volatile organic compounds (VOCs), peroxyacetyl nitrate (PAN), and peroxypropionyl nitrate (PPN). Elevated O3 and its precursors are observed when the wind is from the southeast, the direction of the Permian Basin. We identify 13 days during the July 25 to September 5, 2019 study period when the maximum daily 8-hour average (MDA8) O3 exceeded 65 ppbv; MDA8 O3 exceeded 70 ppbv on 5 of these days. The results of a positive matrix factorization (PMF) analysis are used to identify and attribute source contributions of VOCs and NOx. On days when the winds are from the southeast, there are larger contributions from factors associated with primary O&G emissions; and, on high O3 days, there is more contribution from factors associated with secondary photochemical processing of O&G emissions. The observed ratio of VOCs to NOx is consistently high throughout the study period, consistent with NOx-limited O3 production. Finally, all high O3 days coincide with elevated acyl peroxy nitrate abundances with PPN to PAN ratios > 0.15 ppbv ppbv−1 indicating that anthropogenic VOC precursors, and often alkanes specifically, dominate the photochemistry. Implications: The results above strongly indicate NOx-sensitive photochemistry at Carlsbad Caverns National Park indicating that reductions in NOx emissions should drive reductions in O3. However, the NOx-sensitivity is largely driven by emissions of NOx into a VOC-rich environment, and a high PPN:PAN ratio and its relationship to O3 indicate substantial influence from alkanes in the regional photochemistry. Thus, simultaneous reductions in emissions of NOx and non-methane VOCs from the oil and gas sector should be considered for reducing O3 at Carlsbad Caverns National Park. Reductions in non-methane VOCs will have the added benefit of reducing formation of other secondary pollutants and air toxics.

Seasonal variation characteristics of atmospheric peroxyacetyl nitrate (PAN) and its source apportionment in a megacity in southern China

Owing to its biotoxicity and inductive effect on photochemical pollution, atmospheric peroxyacetyl nitrate (PAN), which is a typical product of atmospheric photochemical reactions, has attracted much research attention. However, to the best of our knowledge, few comprehensive studies have been conducted on the seasonal variation and key influencing factors of PAN concentrations in southern China. In this study, PAN, ozone (O3), precursor volatile organic compound (VOC), and other pollutant concentrations were measured online for 1 year (from October 2021 to September 2022) in Shenzhen, a megacity in the Greater Bay Area of China. The average concentrations of PAN and peroxypropionyl nitrate (PPN) were 0.54 and 0.08 parts per billion (ppb), and the maximum hourly concentrations reached 10.32 and 1.01 ppb, respectively. The results of the generalized additive model (GAM) showed that the atmospheric oxidation capacity and precursor concentration were the most important factors affecting the PAN concentration. According to the steady-state model, the average cumulative contribution to the peroxyacetyl (PA) radical formation rate by six major carbonyl compounds was calculated at 4.2 × 106 molecules cm−3 s−1, and acetaldehyde (63.0 %) and acetone (13.9 %) contributed the most. Furthermore, the photochemical-age-based parameterization method was used to analyze the source contributions of carbonyl compounds and PA radicals. The results showed that although the primary anthropogenic (40.2 %), biogenic (27.8 %), and secondary anthropogenic (16.4 %) sources were the most important contributors of PA radicals, the biogenic and secondary anthropogenic source contributions both increased considerably in summer, and the cumulative proportion of both sources reached ~70 % in July. In addition, a comparison of PAN pollution processes in different seasons revealed that in summer and winter, the PAN concentration was predominantly limited by precursors and meteorological parameters, such as light intensity, respectively.

Product study of the reactions of γ-caprolactone and γ-heptalactone initiated by OH radicals at 298 K and atmospheric pressure: Formation of acyl peroxynitrates (APN).

