Decomposition Of Peroxyacetyl Nitrate Research Articles

Exploring the long-term variations and high concentration episodes of peroxyacetyl nitrate in Megacity Seoul

Over the past few years, peroxyacetyl nitrate (PAN) has drawn significant attention as a key indicator of photochemical pollution owing to its intimate relationship with ozone and associated health effects. This study presents measurements conducted at the Korea University campus in Seoul during the high-ozone seasons from 2018 to 2021. PAN concentration was measured using fast gas chromatography with luminol chemiluminescence detection (GC-LCD), alongside measurements of O3, volatile organic compounds (VOCs), NO, NO2, and meteorological variables, including boundary layer height (BLH).The mean concentrations of PAN and O3 over the years were 0.56 ppbv and 35 ppbv in 2018, 1.29 ppbv and 58 ppbv in 2019, 0.21 ppbv and 50 ppbv 2020, and 0.53 ppbv and 46 ppbv in 2021, respectively. The annual variation observed in Seoul is consistent with trends seen in major cities worldwide during the COVID19 pandemic, reflecting a substantial reduction in urban emissions. Notably, the mean concentration of NOx and VOCs decreased significantly by more than 50 % and 25%, respectively, from 2019 to 2021.At temperatures above 30 °C, PAN decomposition was accelerated, decoupling a consistent positive relationship between PAN and O3 in 2020 and 2021. The results of a 0-D photochemical model (F0AM) calculation demonstrated that PAN formation primarily stems from anthropogenic VOCs, particularly > C2 alkenes. Elevated PAN concentrations during nighttime were attributed to boundary layer expansion and upper-air entrainment. Instances where PAN concentrations surged to at least 3 ppbv or higher in 2019 were attributed to biomass burning impacted air, as evidenced by concurrent elevations in K+ and OC in PM2.5, and O3.This study underscores the complex interplay of factors influencing PAN and ozone enhancements under decreased precursor levels, with an emphasis on dynamic change in the boundary layer, and long-distance transport of non-fossil sources during agricultural burning seasons.

Heterogeneous Reaction of Peroxyacetyl Nitrate on Real-World PM2.5 Aerosols: Kinetics, Influencing Factors, and Atmospheric Implications.

The formation and decomposition of peroxyacetyl nitrate (PAN), an important atmospheric nitrogen oxide reservoir, can impact the level and cycling of free radicals and nitrogen compounds in the atmosphere. PAN sinks are poorly understood, highlighting the importance of elucidating the heterogeneous reaction of PAN on aerosol surfaces. Here, we report for the first time the uptake behavior, kinetics, and potential mechanism of PAN uptake on real-world aerosol PM2.5 using a flow tube system. The uptake coefficients (γ) of PAN increased non-linearly from (1.5 ± 0.7) × 10-5 at 0% relative humidity (RH) to (9.3 ± 2.0) × 10-5 at 80% RH. The γ decrease with increasing initial PAN concentration is consistent with the Langmuir-Hinshelwood mechanism. Organic components of aerosols may promote heterogeneous loss of PAN through redox reactions. Higher γ occurs with higher water content, lower pH, and lower ionic strength in the aqueous phase of aerosols. The present study suggests that heterogeneous reaction of PAN on ambient aerosols plays a non-negligible role in the atmospheric PAN budget and provides new insights into the role of PAN in promoting atmospheric oxidation capacity during hazy periods with cold and wet weather conditions.

Influence of thermal decomposition and regional transport on atmospheric peroxyacetyl nitrate (PAN) observed in a megacity in southern China

