51920294
The influence of semi-volatile and reactive primary emissions on the abundance and properties of global organic aerosol
Abstract. Semi-volatile and reactive primary organic aerosols are modeled on a global scale using the GISS GCM II' "unified" climate model. We employ the volatility basis set framework to simulate emissions, chemical reactions and phase partitioning of primary and secondary organic aerosol (POA and SOA). The model also incorporates the emissions and reactions of intermediate volatility organic compounds (IVOCs) as a source of organic aerosol (OA), one that has been missing in most prior work. Model predictions are evaluated against a broad set of observational constraints including mass concentrations, degree of oxygenation, volatility and isotopic composition. A traditional model that treats POA as non-volatile and non-reactive is also compared to the same set of observations to highlight the progress made in this effort. The revised model predicts a global dominance of SOA and brings the POA/SOA split into better agreement with ambient measurements. This change is due to traditionally defined POA evaporating and the evaporated vapors oxidizing to form non-traditional SOA. IVOCs (traditionally not included in chemical transport models) oxidize to form condensable products that account for a third of total OA, suggesting that global models have been missing a large source of OA. Predictions of the revised model for the SOA fraction at 17 different locations compared much better to observations than predictions from the traditional model. Model-predicted volatility is compared with thermodenuder data collected at three different different field campaigns: FAME-2008, MILAGRO-2006 and SOAR-2005. The revised model predicts the OA volatility much more closely than the traditional model. When compared against monthly averaged OA mass concentrations measured by the IMPROVE network, predictions of the revised model lie within a factor of two in summer and mostly within a factor of five during winter. A sensitivity analysis indicates that the winter comparison can be improved either by increasing POA emissions or lowering the volatility of those emissions. Model predictions of the isotopic composition of OA are compared against those computed via a radiocarbon isotope analysis of field samples. The contemporary fraction, on average, is slightly under-predicted (20 %) during the summer months but is a factor of two lower during the winter months. We hypothesize that the large wintertime under-prediction of surface OA mass concentrations and the contemporary fraction is due to an under-representation of biofuel (particularly, residential wood burning) emissions in the emissions inventory. Overall, the model evaluation highlights the importance of treating POA as semi-volatile and reactive in order to predict accurately the sources, composition and properties of ambient OA.
236806
Health effects of air pollution.
The general public, especially patients with upper or lower respiratory symptoms, is aware from media reports that adverse respiratory effects can occur from air pollution. It is important for the allergist to have a current knowledge of the potential health effects of air pollution and how they might affect their patients to advise them accordingly. Specifically, the allergist-clinical immunologist should be keenly aware that both gaseous and particulate outdoor pollutants might aggravate or enhance the underlying pathophysiology of both the upper and lower airways. Epidemiologic and laboratory exposure research studies investigating the health effects of outdoor air pollution each have advantages and disadvantages. Epidemiologic studies can show statistical associations between levels of individual or combined air pollutants and outcomes, such as rates of asthma, emergency visits for asthma, or hospital admissions, but cannot prove a causative role. Human exposure studies, animal models, and tissue or cellular studies provide further information on mechanisms of response but also have inherent limitations. The aim of this rostrum is to review the relevant publications that provide the appropriate context for assessing the risks of air pollution relative to other more modifiable environmental factors in patients with allergic airways disease.
42885140
Ubiquity and Dominance of Oxygenated Species in Organic Aerosols in
[1] Organic aerosol (OA) data acquired by the Aerosol Mass Spectrometer (AMS) in 37 field campaigns were deconvolved into hydrocarbon-like OA (HOA) and several types of oxygenated OA (OOA) components. HOA has been linked to primary combustion emissions (mainly from fossil fuel) and other primary sources such as meat cooking. OOA is ubiquitous in various atmospheric environments, on average accounting for 64%, 83% and 95% of the total OA in urban, urban downwind, and rural/remote sites, respectively. A case study analysis of a rural site shows that the OOA concentration is much greater than the advected HOA, indicating that HOA oxidation is not an important source of OOA, and that OOA increases are mainly due to SOA. Most global models lack an explicit representation of SOA which may lead to significant biases in the magnitude, spatial and temporal distributions of OA, and in aerosol hygroscopic properties.
7276007
Secondary organic aerosol formation from high-NO(x) photo-oxidation of low volatility precursors: n-alkanes.
Smog chamber experiments were conducted to investigate secondary organic aerosol (SOA) formation from photo-oxidation of low-volatility precursors; n-alkanes were chosen as a model system. The experiments feature atmospherically relevant organic aerosol concentrations (C(OA)). Under high-NO(x) conditions SOA yields increased with increasing carbon number (lower volatility) for n-decane, n-dodecane, n-pentadecane, and n-heptadecane, reaching a yield of 0.51 for heptadecane at a C(OA) of 15.4 microg m(-3). As with other photo-oxidation systems, aerosol yield increased with UV intensity. Due to the log-linear relationship between n-alkane carbon number and vapor pressure as well as a relatively consistent product distribution it was possible to develop an empirical parametrization for SOA yields for n-alkanes between C(12) and C(17). This parametrization was implemented using the volatility basis set framework and is designed for use in chemical transport models. For C(OA) < 2 microg m(-3), the SOA mass spectrum, as measured with an aerosol mass spectrometer, had a large contribution from m/z 44, indicative of highly oxygenated products. At higher C(OA), the mass spectrum was dominated by m/z 30, indicative of organic nitrates. The data support the conclusion that lower volatility organic vapors are important SOA precursors.
10456851
Global distribution and climate forcing of carbonaceous aerosols
The global distribution of carbonaceous aerosols is simulated online in the Goddard Institute for Space Studies General Circulation Model II-prime (GISS GCM II-prime). Prognostic tracers include black carbon (BC), primary organic aerosol (POA), five groups of biogenic volatile organic compounds (BVOCs), and 14 semivolatile products of BVOC oxidation by O_3, OH, and NO_3, which condense to form secondary organic aerosols (SOA) based on an equilibrium partitioning model and experimental observations. Estimated global burdens of BC, organic carbon (OC), and SOA are 0.22, 1.2, and 0.19 Tg with lifetimes of 6.4, 5.3, and 6.2 days, respectively. The predicted global production of SOA is 11.2 Tg yr^(−1), with 91% due to O_3 and OH oxidation. Globally averaged, top of the atmosphere (TOA) radiative forcing by anthropogenic BC is predicted as +0.51 to +0.8 W m^(−2), the former being for BC in an external mixture and the latter for BC in an internal mixture of sulfate, OC, and BC. Globally averaged, anthropogenic BC, OC, and sulfate are predicted to exert a TOA radiative forcing of −0.39 to −0.78 W m^(−2), depending on the exact assumptions of aerosol mixing and water uptake by OC. Forcing estimates are compared with those published previously.
18556507
Regional Visibility Statistics in the United States: Natural and Transboundary Pollution Influences, and Implications for the Regional Haze Rule
The Regional Haze Rule of the US Environmental Protection Agency mandates reduction in US anthropogenic emissions to achieve linear improvement of visibility in wilderness areas over the 2004–18 period toward an endpoint of natural visibility conditions by 2064. Linear improvement is to apply to the mean visibility degradation on the statistically 20% worst days, measured as a Haze Index in units of deciviews (log of aerosol extinction). We use a global chemical transport model (GEOS-Chem) with 11 � 11 horizontal resolution to simulate present-day visibility statistics in the USA, compare them to observations from the Interagency Monitoring of Protected Visual Environments (IMPROVE) surface network, and provide natural and background visibility statistics for application of the Regional Haze Rule. Background is defined by suppression of US anthropogenic emissions but allowance for present-day foreign emissions and associated import of pollution. Our model is highly successful at reproducing the observed variability of visibility statistics for present-day conditions, including the low tail of the frequency distribution that is most representative of natural or background conditions. We find considerable spatial and temporal variability in natural visibility over the USA, especially due to fires in the west. A major uncertainty in estimating natural visibility is the sensitivity of biogenic organic aerosol formation to the availability of preexisting anthropogenic aerosol. Background visibility is more variable than natural visibility and the 20% worst days show large contributions from Canadian and Mexican pollution. Asian pollution, while degrading mean background visibility, is relatively less important on the worst days. Recognizing the influence of uncontrollable transboundary pollution in the Regional Haze Rule would substantially decrease the schedule of emission reductions required in the 2004–18 implementation phase. Meaningful application of the Rule in the future will require projections of future trends in foreign anthropogenic emissions, wildfire frequency, and climate variables. r 2006 Elsevier Ltd. All rights reserved.
