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A product study of the isoprene+NO3 reaction

Oxidation of isoprene through reaction with NO3 radicals is a significant sink for isoprene that persists after dark. The main products of the reaction are multifunctional nitrates. These nitrates constitute a significant NOx sink in the nocturnal boundary layer and they likely play an important role in formation of secondary organic aerosol. Products of the isoprene+NO3 reaction will, in many locations, be abundant enough to affect nighttime radical chemistry and to persist into daytime where they may represent a source of NOx. Product formation in the isoprene + NO3 reaction was studied in a smog chamber at Purdue University. Isoprene nitrates and other hydrocarbon products were observed using Proton Transfer Reaction-Mass Spectrometry (PTR-MS) and reactive nitrogen products were observed using Thermal Dissociation–Laser Induced Fluorescence (TD-LIF). The organic nitrate yield is found to be 65±12% of which the majority was nitrooxy carbonyls and the combined yield of methacrolein and methyl vinyl ketone (MACR+MVK) is found to be &sim;10%. PTR-MS measurements of nitrooxy carbonyls and TD-LIF measurements of total organic nitrates agreed well. The PTR-MS also observed a series of minor oxidation products which were tentatively identified and their yields quantified These other oxidation products are used as additional constraints on the reaction mechanism.
A review of Secondary Organic Aerosol (SOA) formation from isoprene

Recent field and laboratory evidence indicates that the oxidation of isoprene, (2-methyl-1,3-butadiene, C5H8) forms secondary organic aerosol (SOA). Global biogenic emissions of isoprene (600 Tg yr−1) are sufficiently large that the formation of SOA in even small yields results in substantial production of atmospheric particulate matter, likely having implications for air quality and climate. Here we present a review of field measurements, experimental work, and modeling studies aimed at understanding the mechanisms, yield, and atmospheric importance of isoprene-derived SOA. SOA yields depend on a number of factors, including organic aerosol loading (Mo), NOx level (RO2 chemistry), and, because of the importance of multigenerational chemistry, the degree of oxidation. These dependences are not always included in SOA modules used in atmospheric transport models, and instead most yield parameterizations rely on a single set of chamber experiments (carried out over a limited range of conditions); this may lead to very different estimates of the atmospheric importance of isoprene SOA. New yield parameterizations, based on all available laboratory data (Mo=0–50 μg m−3), are presented here, so that SOA formation may be computed as a function of Mo, NOx level, and temperature. Current research needs and future research directions are identified.
Source apportionment of PM2.5 in Seoul, Korea

PM2.5 samples were collected at a centrally located urban monitoring site in Seoul, Korea, every third day from March 2003 to December 2006 and analyzed for their chemical constituents. Sources were identified using positive matrix factorization (PMF). A total of 393 samples were obtained during the sampling period, and 20 chemical species were measured. Nine PM2.5 source categories were identified providing physically realistic profiles and interesting insights into the source contributions to the ambient mass concentrations. The major contributors of PM2.5 were secondary nitrate (20.9%), secondary sulfate (20.5%), gasoline-fueled vehicles (17.2%), and biomass burning (12.1%), with lesser contributions from diesel emissions (8.1%), soil (7.4%), industry (6.7%), road salt and two-stroke vehicles (5.1%), and aged sea salt (2.2%). PM2.5 levels in Seoul were influenced by both local urban activities and regional-scale transport. Conditional probability function (CPF) results identified possible source directions of local sources such as motor vehicles (gasoline and diesel), industry, and road salt. Potential source contribution function (PSCF) results showed that possible source areas contributing to the elevated secondary particle concentrations (sulfate and nitrate) in Seoul to be the major industrial areas in China.
The influence of foreign vs. North American emissions on surface ozone in the US