Peroxyacetyl nitrate (PAN) is a typical secondary product of photochemical smog and is widely considered an indicator when evaluating the severity of photochemical pollution, but there have been few quantitative studies on the thermal decomposition of ambient PAN in southern China. In this study, online sampling of PAN and ozone (O3) was conducted from August to November 2020, which is the most severe photochemical pollution period of the year, in Shenzhen, a megacity in southern China. During the sampling period, two photochemical pollution periods occurred in August (EP1) and October (EP2). The mean O3 concentrations during EP1 and EP2 were very close, 36.3 and 36.9 ppb, respectively, while PAN concentrations were very different (0.66 and 1.06 ppb, respectively). The diurnal variation showed that the PAN formation rate in the initial stage of photochemical reactions (9:00–11:00) during EP1 was significantly faster than that during EP2, while there was significant consumption at noon and almost complete decomposition at night in EP1. Calculating the thermal decomposition of PAN (TPAN), we found that the average concentration of TPAN in EP1 was 8.47 ppb, approximately 9 times that in EP2 (0.94 ppb), which significantly reduced the concentration of PAN in EP1. This indicates that when using PAN as an indicator of photochemical reaction activity, the consumption of PAN due to thermal decomposition must be considered. In addition, we found that regional transport may significantly contribute to the formation of PAN by increasing the concentration of precursor VOCs, although the lifetime of PAN was only a few hours due to a large amount of thermal decomposition.

Formation of peroxyacetyl nitrate (PAN) and its impact on ozone production in the coastal atmosphere of Qingdao, North China.

Peroxyacetyl nitrate (PAN), acting as a relatively long-lived reservoir for both NOx and radicals, plays a crucial role in ozone (O3) formation in the troposphere. However, its quantitative impacts on radical concentrations and O3 production were rarely studied in the coastal atmosphere. In this study, ambient concentrations of PAN, O3, and related species were simultaneously measured from October 5 to November 10, 2018 (autumn), and July 14 to August 24, 2019 (summer) at a rural coastal site in Qingdao, North China. The formation mechanism of PAN and its impact on in-situ O3 production were explored with an observation-based chemical box model. Photochemical formation of PAN and O3 was controlled by both NOx and VOCs, and acetaldehyde and methylglyoxal were the main contributors to PAN formation. However, the sensitivities of PAN to precursors were larger than that of O3 in autumn while smaller in summer, which was mainly caused by the rapid decomposition of PAN at high temperatures. Zero-out sensitivity simulation showed that PAN could either promote or inhibit the in-situ O3 formation by affecting the radical chemistry. It tended to suppress O3 production by competing with precursors and terminating radical chain reactions under low-NOx and low-ROx circumstances but enhanced O3 production by supplying RO2 radicals under conditions with sufficient NOx. This study provides some new complementary insights into the formation mechanism of PAN and its impacts on O3 production, and has implications for the formulation of control policy to mitigate regional photochemical pollution in northern China.

Contribution of regional-scale fire events to ozone and PM2.5 air quality estimated by photochemical modeling approaches

Two specific fires from 2011 are tracked for local to regional scale contribution to ozone (O3) and fine particulate matter (PM2.5) using a freely available regulatory modeling system that includes the BlueSky wildland fire emissions tool, Spare Matrix Operator Kernel Emissions (SMOKE) model, Weather and Research Forecasting (WRF) meteorological model, and Community Multiscale Air Quality (CMAQ) photochemical grid model. The modeling system was applied to track the contribution from a wildfire (Wallow) and prescribed fire (Flint Hills) using both source sensitivity and source apportionment approaches. The model estimated fire contribution to primary and secondary pollutants are comparable using source sensitivity (brute-force zero out) and source apportionment (Integrated Source Apportionment Method) approaches. Model estimated O3 enhancement relative to CO is similar to values reported in literature indicating the modeling system captures the range of O3 inhibition possible near fires and O3 production both near the fire and downwind. O3 and peroxyacetyl nitrate (PAN) are formed in the fire plume and transported downwind along with highly reactive VOC species such as formaldehyde and acetaldehyde that are both emitted by the fire and rapidly produced in the fire plume by VOC oxidation reactions. PAN and aldehydes contribute to continued downwind O3 production. The transport and thermal decomposition of PAN to nitrogen oxides (NOX) enables O3 production in areas limited by NOX availability and the photolysis of aldehydes to produce free radicals (HOX) causes increased O3 production in NOX rich areas. The modeling system tends to overestimate hourly surface O3 at routine rural monitors in close proximity to the fires when the model predicts elevated fire impacts on O3 and Hazard Mapping System (HMS) data indicates possible fire impact. A sensitivity simulation in which solar radiation and photolysis rates were more aggressively attenuated by aerosol in the plume reduced model O3 but does not eliminate this bias. A comparison of model predicted daily average speciated PM2.5 at surface rural routine network sites when the model predicts fire impacts from either of these fires shows a tendency toward overestimation of PM2.5 organic aerosol in close proximity to these fires. The standard version of the CMAQ treats primarily emitted organic aerosol as non-volatile. An alternative approach for treating organic aerosol as semi-volatile resulted in lower PM2.5 organic aerosol from these fires but does not eliminate the bias. Future work should focus on modeling specific fire events that are well characterized in terms of size, emissions, and have extensive measurements taken near the fire and downwind to better constrain model representation of important physical and chemical processes (e.g. aerosol photolysis attenuation and organic aerosol treatment) related to wild and prescribed fires.