128426374
Budget of organic carbon in a polluted atmosphere: Results from the New England Air Quality Study in 2002
[1] An extensive set of volatile organic compounds (VOCs) and particulate organic matter (POM) was measured in polluted air during the New England Air Quality Study in 2002. Using VOC ratios, the photochemical age of the sampled air masses was estimated. This approach was validated (1) by comparing the observed rates at which VOCs were removed from the atmosphere with the rates expected from OH oxidation, (2) by comparing the VOC emission ratios inferred from the data with the average composition of urban air, and (3) by the ability to describe the increase of an alkyl nitrate with time in terms of the chemical kinetics. A large part of the variability observed for oxygenated VOCs (OVOCs) and POM could be explained by a description that includes the removal of the primary anthropogenic emissions, the formation and removal of secondary anthropogenic species, and a biogenic contribution parameterized by the emissions of isoprene. The OVOC sources determined from the data are compared with the available literature, and a satisfactory agreement is obtained. The observed sub-μm POM was highly correlated with secondary anthropogenic gas-phase species, strongly suggesting that the POM was from secondary anthropogenic sources. The results are used to describe the speciation and total mass of gas- and particle-phase organic carbon as a function of the photochemical age of an urban air mass. Shortly after emission the organic carbon mass is dominated by primary VOCs, while after two days the dominant contribution is from OVOCs and sub-μm POM. The total measured organic carbon mass decreased by about 40% over the course of two days. The increase in sub-μm POM could not be explained by the removal of aromatic precursors alone, suggesting that other species must have contributed and/or that the mechanism for POM formation is more efficient than previously assumed.
18090955
A Large Organic Aerosol Source in the Free Troposphere Missing from Current Models
average 4 m gs m 3 in the 2–6.5 km column with little vertical gradient. These values are 10–100 times higher than computed with a global chemical transport model (CTM) including a standard 2-product simulation of secondary organic aerosol (SOA) formation based on empirical fits to smog chamber data. The same CTM reproduces the observed vertical profiles of sulfate and elemental carbon aerosols, which indicate sharp decreases from the boundary layer to the FT due to wet scavenging. Our results suggest a large, sustained source of SOA in the FT from oxidation of long-lived volatile organic compounds. We find that this SOA is the dominant component of aerosol mass in the FT, with implications for intercontinental pollution transport and radiative forcing of climate. Citation: Heald, C. L., D. J. Jacob, R. J. Park, L. M. Russell, B. J. Huebert, J. H. Seinfeld, H. Liao, and R. J. Weber (2005), A large organic aerosol source in the free troposphere missing from current models, Geophys. Res. Lett., 32, L18809, doi:10.1029/2005GL023831.
35016603
Secondary organic aerosol formation from anthropogenic air pollution: Rapid and higher than expected
[1] The atmospheric chemistry of volatile organic compounds (VOCs) in urban areas results in the formation of ‘photochemical smog’, including secondary organic aerosol (SOA). State-of-the-art SOA models parameterize the results of simulation chamber experiments that bracket the conditions found in the polluted urban atmosphere. Here we show that in the real urban atmosphere reactive anthropogenic VOCs (AVOCs) produce much larger amounts of SOA than these models predict, even shortly after sunrise. Contrary to current belief, a significant fraction of the excess SOA is formed from first-generation AVOC oxidation products. Global models deem AVOCs a very minor contributor to SOA compared to biogenic VOCs (BVOCs). If our results are extrapolated to other urban areas, AVOCs could be responsible for additional 3–25 Tg yr−1 SOA production globally, and cause up to −0.1 W m−2 additional top-of-the-atmosphere radiative cooling.
9967031
A Particle-into-Liquid Collector for Rapid Measurement of Aerosol Bulk Chemical Composition
We report on a new instrument developed for rapid automated on-line and continuous measurement of ambient aerosol bulk com- position.The general approach is based on earlier devices (Khlystov et al. 1995; Simon and Dasgupta 1995) in which ambient particles are mixed with saturated water vapor to produce droplets easily collected by inertial techniques. The resulting liquid stream is analyzed with an ion chromatograph to quantitatively measure the bulk aerosol ionic components. In this instrument, a modified ver- sion of a particle size magnifier (Okuyama et al. 1984) is employed to activate and grow particles comprising the fine aerosol mass. A single jet inertial impactor is used to collect the droplets onto a vertical glass plate that is continually washed with a constant water diluent flow of nominally 0.10 ml min-1
20903347
Rethinking Organic Aerosols: Semivolatile Emissions and Photochemical Aging
Most primary organic-particulate emissions are semivolatile; thus, they partially evaporate with atmospheric dilution, creating substantial amounts of low-volatility gas-phase material. Laboratory experiments show that photo-oxidation of diesel emissions rapidly generates organic aerosol, greatly exceeding the contribution from known secondary organic-aerosol precursors. We attribute this unexplained secondary organic-aerosol production to the oxidation of low-volatility gas-phase species. Accounting for partitioning and photochemical processing of primary emissions creates a more regionally distributed aerosol and brings model predictions into better agreement with observations. Controlling organic particulate-matter concentrations will require substantial changes in the approaches that are currently used to measure and regulate emissions.
2061019
Chemically-resolved aerosol volatility measurements from two megacity field studies
Abstract. The volatilities of different chemical species in ambient aerosols are important but remain poorly characterized. The coupling of a recently developed rapid temperature-stepping thermodenuder (TD, operated in the range 54–230°C) with a High-Resolution Time-of-Flight Aerosol Mass Spectrometer (HR-ToF-AMS) during field studies in two polluted megacities has enabled the first direct characterization of chemically-resolved urban particle volatility. Measurements in Riverside, CA and Mexico City are generally consistent and show ambient nitrate as having the highest volatility of any AMS standard aerosol species while sulfate showed the lowest volatility. Total organic aerosol (OA) showed volatility intermediate between nitrate and sulfate, with an evaporation rate of 0.6%·K−1 near ambient temperature, although OA dominates the residual species at the highest temperatures. Different types of OA were characterized with marker ions, diurnal cycles, and positive matrix factorization (PMF) and show significant differences in volatility. Reduced hydrocarbon-like OA (HOA, a surrogate for primary OA, POA), oxygenated OA (OOA, a surrogate for secondary OA, SOA), and biomass-burning OA (BBOA) separated with PMF were all determined to be semi-volatile. The most aged OOA-1 and its dominant ion, CO2+, consistently exhibited the lowest volatility, with HOA, BBOA, and associated ions for each among the highest. The similar or higher volatility of HOA/POA compared to OOA/SOA contradicts the current representations of OA volatility in most atmospheric models and has important implications for aerosol growth and lifetime. A new technique using the AMS background signal was demonstrated to quantify the fraction of species up to four orders-of-magnitude less volatile than those detectable in the MS mode, which for OA represent ~5% of the non-refractory (NR) OA signal. Our results strongly imply that all OA types should be considered semivolatile in models. The study in Riverside identified organosulfur species (e.g. CH3HSO3+ ion, likely from methanesulfonic acid), while both studies identified ions indicative of amines (e.g. C5H12N+) with very different volatility behaviors than inorganic-dominated ions. The oxygen-to-carbon ratio of OA in each ambient study was shown to increase both with TD temperature and from morning to afternoon, while the hydrogen-to-carbon ratio showed the opposite trend.
