Showing papers in "Atmospheric Chemistry and Physics in 2011"

Emission factors for open and domestic biomass burning for use in atmospheric models

Abstract: . Biomass burning (BB) is the second largest source of trace gases and the largest source of primary fine carbonaceous particles in the global troposphere. Many recent BB studies have provided new emission factor (EF) measurements. This is especially true for non-methane organic compounds (NMOC), which influence secondary organic aerosol (SOA) and ozone formation. New EF should improve regional to global BB emissions estimates and therefore, the input for atmospheric models. In this work we present an up-to-date, comprehensive tabulation of EF for known pyrogenic species based on measurements made in smoke that has cooled to ambient temperature, but not yet undergone significant photochemical processing. All EFs are converted to one standard form (g compound emitted per kg dry biomass burned) using the carbon mass balance method and they are categorized into 14 fuel or vegetation types. Biomass burning terminology is defined to promote consistency. We compile a large number of measurements of biomass consumption per unit area for important fire types and summarize several recent estimates of global biomass consumption by the major types of biomass burning. Post emission processes are discussed to provide a context for the emission factor concept within overall atmospheric chemistry and also highlight the potential for rapid changes relative to the scale of some models or remote sensing products. Recent work shows that individual biomass fires emit significantly more gas-phase NMOC than previously thought and that including additional NMOC can improve photochemical model performance. A detailed global estimate suggests that BB emits at least 400 Tg yr−1 of gas-phase NMOC, which is almost 3 times larger than most previous estimates. Selected recent results (e.g. measurements of HONO and the BB tracers HCN and CH3CN) are highlighted and key areas requiring future research are briefly discussed.

Secondary organic aerosol formation in cloud droplets and aqueous particles (aqSOA): a review of laboratory, field and model studies

Abstract: . Progress has been made over the past decade in predicting secondary organic aerosol (SOA) mass in the atmosphere using vapor pressure-driven partitioning, which implies that SOA compounds are formed in the gas phase and then partition to an organic phase (gasSOA). However, discrepancies in predicting organic aerosol oxidation state, size and product (molecular mass) distribution, relative humidity (RH) dependence, color, and vertical profile suggest that additional SOA sources and aging processes may be important. The formation of SOA in cloud and aerosol water (aqSOA) is not considered in these models even though water is an abundant medium for atmospheric chemistry and such chemistry can form dicarboxylic acids and "humic-like substances" (oligomers, high-molecular-weight compounds), i.e. compounds that do not have any gas phase sources but comprise a significant fraction of the total SOA mass. There is direct evidence from field observations and laboratory studies that organic aerosol is formed in cloud and aerosol water, contributing substantial mass to the droplet mode. This review summarizes the current knowledge on aqueous phase organic reactions and combines evidence that points to a significant role of aqSOA formation in the atmosphere. Model studies are discussed that explore the importance of aqSOA formation and suggestions for model improvements are made based on the comprehensive set of laboratory data presented here. A first comparison is made between aqSOA and gasSOA yields and mass predictions for selected conditions. These simulations suggest that aqSOA might contribute almost as much mass as gasSOA to the SOA budget, with highest contributions from biogenic emissions of volatile organic compounds (VOC) in the presence of anthropogenic pollutants (i.e. NOx) at high relative humidity and cloudiness. Gaps in the current understanding of aqSOA processes are discussed and further studies (laboratory, field, model) are outlined to complement current data sets.

Global dust model intercomparison in AeroCom phase I

Abstract: . This study presents the results of a broad intercomparison of a total of 15 global aerosol models within the AeroCom project. Each model is compared to observations related to desert dust aerosols, their direct radiative effect, and their impact on the biogeochemical cycle, i.e., aerosol optical depth (AOD) and dust deposition. Additional comparisons to Angstrom exponent (AE), coarse mode AOD and dust surface concentrations are included to extend the assessment of model performance and to identify common biases present in models. These data comprise a benchmark dataset that is proposed for model inspection and future dust model development. There are large differences among the global models that simulate the dust cycle and its impact on climate. In general, models simulate the climatology of vertically integrated parameters (AOD and AE) within a factor of two whereas the total deposition and surface concentration are reproduced within a factor of 10. In addition, smaller mean normalized bias and root mean square errors are obtained for the climatology of AOD and AE than for total deposition and surface concentration. Characteristics of the datasets used and their uncertainties may influence these differences. Large uncertainties still exist with respect to the deposition fluxes in the southern oceans. Further measurements and model studies are necessary to assess the general model performance to reproduce dust deposition in ocean regions sensible to iron contributions. Models overestimate the wet deposition in regions dominated by dry deposition. They generally simulate more realistic surface concentration at stations downwind of the main sources than at remote ones. Most models simulate the gradient in AOD and AE between the different dusty regions. However the seasonality and magnitude of both variables is better simulated at African stations than Middle East ones. The models simulate the offshore transport of West Africa throughout the year but they overestimate the AOD and they transport too fine particles. The models also reproduce the dust transport across the Atlantic in the summer in terms of both AOD and AE but not so well in winter-spring nor the southward displacement of the dust cloud that is responsible of the dust transport into South America. Based on the dependency of AOD on aerosol burden and size distribution we use model bias with respect to AOD and AE to infer the bias of the dust emissions in Africa and the Middle East. According to this analysis we suggest that a range of possible emissions for North Africa is 400 to 2200 Tg yr−1 and in the Middle East 26 to 526 Tg yr−1.