A product study was performed for the reaction of γ-caprolactone (GCL) and γ-heptalactone (GHL) initiated by OH radicals at (298 ± 2) K and atmospheric pressure, in presence of NOx. The identification and quantification of the products were performed in a glass reactor coupled with in situ FT-IR spectroscopy. The following products were identified and quantified with the corresponding formation yields (in %) for the OH + GCL reaction: peroxy propionyl nitrate (PPN) (52 ± 3), peroxy acetyl nitrate (PAN) (25 ± 1), and succinic anhydride (48 ± 2). For the GHL + OH reaction, the products detected with their corresponding formation yields (in %) were the following: peroxy n-butyryl nitrate (PnBN) (56 ± 2), peroxy propionyl nitrate (PPN) (30 ± 1) and succinic anhydride and (35 ± 1). Upon these results, an oxidation mechanism is postulated for the title reactions. The positions with the highest H-abstraction probabilities for both lactones are analyzed. Specifically, the increased reactivity of the C5 site, as indicated by structure reactivity estimations (SAR), is suggested by the identified products. For both GCL and GHL degradation appears to follow degradation paths including ring preservation and opening. The atmospheric implications of the APN formation as a photochemical pollutant and as NOx reservoirs of species is assessed.

Impacts of Emissions of C2‐C5 Alkanes From the U.S. Oil and Gas Sector on Ozone and Other Secondary Species

AbstractInside many U.S. oil and gas‐producing regions, the oil and gas sector dominates local anthropogenic emission fluxes of C2‐C5 alkanes. Here, we present a detailed analysis of the impact of these emissions on secondary species production over the continental United States using the GEOS‐Chem model. Oil‐ and gas‐producing areas in the central United States show the highest summertime surface ozone (O3) enhancements due to oil and gas C2‐C5 alkane emissions. The Colorado Front Range is the most impacted 8‐hr O3 non‐attainment area in the United States with 3‐hr daytime instantaneous O3 enhancements >4 ppb. From three selected non‐attainment areas, the Colorado Front Range has (1) the lowest monthly mean VOC reactivity (1.5 s−1); (2) the highest percent contribution of oil and gas sources (52%) to calculated VOC reactivity; and (3) the largest relative increases in PAN (peroxyacetyl nitrate), PPN (peroxypropionyl nitrate), and >C4 alkyl nitrates. Enhanced abundances of PAN, PPN, and >C4 alkyl nitrates have the potential to perturb remote O3 production through increased NOx export to remote regions via PAN chemistry. Globally, simulated C2‐C5 alkane emissions from the U.S. oil and gas sector contribute 0.5 Tg (~0.17%) to the tropospheric O3 burden with a ~0.27% contribution in the Northern Hemisphere.

Atmospheric fate of two relevant unsaturated ketoethers: kinetics, products and mechanisms for the reaction of hydroxyl radicals with (<i>E</i>)-4-methoxy-3-buten-2-one and (1<i>E</i>)-1-methoxy-2-methyl-1-penten-3-one

Abstract. The kinetics of the gas phase reactions of hydroxyl radicals with two unsaturated ketoethers (UKEs) at (298±3) K and 1 atm of synthetic air have been studied for the first time using the relative-rate technique in an environmental reaction chamber by in situ Fourier-transform infrared spectroscopy (FTIR). The rate coefficients obtained using propene and isobutene as reference compounds were (in units of 10−10 cm3 molecule−1 s−1) as follows: kTMBO (OH + (E)-4-methoxy-3-buten-2-one) = (1.41±0.11) and kMMPO (OH + (1E)-1-methoxy-2-methyl-1-penten-3-one) = (3.34±0.43). In addition, quantification of the main oxidation products in the presence of NOx has been performed, and degradation mechanisms for these reactions were developed. Methyl formate, methyl glyoxal, peroxyacetyl nitrate (PAN) and peroxypropionyl nitrate (PPN) were identified as main reaction products and quantified for both reactions. The results of the present study provide new insights regarding the contribution of these multifunctional volatile organic compounds (VOCs) in the generation of secondary organic aerosols (SOAs) and long-lived nitrogen containing compounds in the atmosphere. Atmospheric lifetimes and implications are discussed in light of the obtained results.

The abundance and inter-relationship of atmospheric peroxyacetyl nitrate (PAN), peroxypropionyl nitrate (PPN), O3, and NOy during the wintertime in Beijing, China