A semi-Lagrangian view of ozone production tendency in North American outflow in the summers of 2009 and 2010

Abstract. The Pico Mountain Observatory, located at 2225 m a.s.l. in the Azores Islands, was established in 2001 to observe long-range transport from North America to the central North Atlantic. In previous research conducted at the observatory, ozone enhancement (> 55 ppbv) in North American outflows was observed, and efficient ozone production in these outflows was postulated. This study is focused on determining the causes for high d[O3] / d[CO] values (~1 ppbv ppbv−1) observed in the summers of 2009 and 2010. The folded retroplume technique, developed by Owen and Honrath (2009), was applied to combine upwind FLEXPART transport pathways with GEOS-Chem chemical fields. The folded result provides a semi-Lagrangian view of polluted North American outflow in terms of physical properties and chemical processes, including production/loss rate of ozone and NOx produced by lightning and thermal decomposition of peroxy acetyl nitrate (PAN). Two transport events from North America were identified for detailed analysis. High d[O3] / d[CO] was observed in both events, but due to differing transport mechanisms, ozone production tendency differed between the two. A layer of net ozone production was found at 2 km a.s.l. over the Azores in the first event plume, apparently driven by PAN decomposition during subsidence of air mass in the Azores–Bermuda High. In the second event, net ozone loss occurred during transport in the lower free troposphere, yet observed d[O3] / d[CO] was high. We estimate that in both events, CO loss through oxidation contributed significantly to d[O3] / d[CO] enhancement. Thus, it is not appropriate to use CO as a passive tracer of pollution in these events. In general, use of d[O3] / d[CO] as an indicator of net ozone production/loss may be invalid for any situation in which oxidants are elevated. Based on our analysis, use of d[O3] / d[CO] to diagnose ozone enhancement without verifying the assumption of negligible CO loss is not advisable.

Impacts of midlatitude precursor emissions and local photochemistry on ozone abundances in the Arctic

We assess the impact of transport of pollution from midlatitudes on the abundance of ozone in the Arctic in summer 2006 using the GEOS‐Chem global chemical transport model and its adjoint. We find that although the impact of midlatitude emissions on ozone abundances in the Arctic is at a maximum in fall and winter, in July transport from North America, Asia, and Europe together contributed about 25% of surface ozone abundances in the Arctic. Throughout the summer, the dominant source of ozone in the Arctic troposphere was photochemical production within the Arctic, which accounted for more than 50% of the ozone in the Arctic boundary layer and as much as 30%–40% of the ozone in the middle troposphere. An adjoint sensitivity analysis of the impact of NOx emissions on ozone at Alert shows that on synoptic time scales in both the lower and middle troposphere, ozone abundances are more sensitive to emissions between 50°N and 70°N, with important influences from anthropogenic, biomass burning, soil, and lightning sources. Although local surface NOx emissions contribute to ozone formation, transport of NOx in the form of peroxyacetyl nitrate (PAN) from outside the Arctic and from the upper troposphere also contributed to ozone production in the lower troposphere. We find that in late May and June the release of NOx from PAN decomposition accounted for 93% and 55% of ozone production at the Arctic surface, respectively.