Anthropogenic sulfur dioxide emissions: 1850–2005

Abstract: . Sulfur aerosols impact human health, ecosystems, agriculture, and global and regional climate. A new annual estimate of anthropogenic global and regional sulfur dioxide emissions has been constructed spanning the period 1850–2005 using a bottom-up mass balance method, calibrated to country-level inventory data. Global emissions peaked in the early 1970s and decreased until 2000, with an increase in recent years due to increased emissions in China, international shipping, and developing countries in general. An uncertainty analysis was conducted including both random and systemic uncertainties. The overall global uncertainty in sulfur dioxide emissions is relatively small, but regional uncertainties ranged up to 30%. The largest contributors to uncertainty at present are emissions from China and international shipping. Emissions were distributed on a 0.5° grid by sector for use in coordinated climate model experiments.

Sulfur dioxide and primary carbonaceous aerosol emissions in China and India, 1996-2010

Abstract: . China and India are the two largest anthropogenic aerosol generating countries in the world. In this study, we develop a new inventory of sulfur dioxide (SO2) and primary carbonaceous aerosol (i.e., black and organic carbon, BC and OC) emissions from these two countries for the period 1996–2010, using a technology-based methodology. Emissions from major anthropogenic sources and open biomass burning are included, and time-dependent trends in activity rates and emission factors are incorporated in the calculation. Year-specific monthly temporal distributions for major sectors and gridded emissions at a resolution of 0.1°×0.1° distributed by multiple year-by-year spatial proxies are also developed. In China, the interaction between economic development and environmental protection causes large temporal variations in the emission trends. From 1996 to 2000, emissions of all three species showed a decreasing trend (by 9 %–17 %) due to a slowdown in economic growth, a decline in coal use in non-power sectors, and the implementation of air pollution control measures. With the economic boom after 2000, emissions from China changed dramatically. BC and OC emissions increased by 46 % and 33 % to 1.85 Tg and 4.03 Tg in 2010. SO2 emissions first increased by 61 % to 34.0 Tg in 2006, and then decreased by 9.2 % to 30.8 Tg in 2010 due to the wide application of flue-gas desulfurization (FGD) equipment in power plants. Driven by the remarkable energy consumption growth and relatively lax emission controls, emissions from India increased by 70 %, 41 %, and 35 % to 8.81 Tg, 1.02 Tg, and 2.74 Tg in 2010 for SO2, BC, and OC, respectively. Monte Carlo simulations are used to quantify the emission uncertainties. The average 95 % confidence intervals (CIs) of SO2, BC, and OC emissions are estimated to be −16 %–17 %, −43 %–93 %, and −43 %–80 % for China, and −15 %–16 %, −41 %–87 %, and −44 %–92 % for India, respectively. Sulfur content, fuel use, and sulfur retention of hard coal and the actual FGD removal efficiency are the main contributors to the uncertainties of SO2 emissions. Biofuel combustion related parameters (i.e., technology divisions, fuel use, and emission factor determinants) are the largest source of OC uncertainties, whereas BC emissions are also sensitive to the parameters of coal combustion in the residential and industrial sectors and the coke-making process. Comparing our results with satellite observations, we find that the trends of estimated emissions in both China and India are in good agreement with the trends of aerosol optical depth (AOD) and SO2 retrievals obtained from different satellites.

Emulating coupled atmosphere-ocean and carbon cycle models with a simpler model, MAGICC6 - Part 1: Model description and calibration

Abstract: Current scientific knowledge on the future response of the climate system to human-induced perturbations is comprehensively captured by various model intercomparison efforts In the preparation of the Fourth Assessment Report (AR4) of the Intergovernmental Panel on Climate Change (IPCC), intercomparisons were organized for atmosphere-ocean general circulation models (AOGCMs) and carbon cycle models, named "CMIP3" and "C 4 MIP", respectively Despite their tremendous value for the scientific community and policy makers alike, there are some difficulties in interpreting the results For example, radiative forcings were not standardized across the various AOGCM integrations and carbon cycle runs, and, in some models, key forcings were omitted Furthermore, the AOGCM analysis of plausible emissions pathways was restricted to only three SRES scenarios This study attempts to address these issues We present an updated version of MAGICC, the simple carbon cycle-climate model used in past IPCC Assessment Reports with enhanced representation of time-varying climate sensitivities, carbon cycle feedbacks, aerosol forcings and ocean heat uptake characteristics This new version, MAGICC6, is successfully calibrated against the higher complexity AOGCMs and carbon cycle models Parameterizations of MAGICC6 are provided The mean of the emulations presented here using MAGICC6 deviates from the mean AOGCM responses by only 22% on average for the SRES scenarios This enhanced emulation skill in comparison to previous calibrations is primarily due to: making a "like-with-like comparison" using AOGCM-specific subsets of forcings; employing a new calibration procedure; as well as the fact that the updated simple climate model can now successfully emulate some of the climate-state dependent effective climate sensitivities of AOGCMs The diagnosed effective climate sensitivity at the time of CO 2 doubling for the AOGCMs is on average 288 °C, about 033 °C cooler than the mean of the reported slab ocean climate sensitivities In the companion paper (Part 2) of this study, we examine the combined climate system and carbon cycle emulations for the complete range of IPCC SRES emissions scenarios and the new RCP pathways

