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The heterogeneous processing of organic aerosols by trace oxidants has many implications to atmospheric chemistry and climate regulation. This review covers a model heterogeneous reaction system (HRS): the oleic acid-ozone HRS and other reaction systems featuring fatty acids, and their derivatives. The analysis of the commonly observed aldehyde and organic acid products of ozonolysis (azelaic acid, nonanoic acid, 9-oxononanoic acid, nonanal) is described. The relative product yields are noted and explained by the observation of secondary chemical reactions. The secondary reaction products arising from reactive Criegee intermediates are mainly peroxidic, notably secondary ozonides and α-acyloxyalkyl hydroperoxide oligomers and polymers, and their formation is in accord with solution and liquid-phase ozonolysis. These highly oxygenated products are of low volatility and hydrophilic which may enhance the ability of particles to act as cloud condensation nuclei (CCN). The kinetic description of this HRS is critically reviewed. Most kinetic studies suggest this oxidative processing is either a near surface reaction that is limited by the diffusion of ozone or a surface based reaction. Internally mixed particles and coatings represent the next stage in the progression towards more realistic proxies of tropospheric organic aerosols and a description of the products and the kinetics resulting from the ozonolysis of these proxies, which are based on fatty acids or their derivatives, is presented. Finally, the main atmospheric implications of oxidative processing of particulate containing fatty acids are presented. These implications include the extended lifetime of unsaturated species in the troposphere facilitated by the presence of solids, semi-solids or viscous phases, and an enhanced rate of ozone uptake by particulate unsaturates compared to corresponding gas-phase organics. Ozonolysis of oleic acid enhances its CCN activity, which implies that oxidatively processed particulate may contribute to indirect forcing of radiation.
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The accumulation of secondary acids and ammonium on individual mineral dust particles during ACE-Asia has been measured with an online single-particle mass spectrometer, the ATOFMS. Changes in the amounts of sulphate, nitrate, and chloride mixed with dust particles correlate with air masses from different source regions. The uptake of secondary acids depended on the individual dust particle mineralogy; high amounts of nitrate accumulated on calcium-rich dust while high amounts of sulphate accumulated on aluminosilicate-rich dust. Oxidation of S(IV) to S(VI) by iron in the aluminosilicate dust is a possible explanation for this enrichment of sulphate, which has important consequences for the fertilization of remote oceans by soluble iron. This study shows the segregation of sulphate from nitrate and chloride in individual aged dust particles for the first time. A transport and aging timeline provides an explanation for the observed segregation. Our data suggests that sulphate became mixed with the dust first. This implies that the transport pathway is more important than the reaction kinetics in determining which species accumulate on mineral dust. Early in the study, dust particles in volcanically influenced air masses were mixed predominately with sulphate. Dust mixed with chloride then dominated over sulphate and nitrate when a major dust front reached the R. V. Ronald Brown. We hypothesize that the rapid increase in chloride on dust was due to mixing with HCl(g) released from acidified sea salt particles induced by heterogeneous reaction with volcanic SO<sub>2</sub>(g), prior to the arrival of the dust front. The amount of ammonium mixed with dust correlated strongly with the total amount of secondary acid reaction products in the dust. Submicron dust and ammonium sulphate were internally mixed, contrary to frequent reports that they exist as external mixtures. The size distribution of the mixing state of dust with these secondary species validates previous mechanisms of the atmospheric processing of dust and generally agrees with simulated aerosol chemistry from the STEM-2K3 model. This series of novel results has important implications for improving the treatment of dust in global chemistry models and highlights a number of key processes that merit further investigation through laboratory and field studies.
