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The predicted distribution of semi-volatile organic components between the gaseous and condensed phase as a function of ambient relative humidity and the specific form of the partitioning model used has been investigated. A mole fraction based model, modified so as not to use molar mass in the calculation, was found to predict identical RH dependence of component partitioning to that predicted by the conventional mass-based partitioning model which uses a molar mass averaged according to the number of moles in the condensed phase. A recently reported third version of the partitioning model using individual component molar masses was shown to give significantly different results to the other two models. Further sensitivities to an assumed pre-existing particulate loading and to parameterised organic component non-ideality are explored and shown to contribute significantly to the variation in predicted secondary organic particulate loading.
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The organic aerosol (OA) dataset from an Aerodyne Aerosol Mass Spectrometer (Q-AMS) collected at the Pittsburgh Air Quality Study (PAQS) in September 2002 was analyzed with Positive Matrix Factorization (PMF). Three components – hydrocarbon-like organic aerosol OA (HOA), a highly-oxygenated OA (OOA-1) that correlates well with sulfate, and a less-oxygenated, semi-volatile OA (OOA-2) that correlates well with nitrate and chloride – are identified and interpreted as primary combustion emissions, aged SOA, and semivolatile, less aged SOA, respectively. The complexity of interpreting the PMF solutions of unit mass resolution (UMR) AMS data is illustrated by a detailed analysis of the solutions as a function of number of components and rotational forcing. A public web-based database of AMS spectra has been created to aid this type of analysis. Realistic synthetic data is also used to characterize the behavior of PMF for choosing the best number of factors, and evaluating the rotations of non-unique solutions. The ambient and synthetic data indicate that the variation of the PMF quality of fit parameter (<i>Q</i>, a normalized chi-squared metric) vs. number of factors in the solution is useful to identify the minimum number of factors, but more detailed analysis and interpretation are needed to choose the best number of factors. The maximum value of the rotational matrix is not useful for determining the best number of factors. In synthetic datasets, factors are "split" into two or more components when solving for more factors than were used in the input. Elements of the "splitting" behavior are observed in solutions of real datasets with several factors. Significant structure remains in the residual of the real dataset after physically-meaningful factors have been assigned and an unrealistic number of factors would be required to explain the remaining variance. This residual structure appears to be due to variability in the spectra of the components (especially OOA-2 in this case), which is likely to be a key limit of the retrievability of components from AMS datasets using PMF and similar methods that need to assume constant component mass spectra. Methods for characterizing and dealing with this variability are needed. Interpretation of PMF factors must be done carefully. Synthetic data indicate that PMF internal diagnostics and similarity to available source component spectra together are not sufficient for identifying factors. It is critical to use correlations between factor and external measurement time series and other criteria to support factor interpretations. True components with <5% of the mass are unlikely to be retrieved accurately. Results from this study may be useful for interpreting the PMF analysis of data from other aerosol mass spectrometers. Researchers are urged to analyze future datasets carefully, including synthetic analyses, and to evaluate whether the conclusions made here apply to their datasets.
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We have performed a series of simulations with an aerosol dynamics box model to study the connection between new particle formation and sulphuric acid concentration. For nucleation either activation mechanism with a linear dependence on the sulphuric acid concentration, kinetic mechanism with a squared dependence on the sulphuric acid concentration or ternary H<sub>2</sub>O-H<sub>2</sub>SO<sub>4</sub>-NH<sub>3</sub> nucleation was assumed. The aim was to study the factors that affect the sulphuric acid dependence during the early stages of particle growth, and specifically to find conditions which would yield the linear dependence between the particle number concentration at 3–6 nm and sulphuric acid, as observed in field experiments. The simulations showed that the correlation with sulphuric acid may change during the growth from nucleation size to 3–6 nm size range, the main reason being the size dependent growth rate between 1 and 3 nm. In addition, the assumed size for the nucleated clusters had a crucial impact on the sulphuric acid dependence at 3 nm. A linear dependence between the particle number concentration at 3 nm and sulphuric acid was achieved, when activation nucleation mechanism was used with a low saturation vapour pressure for the condensable organic vapour, or with nucleation taking place at ~2 nm instead of ~1 nm. Simulations with activation, kinetic and ternary nucleation showed that ternary nucleation reproduces too steep dependence on sulphuric acid as compared to the linear or square dependence observed in field measurements.
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Field and lab measurements suggest that low-molecular weight (MW) organic acids and bases exist in accumulation and nucleation mode particles, despite their relatively high pure-liquid vapor pressures. The mechanism(s) by which such compounds contribute to the mass growth of existing aerosol particles and newly formed particles has not been thoroughly explored. One mechanism by which low-MW compounds may contribute to new particle growth is through the formation of organic salts. In this paper we use thermodynamic modeling to explore the potential for organic salt formation by atmospherically relevant organic acids and bases for two system types: one in which the relative contribution of ammonia vs. amines in forming organic salts was evaluated, the other in which the decrease in volatility of organic acids and bases due to organic salt formation was assessed. The modeling approach employed relied heavily on group contribution and other estimation methods for necessary physical and chemical parameters. The results of this work suggest that amines may be an important contributor to organic salt formation, and that experimental data are greatly needed to improve our understanding of organic salt formation in atmospherically relevant systems and to accurately predict the potential contribution of such salts to new particle growth.