Earth's energy imbalance and implications

Abstract: . Improving observations of ocean heat content show that Earth is absorbing more energy from the Sun than it is radiating to space as heat, even during the recent solar minimum. The inferred planetary energy imbalance, 0.58 ± 0.15 W m −2 during the 6-yr period 2005–2010, confirms the dominant role of the human-made greenhouse effect in driving global climate change. Observed surface temperature change and ocean heat gain together constrain the net climate forcing and ocean mixing rates. We conclude that most climate models mix heat too efficiently into the deep ocean and as a result underestimate the negative forcing by human-made aerosols. Aerosol climate forcing today is inferred to be −1.6 ± 0.3 W m −2 , implying substantial aerosol indirect climate forcing via cloud changes. Continued failure to quantify the specific origins of this large forcing is untenable, as knowledge of changing aerosol effects is needed to understand future climate change. We conclude that recent slowdown of ocean heat uptake was caused by a delayed rebound effect from Mount Pinatubo aerosols and a deep prolonged solar minimum. Observed sea level rise during the Argo float era is readily accounted for by ice melt and ocean thermal expansion, but the ascendency of ice melt leads us to anticipate acceleration of the rate of sea level rise this decade.

Characteristics of PM 2.5 speciation in representative megacities and across China

Abstract: . Based on PM2.5 chemical data sets from literature and from our surface observations, chemical species and reconstructed speciation of PM2.5 in representative Chinese megacities and across China were compared to draw insights into the characteristics of PM2.5 speciation. PM2.5 mass concentrations and speciation compositions varied substantially over geographical regions in China. Near six-fold variations in average PM2.5 concentrations (34.0–193.4 μg m−3) across China were found with high PM2.5 levels (>100 μg m−3) appearing in the cities in the northern and western regions and low levels (

A two-dimensional volatility basis set: 1. organic-aerosol mixing thermodynamics

Abstract: We develop the thermodynamic underpinnings of a two-dimensional volatility basis set (2D-VBS) employ- ing saturation mass concentration (C o ) and the oxygen con- tent (O:C) to describe volatility, mixing thermodynamics, and chemical evolution of organic aerosol. The work ad- dresses a simple question: "Can we reasonably constrain organic-aerosol composition in the atmosphere based on only two measurable organic properties, volatility and the extent of oxygenation?" This is an extension of our earlier one- dimensional approach employing volatility only (C = C o , where is an activity coefficient). Using available con- straints on bulk organic-aerosol composition, we argue that one can reasonably predict the composition of organics (car- bon, oxygen and hydrogen numbers) given a location in the C o - O:C space. Further, we argue that we can constrain the activity coefficients at various locations in this space based on the O:C of the organic aerosol.

Effects of aging on organic aerosol from open biomass burning smoke in aircraft and laboratory studies

Abstract: . Biomass burning (BB) is a large source of primary and secondary organic aerosols (POA and SOA). This study addresses the physical and chemical evolution of BB organic aerosols. Firstly, the evolution and lifetime of BB POA and SOA signatures observed with the Aerodyne Aerosol Mass Spectrometer are investigated, focusing on measurements at high-latitudes acquired during the 2008 NASA ARCTAS mission, in comparison to data from other field studies and from laboratory aging experiments. The parameter f 60 , the ratio of the integrated signal at m/z 60 to the total signal in the organic component mass spectrum, is used as a marker to study the rate of oxidation and fate of the BB POA. A background level of f 60 ~0.3% ± 0.06% for SOA-dominated ambient OA is shown to be an appropriate background level for this tracer. Using also f 44 as a tracer for SOA and aged POA and a surrogate of organic O:C, a novel graphical method is presented to characterise the aging of BB plumes. Similar trends of decreasing f 60 and increasing f 44 with aging are observed in most field and lab studies. At least some very aged BB plumes retain a clear f 60 signature. A statistically significant difference in f 60 between highly-oxygenated OA of BB and non-BB origin is observed using this tracer, consistent with a substantial contribution of BBOA to the springtime Arctic aerosol burden in 2008. Secondly, a summary is presented of results on the net enhancement of OA with aging of BB plumes, which shows large variability. The estimates of net OA gain range from ΔOA/ΔCO(mass) = −0.01 to ~0.05, with a mean ΔOA/POA ~19%. With these ratios and global inventories of BB CO and POA a global net OA source due to aging of BB plumes of ~8 ± 7 Tg OA yr −1 is estimated, of the order of 5 % of recent total OA source estimates. Further field data following BB plume advection should be a focus of future research in order to better constrain this potentially important contribution to the OA burden.