15895913
Evolving mass spectra of the oxidized component of organic aerosol : results from aerosol mass spectrometer analyses of aged diesel emissions
The species and chemistry responsible for secondary organic aerosol (SOA) formation remain highly uncertain. Laboratory studies of the oxidation of individual, high-flux SOA precursors do not lead to particles with mass spectra (MS) matching those of ambient aged organic material. Additionally, the complexity of real organic particles challenges efforts to identify their chemical origins. We have previously hypothesized that SOA can form from the atmospheric oxidation of a large suite of precursors with varying vapor pressures. Here, we support this hypothesis by using an aerosol mass spectrometer to track the chemical evolution of diesel exhaust as it is photochemically oxidized in an environmental chamber. With explicit knowledge of the condensed-phase MS of the primary emissions from our engine, we are able to decompose each recorded MS into contributing primary and secondary spectra throughout the experiment. We find that the SOA becomes increasingly oxidized as a function of time, quickly approaching a final MS that closely resembles that of ambient aged organic particulate matter. This observation is consistent with our hypothesis of an evolving suite of SOA precursors. Low vapor pressure, semi-volatile organic emissions can form condensable products with even a single generation of oxidation, resulting in an early-arising, relatively less-oxidized SOA. Continued gas-phase oxidation can form highly oxidized SOA in surprisingly young air masses via reaction mechanisms that can add multiple oxygen atoms per generation and result in products with sustained or increased reactivity toward OH. Correspondence to: N. M. Donahue (nmd@cmu.edu)
17968644
Laboratory investigation of photochemical oxidation of organic aerosol from wood fires 1: measurement and simulation of organic aerosol evolution
Abstract. Experiments were conducted to investigate the effects of photo-oxidation on organic aerosol (OA) emissions from flaming and smoldering hard- and soft-wood fires under plume-like conditions. This was done by exposing the dilute emissions from a small wood stove to UV light in a smog chamber and measuring the gas- and particle-phase pollutant concentrations with a suite of instruments including a Proton Transfer Reaction Mass Spectrometer (PTR-MS), an Aerosol Mass Spectrometer (AMS) and a thermodenuder. The measurements highlight how atmospheric processing can lead to considerable evolution of the mass and volatility of biomass-burning OA. Photochemical oxidation produced substantial new OA, increasing concentrations by a factor of 1.5 to 2.8 after several hours of exposure to typical summertime hydroxyl radical (OH) concentrations. Less than 20% of this new OA could be explained using a state-of-the-art secondary organic aerosol model and the measured decay of traditional SOA precursors. The thermodenuder data indicate that the primary OA is semivolatile; at 50°C between 50 and 80% of the fresh primary OA evaporated. Aging reduced the volatility of the OA; at 50°C only 20 to 40% of aged OA evaporated. The predictions of a volatility basis-set model that explicitly tracks the partitioning and aging of low-volatility organics was compared to the chamber data. The OA production can be explained by the oxidation of low-volatility organic vapors; the model can also reproduce observed changes in OA volatility and composition. The model was used to investigate the competition between photochemical processing and dilution on OA concentrations in plumes.
206997654
Photo-oxidation of low-volatility organics found in motor vehicle emissions: production and chemical evolution of organic aerosol mass.
Recent research has proposed that low-volatility organic vapors are an important class of secondary organic aerosol (SOA) precursors. Mixtures of low-volatility organics were photo-oxidized in a smog chamber under low- and high-NO(x) conditions. Separate experiments addressed emission surrogates (diesel fuel and motor oil) and single components (n-pentacosane). Both diesel fuel and motor oil are major components of exhaust from diesel engines. Diesel fuel is a complex mixture of intermediate volatility organic compounds (IVOCs), whereas motor oil is a complex mixture of semivolatile organic compounds (SVOCs). IVOCs exist exclusively in the vapor phase, while SVOCs exist in both the aerosol and vapor phase. Oxidation of SVOC vapors (motor oil and n-pentacosane) creates substantial SOA, but this SOA is largely offset by evaporation of primary organic aerosol (POA). The net effect is a cycling or pumping of SVOCs between the gas and particle phases, which creates more oxygenated organic aerosol (OA) but little new OA mass. Since gas-phase reactions are much faster than heterogeneous ones, the processing of SVOC vapors likely contributes to the production of highly oxidized OA. The interplay between gas-particle partitioning and chemistry also blurs traditional definitions of POA and SOA. Photo-oxidation of diesel fuel (IVOCs) rapidly creates substantial new OA mass, similar to published aging experiments with dilute diesel exhaust. However, aerosol mass spectrometer (AMS) data indicated that the SOA formed from emission surrogates is less oxidized than either the oxygenated organic aerosol (OOA) measured in the atmosphere or SOA formed from the photo-oxidation of dilute diesel exhaust. Therefore, photo-oxidation of IVOCs helps explain the substantial SOA mass produced from aging diesel exhaust, but some component is missing from these emission surrogate experiments that leads to the rapid production of highly oxygenated SOA.
32946766
Simulating the formation of semivolatile primary and secondary organic aerosol in a regional chemical transport model.
Recent developments in our understanding of atmospheric organic particulate matter formation have been used to develop a state-of-the-art organic aerosol module for regional chemical transport models (CTMs). The module has been added to the regional CTM, PMCAMx, and has been evaluated against observations in the eastern U.S. The new module uses the volatility basis set framework to simulate primary organic aerosol (POA) partitioning between the gas and particulate phases and the gas-phase oxidation of the corresponding vapors. The formation and chemical aging of secondary organic aerosol (SOA) are modeled using the same volatility distribution approach. The module uses recent results from smog chamber studies for the formation of SOA from anthropogenic and biogenic hydrocarbons. Hourly organic aerosol predictions are evaluated using data from the Pittsburgh Air Quality Study (PAQS), and daily averaged predictions for July 2001 are compared to ambient measurements from the EPA Speciated Trends Network (STN) and the Interagency Monitoring of Protected Visual Environments (IMPROVE). The model reproduces both the absolute organic aerosol concentrations in urban and rural locations as well as the high degree of oxidation of these compounds. The chemical aging of anthropogenic SOA is consistent with the ambient organic aerosol concentration field and has a significant impact on the absolute ground-level concentrations of these compounds.
129731787
Use of on-line tracers as a diagnostic tool in general circulation model development 1. Horizontal and vertical transport in the troposphere
The use of passive on-line tracers in a general circulation model (GCM) developmental process is discussed. CFC-11 and 85Kr are used to evaluate interhemispheric transport. It is shown that new boundary layer and convective parameterizations lead to reductions in the interhemispheric exchange times to values in close agreement with observations of little more than one year. Radon 222 is used to evaluate vertical mixing away from the surface. The new convection scheme produces smaller convective fluxes, which substantially reduce the high-altitude concentrations of 222Rn equatorward of 30° latitude. While this result is in better agreement with other models, scarcity of observations prevent any conclusion as to which formulation is more accurate. The effect of altered numerical schemes for solution of the momentum and energy equations in the GCM is shown to have little influence on the model's interhemispheric transport or vertical mixing. Finer vertical resolution increases convective mixing of 222Rn somewhat and allows for larger pollution concentrations of CFC-11 in the boundary layer. Employing on-line passive tracers in the course of model development should allow for improvements in a GCM's horizontal and vertical fluxes and optimization of the model for atmospheric chemistry purposes.