Mechanism for the gas-phase hydrogen fluoride-mediated decomposition of peroxyacetyl nitrate (PAN) studied by DFT method

Density functional theory has been used to study the mechanism of the decomposition of peroxyacetyl nitrate (CH3C(O)OONO2) in hydrogen fluoride clusters containing one to three hydrogen fluoride molecules at the B3LYP/6-311++G(d,p) and B3LYP/6-311+G(3df,3pd) levels. The calculations clarify some of the uncertainties in the mechanism of PAN decomposition in the gas phase. The energy barrier decreases from 30.5 kcal mol−1 (single hydrogen fluoride) to essentially 18.5 kcal mol−1 when catalyzed by three hydrogen fluoride molecules. As the size of the hydrogen fluoride cluster is increased, PAN shows increasing ionization along the ON bond, consistent with the proposed predissociation in which the electrophilicity of the nitrogen atom is enhanced. This reaction is found to proceed through an attack of a fluorine to the PAN nitrogen in concert with a proton transfer to a PAN oxygen. On the basis of our calculations, an alternative reaction mechanism for the decomposition of PAN is proposed. © 2009 Wiley Periodicals, Inc. Int J Quantum Chem, 2010

Role of climate change in global predictions of future tropospheric ozone and aerosols

A unified tropospheric chemistry‐aerosol model within the Goddard Institute for Space Studies general circulation model II′ is applied to simulate an equilibrium CO2‐forced climate in the year 2100 to examine the effects of climate change on global distributions of tropospheric ozone and sulfate, nitrate, ammonium, black carbon, primary organic carbon, secondary organic carbon, sea salt, and mineral dust aerosols. The year 2100 CO2 concentration as well as the anthropogenic emissions of ozone precursors and aerosols/aerosol precursors are based on the Intergovernmental Panel on Climate Change Special Report on Emissions Scenarios (SRES) A2. Year 2100 global O3 and aerosol burdens predicted with changes in both climate and emissions are generally 5–20% lower than those simulated with changes in emissions alone; as exceptions, the nitrate burden is 38% lower, and the secondary organic aerosol burden is 17% higher. Although the CO2‐driven climate change alone is predicted to reduce the global O3 burden as a result of faster removal of O3 in a warmer climate, it is predicted to increase surface layer O3 concentrations over or near populated and biomass burning areas because of slower transport, enhanced biogenic hydrocarbon emissions, decomposition of peroxyacetyl nitrate at higher temperatures, and the increase of O3 production by increased water vapor at high NOx levels. The warmer climate influences aerosol burdens by increasing aerosol wet deposition, altering climate‐sensitive emissions, and shifting aerosol thermodynamic equilibrium. Climate change affects the estimates of the year 2100 direct radiative forcing as a result of the climate‐induced changes in burdens and different climatological conditions; with full gas‐aerosol coupling and accounting for ozone and aerosols from both natural and anthropogenic sources, year 2100 global mean top of the atmosphere direct radiative forcings by O3, sulfate, nitrate, black carbon, and organic carbon are predicted to be +0.93, −0.72, −1.0, +1.26, and −0.56 W m−2, respectively, using present‐day climate and year 2100 emissions, while they are predicted to be +0.76, −0.72, −0.74, +0.97, and −0.58 W m−2, respectively, with year 2100 climate and emissions.

An ab Initio Molecular Orbital Study of the Mechanism for the Gas-Phase Water-Mediated Decomposition and the Formation of Hydrates of Peroxyacetyl Nitrate (PAN)

There is uncertainty in the mechanism for the hydrolysis of peroxyacetyl nitrate (PAN), and experimental attempts to detect products of the direct reaction have been unsuccessful. Ab initio calculations are used to examine the energetics of water-mediated decomposition of gas-phase PAN into acetic acid and peroxynitric acid. On the basis of ab initio calculations, an alternative reaction mechanism for the decomposition of PAN is proposed. The calculations indicate that the barrier for one water addition to PAN is large. However, including additional water molecules reveals a substantially lower energy route. The calculations suggest that the formation of PAN hydrate complexes are energetically favorable and stable. Additional waters are increasingly efficient at stabilizing hydrated PAN.