Global distribution of sea salt aerosols: new constraints from in situ and remote sensing observations

Abstract: . We combine in situ measurements of sea salt aerosols (SS) from open ocean cruises and ground-based stations together with aerosol optical depth (AOD) observations from MODIS and AERONET, and the GEOS-Chem global chemical transport model to provide new constraints on SS emissions over the world's oceans. We find that the GEOS-Chem model using the Gong (2003) source function overestimates cruise observations of coarse mode SS mass concentrations by factors of 2–3 at high wind speeds over the cold waters of the Southern, North Pacific and North Atlantic Oceans. Furthermore, the model systematically underestimates SS over the warm tropical waters of the Central Pacific, Atlantic, and Indian Oceans. This pattern is confirmed by SS measurements from a global network of 15 island and coastal stations. The model discrepancy at high wind speeds (>6 m s −1 ) has a clear dependence on sea surface temperature (SST). We use the cruise observations to derive an empirical SS source function depending on both wind speed and SST. Implementing this new source function in GEOS-Chem results in improved agreement with in situ observations, with a decrease in the model bias from +64% to +33% for the cruises and from +32% to −5% for the ground-based sites. We also show that the wind speed-SST source function significantly improves agreement with MODIS and AERONET AOD, and provides an explanation for the high AOD observed over the tropical oceans. With the wind speed-SST formulation, global SS emissions show a small decrease from 5200 Mg yr −1 to 4600 Mg yr −1 , while the SS burden decreases from 9.1 to 8.5 mg m −2 . The spatial distribution of SS, however, is greatly affected, with the SS burden increasing by 50% in the tropics and decreasing by 40% at mid- and high-latitudes. Our results imply a stronger than expected halogen source from SS in the tropical marine boundary layer. They also imply stronger radiative forcing of SS in the tropics and a larger response of SS emissions to climate change than previously thought.

Changes in organic aerosol composition with aging inferred from aerosol mass spectra

Abstract: Organic aerosols (OA) can be separated with factor analysis of aerosol mass spectrometer (AMS) data into hydrocarbon-like OA (HOA) and oxygenated OA (OOA). We develop a new method to parameterize H:C of OOA in terms of f_(43)(ratio of m/z 43, mostly C_2H_3O^+, to total signal in the component mass spectrum). Such parameterization allows for the transformation of large database of ambient OOA components from the f_(44) (mostly CO^+_2, likely from acid groups) vs. f_(43) space ("triangle plot") (Ng et al., 2010) into the Van Krevelen diagram (H:C vs. O:C) (Van Krevelen, 1950). Heald et al. (2010) examined the evolution of total OA in the Van Krevelen diagram. In this work total OA is deconvolved into components that correspond to primary (HOA and others) and secondary (OOA) organic aerosols. By deconvolving total OA into different components, we remove physical mixing effects between secondary and primary aerosols which allows for examination of the evolution of OOA components alone in the Van Krevelen space. This provides a unique means of following ambient secondary OA evolution that is analogous to and can be compared with trends observed in chamber studies of secondary organic aerosol formation. The triangle plot in Ng et al. (2010) indicates that f_(44) of OOA components increases with photochemical age, suggesting the importance of acid formation in OOA evolution. Once they are transformed with the new parameterization, the triangle plot of the OOA components from all sites occupy an area in Van Krevelen space which follows a ΔH:C/ΔO:C slope of ~ −0.5. This slope suggests that ambient OOA aging results in net changes in chemical composition that are equivalent to the addition of both acid and alcohol/peroxide functional groups without fragmentation (i.e. C-C bond breakage), and/or the addition of acid groups with fragmentation. These results provide a framework for linking the bulk aerosol chemical composition evolution to molecular-level studies.

A very high-resolution (1 km×1 km) global fossil fuel CO 2 emission inventory derived using a point source database and satellite observations of nighttime lights

Abstract: . Emissions of CO 2 from fossil fuel combustion are a critical quantity that must be accurately given in established flux inversion frameworks. Work with emerging satellite-based inversions requires spatiotemporally-detailed inventories that permit analysis of regional natural sources and sinks. Conventional approaches for disaggregating national emissions beyond the country and city levels based on population distribution have certain difficulties in their application. We developed a global 1 km×1 km annual fossil fuel CO 2 emission inventory for the years 1980–2007 by combining a worldwide point source database and satellite observations of the global nightlight distribution. In addition to estimating the national emissions using global energy consumption statistics, emissions from point sources were estimated separately and were spatially allocated to exact locations indicated by the point source database. Emissions from other sources were distributed using a special nightlight dataset that had fewer saturated pixels compared with regular nightlight datasets. The resulting spatial distributions differed in several ways from those derived using conventional population-based approaches. Because of the inherent characteristics of the nightlight distribution, source regions corresponding to human settlements and land transportation were well articulated. Our distributions showed good agreement with a high-resolution inventory across the US at spatial resolutions that were adequate for regional flux inversions. The inventory can be extended to the future using updated data, and is expected to be incorporated into models for operational flux inversions that use observational data from the Japanese Greenhouse Gases Observing SATellite (GOSAT).