Although atmospheric peroxyacetyl nitrate (PAN) and O3 have been extensively measured in Beijing during the summertime, the abundances of PAN, peroxypropionyl nitrate (PPN) and the total odd-reactive nitrogen budget (NOy) and their inter-relationship have been studied comparatively less in the winter. Here we measured atmospheric PAN, PPN, O3, NOx, and NOy in Beijing from Nov. 2012 to Jan. 2013. Compared with our previous results in the summertime, much lower levels were observed in the winter, with the mean and maximum values of 311.8 and 1465 pptv for PAN, 52.8 and 850.6 pptv for PPN, and 11.6 and 36.7 ppbv for O3. In contrast, high levels were found as 94.2 and 374.9 ppbv for NOy, with a major constituent of NOx (75.9%). The source to the west and northwest made the significant contribution to the relatively high O3 concentrations during nighttime. PAN concentrations were highly related with the PAN-rich air mass transported from the southeast during the nighttime, whereas predominated by local photochemical production during the daylight. The distributions of NOx and NOy were dominated by local emission and photochemical production during daylight but also influenced by air masses transported from south direction during nighttime. Significant positive correlation (R2 = 0.9, p < 0.0001) between PAN and PPN with a slope (∆PPN/∆PAN) of 0.17 indicated that anthropogenic volatile organic compounds (AVOCs) dominated the photochemical formation of PANs in Beijing, and the independent relationship between the PPN/PAN ratio and PAN (>500 pptv) implied a steady state between PAN and PPN achieving rapidly in the polluted air masses. Negative correlation and slopes between PAN and O3 likely resulted from their weak photochemical productions in the winter, coupled with the large NO sources which acted as a local sink for O3, but much less so for PAN due to its enhanced thermal stability under low temperature.

Acyl Peroxy Nitrates Link Oil and Natural Gas Emissions to High Ozone Abundances in the Colorado Front Range During Summer 2015

AbstractWe present measurements of ozone (O3), acyl peroxy nitrates (APNs), and a suite of O3precursors made at the Boulder Atmospheric Observatory in Erie, Colorado, during summer 2015. We employ an empirical analysis of the APNs and a previously described positive matrix factorization of the volatile organic compounds (VOCs) to investigate the contribution of different VOC sources to high O3abundances at Boulder Atmospheric Observatory. Based on the ratio of peroxypropionyl nitrate (PPN) to peroxyacetyl nitrate (PAN), we find that anthropogenic VOC precursors dominate APN production when O3is most elevated. Propane and larger alkanes, primarily from oil and natural gas emissions in the Colorado Front Range, drive these elevated PPN to PAN ratios during high O3events. The percentage of OH reactivity associated with oil and gas emissions is also positively correlated with O3and PPN/PAN. Idealized box model simulations are used to probe the chemical mechanisms potentially responsible for these observations. We find that observed abundances of long‐lived oil and natural gas‐related VOCs are likely high enough such that the oxidation of these VOCs in a single photochemical day produces sufficient peroxy radicals to contribute to O3formation in the northern Colorado Front Range. Based on our empirical observations and box model simulations, we conclude that oil and natural gas emissions contribute to O3production on high O3days in this region during summer 2015.

Importance of biogenic volatile organic compounds to acyl peroxy nitrates (APN) production in the southeastern US during SOAS 2013

Abstract. Gas-phase atmospheric concentrations of peroxyacetyl nitrate (PAN), peroxypropionyl nitrate (PPN), and peroxymethacryloyl nitrate (MPAN) were measured on the ground using a gas chromatograph electron capture detector (GC-ECD) during the Southern Oxidants and Aerosols Study (SOAS) 2013 campaign (1 June to 15 July 2013) in Centreville, Alabama, in order to study biosphere–atmosphere interactions. Average levels of PAN, PPN, and MPAN were 169, 5, and 9 pptv, respectively, and the sum accounts for an average of 16 % of NOy during the daytime (10:00 to 16:00 local time). Higher concentrations were seen on average in air that came to the site from the urban NOx sources to the north. PAN levels were the lowest observed in ground measurements over the past two decades in the southeastern US. A multiple regression analysis indicates that biogenic volatile organic compounds (VOCs) account for 66 % of PAN formation during this study. Comparison of this value with a 0-D model simulation of peroxyacetyl radical production indicates that at least 50 % of PAN formation is due to isoprene oxidation. MPAN has a statistical correlation with isoprene hydroxynitrates (IN). Organic aerosol mass increases with gas-phase MPAN and IN concentrations, but the mass of organic nitrates in particles is largely unrelated to MPAN.