As part of the Hemispheric Transport of Air Pollution (HTAP; <a href="http://www.htap.org" target="_blank">http:// www.htap.org</a>) project, we analyze results from 15 global and 1 hemispheric chemical transport models and compare these to Clean Air Status and Trends Network (CASTNet) observations in the United States (US) for 2001. Using the policy-relevant maximum daily 8-h average ozone (MDA8 O3) statistic, the multi-model ensemble represents the observations well (mean r2=0.57, ensemble bias = +4.1 ppbv for all US regions and all seasons) despite a wide range in the individual model results. Correlations are strongest in the northeastern US during spring and fall (r2=0.68); and weakest in the midwestern US in summer (r2=0.46). However, large positive mean biases exist during summer for all eastern US regions, ranging from 10–20 ppbv, and a smaller negative bias is present in the western US during spring (~3 ppbv). In nearly all other regions and seasons, the biases of the model ensemble simulations are ≤5 ppbv. Sensitivity simulations in which anthropogenic O3-precursor emissions (NOx + NMVOC + CO + aerosols) were decreased by 20% in four source regions: East Asia (EA), South Asia (SA), Europe (EU) and North America (NA) show that the greatest response of MDA8 O3 to the summed foreign emissions reductions occurs during spring in the West (0.9 ppbv reduction due to 20% emissions reductions from EA + SA + EU). East Asia is the largest contributor to MDA8 O3 at all ranges of the O3 distribution for most regions (typically ~0.45 ppbv) followed closely by Europe. The exception is in the northeastern US where emissions reductions in EU had a slightly greater influence than EA emissions, particularly in the middle of the MDA8 O3 distribution (response of ~0.35 ppbv between 35–55 ppbv). EA and EU influences are both far greater (about 4x) than that from SA in all regions and seasons. In all regions and seasons O3-precursor emissions reductions of 20% in the NA source region decrease MDA8 O3 the most – by a factor of 2 to nearly 10 relative to foreign emissions reductions. The O3 response to anthropogenic NA emissions is greatest in the eastern US during summer at the high end of the O3 distribution (5–6 ppbv for 20% reductions). While the impact of foreign emissions on surface O3 in the US is not negligible – and is of increasing concern given the recent growth in Asian emissions – domestic emissions reductions remain a far more effective means of decreasing MDA8 O3 values, particularly those above 75 ppb (the current US standard).
Attribution of ozone radiative forcing trend to individual NOx sources

Decadal means of ozone fields from transient E39/C climate-chemistry simulations (1960–2019) are analysed and temporally developing ozone radiative forcings (RF) are investigated which result from individual ozone precursor sources like road traffic, industry, air traffic, etc. We study how effective NOx emissions from different sources produce ozone. This ozone production efficiency is mainly dependent on the altitude of NOx emission and on the amount of background NOx. For example, our study shows that the ozone production efficiency of lightning and air traffic have a five and two time higher ozone production efficiency than ground based sources. The radiative efficiency of ozone (i.e. the radiative forcing per molecule) is mainly dependent on the surface temperature, but also, to a lesser degree, on the altitude of added ozone. Lightning, for example, causes the highest specific RF due to the fact that lightning primarily enhances ozone in low latitudes in the mid-troposphere. Superimposed on these effects, is a saturation effect which causes a decreasing RF efficiency with increasing background ozone. A consequence of this saturation effect is an underestimation of total RF by about 10% if the component RFs of individual ozone sources are calculated separately and added up afterwards. The results show that the time development of emissions (1960–2019) control the RF changes for most sources. RF changes are slightly reduced due to a changing atmospheric composition (10–25%) for all but the aircraft sources, and due to RF saturation (2–5%).
In-cloud processes of methacrolein under simulated conditions – Part 1: Aqueous phase photooxidation

The photooxidation of methacrolein was studied in the aqueous phase under simulated cloud droplet conditions. The obtained rate constant of OH-oxidation of methacrolein at 6°C in unbuffered solutions was 5.8(±0.9)×109 M−1 s−1. The measured rate coefficient is consistent with OH-addition on the C=C bond. This was confirmed by the mechanism established on the study of the reaction products (at 25°C in unbuffered solutions) where methylglyoxal, formaldehyde, hydroxyacetone and acetic acid/acetate were the main reaction products. An upper limit for the total carbon yield was estimated to range from 53 to 85%, indicating that some reaction products remain unidentified. A possible source of this mismatch is the formation of higher molecular weight compounds as primary reaction products which are presented in El Haddad et al. (2009) and Michaud et al. (2009).
First steps towards the assimilation of IASI ozone data into the MOCAGE-PALM system

With the use of data assimilation, we study the quality of the Infrared Atmospheric Sounding Interferometer (IASI) total ozone column measurements. The IASI data are provided by the inversion of IASI radiances performed at the Laboratoire ATmosphères, Milieux, Observations Spatiales (LATMOS). This data set is initially compared on a five-month period to a three-dimensional time varying ozone field that we take as a reference. This reference field results from the combined assimilation of ozone profiles from the Microwave Limb Sounder (MLS) instrument and of total ozone columns from the SCanning Imaging Absorption spectroMeter for Atmospheric CHartographY (SCIAMACHY) instrument. It has low systematic and random errors when compared to ozonesondes and Ozone Monitoring Instrument (OMI) data. The comparison shows that on average, the LATMOS-IASI data tends to overestimate the total ozone columns by 2% to 8%. The random observation error of the LATMOS-IASI data is estimated to about 7%, except over polar regions and deserts where it is higher. The daytime data have generally lower biases but higher random error than the nighttime data. Using this information, the LATMOS-IASI data are then assimilated, combined with the MLS data. This first LATMOS-IASI data assimilation experiment shows that the resulting analysis is quite similar to the one obtained from the combined MLS and SCIAMACHY data assimilation. The differences are mainly due to the lack of SCIAMACHY measurements during polar night, and to the higher LATMOS-IASI random errors especially over the southern polar region.
In-cloud processes of methacrolein under simulated conditions – Part 2: Formation of secondary organic aerosol