Aerosol mass spectrometer constraint on the global secondary organic aerosol budget

Abstract: . The budget of atmospheric secondary organic aerosol (SOA) is very uncertain, with recent estimates suggesting a global source of between 12 and 1820 Tg (SOA) a−1. We used a dataset of aerosol mass spectrometer (AMS) observations from 34 different surface locations to evaluate the GLOMAP global chemical transport model. The standard model simulation (which included SOA from monoterpenes only) underpredicted organic aerosol (OA) observed by the AMS and had little skill reproducing the variability in the dataset. We simulated SOA formation from biogenic (monoterpenes and isoprene), lumped anthropogenic and lumped biomass burning volatile organic compounds (VOCs) and varied the SOA yield from each precursor source to produce the best overall match between model and observations. We assumed that SOA is essentially non-volatile and condenses irreversibly onto existing aerosol. Our best estimate of the SOA source is 140 Tg (SOA) a−1 but with a large uncertainty range which we estimate to be 50–380 Tg (SOA) a−1. We found the minimum in normalised mean error (NME) between model and the AMS dataset when we assumed a large SOA source (100 Tg (SOA) a−1) from sources that spatially matched anthropogenic pollution (which we term antropogenically controlled SOA). We used organic carbon observations compiled by Bahadur et al. (2009) to evaluate our estimated SOA sources. We found that the model with a large anthropogenic SOA source was the most consistent with these observations, however improvement over the model with a large biogenic SOA source (250 Tg (SOA) a−1) was small. We used a dataset of 14C observations from rural locations to evaluate our estimated SOA sources. We estimated a maximum of 10 Tg (SOA) a−1 (10 %) of the anthropogenically controlled SOA source could be from fossil (urban/industrial) sources. We suggest that an additional anthropogenic source is most likely due to an anthropogenic pollution enhancement of SOA formation from biogenic VOCs. Such an anthropogenically controlled SOA source would result in substantial climate forcing. We estimated a global mean aerosol direct effect of −0.26 ± 0.15 Wm−2 and indirect (cloud albedo) effect of −0.6+0.24−0.14 Wm−2 from anthropogenically controlled SOA. The biogenic and biomass SOA sources are not well constrained with this analysis due to the limited number of OA observations in regions and periods strongly impacted by these sources. To further improve the constraints by this method, additional OA observations are needed in the tropics and the Southern Hemisphere.

Quantifying the uncertainties of a bottom-up emission inventory of anthropogenic atmospheric pollutants in China

Abstract: . The uncertainties of a national, bottom-up inventory of Chinese emissions of anthropogenic SO2, NOx, and particulate matter (PM) of different size classes and carbonaceous species are comprehensively quantified, for the first time, using Monte Carlo simulation. The inventory is structured by seven dominant sectors: coal-fired electric power, cement, iron and steel, other industry (boiler combustion), other industry (non-combustion processes), transportation, and residential. For each parameter related to emission factors or activity-level calculations, the uncertainties, represented as probability distributions, are either statistically fitted using results of domestic field tests or, when these are lacking, estimated based on foreign or other domestic data. The uncertainties (i.e., 95% confidence intervals around the central estimates) of Chinese emissions of SO2, NOx, total PM, PM10, PM2.5, black carbon (BC), and organic carbon (OC) in 2005 are estimated to be −14%~13%, −13%~37%, −11%~38%, −14%~45%, −17%~54%, −25%~136%, and −40%~121%, respectively. Variations at activity levels (e.g., energy consumption or industrial production) are not the main source of emission uncertainties. Due to narrow classification of source types, large sample sizes, and relatively high data quality, the coal-fired power sector is estimated to have the smallest emission uncertainties for all species except BC and OC. Due to poorer source classifications and a wider range of estimated emission factors, considerable uncertainties of NOx and PM emissions from cement production and boiler combustion in other industries are found. The probability distributions of emission factors for biomass burning, the largest source of BC and OC, are fitted based on very limited domestic field measurements, and special caution should thus be taken interpreting these emission uncertainties. Although Monte Carlo simulation yields narrowed estimates of uncertainties compared to previous bottom-up emission studies, the results are not always consistent with those derived from satellite observations. The results thus represent an incremental research advance; while the analysis provides current estimates of uncertainty to researchers investigating Chinese and global atmospheric transport and chemistry, it also identifies specific needs in data collection and analysis to improve on them. Strengthened quantification of emissions of the included species and other, closely associated ones – notably CO2, generated largely by the same processes and thus subject to many of the same parameter uncertainties – is essential not only for science but for the design of policies to redress critical atmospheric environmental hazards at local, regional, and global scales.