Ab initio studies of isomerization and dissociation reactions of peroxyacetyl nitrate (PAN)

The complex potential energy surface for the unimolecular isomerization and decomposition of peroxyacetyl nitrate (PAN, CH3C(O)OONO2), including 11 isomers, 45 interconversion transition states and 18 major dissociation products, is probed theoretically at the G2MP2//B3LYP/6-311G(2d,2p) level of theory. The geometries and relative energies for various stationary points are determined. Based on the calculated G2MP2 potential energy surface, the possible unimolecular decomposition mechanism of PAN is proposed. It is shown that the most feasible decomposition channels of PAN are those leading to 2CH3C(O)OO+NO2, 2CH3C(O)O+2NO3, and 2CH3+CO2+2NO3, respectively. Among them, the formations of the products of the first two channels are produced by the homolytic O–N and O–O bond ruptures of PAN with the bond dissociation energies of 32.3 and 33.9 kcal/mol, respectively, while the last one is initiated by the concerted C–C and O–O bond fissions via a barrier of 36.5 kcal/mol. Our results suggest that besides the first two decomposition pathways which have been reported by the literature, the last concerted bond fission dissociation channel via a well-defined transition state is also feasible, which has been confirmed by using CBS-Q and CBS-QB3 methods. Therefore, PAN dissociation occurs mainly via the homolytic O–N or O–O bond ruptures or via the concerted C–C and O–O bond fissions while the first channel is more favorable than the last two channels.

Ozone production in transpacific Asian pollution plumes and implications for ozone air quality in California

We examine the ozone production efficiency in transpacific Asian pollution plumes, and the implications for ozone air quality in California, by using aircraft and surface observations in April–May 2002 from the Intercontinental Transport and Chemical Transformation 2002 (ITCT 2K2) campaign off the California coast and the Pacific Exploration of Asian Continental Emission–B (PEACE‐B) campaign over the northwest Pacific. The observations are interpreted with a global three‐dimensional chemical transport model (GEOS‐CHEM). The model reproduces the mean features observed for CO, reactive nitrogen oxides (NOy), and ozone but underestimates the strong (∼20 ppbv) stratospheric contribution to ozone in the middle troposphere. The ITCT 2K2 aircraft sampled two major transpacific Asian pollution plumes, one on 5 May at 5–8 km altitude with CO up to 275 ppbv but no elevated ozone and one on 17 May at 2.5–4 km altitude with CO up to 225 ppbv and ozone up to 90 ppbv. We show that the elevated ozone in the latter plume is consistent with production from peroxyacetylnitrate (PAN) decomposition during subsidence of the plume over the northeast Pacific. This production is particularly efficient because of the strong radiation and low humidity of the subsiding environment. We argue that such PAN decomposition represents a major and possibly dominant component of the ozone enhancement in transpacific Asian pollution plumes. Strong dilution of Asian pollution plumes takes place during entrainment in the U.S. boundary layer, greatly reducing their impact at U.S. surface sites. California mountain sites are more sensitive to Asian pollution because of their exposure to the free troposphere. Model results indicate a mean Asian pollution enhancement of 7 ppbv ozone at Sequoia National Park in May 2002 on those days when the 8‐hour average ozone concentration exceeded 80 ppbv.

Thermal decomposition of peroxy acetyl nitrate CH3C(O)OONO2.

The thermal decomposition of peroxy acetyl nitrate (PAN) is investigated by low pressure flash thermolysis of PAN highly diluted in noble gases and subsequent isolation of the products in noble gas matrices at low temperatures and by density functional computations. The IR spectroscopically observed formation of CH3C(O)OO and H2CCO (ketene) besides NO2, CO2, and HOO implies a unimolecular decay pathway for the thermal decomposition of PAN. The major decomposition reaction of PAN is bond fission of the O-N single bond yielding the peroxy radical. The O-O bond fission pathway is a minor route. In the latter case the primary reaction products undergo secondary reactions whose products are spectroscopically identified. No evidence for rearrangement processes as the formation of methyl nitrate is observed. A detailed mapping of the reaction pathways for primary and secondary reactions using quantum chemical calculations is in good agreement with the experiment and predicts homolytic O-N and O-O bond fissions within the PAN molecule as the lowest energetic primary processes. In addition, the first IR spectroscopic characterization of two rotameric forms for the radical CH3C(O)OO is given.