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We investigate the influence of African biomass burning, biogenic, lightning and anthropogenic emissions on the tropospheric ozone over Africa and globally using a coupled global chemistry climate model. Our model studies indicate that surface ozone concentration may rise by up to 50 ppbv in the burning region during the biomass burning seasons. Biogenic emissions yield between 5–30 ppbv increase in the near surface ozone concentration over tropical Africa. The impact of lightning on surface ozone is negligible, while anthropogenic emissions yield a maximum of 7 ppbv increase in the annual-mean surface ozone concentration over Nigeria, South Africa and Egypt. Our results show that biogenic emissions are the most important African emission source affecting total tropospheric ozone. The influence of each of the African emissions on the global tropospheric ozone burden (TOB) of 384 Tg yields about 9.5 Tg, 19.6 Tg, 9.0 Tg and 4.7 Tg for biomass burning, biogenic, lightning and anthropogenic emissions emitted in Africa respectively. The impact of each of these emission categories on African TOB of 33 Tg is 2.5 Tg, 4.1 Tg, 1.75 Tg and 0.89 Tg respectively, which together represents about 28% of the total TOB calculated over Africa. Our model calculations also suggest that more than 70% of the tropospheric ozone produced by each of the African emissions is found outside the continent, thus exerting a noticeable influence on a large part of the tropical troposphere. Apart from the Atlantic and Indian Ocean, Latin America experiences the largest impact of African emissions, followed by Oceania, the Middle East, Southeast and south-central Asia, northern North America (i.e. the United States and Canada), Europe and north-central Asia, for all the emission categories.
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Monoterpenes, emitted in large quantities by trees to attract pollinators and repel herbivores, can exist in mirror image forms called enantiomers. In this study such enantiomeric pairs have been measured in ambient air over extensive forest ecosystems in South America and northern Europe. For the dominant monoterpene, α-pinene, the (−)-form was measured in large excess over the (+)-form over the Tropical rainforest, whereas the reverse was observed over the Boreal forest. Interestingly, over the Tropical forest (−)-α-pinene did not correlate with its own enantiomer, but correlated well with isoprene. The results indicate a remarkable ecosystem scale enantiomeric fingerprint and a nexus between the biosphere and atmosphere.
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This article, the third in the series, presents kinetic and photochemical data evaluated by the IUPAC Subcommittee on Gas Kinetic Data Evaluation for Atmospheric Chemistry. It covers the gas phase and photochemical reactions of inorganic halogen species, which were last published in J. Phys. Chem. Ref. Data, in 2000 (Atkinson et al., 2000), were updated on the IUPAC website in 2003 and are updated again in the present evaluation. The article consists of a summary sheet, containing the recommended kinetic parameters for the evaluated reactions, and five appendices containing the data sheets, which provide information upon which the recommendations were made.
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Sulfate aerosol produced after injection of sulfur dioxide (SO<sub>2</sub>) into the stratosphere by volcanic eruptions can trigger climate change. We present new satellite data from the Ozone Monitoring Instrument (OMI) and Cloud-Aerosol Lidar and Infrared Pathfinder Satellite Observations (CALIPSO) missions that reveal the composition, structure and longevity of a stratospheric SO<sub>2</sub> cloud and derived sulfate layer following a modest eruption (0.2 Tg total SO<sub>2</sub>) of Soufriere Hills volcano, Montserrat on 20 May 2006. The SO<sub>2</sub> cloud alone was tracked for over 3 weeks and a distance of over 20 000 km; unprecedented for an eruption of this size. Derived sulfate aerosol at an altitude of ~20 km had circled the globe by 22 June and remained visible in CALIPSO data until at least 6 July. These synergistic NASA A-Train observations permit a new appreciation of the potential effects of frequent, small-to-moderate volcanic eruptions on stratospheric composition and climate.
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We present long-term time-series of strato-mesospheric CO vertical columns measured from stations located in Antarctica, mid-latitudes and the Arctic, covering the period from 1997–2005. The instrument and the measurement technique allows the separation of tropospheric and strato-mesospheric contributions to the CO column, therefore providing information on the chemistry and dynamics both at low and high altitudes. Data from polar stations show a similar annual variability of strato-mesospheric CO with a strong maximum in late winter and spring. A small enhancement in late summer for some stations, which we call the "summer bulge", can be seen occasionally. Generally, the mid-latitude stations show no significant annual variability of strato-mesospheric CO columns. Measurements were compared with a two-dimensional chemistry-transport model of the middle atmosphere. The annual and latitudinal variations of CO are reproduced well by a model run including thermospheric CO. Comparison with two model scenarios show that the polar winter maximum is due solely to downward transport of thermospheric CO, while CHO<sub>x</sub> chemistry in the stratosphere could probably contribute to the summer maximum.