Iodine's impact on tropospheric oxidants: a global model study in GEOS-Chem

Abstract. We present a global simulation of tropospheric iodine chemistry within the GEOS-Chem chemical transport model. This includes organic and inorganic iodine sources, standard gas-phase iodine chemistry, and simplified higher iodine oxide (I2OX, X = 2, 3, 4) chemistry, photolysis, deposition, and parametrized heterogeneous reactions. In comparisons with recent iodine oxide (IO) observations, the simulation shows an average bias of ∼ +90 % with available surface observations in the marine boundary layer (outside of polar regions), and of ∼ +73 % within the free troposphere (350 hPa &lt; p &lt; 900 hPa) over the eastern Pacific. Iodine emissions (3.8 Tg yr−1) are overwhelmingly dominated by the inorganic ocean source, with 76 % of this emission from hypoiodous acid (HOI). HOI is also found to be the dominant iodine species in terms of global tropospheric IY burden (contributing up to 70 %). The iodine chemistry leads to a significant global tropospheric O3 burden decrease (9.0 %) compared to standard GEOS-Chem (v9-2). The iodine-driven OX loss rate1 (748 Tg OX yr−1) is due to photolysis of HOI (78 %), photolysis of OIO (21 %), and reaction between IO and BrO (1 %). Increases in global mean OH concentrations (1.8 %) by increased conversion of hydroperoxy radicals exceeds the decrease in OH primary production from the reduced O3 concentration. We perform sensitivity studies on a range of parameters and conclude that the simulation is sensitive to choices in parametrization of heterogeneous uptake, ocean surface iodide, and I2OX (X = 2, 3, 4) photolysis. The new iodine chemistry combines with previously implemented bromine chemistry to yield a total bromine- and iodine-driven tropospheric O3 burden decrease of 14.4 % compared to a simulation without iodine and bromine chemistry in the model, and a small increase in OH (1.8 %). This is a significant impact and so halogen chemistry needs to be considered in both climate and air quality models. 1 Here OX is defined as O3 + NO2 + 2NO3 + PAN + PMN+PPN + HNO4 + 3N2O5 + HNO3 + BrO + HOBr + BrNO2+2BrNO3 + MPN + IO + HOI + INO2 + 2INO3 + 2OIO+2I2O2 + 3I2O3 + 4I2O4, where PAN = peroxyacetyl nitrate, PPN = peroxypropionyl nitrate, MPN = methyl peroxy nitrate, and MPN = peroxymethacryloyl nitrate.

Photolysis of n-Propyl Formate in the Presence of O2 and NO2: Peroxy Formyl Propyl Nitrate CH3CH2CH2OC(O)OONO2 Synthesis and Characterization.

The photo-oxidation of n-propyl formate (initiated by chlorine atoms) was studied in the presence of NO2, and the products were identified. The Cl atom attack to the molecule occurs in four sites, leading to the formation of formic acid, carbon dioxide, dicarbonylic products, nitrates, peroxy propionyl nitrate (CH3CH2C(O)OONO2, PPN), and a new peroxynitrate, peroxy formyl propyl nitrate (CH3CH2CH2OC(O)OONO2, PFPN). To characterize bulk quantities of the PFPN, its synthesis was carried out by the photolysis of mixtures of CH3CH2CH2OC(O)H, NO2, Cl2, and O2. After purification, its infrared spectrum and thermal stability were determined. The main infrared absorption bands and their corresponding cross sections are 796, 1219, 1302, 1741, and 1831 cm(-1) (1.16, 3.11, 0.88, 2.42, and 1.34 × 10(-18) cm(2) molec(-1), respectively). Thermal decomposition was studied as a function of pressure from 6.0 to 1000 mbar at 298 K, and the activation energy was determined between 293 and 304 K at total pressures of 9.0 and 1000 mbar (Ea = 98 ± 3 and 110 ± 2 kJ/mol, respectively). The atmospheric thermal lifetimes were obtained from kinetic parameters.