102817745
Use of On-Line Tracers as a Diagnostic Tool in General Circulation Model Development
A key component of climate/chemistry modeling is how to handle the influx into (and egress from) the troposphere. This is especially important when considering tropospheric ozone, and its precursors (e.g., NO(x) from aircraft). A study has been conducted with various GISS models to determine the minimum requirements necessary for producing realistic troposphere-stratosphere exchange. Four on-line tracers are employed: CFC-11 and SF6 for mixing from the troposphere into the stratosphere, Rn222 for vertical mixing within the troposphere, and 14C for mixing from the stratosphere into the troposphere. Four standard models are tested, with varying vertical resolution, gravity wave drag and location of the model top, and additional subsidiary models are employed to examine specific features. The results show that proper vertical transport between the troposphere and stratosphere in the GISS models requires lifting the top of the model considerably out of the stratosphere, and including gravity wave drag in the lower stratosphere. Increased vertical resolution without these aspects does not improve troposphere-stratosphere exchange. The transport appears to be driven largely by the residual circulation within the stratosphere; associated E-P flux convergences require both realistic upward propagating energy from the troposphere, and realistic pass-through possibilities. A 23 layer version with a top at the mesopause and incorporating gravity wave drag appears to have reasonable stratospheric-tropospheric exchange, in terms of both the resulting tracer distributions and atmospheric mass fluxes.
988840
Global radiative forcing of coupled tropospheric ozone and aerosols in a unified general circulation model
Space Studies (GISS) GCM II 0 , that simulates coupled tropospheric ozone-NOxhydrocarbon chemistry and sulfate, nitrate, ammonium, black carbon, primary organic carbon, and secondary organic carbon aerosols. The fully coupled gas-aerosol unified GCM allows one to evaluate the extent to which global burdens, radiative forcing, and eventually climate feedbacks of ozone and aerosols are influenced by gas-aerosol chemical interactions. Estimated present-day global burdens of sea salt and mineral dust are 6.93 and 18.1 Tg with lifetimes of 0.4 and 3.9 days, respectively. The GCM is applied to estimate current top of atmosphere (TOA) and surface radiative forcing by tropospheric ozone and all natural and anthropogenic aerosol components. The global annual mean value of the radiative forcing by tropospheric ozone is estimated to be +0.53 W m � 2 at TOA and +0.07 W m � 2 at the Earth’s surface. Global, annual average TOA and surface radiative forcing by all aerosols are estimated as � 0.72 and � 4.04 W m � 2 , respectively. While the predicted highest aerosol cooling and heating at TOA are � 10 and +12 W m � 2 , respectively, surface forcing can reach values as high as � 30 W m � 2 , mainly caused by the absorption by black carbon, mineral dust, and OC. We also estimate the effects of chemistry-aerosol coupling on forcing estimates based on currently available understanding of heterogeneous reactions on aerosols. Through altering the burdens of sulfate, nitrate, and ozone, heterogeneous reactions are predicted to change the global mean TOA forcing of aerosols by 17% and influence global mean TOA forcing of tropospheric ozone by 15%. INDEX TERMS: 0305 Atmospheric Composition and Structure: Aerosols and particles (0345, 4801); 0345 Atmospheric Composition and Structure: Pollution—urban and regional (0305); 0365 Atmospheric Composition and Structure: Troposphere—composition and chemistry;
129317527
Global concentrations of tropospheric sulfate, nitrate, and ammonium aerosol simulated in a general circulation model
Global sulfate aerosol composition is simulated online in the Goddard Institute for Space Studies general circulation model II′ (GISS GCM II-prime). Four sulfur species, hydrogen peroxide, gas phase ammonia, and particulate ammonium are the prognostic tracer species, the emissions, transport, and deposition of which are explicitly simulated. Nitric acid fields are prescribed based on a global chemical transport model. An online thermodynamic equilibrium calculation determines the partitioning of ammonia and nitrate between gas and aerosol phases, and the quantity of aerosol water based on the temperature, relative humidity, and sulfate concentration in each GCM grid cell. The total global burden of sulfate, nitrate, ammonium, and aerosol water is 7.5 Tg and is most sensitive to changes in sulfur emissions. Tropospheric lifetimes for ammonium and ammonia are 4.2 and 0.9 days, respectively; the tropospheric ammonium burden is 0.30 Tg N, compared with 0.14 Tg N for ammonia. Simulated ammonium concentrations are generally within a factor of 2 of observations. Subgrid variability in measured concentrations hinders comparison of observations to predictions. Ammonium nitrate aerosol plays an important role in determining total aerosol mass in polluted continental areas. In the upper troposphere and near the poles, cold temperatures allow unneutralized nitric acid to condense into the aerosol phase. Acidic aerosol species tend to be neutralized by ammonia to a greater degree over continents than over oceans. The aerosol is most basic and gas phase ammonia concentrations are highest over India. Water uptake per mole of sulfate aerosol varies by two orders of magnitude because of changes in relative humidity and aerosol composition. Spatial variations in aerosol composition and water uptake have implications for direct and indirect aerosol radiative forcing.
17442370
Modeling global secondary organic aerosol formation and processing with the volatility basis set: Implications for anthropogenic secondary organic aerosol
[1] The volatility basis set, a computationally efficient framework for the description of organic aerosol partitioning and chemical aging, is implemented in the Goddard Institute for Space Studies General Circulation Model II' for a coupled global circulation and chemical transport model to simulate secondary organic aerosol (SOA) formation. The latest smog chamber information about the yields of anthropogenic and biogenic precursors is incorporated in the model. SOA formation from monoterpenes, sesquiterpenes, isoprene, and anthropogenic precursors is estimated as 17.2, 3.9, 6.5, and 1.6 Tg yr -1 , respectively. Reducing water solubility of secondary organic gas from 10 5 to 10 3 mol L -1 atm -1 (1 atm = 1.01325 x 10 5 N m -2 ) leads to a 90% increase in SOA production and an increase of over 340% in total atmospheric burden, from 0.54 to 2.4 Tg. Increasing the temperature sensitivity of SOA leads to a 30% increase in production, to 38.2 Tg yr -1 . Since the additional SOA is formed at high altitude, where deposition time scales are longer, the average lifetime is doubled from 6.8 to 14.3 days, resulting in a near tripling of atmospheric burden to 1.5 Tg. Chemical aging of anthropogenic SOA by gas-phase reaction of the SOA components with the hydroxyl radical adds an additional 2.7-9.3 Tg yr -1 of anthropogenic SOA to the above production rates and nearly doubles annual average total SOA burdens. The possibility of such high anthropogenic SOA production rates challenges the assumption that anthropogenic volatile organic compounds are not important SOA precursors on a global scale. Model predictions with and without SOA aging are compared with data from two surface observation networks: the Interagency Monitoring of Protected Visual Environments for the United States and the European Monitoring and Evaluation Programme.