Air‐surface exchange of peroxyacetyl nitrate at a grassland site

Direct measurements of the dry deposition velocity of peroxyacetyl nitrate (PAN) were made during the daytime between the months of July and October above a grassland surface in northern Illinois by a modified Bowen ratio technique. Differences in the air temperature, water vapor content, and PAN concentration were measured between the heights of 3.0 m and 0.92 m. Although the measurement uncertainties were large, the cumulative data indicate a slight downward flux of PAN, with an average and standard error of 0.13 ± 0.13 cm s−1 for the dry deposition velocity. Theoretical calculations showed that thermochemical decomposition of PAN on leaf and soil surfaces heated to temperatures above the ambient air levels would contribute less than 15% of the total PAN flux at the elevations of the PAN measurements. A theoretical evaluation of the transfer of PAN through leaf stomata and the plant cuticular membrane indicated that uptake of PAN by vegetation during the daytime is controlled by transfer through the leaf stomata rather than the cuticular membrane. The stomatal resistance for PAN is greater by a factor of 1.6 than the value for O3. The mesophyll resistance for O3 is also expected to be less than the value for PAN, because O3 has more reaction sites within plant cells and reacts faster than PAN with protein thiols of the cell membranes. Measurements from other studies indicate that the dry deposition velocity for PAN above a vegetated surface during the daytime is lower by a factor of 0.5–0.3 than for O3. Our measurements of the PAN deposition velocity agree with the results of previous studies and with theoretical calculations based on the physicochemical properties of PAN and the grassland surface. These measurements imply that removal of PAN from the daytime atmospheric boundary layer by thermochemical decomposition is more rapid than dry deposition to a grassland surface.

Asian outflow and trans‐Pacific transport of carbon monoxide and ozone pollution: An integrated satellite, aircraft, and model perspective

Satellite observations of carbon monoxide (CO) from the Measurements of Pollution in the Troposphere (MOPITT) instrument are combined with measurements from the Transport and Chemical Evolution Over the Pacific (TRACE‐P) aircraft mission over the northwest Pacific and with a global three‐dimensional chemical transport model (GEOS‐CHEM) to quantify Asian pollution outflow and its trans‐Pacific transport during spring 2001. Global CO column distributions in MOPITT and GEOS‐CHEM are highly correlated (R2 = 0.87), with no significant model bias. The largest regional bias is over Southeast Asia, where the model is 18% too high. A 60% decrease of regional biomass burning emissions in the model (to 39 Tg yr−1) would correct the discrepancy; this result is consistent with TRACE‐P observations. MOPITT and TRACE‐P also give consistent constraints on the Chinese source of CO from fuel combustion (181 Tg CO yr−1). Four major events of trans‐Pacific transport of Asian pollution in spring 2001 were seen by MOPITT, in situ platforms, and GEOS‐CHEM. One of them was sampled by TRACE‐P (26–27 February) as a succession of pollution layers over the northeast Pacific. These layers all originated from one single event of Asian outflow that split into northern and southern plumes over the central Pacific. The northern plume (sampled at 6–8 km off California) had no ozone enhancement. The southern subsiding plume (sampled at 2–4 km west of Hawaii) contained a 8–17 ppbv ozone enhancement, driven by decomposition of peroxyacetylnitrate (PAN) to nitrogen oxides (NOx). This result suggests that PAN decomposition in trans‐Pacific pollution plumes subsiding over the United States could lead to significant enhancements of surface ozone.