Summertime distributions of peroxyacetyl nitrate (PAN) and peroxypropionyl nitrate (PPN) in Beijing: Understanding the sources and major sink of PAN

Peroxyacetyl nitrate (PAN), a major secondary pollutant in the atmosphere, has received much concern for its particular importance in atmospheric chemistry and adverse effects on human and plants. Atmospheric PAN and PPN were measured by using a gas chromatograph equipped with electron capture detector (GC-ECD) from June to September 2010, and the source and major sink for PAN were firstly studied in Beijing. The distinct diurnal variations of PAN and PPN with maximum in the afternoon were observed, and the mean and maximum values were 2.61 ± 2.57 ppbv (N = 839) and 12.5 ppbv for PAN and 0.52 ± 0.38 ppbv (N = 152) and 2.16 ppbv for PPN during the measuring period, respectively. Good correlation (R = 0.85) between PAN and PPN with a slope (ΔPPN/ΔPAN) of 0.134 indicated that anthropogenic volatile organic compounds (AVOCs) dominated the photochemical formation of PANs in Beijing. Further, we found acetaldehyde was the predominant carbonyl precursor of PAN with the contribution of 59.7% to the total peroxyacetyl (PA) radical. Methyl glyoxal, methacrolein, acetone, methyl vinyl ketone, and biacetyl contributed 7.1%, 8.8%, 19.7%, 3.4%, and 1.3% to total PA radical, respectively. Anti-correlation between PAN concentrations and the NO/NO2 ratios was found during the whole investigating period. In addition, the amount of PAN lost by thermal decomposition (TPAN) accounted for remarkable fractions of PAN observed under high temperature during both daytime and nighttime.

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 CCl4 was 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 O3 showed 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 (ΔO3/ΔPAN) ranging from 9.92 to 18.0 indicated serious air pollution in Beijing, and strong negative correlation in winter reflected strong O3 consumption by NO titration and less thermal decompositin of PAN.

Direct and simultaneous determination of trace-level carbon tetrachloride, peroxyacetyl nitrate, and peroxypropionyl nitrate using gas chromatography-electron capture detection

Gas chromatography equipped with electron capture detector (GC-ECD) has been widely used for detecting atmospheric peroxyacetyl nitrate (PAN) and peroxypropionyl nitrate (PPN). However, to the best of our knowledge, only a few capillary columns have been adopted for separation to achieve the direct and simultaneous analysis of the two atmospheric pollutants. This paper demonstrates a novel method for directly and simultaneously measuring atmospheric carbon tetrachloride (CCl4), PAN, and PPN using GC-ECD with a DB-1 separation column. The responses of the GC-ECD to PAN, PPN, and CCl4 were individually calibrated by using gas mixtures prepared via volatilization of synthesized solutions of PAN and PPN or high-purity CCl4 reagent in a Teflon Bag. The concentrations of PAN and PPN in the synthesized solutions were quantified by ion chromatography (IC). Further calibration of the GC-ECD for PAN was conducted by in situ photochemical formation of gaseous PAN which was quantified by a NOx analyzer. The two calibration methods agreed well with each other, and the overall uncertainties for measuring atmospheric PAN were estimated to be ±13% and ±15% based on the calibrations of IC and NOx, respectively. The detection limits (three times the signal to noise ratio) for PAN, PPN, and CCl4 were estimated to be 22, 36, and 5pptv (parts per trillion by volume), respectively. The atmospheric concentrations of these compounds were measured for several days in August in Beijing, and the values obtained in this study were found to be in good agreement with the data reported in the literature for Beijing using other GC-ECD methods.

Analysis of Atmospheric Peroxypropionyl Nitrate (PPN) with a Gas Chromatograph-Two ECD Accompanied a Cryogenic Collection Method

Analysis of Atmospheric Peroxypropionyl Nitrate (PPN) with a Gas Chromatograph-Two ECD Accompanied a Cryogenic Collection Method

Atmospheric chemistry of 2-ethyl hexanal: Photochemistry and oxidation in the presence of NO 2

The photolysis and oxidation mechanism of 2-ethyl hexanal (C 4H 9CH(C 2H 5)C(O)H—2-Ethal) have been investigated. The UV absorption cross sections were recorded over the range 200–350 nm at 298 K. The quantum yield for photolysis at 254 nm was determined to be 0.51 ± 0.09. Photolysis of 2-Ethal occurs by two primary paths: a concerted elimination path and a radical formation path, the latter being the main path. CO, heptane, 3-heptanol, and 3-heptanone were identified as the main products. The rate constant for the reaction with Cl atoms was determined using the relative rate technique with isopentane and cyclohexane as reference gases. The average rate constant obtained was k = (2.8 ± 0.9) × 10 −10 cm 3 molecule −1 s −1. The most important path in the oxidation mechanism was the acyl radical forming channel, which was corroborated by the analysis of the products formed via photolysis in the presence of NO 2. Those products were CO 2, CO, peroxyacetyl nitrate, peroxypropionyl nitrate, and ethyl nitrate.