140692488
Global impacts of gas‐phase chemistry‐aerosol interactions on direct radiative forcing by anthropogenic aerosols and ozone
[1] We present here a first global modeling study on the influence of gas-phase chemistry/aerosol interactions on estimates of anthropogenic forcing by tropospheric O3 and aerosols. Concentrations of gas-phase species and sulfate, nitrate, ammonium, black carbon, primary organic carbon, secondary organic carbon, sea salt, and mineral dust aerosols in the preindustrial, present-day, and year 2100 (IPCC SRES A2) atmospheres are simulated online in the Goddard Institute for Space Studies general circulation model II' (GISS GCM II'). With fully coupled chemistry and aerosols, the preindustrial, present-day, and year 2100 global burdens of tropospheric ozone are predicted to be 190, 319, and 519 Tg, respectively. The burdens of sulfate, nitrate, black carbon, and organic carbon are predicted respectively to be 0.32. 0.18, 0.01, 0.33 Tg in preindustrial time, 1.40, 0.48, 0.23, 1.60 Tg in present-day, and 1.37, 1.97, 0.54, 3.31 Tg in year 2100. Anthropogenic O3 is predicted to have a globally and annually averaged present-day forcing of +0.22 W m−2 and year 2100 forcing of +0.57 W m−2 at the top of the atmosphere (TOA). Net anthropogenic TOA forcing by internally mixed sulfate, nitrate, organic carbon, and black carbon aerosols is estimated to be virtually zero in the present-day and +0.34 W m−2 in year 2100, whereas it is predicted to be −0.39 W m−2 in present-day and −0.61 W m−2 in year 2100 if the aerosols are externally mixed. Heterogeneous reactions are shown to be important in affecting anthropogenic forcing. When reactions of N2O5, NO3, NO2, and HO2 on aerosols are accounted for, TOA anthropogenic O3 forcing is less by 20–45% in present-day and by 20–32% in year 2100 at mid to high latitudes in the Northern Hemisphere, as compared with values predicted in the absence of heterogeneous gas-aerosol reactions. Mineral dust uptake of HNO3 and O3 is shown to have practically no influence on anthropogenic O3 forcing. Heterogeneous reactions of N2O5, NO3, NO2, and HO2 are predicted to have noticeable impacts on anthropogenic aerosol forcing over industrialized areas, leading to 0–2 W m−2 more anthropogenic aerosol cooling in present-day and 2–8 W m−2 more cooling in year 2100 in these areas as compared with forcings calculated in the absence of heterogeneous reactions. Sea salt uptake of SO2 reduces the magnitude of TOA aerosol cooling by 0.5–1 W m−2 over the oceans around 60°N in the present-day and year 2100 scenarios. Near dust sources, mineral dust uptake of SO2 and HNO3 leads to less anthropogenic aerosol cooling by 0.5–1 W m−2 in the present-day and 1–2 W m−2 in year 2100.
31242575
Coupled partitioning, dilution, and chemical aging of semivolatile organics.
A unified framework of semi-volatile partitioning permits models to efficiently treat both semi-volatile primary emissions and secondary organic aerosol production (SOA), and then to treat the chemical evolution (aging) of the aggregate distribution of semi-volatile material. This framework also reveals critical deficiencies in current emissions and SOA formation measurements. The key feature of this treatment is a uniform basis set of saturation vapor pressures spanning the range of ambient organic saturation concentrations, from effectively nonvolatile material at 0.01 microg m(-3) to vapor-phase effluents at 100 mg m(-3). Chemical evolution can be treated by a transformation matrix coupling the various basis vectors. Using this framework, we show that semi-volatile partitioning can be described in a self-consistent way, with realistic behavior with respect to temperature and varying organic aerosol loading. The time evolution strongly suggests that neglected oxidation of numerous "intermediate volatility" vapors (IVOCs, with saturation concentrations above approximately 1 mg m(-3)) may contribute significantly to ambient SOA formation.
128677567
Mixing and phase partitioning of primary and secondary organic aerosols
[1] Predicting primary and secondary organic aerosol (POA and SOA) concentrations requires understanding the phase partitioning of semi-volatile organic species. A well-mixed single phase organic aerosol can absorb greater amounts of semi-volatile species but little experimental evidence exists on the phase distribution of particulate organics. We investigated the phase partitioning and mixing of semi-volatile POA and SOA in a smog chamber. Particle time of flight (PToF) data from an Aerodyne aerosol mass spectrometer (AMS) were used to quantify the extent of mixing. The SOA plus motor oil and diesel fuel combination produced a weakly mixed system, in which two particulate organic phases coexist. However, the POA in diesel exhaust readily mixed with SOA, forming a single phase after one hour. Although both POA types contain semi-volatile components, there is a fundamental difference in their partitioning behavior with SOA. The high resolution AMS data reveal minor differences in composition between the two types of POA. This work provides further evidence that there exists a set of unidentified components that influence particulate mixing that affect OA formation and suggests the extent of absorbent phase mixing (strong versus weak) can be observed and quantified with PToF data.
54219747
Effect of hydrophobic primary organic aerosols on secondary organic aerosol formation from ozonolysis of α‐pinene
[1] Semi-empirical secondary organic aerosol (SOA) models typically assume a well-mixed organic aerosol phase even in the presence of hydrophobic primary organic aerosols (POA). This assumption significantly enhances the modeled SOA yields as additional organic mass is made available to absorb greater amounts of oxidized secondary organic gases than otherwise. We investigate the applicability of this critical assumption by measuring SOA yields from ozonolysis of a-pinene (a major biogenic SOA precursor) in a smog chamber in the absence and in the presence of dioctyl phthalate (DOP) and lubricating oil seed aerosol. These particles serve as surrogates for urban hydrophobic POA. The results show that these POA did not enhance the SOA yields. If these results are found to apply to other biogenic SOA precursors, then the semiempirical models used in many global models would predict significantly less biogenic SOA mass and display reduced sensitivity to anthropogenic POA emissions than previously thought. Citation: Song, C., R. A. Zaveri, M. L. Alexander, J. A. Thornton, S. Madronich, J. V. Ortega, A. Zelenyuk, X.-Y. Yu, A. Laskin, and D. A. Maughan (2007), Effect of hydrophobic primary organic aerosols on secondary organic aerosol formation from ozonolysis of a-pinene, Geophys. Res. Lett., 34, L20803,
22748556
Updating the Conceptual Model for Fine Particle Mass Emissions from Combustion Systems Allen L. Robinson
Abstract Atmospheric transformations determine the contribution of emissions from combustion systems to fine particulate matter (PM) mass. For example, combustion systems emit vapors that condense onto existing particles or form new particles as the emissions are cooled and diluted. Upon entering the atmosphere, emissions are exposed to atmospheric oxidants and sunlight, which causes them to evolve chemically and physically, generating secondary PM. This review discusses these transformations, focusing on organic PM. Organic PM emissions are semi -volatile at atmospheric conditions and thus their partitioning varies continuously with changing temperature and concentration. Because organics contribute a large portion of the PM mass emitted by most combustion sources, these emissions cannot be represented using a traditional, static emission factor. Instead, knowledge of the volatility distribution of emissions is required to explicitly account for changes in gas-particle partitioning. This requires updating how PM emissions from combustion systems are measured and simulated from combustion systems. Secondary PM production often greatly exceeds the direct or primary PM emissions; therefore, secondary PM must be included in any assessment of the contribution of combustion systems to ambient PM concentrations. Low-volatility organic vapors emitted by combustion systems appear to be very important secondary PM precursors that are poorly accounted for in inventories and models. The review concludes by discussing the implications that the dynamic nature of these PM emissions have on source testing for emission inventory development and regulatory purposes. This discussion highlights important linkages between primary and secondary PM, which could lead to simplified certification test procedures while capturing the emission components that contribute most to atmospheric PM mass.
21044921
Measurement of emissions from air pollution sources. 3. C1-C29 organic compounds from fireplace combustion of wood.
Organic compound emission rates for volatile organic compounds (VOC), gas-phase semivolatile organic compounds, and particle-phase organic compounds are measured from residential fireplace combustion of wood. Firewood from a conifer tree (pine) and from two deciduous trees (oak and eucalyptus) is burned to determine organic compound emissions profiles for each wood type including the distribution of the alkanes, alkenes, aromatics, polycyclic aromatic hydrocarbons (PAH), phenol and substituted phenols, guaiacol and substituted guaiacol, syringol and substituted syringols, carbonyls, alkanoic acids, resin acids, and levoglucosan. Levoglucosan is the major constituent in the fine particulate emissions from all three wood types, contributing 18-30% of the fine particulate organic compound emissions. Guaiacol (2-methoxyphenol), and guaiacols with additional substituents at position 4 on the molecule, and resin acids are emitted in significant quantities from pine wood combustion. Syringol (2,6-dimethoxyphenol) and syringols with additional substituents at position 4 on the molecule are emitted in large amounts from oak and eucalyptus firewood combustion, but these compounds are not detected in the emissions from pine wood combustion. Syringol and most of the substituted syringols are found to be semivolatile compounds that are present in both the gas and particle phases, but two substituted syringols that have not been previously quantified in wood smoke emissions, propionylsyringol and butyrylsyringol, are found exclusively in the particle phase and can be used to help trace hardwood smoke particles in the atmosphere. Benzene, ethene, and acetylene are often used as tracers for motor vehicle exhaust in the urban atmosphere. The contribution of wood smoke to the ambient concentrations of benzene, ethene, and acetylene could lead to an overestimate of the contribution of motor vehicle tailpipe exhaust to atmospheric VOC concentrations.