Evidence of the impact of urban plumes on remote sites in the Eastern Mediterranean

Peroxyacetyl nitrate (PAN) is a well-known tracer of anthropogenically related impacts in photochemical smog formation and is usually found in heavily polluted urban air worldwide. Over the last decades its abundance in urban air has also been confirmed for Greek urban sites such as Athens or Thessaloniki. Due to the strong temperature dependence of PAN decomposition, PAN has also been identified as a long distance tracer of human activities. This behaviour is clearly discernible at low temperatures either under corresponding meteorological conditions or at higher altitudes. Information about the medium-range impact of PAN in the Eastern Mediterranean is still scarce. This study analyses PAN time series obtained simultaneously at two sites on the island of Crete located at two different altitudes (coastal site, mountain site at 1020 m a.s.l.; distance between the sites about 20 km) during the photochemical activity and solar ultraviolet radiation (PAUR-II) campaign in May/June 1999. Within the range of 270 km no metropolitan area is located, and the surrounding water surfaces represent an area almost free of stationary emission sources. The results from the PAUR-II campaign both show uniform diurnal variations of PAN at both sites indicating regional formation, as well as completely different patterns indicating that medium-range transport is effective. The metropolitan areas of Athens and Istanbul are likely emission sources.

Global chemical model analysis of biomass burning and lightning influences over the South Pacific in austral spring

A global three‐dimensional model of tropospheric chemistry driven by reanalyzed European Centre for Medium‐Range Weather Forecasts meteorological data is used to examine the sources of O3, CO, and nitrogen oxides (NOx = NO + NO2) in the South Pacific troposphere during the NASA Pacific Exploratory Mission to the Tropics (PEM‐Tropics A) in September–October 1996. Aircraft observations up to 12 km during that mission revealed considerable biomass burning influence on O3 and CO in terms of elevated pollution layers and regional enhancements. The model reproduces the long‐range transport of biomass burning effluents from southern Africa and South America in the westerly subtropical flow over the South Pacific. Meteorological conditions in 1996 were particularly favorable for this transport. Africa and South America make comparable contributions to the biomass burning pollution over the South Pacific; the contribution from Australia and Indonesia is much less. Biomass burning dominates the supply of NOx in the lower troposphere over the South Pacific (through long‐range transport and decomposition of peroxyacetylnitrate), but lightning dominates in the upper troposphere. Observations in PEM‐Tropics A and elsewhere indicate low HNO3/NOx concentration ratios and an imbalance in the chemical budget of NOx in the upper troposphere. We reproduce these observations in our model and show that they reflect the subsidence of primary NOx injected by lightning into the uppermost troposphere, rather than any fast chemistry recycling HNO3 to NOx. We find that biomass burning and lightning made similar contributions to O3 production over the South Pacific during PEM‐Tropics A. Biomass burning plumes sampled in PEM‐Tropics A contained little NOx, and the O3 enhancements observed in these plumes originated from production over the source continents rather than over the South Pacific.

Ozone photochemistry and the role of peroxyacetyl nitrate in the springtime northeastern Pacific troposphere: Results from the Photochemical Ozone Budget of the Eastern North Pacific Atmosphere (PHOBEA) campaign

In the spring of 1999 airborne measurements of NO, O3, peroxyacetyl nitrate (PAN), CO, CH4, H2O, volatile organic compounds, aerosols (particle count, light scattering, and light absorption), NO2 photolysis frequency, and standard meteorological variables were made off the coast of Washington State as part of the Photochemical Ozone Budget of the Eastern North Pacific Atmosphere (PHOBEA) experiment. These measurements were used to constrain a photochemical box model to calculate the ozone photochemical tendency, T(O3), in this region. T(O3) in marine flow from the remote Pacific was found to be weakly ozone destroying from the surface up to 8 km. Values of T(O3) increased from −0.83 ppbv d−1 in the 0–2 km layer to −0.11 ppbv d−1 in the 6–8 km layer. These results are compared to T(O3) from other photochemistry experiments in the springtime Pacific. We also used the model to investigate the impacts of PAN decomposition on the mixing ratio of NOx (defined here as NO+NO2+NO3+2N2O5+ HNO2 +HNO4) and on T(O3). PAN decomposition was found to contribute from 11 to 30% toward NOx production and to enhance T(O3) by 0.13 to 0.41 ppbv d−1. The impacts of PAN decomposition were further investigated in a case study where measurements were made in a strongly subsiding air mass. In this air mass, PAN induced perturbations to IMOx and T(O3) reached 20.1 pptv and 1.45 ppbv d−1, respectively, more than three times that found in marine background average. Finally, we estimate how T(O3) in the northeast Pacific atmosphere may change as a result of increasing anthropogenic NOx emissions from Asia. The calculations suggest that while O3 mixing ratios in the northeast Pacific are likely to increase, T(O3) will remain close to its current value as a result of offsetting factors.