Primary anthropogenic aerosol emission trends for China, 1990–2005

Abstract: An inventory of anthropogenic primary aerosol emissions in China was developed for 1990–2005 using a technology-based approach. Taking into account changes in the technology penetration within industry sectors and improvements in emission controls driven by stricter emission standards, a dynamic methodology was derived and implemented to estimate inter-annual emission factors. Emission factors of PM 2.5 decreased by 7%–69% from 1990 to 2005 in different industry sectors of China, and emission factors of TSP decreased by 18%–80% as well, with the measures of controlling PM emissions implemented. As a result, emissions of PM 2.5 and TSP in 2005 were 11.0 Tg and 29.7 Tg, respectively, less than what they would have been without the adoption of these measures. Emissions of PM 2.5 , PM 10 and TSP presented similar trends: they increased in the first six years of 1990s and decreased until 2000, then increased again in the following years. Emissions of TSP peaked (35.5 Tg) in 1996, while the peak of PM 10 (18.8 Tg) and PM 2.5 (12.7 Tg) emissions occurred in 2005. Although various emission trends were identified across sectors, the cement industry and biofuel combustion in the residential sector were consistently the largest sources of PM 2.5 emissions, accounting for 53%–62% of emissions over the study period. The non-metallic mineral product industry, including the cement, lime and brick industries, accounted for 54%–63% of national TSP emissions. There were no significant trends of BC and OC emissions until 2000, but the increase after 2000 brought the peaks of BC (1.51 Tg) and OC (3.19 Tg) emissions in 2005. Although significant improvements in the estimation of primary aerosols are presented here, there still exist large uncertainties. More accurate and detailed activity information and emission factors based on local tests are essential to further improve emission estimates, this especially being so for the brick and coke industries, as well as for coal-burning stoves and biofuel usage in the residential sector.

A novel calibration approach of MODIS AOD data to predict PM 2.5 concentrations

Abstract: . Epidemiological studies investigating the human health effects of PM2.5 are susceptible to exposure measurement errors, a form of bias in exposure estimates, since they rely on data from a limited number of PM2.5 monitors within their study area. Satellite data can be used to expand spatial coverage, potentially enhancing our ability to estimate location- or subject-specific exposures to PM2.5, but some have reported poor predictive power. A new methodology was developed to calibrate aerosol optical depth (AOD) data obtained from the Moderate Resolution Imaging Spectroradiometer (MODIS). Subsequently, this method was used to predict ground daily PM2.5 concentrations in the New England region. 2003 MODIS AOD data corresponding to the New England region were retrieved, and PM2.5 concentrations measured at 26 US Environmental Protection Agency (EPA) PM2.5 monitoring sites were used to calibrate the AOD data. A mixed effects model which allows day-to-day variability in daily PM2.5-AOD relationships was used to predict location-specific PM2.5 levels. PM2.5 concentrations measured at the monitoring sites were compared to those predicted for the corresponding grid cells. Both cross-sectional and longitudinal comparisons between the observed and predicted concentrations suggested that the proposed new calibration approach renders MODIS AOD data a potentially useful predictor of PM2.5 concentrations. Furthermore, the estimated PM2.5 levels within the study domain were examined in relation to air pollution sources. Our approach made it possible to investigate the spatial patterns of PM2.5 concentrations within the study domain.

Organic condensation: a vital link connecting aerosol formation to cloud condensation nuclei (CCN) concentrations

Abstract: Atmospheric aerosol particles influence global climate as well as impair air quality through their effects on atmospheric visibility and human health Ultrafine (

Recent progress in understanding physical and chemical properties of African and Asian mineral dust

Abstract: . This paper presents a review of recently acquired knowledge on the physico-chemical properties of mineral dust from Africa and Asia based on data presented and discussed during the Third International Dust Workshop, held in Leipzig (Germany) in September 2008. Various regional field experiments have been conducted in the last few years, mostly close to source regions or after short-range transport. Although significant progress has been made in characterising the regional variability of dust properties close to source regions, in particular the mineralogy of iron and the description of particle shape and mixing state, difficulties remain in estimating the range of variability of those properties within one given source region. As consequence, the impact of these parameters on aerosol properties like optical properties, solubility, hygroscopicity, etc. – determining the dust impact on climate – is only partly understood. Long-term datasets in remote regions such as the dust source regions remain a major desideratum. Future work should also focus on the evolution of dust properties during transport. In particular, the prediction of the mineral dust size distribution at emission and their evolution during transport should be considered as a high-priority. From the methodological point of view, a critical assessment and standardisation of the experimental and analytical techniques is highly recommended. Techniques to characterize the internal state of mixing of dust particles, particularly with organic material, should be further developed.