12570034
Measurement of emissions from air pollution sources. 5. C1-C32 organic compounds from gasoline-powered motor vehicles.
Gas- and particle-phase organic compounds present in the tailpipe emissions from an in-use fleet of gasoline-powered automobiles and light-duty trucks were quantified using a two-stage dilution source sampling system. The vehicles were driven through the cold-start Federal Test Procedure (FTP) urban driving cycle on a transient dynamometer. Emission rates of 66 volatile hydrocarbons, 96 semi-volatile and particle-phase organic compounds, 27 carbonyls, and fine particle mass and chemical composition were quantified. Six isoprenoids and two tricyclic terpanes, which are quantified using new source sampling techniques for semi-volatile organic compounds, have been identified as potential tracers for gasoline-powered motor vehicle emissions. A composite of the commercially distributed California Phase II Reformulated Gasoline used in these tests was analyzed by several analytical methods to quantify the gasoline composition, including some organic compounds that are found in the atmosphere as semi-volatile and particle-phase organic compounds. These results allow a direct comparison of the semi-volatile and particle-phase organic compound emissions from gasoline-powered motor vehicles to the gasoline burned by these vehicles. The distribution of n-alkanes and isoprenoids emitted from the catalyst-equipped gasoline-powered vehicles is the same as the distribution of these compounds found in the gasoline used, whereas the distribution of these compounds in the emissions from the noncatalyst vehicles is very different from the distribution in the fuel. In contrast, the distribution of the polycyclic aromatic hydrocarbons and their methylated homologues in the gasoline is significantly different from the distribution of the PAH in the tailpipe emissions from both types of vehicles.
18086207
A technology‐based global inventory of black and organic carbon emissions from combustion
[1] We present a global tabulation of black carbon (BC) and primary organic carbon (OC) particles emitted from combustion. We include emissions from fossil fuels, biofuels, open biomass burning, and burning of urban waste. Previous ‘‘bottom-up’’ inventories of black and organic carbon have assigned emission factors on the basis of fuel type and economic sector alone. Because emission rates are highly dependent on combustion practice, we consider combinations of fuel, combustion type, and emission controls and their prevalence on a regional basis. Central estimates of global annual emissions are 8.0 Tg for black carbon and 33.9 Tg for organic carbon. These estimates are lower than previously published estimates by 25–35%. The present inventory is based on 1996 fuel-use data, updating previous estimates that have relied on consumption data from 1984. An offset between decreased emission factors and increased energy use since the base year of the previous inventory prevents the difference between this work and previous inventories from being greater. The contributions of fossil fuel, biofuel, and open burning are estimated as 38%, 20%, and 42%, respectively, for BC, and 7%, 19%, and 74%, respectively, for OC. We present a bottom-up estimate of uncertainties in source strength by combining uncertainties in particulate matter emission factors, emission characterization, and fuel use. The total uncertainties are about a factor of 2, with uncertainty ranges of 4.3–22 Tg/yr for BC and 17–77 Tg/yr for OC. Low-technology combustion contributes greatly to both the emissions and the uncertainties. Advances in emission characterization for small residential, industrial, and mobile sources and topdown analysis combining field measurements and transport modeling with iterative inventory development will be required to reduce the uncertainties further. INDEX TERMS: 0305 Atmospheric Composition and Structure: Aerosols and particles (0345, 4801); 0322 Atmospheric Composition and Structure: Constituent sources and sinks; 0345 Atmospheric Composition and Structure: Pollution—urban and regional (0305); 0360 Atmospheric Composition and Structure: Transmission and scattering of radiation; 0365 Atmospheric Composition and Structure: Troposphere—composition and chemistry; KEYWORDS: emission, black carbon, organic carbon, fossil fuel, biofuel, biomass burning
128563484
Construction of a 1° × 1° fossil fuel emission data set for carbonaceous aerosol and implementation and radiative impact in the ECHAM4 model
Global-scale emissions of carbonaceous aerosol from fossil fuel usage have been calculated with a resolution of 1° × 1°. Emission factors for black and organic carbon have been gathered from the literature and applied to domestic, transport, and industrial combustion of various fuel types. In addition, allowance has been made for the level of development when calculating emissions from a country. Emissions have been calculated for 185 countries for the domestic, industrial, and transport sectors using a fuel usage database published by the United Nations [1993]. Some inconsistencies were found for a small number of countries with regard to the distribution of fuel usage between the industrial and domestic sectors. Care has been taken to correct for this using data from the fuel use database for the period 1970–1990. Emissions based on total particulate matter (TPM) and submicron emission factors have been calculated. Global emissions for 1984 of black carbon total 6.4 TgC yr−1 and organic carbon emissions of 10.1 TgC yr−1 were found using bulk aerosol emission factors, while global black carbon emissions of 5.1 TgC yr−1 and organic carbon emissions of 7.0 TgC yr−1 were found using submicron emission factors. Use of the database is quite flexible and can be easily updated as emission factor data are updated. There is at least a factor of 2 uncertainty in the derived emissions due to the lack of exactly appropriate emission data. The emission fields have been introduced into the ECHAM4 atmospheric general circulation model and run for 5 model years. Monthly mean model results are compared to measurements in regions influenced by anthropogenic fossil fuel emissions. The resultant aerosol fields have been used to calculate the instantaneous solar radiative forcing at the top of the troposphere due to an external mixture of fossil fuel derived black carbon and organic carbon aerosol. Column burdens of 0.143 mgBC m−2 and 0.170 mgOC m−2 were calculated. Because of secondary production of organic carbon aerosol, it is recommended that the burden of organic carbon aerosol be doubled to 0.341 mgOC m−2. The resultant forcing when clouds are included is +0.173 W m−2 for black carbon and −0.024 W m−2 for organic carbon (×2) as a global annual average. The results are compared to previous works, and the differences are discussed.
11155510
Determination of the organic aerosol mass to organic carbon ratio in IMPROVE samples.
The ratio of organic mass (OM) to organic carbon (OC) in PM(2.5) aerosols at US national parks in the IMPROVE network was estimated experimentally from solvent extraction of sample filters and from the difference between PM(2.5) mass and chemical constituents other than OC (mass balance) in IMPROVE samples from 1988 to 2003. Archived IMPROVE filters from five IMPROVE sites were extracted with dichloromethane (DCM), acetone and water. The extract residues were weighed to determine OM and analyzed for OC by thermal optical reflectance (TOR). On average, successive extracts of DCM, acetone, and water contained 64%, 21%, and 15%, respectively, of the extractable OC, respectively. On average, the non-blank-corrected recovery of the OC initially measured in these samples by TOR was 115+/-42%. OM/OC ratios from the combined DCM and acetone extracts averaged 1.92 and ranged from 1.58 at Indian Gardens, AZ in the Grand Canyon to 2.58 at Mount Rainier, WA. The average OM/OC ratio determined by mass balance was 2.07 across the IMPROVE network. The sensitivity of this ratio to assumptions concerning sulfate neutralization, water uptake by hygroscopic species, soil mass, and nitrate volatilization were evaluated. These results suggest that the value of 1.4 for the OM/OC ratio commonly used for mass and light extinction reconstruction in IMPROVE is too low.
24331961
Constraining the volatility distribution and gas-particle partitioning of combustion aerosols using isothermal dilution and thermodenuder measurements.