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Toluene and other aromatics have long been viewed as the dominant anthropogenic secondary organic aerosol (SOA) precursors, but the SOA mass yields from toluene reported in previous studies vary widely. Experiments conducted in the Carnegie Mellon University environmental chamber to study SOA formation from the photo-oxidation of toluene show significantly larger SOA production than parameterizations employed in current air-quality models. Aerosol mass yields depend on experimental conditions: yields are higher under higher UV intensity, under low-NO<sub>x</sub> conditions and at lower temperatures. The extent of oxidation of the aerosol also varies with experimental conditions, consistent with ongoing, progressive photochemical aging of the toluene SOA. Measurements using a thermodenuder system suggest that the aerosol formed under high- and low-NO<sub>x</sub> conditions is semi-volatile. These results suggest that SOA formation from toluene depends strongly on ambient conditions. An approximate parameterization is proposed for use in air-quality models until a more thorough treatment accounting for the dynamic nature of this system becomes available.
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The second generation Collection 005 (C005) MODIS operational algorithm for retrieval of aerosol properties was evaluated and validated for the greater Mediterranean basin (29.5° N–46.5° N and 10.5° W–38.5° E), a region with an atmosphere under siege by air pollution and diminishing water resources that are exacerbated by high aerosol loads and climatic change. The present study aims to quantify the differences between the C005 and the previous (C004) MODIS collections, and re-assess the results of previous studies that have been performed for the region using MODIS C004 aerosol optical depth (AOD) products. Daily data of AOD from EOS-Terra covering the 6-year period 2000–2006 were taken from both C005 and C004 Level-3 datasets, and were inter-compared and validated against ground-based measurements from 29 AERONET stations. The C005 data were found to significantly better agree with the AERONET data than those of C004. The correlation coefficient between MODIS and AERONET was found to increase from 0.66 to 0.76 and the slope of linear regression MODIS/AERONET from 0.79 to 0.85. The MODIS C005 data still overestimate/underestimate the AERONET AOD values smaller/larger than 0.25, but to a much smaller extent than C004 data. The better agreement of C005 with AERONET data arises from the generally lower C005 values, with regional mean AOD values equal to 0.27 and 0.22 for C004 and C005, respectively. This decrease, however, is not uniform over the region and involves a significant decrease over land and a small increase over the ocean for AOD values greater than 0.1 (opposite changes were found under aerosol-clean conditions). Both data sets indicate a decrease in the regional mean AOD over the period 2000–2006, equal to 20% based on C005 and 17% based on C004 datasets, though the intra-annual and inter-annual variation did not change significantly, thus indicating a systematic correction to C004 values.
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Isoprene is the largest single VOC emission to the atmosphere. Although it is primarily oxidized photochemically during daylight hours, late-day emissions that remain in the atmosphere at sunset undergo oxidation by NO<sub>3</sub> in regionally polluted areas with large NO<sub>x</sub> levels. A recent aircraft study examined isoprene and its nocturnal oxidants in a series of night flights across the Northeast US, a region with large emissions of both isoprene and NO<sub>x</sub>. Substantial amounts of isoprene that were observed after dark were strongly anticorrelated with measured NO<sub>3</sub> and were the most important factor determining the lifetime of this radical. The products of photochemical oxidation of isoprene, methyl vinyl ketone and methacrolein, were more uniformly distributed, and served as tracers for the presence of isoprene at sunset, prior to its oxidation by NO<sub>3</sub>. A determination of the mass of isoprene oxidized in darkness showed it to be a large fraction (>20%) of emitted isoprene. Organic nitrates produced from the NO<sub>3</sub>+isoprene reaction, though not directly measured, were estimated to account for 2–9% of total reactive nitrogen. The mass of isoprene oxidized by NO<sub>3</sub> was comparable to and correlated with the organic aerosol loading for flights with relatively low organic aerosol background. The contribution of nocturnal isoprene oxidation to secondary organic aerosol was determined in the range 1–17%, and isoprene SOA mass derived from NO<sub>3</sub> was calculated to exceed that due to OH by approximately 50%.