Characterization of the sources and processes of organic and inorganic aerosols in New York city with a high-resolution time-of-flight aerosol mass apectrometer

Abstract: Submicron aerosol particles (PM1) were measured in-situ using a High-Resolution Time-of-Flight Aerosol Mass Spectrometer during the summer 2009 Field Intensive Study at Queens College in New York, NY Organic aerosol (OA) and sulfate are the two dominant species, accounting for 54% and 24%, respectively, of the total PM1 mass The average mass-based size distribution of OA presents a small mode peaking at ~150 nm (Dva) and an accumulation mode (~550 nm) that is internally mixed with sulfate, nitrate, and ammonium The diurnal cycles of both sulfate and OA peak between 01:00–02:00 pm EST due to photochemical production The average (±σ) oxygen-to-carbon (O/C), hydrogen-to-carbon (H/C), and nitrogen-to-carbon (N/C) ratios of OA in NYC are 036 (±009), 149 (±008), and 0012 (±0005), respectively, corresponding to an average organic mass-to-carbon (OM/OC) ratio of 162 (±011) Positive matrix factorization (PMF) of the high resolution mass spectra identified two primary OA (POA) sources, traffic and cooking, and three secondary OA (SOA) components including a highly oxidized, regional low-volatility oxygenated OA (LV-OOA; O/C = 063), a less oxidized, semi-volatile SV-OOA (O/C = 038) and a unique nitrogen-enriched OA (NOA; N/C = 0053) characterized with prominent CxH2x + 2N+ peaks likely from amino compounds Our results indicate that cooking and traffic are two distinct and mass-equivalent POA sources in NYC, together contributing ~30% of the total OA mass during this study The OA composition is dominated by secondary species, especially during high PM events SV-OOA and LV-OOA on average account for 34% and 30%, respectively, of the total OA mass The chemical evolution of SOA in NYC appears to progress with a continuous oxidation from SV-OOA to LV-OOA, which is further supported by a gradual increase of O/C ratio and a simultaneous decrease of H/C ratio in total OOA Detailed analysis of NOA (58% of OA) presents evidence that organic nitrogen species such as amines might have played an important role in the atmospheric processing of OA in NYC, likely involving both acid-base chemistry and photochemistry In addition, analysis of air mass trajectories and satellite imagery of aerosol optical depth (AOD) indicates that the high potential source regions of secondary sulfate and aged OA are mainly located in regions to the west and southwest of the city

Determination of time- and height-resolved volcanic ash emissions and their use for quantitative ash dispersion modeling: the 2010 Eyjafjallajökull eruption

Abstract: . The April–May, 2010 volcanic eruptions of Eyjafjallajokull, Iceland caused significant economic and social disruption in Europe whilst state of the art measurements and ash dispersion forecasts were heavily criticized by the aviation industry. Here we demonstrate for the first time that large improvements can be made in quantitative predictions of the fate of volcanic ash emissions, by using an inversion scheme that couples a priori source information and the output of a Lagrangian dispersion model with satellite data to estimate the volcanic ash source strength as a function of altitude and time. From the inversion, we obtain a total fine ash emission of the eruption of 8.3 ± 4.2 Tg for particles in the size range of 2.8–28 μm diameter. We evaluate the results of our model results with a posteriori ash emissions using independent ground-based, airborne and space-borne measurements both in case studies and statistically. Subsequently, we estimate the area over Europe affected by volcanic ash above certain concentration thresholds relevant for the aviation industry. We find that during three episodes in April and May, volcanic ash concentrations at some altitude in the atmosphere exceeded the limits for the "Normal" flying zone in up to 14 % (6–16 %), 2 % (1–3 %) and 7 % (4–11 %), respectively, of the European area. For a limit of 2 mg m−3 only two episodes with fractions of 1.5 % (0.2–2.8 %) and 0.9 % (0.1–1.6 %) occurred, while the current "No-Fly" zone criterion of 4 mg m−3 was rarely exceeded. Our results have important ramifications for determining air space closures and for real-time quantitative estimations of ash concentrations. Furthermore, the general nature of our method yields better constraints on the distribution and fate of volcanic ash in the Earth system.

New considerations for PM, Black Carbon and particle number concentration for air quality monitoring across different European cities

Abstract: In many large cities of Europe standard air quality limit values of particulate matter (PM) are exceeded. Emis- sions from road traffic and biomass burning are frequently reported to be the major causes. As a consequence of these exceedances a large number of air quality plans, most of them focusing on traffic emissions reductions, have been imple- mented in the last decade. In spite of this implementation, a number of cities did not record a decrease of PM levels. Thus, is the efficiency of air quality plans overestimated? Do the road traffic emissions contribute less than expected to am- bient air PM levels in urban areas? Or do we need a more specific metric to evaluate the impact of the above emissions on the levels of urban aerosols? This study shows the results of the interpretation of the 2009 variability of levels of PM, Black Carbon (BC), aerosol number concentration (N) and a number of gaseous pollu- tants in seven selected urban areas covering road traffic, ur- ban background, urban-industrial, and urban-shipping envi- ronments from southern, central and northern Europe. The results showed that variations of PM and N levels do not always reflect the variation of the impact of road traf-