Characterization of a thermal decomposition chemical ionization mass spectrometer for the measurement of peroxy acyl nitrates (PANs) in the atmosphere

Abstract. This paper presents a detailed laboratory characterization of a thermal dissociation chemical ionization mass spectrometer (TD-CIMS) for the atmospheric measurement of Peroxyacetyl nitrate (PAN) and its homologues (PANs). PANs are efficiently dissociated in a heated inlet and the resulting peroxy acyl radicals are reacted with I− ions in a flow tube. The mass spectrometer detects the corresponding carboxylate ions. PAN, peroxypropionyl nitrate (PPN), peroxyisobutyryl nitrate (PiBN), peroxy-n-butyryl nitrate (PnBN), peroxyacryloyl nitrate (APAN), peroxycrotonyl nitrates (CPAN) and peroxymethacryloyl nitrate (MPAN) were cross-calibrated with both a dual channel GC/ECD and a total odd-nitrogen (NOy) instrument for the NCAR TD-CIMS' typical aircraft operation conditions. In addition, the instrument sensitivity to a number of more exotic PANs (peroxyhydroxyacetyl nitrate, methoxyformyl peroxynitrate, and peroxybenzoyl nitrate) was evaluated qualitatively by comparisons with a long-path FTIR instrument. The sensitivity for PPN is slightly higher than that of PAN. Larger aliphatic and olefinic PAN compounds generally showed lower sensitivities. We postulate that these differences are owing to secondary reactions in the thermal decomposition region, which either reduce the yield of peroxy acyl radicals or cause losses of these radicals through intramolecular decomposition. The relative importance of these secondary reactions varies considerably between different PAN species. Results also indicate that the reaction of the larger peroxy acyl radicals with the ion-water cluster, I−(H2O)n proceeds about an order of magnitude faster than with I− alone, as has been observed for peroxy acetyl radicals. Sensitivity variations among the individual PAN species at very low water vapor were observed. The results call for careful evaluation of each PAN species to be measured and for each desired operating condition of a TD-CIMS instrument.

An aircraft-borne chemical ionization – ion trap mass spectrometer (CI-ITMS) for fast PAN and PPN measurements

Abstract. An airborne chemical ionization ion trap mass spectrometer instrument (CI-ITMS) has been developed for tropospheric and stratospheric fast in-situ measurements of PAN (peroxyacetyl nitrate) and PPN (peroxypropionyl nitrate). The first scientific deployment of the FASTPEX instrument (FASTPEX = Fast Measurement of Peroxyacyl nitrates) took place in the Arctic during 18 missions aboard the DLR research aircraft Falcon, within the framework of the POLARCAT-GRACE campaign in the summer of 2008. The FASTPEX instrument is described and characteristic properties of the employed ion trap mass spectrometer are discussed. Atmospheric data obtained at altitudes of up to ~12 km are presented, from the boundary layer to the lowermost stratosphere. Data were sampled with a time resolution of 2 s and a 2σ detection limit of 25 pmol mol−1. An isotopically labelled standard was used for a permanent on-line calibration. For this reason the accuracy of the PAN measurements is better than ±10% for mixing ratios greater than 200 pmol mol−1. PAN mixing ratios in the summer Arctic troposphere were in the order of a few hundred pmol mol−1 and generally correlated well with CO. In the Arctic boundary layer and lowermost stratosphere smaller PAN mixing ratios were observed due to a combination of missing local sources of PAN precursor gases and efficient removal processes (thermolysis/photolysis). PPN, the second most abundant PAN homologue, was measured simultaneously. Observed PPN/PAN ratios range between ~0.03 and 0.3.