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The mechanisms responsible for the extreme dryness of the stratosphere have been debated for decades. A key difficulty has been the lack of comprehensive models which are able to reproduce the observations. Here we examine results from the coupled lower-middle atmosphere chemistry general circulation model ECHAM5/MESSy1 together with satellite observations. Our model results match observed temperatures in the tropical lower stratosphere and realistically represent the seasonal and inter-annual variability of water vapor. The model reproduces the very low water vapor mixing ratios (below 2 ppmv) periodically observed at the tropical tropopause near 100 hPa, as well as the characteristic tape recorder signal up to about 10 hPa, providing evidence that the dehydration mechanism is well-captured. Our results confirm that the entry of tropospheric air into the tropical stratosphere is forced by large-scale wave dynamics, whereas radiative cooling regionally decelerates upwelling and can even cause downwelling. Thin cirrus forms in the cold air above cumulonimbus clouds, and the associated sedimentation of ice particles between 100 and 200 hPa reduces water mass fluxes by nearly two orders of magnitude compared to air mass fluxes. Transport into the stratosphere is supported by regional net radiative heating, to a large extent in the outer tropics. During summer very deep monsoon convection over Southeast Asia, centered over Tibet, moistens the stratosphere.
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An episodic simulation is conducted to characterize midday (12:00–17:00 CDT) ozone (O<sub>3</sub>) photochemical production and to investigate its sensitivity to emission changes of ozone precursors in the Mexico City Metropolitan Area (MCMA) during an "O<sub>3</sub>-South" meteorological episode using the Comprehensive Air Quality Model with extensions (CAMx). High O<sub>x</sub> (O<sub>3</sub>+NO<sub>2</sub>) photochemical production rates of 10–80 ppb/h are predicted due to the high reactivity of volatile organic compounds (VOCs) in which alkanes, alkenes, and aromatics exert comparable contributions. The predicted ozone production efficiency is between 4–10 O<sub>3</sub> molecules per NO<sub>x</sub> molecule oxidized, and increases with VOC-to-NO<sub>2</sub> reactivity ratio. Process apportionment analyses indicate significant outflow of pollutants such as O<sub>3</sub> and peroxyacetyl nitrate (PAN) from the urban area to the surrounding regional environment. PAN is not in chemical-thermal equilibrium during the photochemically active periods. Sensitivity studies of O<sub>3</sub> production suggest that O<sub>3</sub> formation in the MCMA urban region with less chemical aging (NO<sub>z</sub>/NO<sub>y</sub><0.3) is VOC-limited. Both the simulated behavior of O<sub>3</sub> production and its sensitivities to precursors suggest that midday O<sub>3</sub> formation during this episode is VOC-sensitive in the urban region on the basis of the current emissions inventory estimates, and current NO<sub>x</sub> levels depress the O<sub>3</sub> production.
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Atmospheric cloud condensation nuclei (CCN) concentrations are a key uncertainty in the assessment of the effect of anthropogenic aerosol on clouds and climate. The ability of new ultrafine particles to grow to become CCN varies throughout the atmosphere and must be understood in order to understand CCN formation. We have developed the Probability of Ultrafine particle Growth (PUG) model to answer questions regarding which growth and sink mechanisms control this growth, how the growth varies between different parts of the atmosphere and how uncertainties with respect to the magnitude and size distribution of ultrafine emissions translates into uncertainty in CCN generation. The inputs to the PUG model are the concentrations of condensable gases, the size distribution of ambient aerosol, particle deposition timescales and physical properties of the particles and condensable gases. It was found in most cases that condensation is the dominant growth mechanism and coagulation with larger particles is the dominant sink mechanism for ultrafine particles. In this work we found that the probability of a new ultrafine particle generating a CCN varies from <0.1% to ~90% in different parts of the atmosphere, though in the boundary layer a large fraction of ultrafine particles have a probability between 1% and 40%. Some regions, such as the tropical free troposphere, are areas with high probabilities; however, variability within regions makes it difficult to predict which regions of the atmosphere are most efficient for generating CCN from ultrafine particles. For a given mass of primary ultrafine aerosol, an uncertainty of a factor of two in the modal diameter can lead to an uncertainty in the number of CCN generated as high as a factor for eight. It was found that no single moment of the primary aerosol size distribution, such as total mass or number, is a robust predictor of the number of CCN ultimately generated. Therefore, a complete description of the emissions size distribution is generally required for global aerosol microphysics models.