The fate of methacrolein in cloud evapo-condensation cycles was experimentally investigated. To this end, aqueous-phase reactions of methacrolein with OH radicals were performed (as described in Liu et al., 2009), and the obtained solutions were then nebulized and dried into a mixing chamber. ESI-MS and ESI-MS/MS analyses of the aqueous phase composition denoted the formation of high molecular weight multifunctional products containing hydroxyl, carbonyl and carboxylic acid moieties. The time profiles of these products suggest that their formation can imply radical pathways. These high molecular weight organic products are certainly responsible for the formation of secondary organic aerosol (SOA) observed during the nebulization experiments. The size, number and mass concentration of these particles increased significantly with the reaction time: after 22 h of reaction, the aerosol mass concentration was about three orders of magnitude higher than the initial aerosol quantity. The evaluated SOA yield ranged from 2 to 12%. These yields were confirmed by another estimation method based on the hygroscopic and volatility properties of the obtained SOA measured and reported by Michaud et al. (2009). These results provide, for the first time to our knowledge, strong experimental evidence that cloud processes can act, through photooxidation reactions, as important contributors to secondary organic aerosol formation in the troposphere.
Quantifying atmospheric nitrate formation pathways based on a global model of the oxygen isotopic composition (Δ17O) of atmospheric nitrate

The oxygen isotopic composition (Δ17O) of atmospheric nitrate is a function of the relative abundance of atmospheric oxidants (O3, ROx=OH+HO2+RO2) and the formation pathway of nitrate from its precursor NOx (=NO+NO2). Coupled observations and modeling of nitrate Δ17O can be used to quantify the relative importance of chemical formation pathways leading to nitrate formation and reduce uncertainties in the budget of reactive nitrogen chemistry in the atmosphere. We present the first global model of atmospheric nitrate Δ17O and compare with available observations. The largest uncertainty for calculations of nitrate Δ17O is the unconstrained variability in the Δ17O value of tropospheric ozone. The model shows the best agreement with a global compilation of observations when assuming a Δ17O value of tropospheric ozone equal to 35&permil; and preferential oxidation of NOx by the terminal oxygen atoms of ozone. Calculated values of annual-mean nitrate Δ17O in the lowest model layer (0–200 m above the surface) vary from 7&permil; in the tropics to 41&permil; in the polar-regions. The global, annual-mean tropospheric inorganic nitrate burden is dominated by nitrate formation via NO2+OH (76%), followed by N2O5 hydrolysis (18%) and NO3+DMS/HC (4%). Calculated nitrate Δ17O is sensitive to the relative importance of each nitrate formation pathway, suggesting that observations of nitrate Δ17O can be used to quantify the importance of individual reactions (e.g. N2O5 hydrolysis) leading to nitrate formation if the Δ17O value of ozone is known.
Modelling chemistry over the Dead Sea: bromine and ozone chemistry

Measurements of O3 and BrO concentrations over the Dead Sea indicate that Ozone Depletion Events (ODEs), widely known to happen in polar regions, are also occuring over the Dead Sea due to the very high bromine content of the Dead Sea water. However, we show that BrO and O3 levels as they are detected cannot solely be explained by high Br− levels in the Dead Sea water and the release of gas phase halogen species out of sea borne aerosol particles and their conversion to reactive halogen species. It is likely that other sources for reactive halogen compounds are needed to explain the observed concentrations for BrO and O3. To explain the chemical mechanism taking place over the Dead Sea leading to BrO levels of several pmol/mol we used the one-dimensional model MISTRA which calculates microphysics, meteorology, gas and aerosol phase chemistry. We performed pseudo Lagrangian studies by letting the model column first move over the desert which surrounds the Dead Sea region and then let it move over the Dead Sea itself. To include an additional source for gas phase halogen compounds, gas exchange between the Dead Sea water and the atmosphere is treated explicitly. Model calculations indicate that this process has to be included to explain the measurements.