Effect of Asian Dust Storms on the Ambient SO&amp;lt;sub&amp;gt;2&amp;lt;/sub&amp;gt; Concentration over North-East India: A Case Study

Ambient SO2 concentration at a high rain fall site, Shillong (25.67oN, 91.91oE, 1064 m ASL), located in North-East India, was measured during March 2009 and January 2010 with the aim to understand the effect of long range transport of pollutants from North-East Asia on the ambient SO2 levels at this relatively clean site. The concentrations recorded during the former sampling period were very high (Max: 262.3 ppb)—which decayed down gradually towards the end the sampling period—whereas those during the latter sampling period were well within the acceptable limits (Max: 29.7 ppb). This elevated SO2 concentrations during March 2009 is proposed to have association with a major cold air outbreak and an associated cyclone preceding one of the dust storm events reported in China, and a resultant sudden change in wind trajectory leading to the long range transport of pollutants to the sampling site. The argument is formulated on the basis of the back trajectory analysis performed using HYSPLIT for the month of March 2009—the plots clearly showed a drastic change in wind trajectories between 8th and 15th of March 2009 wherein the winds traveled over some of the highly polluted regions such as the Perm region of Russia—and on the results from model runs performed using the global 3-D model of tropospheric chemistry, GEOS-Chem (v8-03-01)—it clearly showed the tropospheric SO2 over Perm region in Russia peaking during Nov, Dec, Jan, Feb and Mar every year, possibly due to central heating. The observation of long range transport of SO2 from the highly industrialized areas of Perm in Russia to North-East India during dust storm events has important implications to the present understanding on its relative contribution to the Asian pollutant outflow to the Pacific during spring as the GEOS-Chem model runs also showed regions in and around Russia with relatively high concentrations of atmospheric NOx, Peroxyacetyl Nitrate, Lumped Peroxypropionyl Nitrate, HNO3, HNO4,C3H8, C2H6, SO4, NH4, Inorganic Sulphur Nitrates and Lumped Alkyl Nitrate.

Ground-based on-line measurements of peroxyacetyl nitrate (PAN) and peroxypropionyl nitrate (PPN) in the Pearl River Delta, China

Aiming at understanding the regional O3 problem and the impacts of city to rural areas, ambient peroxyacetyl nitrate (PAN) and peroxypropionyl nitrate (PPN) were measured by an on-line instrument at a back garden site (BGS), and a receptor site for urban plume from Guangzhou city. The highest mixing ratios for PAN and PPN were 3.9 and 0.7 ppbv, respectively. PAN and PPN had a similar diurnal pattern as that of O3. As revealed by the slope of the linear regression line between PPN and PAN, anthropogenic volatile organic compounds (AVOCs) dominated photochemical O3 production most of the time. From the correlation between PAN and O3, the regional background level of O3 was derived to be 28 ± 15 ppbv. Two night-time plumes containing elevated PAN and O3 were observed, and the backward-trajectory analysis supported the transport of urban plume from Guangzhou city. Based on the temporal variation of PPN/PAN, two day-time episodes were also selected to discuss the influence from Guangzhou.

Eddy covariance fluxes of acyl peroxy nitrates (PAN, PPN and MPAN) above a Ponderosa pine forest

Abstract. During the Biosphere Effects on AeRosols and Photochemistry EXperiment 2007 (BEARPEX-2007), we observed eddy covariance (EC) fluxes of speciated acyl peroxy nitrates (APNs), including peroxyacetyl nitrate (PAN), peroxypropionyl nitrate (PPN) and peroxymethacryloyl nitrate (MPAN), above a Ponderosa pine forest in the western Sierra Nevada. All APN fluxes are net downward during the day, with a median midday PAN exchange velocity of −0.3 cm s−1; nighttime storage-corrected APN EC fluxes are smaller than daytime fluxes but still downward. Analysis with a standard resistance model shows that loss of PAN to the canopy is not controlled by turbulent or molecular diffusion. Stomatal uptake can account for 25 to 50% of the observed downward PAN flux. Vertical gradients in the PAN thermal decomposition (TD) rate explain a similar fraction of the flux, suggesting that a significant portion of the PAN flux into the forest results from chemical processes in the canopy. The remaining "unidentified" portion of the net PAN flux (~15%) is ascribed to deposition or reactive uptake on non-stomatal surfaces (e.g. leaf cuticles or soil). Shifts in temperature, moisture and ecosystem activity during the summer – fall transition alter the relative contribution of stomatal uptake, non-stomatal uptake and thermochemical gradients to the net PAN flux. Daytime PAN and MPAN exchange velocities are a factor of 3 smaller than those of PPN during the first two weeks of the measurement period, consistent with strong intra-canopy chemical production of PAN and MPAN during this period. Depositional loss of APNs can be 3–21% of the gross gas-phase TD loss depending on temperature. As a source of nitrogen to the biosphere, PAN deposition represents approximately 4–19% of that due to dry deposition of nitric acid at this site.