The gas-particle partitioning of primary organic aerosol (POA) emissions from a diesel engine and the combustion of hard- and soft-woods in a stove was investigated by isothermally diluting them in a smog chamber or by passing them through a thermodenuder and measuring the extent of evaporation. The experiments were conducted at atmospherically relevant conditions: low concentrations and small temperature perturbations. The partitioning of the POA emissions from both sources varied continuously with changing concentration and temperature. Although the POA emissions are semivolatile, they do not completely evaporate at typical atmospheric conditions. The overall partitioning characteristics of diesel and wood smoke POA are similar, with wood smoke being somewhat less volatile than the diesel exhaust. The gas-particle partitioning of aerosols formed from flash-vaporized engine lubricating oil was also studied; diesel POA is somewhat more volatile than the oil aerosol. The experimental data from the dilution- and thermodenuder-based techniques were fit using absorptive partitioning theory to derive a volatility distribution of the POA emissions from each source. These distributions are suitable for use in chemical transport models that simulate POA concentrations.
1063623
Carbon oxidation state as a metric for describing the chemistry of atmospheric organic aerosol.
A detailed understanding of the sources, transformations and fates of organic species in the environment is crucial because of the central roles that they play in human health, biogeochemical cycles and the Earth's climate. However, such an understanding is hindered by the immense chemical complexity of environmental mixtures of organics; for example, atmospheric organic aerosol consists of at least thousands of individual compounds, all of which likely evolve chemically over their atmospheric lifetimes. Here, we demonstrate the utility of describing organic aerosol (and other complex organic mixtures) in terms of average carbon oxidation state, a quantity that always increases with oxidation, and is readily measured using state-of-the-art analytical techniques. Field and laboratory measurements of the average carbon oxidation state, using several such techniques, constrain the chemical properties of the organics and demonstrate that the formation and evolution of organic aerosol involves simultaneous changes to both carbon oxidation state and carbon number.
54069444
Tropospheric sulfur simulation and sulfate direct radiative forcing in the Goddard Institute for Space Studies general circulation model
Global simulations of tropospheric sulfur are performed in the Goddard Institute for Space Studies (GISS) general circulation model (GCM) and used to calculate anthropogenic sulfate direct radiative forcing. Prognostic species are in-cloud oxidant H2O2, dimethylsulfide (DMS), methanesulfonic acid (MSA), SO2 and sulfate. Compared with most previous models (except others with prognostic H2O2), this model has relatively high anthropogenic SO2 and sulfate burden. We show that this is due partly to the depletion of the prognostic H2O2 and that moist convection delivers significant levels of SO2 to the free troposphere in polluted regions. Model agreement with surface observations is not remarkably different from previous studies. Following some previous studies, we propose that an additional in-cloud or heterogeneous oxidant is likely to improve the simulation near the surface. Our DMS source is lower than sources in previous studies, and sulfur values in remote regions are generally lower than those observed. Because of the high flux of SO2 to the free troposphere and the relatively low natural source, our model indicates a larger global anthropogenic contribution to the sulfate burden (77%) than was estimated by previous global models. Additional high-altitude observations of the sulfur species are needed for model validation and resolution of this issue. Direct radiative forcing calculations give an annual average anthropogenic sulfate forcing of −0.67 W/m2. We compare the radiative forcings due to online (hourly varying) versus offline (monthly average) sulfate and find little difference on a global average, but we do find differences as great as 10% in some regions. Thus, for example, over some polluted continental regions the forcing due to offline sulfate exceeds that of online sulfate, while over some oceanic regions the online sulfate forcing is larger. We show that these patterns are probably related to the correlation between clouds and sulfate, with positive correlations occuring over some polluted continental regions and negative correlations over high-latitude oceanic regions.
128825462
A Prognostic Cloud Water Parameterization for Global Climate Models
Abstract An efficient new prognostic cloud water parameterization designed for use in global climate models is described. The scheme allows for life cycle effects in stratiform clouds and permits cloud optical properties to be determined interactively. The parameterization contains representations of all important microphysical processes, including autoconversion, accretion, Bergeron–Findeisen diffusional growth, and cloud/rain water evaporation. Small-scale dynamical processes, including detrainment of convective condensate, cloud-top entrainment instability, and stability-dependent cloud physical thickness variations, are also taken into account. Cloud optical thickness is calculated from the predicted liquid/ice water path and a variable droplet effective radius estimated by assuming constant droplet number concentration. Microphysical and radiative properties are assumed to be different for liquid and ice clouds, and for liquid clouds over land and ocean. The parameterization is validated in several s...
1780311
A semiempirical correlation between enthalpy of vaporization and saturation concentration for organic aerosol.
To model the temperature-induced partitioning of semivolatile organics in laboratory experiments or atmospheric models, one must know the appropriate heats of vaporization. Current treatments typically assume a constant value of the heat of vaporization or else use specific values from a small set of surrogate compounds. With published experimental vapor-pressure data from over 800 organic compounds, we have developed a semiempirical correlation between the saturation concentration (C*, microg m(-3)) and the heat of vaporization (deltaH(VAP), kJ mol(-1)) for organics in the volatility basis set. Near room temperature, deltaH(VAP) = -11 log(10)C(300)(*) + 129. Knowledge of the relationship between C* and deltaH(VAP) constrains a free parameter in thermodenuder data analysis. A thermodenuder model using our deltaH(VAP) values agrees well with thermal behavior observed in laboratory experiments.
16900410
Secondary organic aerosol formation from photooxidation of naphthalene and alkylnaphthalenes: implications for oxidation of intermediate volatility organic compounds (IVOCs)
Abstract. 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-m3 chambers. Under high-NOx conditions and aerosol mass loadings between 10 and 40 μg m−3, 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-NOx 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-NOx conditions and essentially nonvolatile under low-NOx conditions, owing to the higher fraction of ring-retaining products formed under low-NOx 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.
93798408
Secondary organic aerosol in the global aerosol – chemical transport model Oslo CTM2
The global chemical transport model Oslo CTM2 has been extended to include the formation, transport and deposition of secondary organic aerosol (SOA). Precursor hydrocarbons which are oxidised to form condensible species include both biogenic species such as terpenes and isoprene, as well as species emitted predominantly by anthropogenic activities (toluene, m-xylene, methylbenzene and other aromatics). A model simulation for 2004 gives an annual global SOA production of approximately 55 Tg. Of this total, 2.5 Tg is found to consist of the oxidation products of anthropogenically emitted hydrocarbons, and about 15 Tg is formed by the oxidation products of isoprene. The global production of SOA is increased to about 69 Tg yr −1 by allowing semi-volatile species to partition to ammonium sulphate aerosol. This brings modelled organic aerosol values closer to those observed, however observations in Europe remain significantly underestimated. Allowing SOA to partition into ammonium sulphate aerosol increases the contribution of anthropogenic SOA from about 4.5% to 9.4% of the total production. Total modelled organic aerosol (OA) values are found to represent a lower fraction of the measured values in winter (when primary organic aerosol (POA) is the dominant OA component) than in summer, which may be an indication that estimates of POA emissions are too low. Additionally, for measurement stations where the summer OA values are higher than in winter, the model generally underestimates the increase in summertime OA. In order to correctly model the observed increase in OA in summer, additional SOA sources or formation mechanisms may be necessary. The importance of NO 3 as an oxidant of SOA precursors is found to vary regionally, causing up to 50%–60% of the total amount of SOA near the surface in polluted regions and less than 25% in more remote areas, if the yield of condensible oxidation products for β-pinene is used for NO 3 oxidation of all terpenes. Reducing the yield for α-pinene and limonene oxidation in line with recent measurements reduces the global fraction of SOA formed from NO 3 oxidation products from 27% to about 21%. This study underscores the need for SOA to be represented in a more realistic way in global aerosol models in order to better reproduce observations of organic aerosol burdens in industrialised and biomass burning regions.