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The sensitivity of the climate impact of Mt. Pinatubo eruption in the tropics and extratropics to different QBO phases is investigated. Mt. Pinatubo erupted in June 1991 during the easterly phase of the QBO at 30 hPa and the phase change to westerly took place in August 1992. Here, the consequences are analyzed if the QBO phase had been in the opposite phase during the eruption of Mt. Pinatubo. Hence, in this study, simulations are carried out using the middle atmosphere configuration of ECHAM5 general circulation model for two cases – one with the observed QBO phase and the other with the opposite QBO phase. The response of temperature and geopotential height in the lower stratosphere is evaluated for the following cases – (1) when only the effects of the QBO are included and (2) when the effects of aerosols, QBO and SSTs (combined response) are included. The tropical QBO signature in the lower stratospheric temperature is well captured in the pure QBO responses and in the combined (aerosol + ocean + QBO) responses. The response of the extratropical atmosphere to the QBO during the second winter after the eruption is captured realistically in the case of the combined forcing showing a strengthening of the polar vortex when the QBO is in its westerly phase and a warm, weak polar vortex in the easterly QBO phase. The vortex is disturbed during the first winter irrespective of the QBO phases in the combined responses and this may be due to the strong influences of El Niño during the first winters after eruption. However, the pure QBO experiments do not realistically reproduce a strengthening of the polar vortex in the westerly QBO phase, even though below normal temperatures in the high latitudes are seen in October-November-December months when the opposite QBO phase is prescribed instead of the December-January-February winter months used here for averaging.
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We used the seasonality of a combination of atmospheric trace gases and idealized tracers to examine stratosphere-to-troposphere transport and its influence on tropospheric composition in the Arctic. Maximum stratosphere-to-troposphere transport of CFCs and O<sub>3</sub> occurs in April as driven by the Brewer-Dobson circulation. Stratosphere-troposphere exchange (STE) occurs predominantly between 40° N to 80° N with stratospheric influx in the mid-latitudes (30–70° N) accounting for 67–81% of the air of stratospheric origin in the Northern Hemisphere extratropical troposphere. Transport from the lower stratosphere to the lower troposphere (LT) takes three months on average, one month to cross the tropopause, the second month to travel from the upper troposphere (UT) to the middle troposphere (MT), and the third month to reach the LT. During downward transport, the seasonality of a trace gas can be greatly impacted by wet removal and chemistry. A comparison of idealized tracers with varying lifetimes suggests that when initialized with the same concentrations and seasonal cycles at the tropopause, trace gases that have shorter lifetimes display lower concentrations, smaller amplitudes, and earlier seasonal maxima during transport to the LT. STE contributes to O<sub>3</sub> in the Arctic troposphere directly from the transport of O<sub>3</sub> and indirectly from the transport of NO<sub>y</sub>. Direct transport of O<sub>3</sub> from the stratosphere accounts for 78% of O<sub>3</sub> in the Arctic UT with maximum contributions occurring from March to May. The stratospheric contribution decreases significantly in the MT/LT (20–25% of total O<sub>3</sub>) and shows a very weak March–April maximum. Our NO<sub>x</sub> budget analysis in the Arctic UT shows that during spring and summer, the stratospheric injection of NO<sub>y</sub>-rich air increases NO<sub>x</sub> concentrations above the 20 pptv threshold level, thereby shifting the Arctic UT from a regime of net photochemical ozone loss to one of net production with rates as high as +16 ppbv/month.
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Current atmospheric models do not include secondary organic aerosol (SOA) production from gas-phase reactions of polycyclic aromatic hydrocarbons (PAHs). Recent studies have shown that primary emissions undergo oxidation in the gas phase, leading to SOA formation. This opens the possibility that low-volatility gas-phase precursors are a potentially large source of SOA. In this work, SOA formation from gas-phase photooxidation of naphthalene, 1-methylnaphthalene (1-MN), 2-methylnaphthalene (2-MN), and 1,2-dimethylnaphthalene (1,2-DMN) is studied in the Caltech dual 28-m<sup>3</sup> chambers. Under high-NO<sub>x</sub> conditions and aerosol mass loadings between 10 and 40 μg m<sup>−3</sup>, the SOA yields (mass of SOA per mass of hydrocarbon reacted) ranged from 0.19 to 0.30 for naphthalene, 0.19 to 0.39 for 1-MN, 0.26 to 0.45 for 2-MN, and constant at 0.31 for 1,2-DMN. Under low-NO<sub>x</sub> conditions, the SOA yields were measured to be 0.73, 0.68, and 0.58, for naphthalene, 1-MN, and 2-MN, respectively. The SOA was observed to be semivolatile under high-NO<sub>x</sub> conditions and essentially nonvolatile under low-NO<sub>x</sub> conditions, owing to the higher fraction of ring-retaining products formed under low-NO<sub>x</sub> conditions. When applying these measured yields to estimate SOA formation from primary emissions of diesel engines and wood burning, PAHs are estimated to yield 3–5 times more SOA than light aromatic compounds over photooxidation timescales of less than 12 h. PAHs can also account for up to 54% of the total SOA from oxidation of diesel emissions, representing a potentially large source of urban SOA.