Oxidized nitrogen and ozone production efficiencies in the springtime free troposphere over the Alps

The Free Tropospheric Experiment (FREETEX’98) was conducted at the Jungfraujoch Observatory in the Swiss Alps (3580 in above sea level) during the well‐documented spring maximum in ozone. In spring the Jungfraujoch frequently lies in the free troposphere but can also be influenced by air from the planetary boundary layer. Measurements of NOx, NOy, peroxy‐acetylnitrate (PAN), HCHO, O3, CO, nonmethane hydrocarbons, peroxy radicals, j(O1D), j(NO2), and a variety of other tropospheric constituents crucial to ozone photochemical cycles were made over a 1‐month period. Two independent measurements of NOx, NOy, and PAN showed good agreement. Average free tropospheric daytime NO levels were about 50 pptv, sufficient to sustain photochemical ozone formation. Although high mixing ratios were encountered, PAN decomposition did not contribute to NOx production during FREETEX’98. Ozone production efficiencies (E N) derived from observed ΔO3/(NOz) ratios in free tropospheric air were 20–30 molecules of O3 produced per NOx molecule oxidized and agreed well with a photochemical model. A much lower ozone production efficiency of 4 was determined in a photochemically aged air mass arriving from southern Europe, in line with other measurements and calculations in regimes containing high levels of oxidized nitrogen. Model simulations indicated that by sequestering NOx and HO2, low‐temperature formation of peroxynitric acid (PNA) decreased ozone production by 20% and instantaneous ozone production efficiencies by 40%, whereas PAN formation had little effect. The model reproduced well the observed sharp transformation from ozone production to ozone destruction (defined as ΔO3/Delta;(NOz) = 0) at 20–25 pptv NO. The observed and calculated strong dependence of EN on NOx concentration in the low‐NOx regime highlights the difficulty in assigning a single O3 production efficiency value to remote regions, where most of the CO and CH4 in the atmosphere are oxidized.

Peroxyacetyl nitrate (PAN) concentrations in the Antarctic troposphere measured during the photochemical experiment at Neumayer (PEAN'99)

Because investigations of PAN at higher southern latitudes are very scarce, we measured surface PAN concentrations for the first time in Antarctica. During the Photochemical Experiment at Neumayer (PEAN'99) campaign mean surface PAN mixing ratios of 13±7 pptv and maximum values of 48 pptv were found. When these PAN mixing ratios were compared to the sum of NO x and inorganic nitrate they were found to be equal or higher. Low ambient air temperatures and low PAN concentrations caused a slow homogeneous PAN decomposition rate of approximately 5×10 −2 pptv h −1. These slow decay rates were not sufficient to firmly establish the simultaneously observed NO x concentrations. In addition, low concentration ratios of [HNO 3]/[NO x ] imply that the photochemical production of NO x within the snow pack can influence surface NO x mixing ratios in Antarctica. Alternate measurements of PAN mixing ratios at two different heights above the snow surface were performed to derive fluxes between the lower troposphere and the underlying snow pack using calculated friction velocities. Most of the concentration differences were below the precision of the measurements. Therefore, only an upper limit for the PAN flux of ±1×10 13 molecules m −2 s −1 without a predominant direction can be estimated. However, PAN fluxes below this limit can still influence both the transfer of nitrogen compounds between atmosphere and ice, and the PAN budget in higher southern latitudes.