17825897
Predicted change in global secondary organic aerosol concentrations in response to future climate, emissions, and land use change
[1] The sensitivity of secondary organic aerosol (SOA) concentration to changes in climate and emissions is investigated using a coupled global atmosphere-land model driven by the year 2100 IPCC A1B scenario predictions. The Community Atmosphere Model (CAM3) is updated with recent laboratory determined yields for SOA formation from monoterpene oxidation, isoprene photooxidation and aromatic photooxidation. Biogenic emissions of isoprene and monoterpenes are simulated interactively using the Model of Emissions of Gases and Aerosols (MEGAN2) within the Community Land Model (CLM3). The global mean SOA burden is predicted to increase by 36% in 2100, primarily the result of rising biogenic and anthropogenic emissions which independently increase the burden by 26% and 7%. The later includes enhanced biogenic SOA formation due to increased emissions of primary organic aerosol (5–25% increases in surface SOA concentrations in 2100). Climate change alone (via temperature, removal rates, and oxidative capacity) does not change the global mean SOA production, but the global burden increases by 6%. The global burden of anthropogenic SOA experiences proportionally more growth than biogenic SOA in 2100 from the net effect of climate and emissions (67% increase predicted). Projected anthropogenic land use change for 2100 (A2) is predicted to reduce the global SOA burden by 14%, largely the result of cropland expansion. South America is the largest global source region for SOA in the present day and 2100, but Asia experiences the largest relative growth in SOA production by 2100 because of the large predicted increases in Asian anthropogenic aromatic emissions. The projected decrease in global sulfur emissions implies that SOA will contribute a progressively larger fraction of the global aerosol burden.
24235838
O/C and OM/OC ratios of primary, secondary, and ambient organic aerosols with high-resolution time-of-flight aerosol mass spectrometry.
A recently developed method to rapidly quantify the elemental composition of bulk organic aerosols (OA) using a high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS) is improved and applied to ambient measurements. Atomic oxygen-to-carbon (O/C) ratios characterize the oxidation state of OA, and O/C from ambient urban OA ranges from 0.2 to 0.8 with a diurnal cycle that decreases with primary emissions and increases because of photochemical processing and secondary OA (SOA) production. Regional O/C approaches approximately 0.9. The hydrogen-to-carbon (H/C, 1.4--1.9) urban diurnal profile increases with primary OA (POA) as does the nitrogen-to-carbon (N/C, approximately 0.02). Ambient organic-mass-to-organic-carbon ratios (OM/OC) are directly quantified and correlate well with O/C (R2 = 0.997) for ambient OA because of low N/C. Ambient O/C and OM/OC have values consistent with those recently reported from other techniques. Positive matrix factorization applied to ambient OA identifies factors with distinct O/C and OM/OC trends. The highest O/C and OM/OC (1.0 and 2.5, respectively) are observed for aged ambient oxygenated OA, significantly exceeding values for traditional chamber SOA,while laboratory-produced primary biomass burning OA (BBOA) is similar to ambient BBOA, O/C of 0.3--0.4. Hydrocarbon-like OA (HOA), a surrogate for urban combustion POA, has the lowest O/C (0.06--0.10), similar to vehicle exhaust. An approximation for predicting O/C from unit mass resolution data is also presented.
131008642
A global three‐dimensional model study of carbonaceous aerosols
We have developed detailed emission inventories for the amount of both black and organic carbon particles from biomass burning sources (wood fuel, charcoal burning, dung, charcoal production, agricultural, savanna and forest fires). We have also estimated an inventory for organic carbon particles from fossil fuel burning and urban activities from an existing inventory for fossil fuel sources of black carbon. We also provide an estimate for the natural source of organic matter. These emissions have been used together with our global aerosol model to study the global distribution of carbonaceous aerosols. The accuracy of the inventories and the model formulation has been tested by comparing the model simulations of carbonaceous aerosols in the atmosphere and in precipitation with observations reported in the literature. For most locations and seasons, the predicted concentrations are in reasonable agreement with the observations, although the model underpredicts black carbon concentrations in polar regions. The predicted concentrations in remote areas are extremely sensitive to both the rate of removal by wet deposition and the height of injection of the aerosols. Finally, a global map of the aerosol single scattering albedo was developed from the simulated carbonaceous particle distribution and a previously developed model for aerosol sulfates. The computed aerosol single scattering albedos compare well with observations, suggesting that most of the important aerosol species have been included in the model. For most locations and seasons, the single scattering albedo is larger than 0.85, indicating that these aerosols, in general, lead to a net cooling.
97871399
Atmospheric organic particulate matter: From smoke to secondary organic aerosol
We present an overview of the development of our understanding of the sources, formation mechanisms, physical and chemical transformations of atmospheric organic aerosol (OA) during the last thirty years. Until recently, organic particulate material was simply classified as either primary or secondary with the primary component being treated in models as nonvolatile and inert. However, this oversimplified view fails to explain the highly oxygenated nature of ambient OA, the relatively small OA concentration gradients between urban areas and their surroundings, and the concentrations of OA during periods of high photochemical activity. A unifying framework for the description of all components based on their volatility distribution (the volatility basis set) can be used for the treatment of a wide range of processes affecting organic aerosol loadings and composition in the atmosphere. These processes include direct organic particle and vapor emissions, chemical production of organic PM from volatile precursors, chemical reactions (aging) in all phases, as well as deposition of both particles and vapors and chemical losses to volatile products. The combination of this new framework with the recent results of laboratory studies can resolve some of the discrepancies between OA observations and laboratory results. The mass balance of the organic material as a function of its volatility is investigated and used to frame the corresponding constraints on the system. Finally we revisit the traditional definitions of primary and secondary organic aerosol and propose a new set of terms and definitions based on the improvements of our understanding.
53138894
Radiocarbon analysis of carbonaceous aerosols: recent developments
Carbonaceous aerosols are a major fraction of airborne particulate matter. They contribute to climate and health effects of the total aerosol burden of the atmosphere by counteracting the current trend of global warming and inducing respiratory and cardiovascular diseases, respectively. In spite of this general importance, only little is known about composition and sources of carbonaceous aerosols. Analysis of the long-lived radioactive isotope 14 C (radiocarbon) is a unique source apportionment tool: it unambiguously separates fossil from non-fossil sources, as 14 C has completely decayed in fossil fuels, whereas modern materials have the contemporary radiocarbon level. A novel separation method was developed for the direct determination of 14 C in organic carbon (OC) and elemental carbon (EC), two sub-fractions of total carbon (TC). The implementation of a gas ion source for measurement with accelerator mass spectrometry (AMS) made 14 C analysis more simple and robust. Based on this technique, all major contributions to the carbonaceous aerosol can be identified, which originate from fossil-fuel, biomass-burning and biogenic emissions. A survey of results from different field campaigns is shown.
94722635
Simulating secondary organic aerosol formation using the volatility basis-set approach in a chemical transport model
Abstract The secondary organic aerosol (SOA) module in PMCAMx, a three-dimensional chemical transport model, has been updated based on laboratory results from recent smog chamber experiments. A new modeling framework is used based on the SOA volatility basis-set approach instead of the two-product approach used in existing models. The different scenarios are simulated for July 2001, and the predicted organic aerosol (OA) concentrations are compared to the available ambient measurements from the EPA Speciation Trends Network (STN) and the Interagency Monitoring of Protected Visual Environments (IMPROVE). The base-case OA simulation slightly overpredicts the ambient measured OA concentrations at the rural IMPROVE monitoring sites with a bias of 0.33 μg m−3. Compared to the urban STN sites, the base-case scenario still underpredicts the observed OA concentrations but is performing significantly better than the two-product module in PMCAMx compared to observations. The contribution of biogenic and anthropogenic SOA to the predicted organic aerosol concentrations and the potential role of chemical aging are investigated. The higher yields of SOA from anthropogenic precursors reported in the most recent studies improve the model performance in urban areas.