Airborne observations of the Eyjafjalla volcano ash cloud over Europe during air space closure in April and May 2010

Abstract: . Airborne lidar and in-situ measurements of aerosols and trace gases were performed in volcanic ash plumes over Europe between Southern Germany and Iceland with the Falcon aircraft during the eruption period of the Eyjafjalla volcano between 19 April and 18 May 2010. Flight planning and measurement analyses were supported by a refined Meteosat ash product and trajectory model analysis. The volcanic ash plume was observed with lidar directly over the volcano and up to a distance of 2700 km downwind, and up to 120 h plume ages. Aged ash layers were between a few 100 m to 3 km deep, occurred between 1 and 7 km altitude, and were typically 100 to 300 km wide. Particles collected by impactors had diameters up to 20 μm diameter, with size and age dependent composition. Ash mass concentrations were derived from optical particle spectrometers for a particle density of 2.6 g cm−3 and various values of the refractive index (RI, real part: 1.59; 3 values for the imaginary part: 0, 0.004 and 0.008). The mass concentrations, effective diameters and related optical properties were compared with ground-based lidar observations. Theoretical considerations of particle sedimentation constrain the particle diameters to those obtained for the lower RI values. The ash mass concentration results have an uncertainty of a factor of two. The maximum ash mass concentration encountered during the 17 flights with 34 ash plume penetrations was below 1 mg m−3. The Falcon flew in ash clouds up to about 0.8 mg m−3 for a few minutes and in an ash cloud with approximately 0.2 mg m−3 mean-concentration for about one hour without engine damage. The ash plumes were rather dry and correlated with considerable CO and SO2 increases and O3 decreases. To first order, ash concentration and SO2 mixing ratio in the plumes decreased by a factor of two within less than a day. In fresh plumes, the SO2 and CO concentration increases were correlated with the ash mass concentration. The ash plumes were often visible slantwise as faint dark layers, even for concentrations below 0.1 mg m−3. The large abundance of volatile Aitken mode particles suggests previous nucleation of sulfuric acid droplets. The effective diameters range between 0.2 and 3 μm with considerable surface and volume contributions from the Aitken and coarse mode aerosol, respectively. The distal ash mass flux on 2 May was of the order of 500 (240–1600) kg s−1. The volcano induced about 10 (2.5–50) Tg of distal ash mass and about 3 (0.6–23) Tg of SO2 during the whole eruption period. The results of the Falcon flights were used to support the responsible agencies in their decisions concerning air traffic in the presence of volcanic ash.

Chemical and physical transformations of organic aerosol from the photo-oxidation of open biomass burning emissions in an environmental chamber

Abstract: . Smog chamber experiments were conducted to investigate the chemical and physical transformations of organic aerosol (OA) during photo-oxidation of open biomass burning emissions. The experiments were carried out at the US Forest Service Fire Science Laboratory as part of the third Fire Lab at Missoula Experiment (FLAME III). We investigated emissions from 12 different fuels commonly burned in North American wildfires. The experiments feature atmospheric and plume aerosol and oxidant concentrations; aging times ranged from 3 to 4.5 h. OA production, expressed as a mass enhancement ratio (ratio of OA to primary OA (POA) mass), was highly variable. OA mass enhancement ratios ranged from 2.9 in experiments where secondary OA (SOA) production nearly tripled the POA concentration to 0.7 in experiments where photo-oxidation resulted in a 30 % loss of the OA mass. The campaign-average OA mass enhancement ratio was 1.7 ± 0.7 (mean ± 1σ); therefore, on average, there was substantial SOA production. In every experiment, the OA was chemically transformed. Even in experiments with net loss of OA mass, the OA became increasingly oxygenated and less volatile with aging, indicating that photo-oxidation transformed the POA emissions. Levoglucosan concentrations were also substantially reduced with photo-oxidation. The transformations of POA were extensive; using levoglucosan as a tracer for POA, unreacted POA only contributed 17 % of the campaign-average OA mass after 3.5 h of exposure to typical atmospheric hydroxyl radical (OH) levels. Heterogeneous reactions with OH could account for less than half of this transformation, implying that the coupled gas-particle partitioning and reaction of semi-volatile vapors is an important and potentially dominant mechanism for POA processing. Overall, the results illustrate that biomass burning emissions are subject to extensive chemical processing in the atmosphere, and the timescale for these transformations is rapid.

Observed and model simulated 20th century Arctic temperature variability: Canadian Earth System Model CanESM2

Abstract: . We present simulations of the 20th century Arctic temperature anomaly from the second generation Canadian Earth System Model (CanESM2). The new model couples together an atmosphere-ocean general circulation model, a land-vegetation model and terrestrial and oceanic interactive carbon cycle. It simulates well the observed 20th century Arctic temperature variability that includes the early and late 20th century warming periods and the intervening 1940–1970 period of substantial cooling. The addition of the land-vegetation model and the terrestrial and oceanic interactive carbon cycle to the coupled atmosphere-ocean model improves the agreement with observations from 1900–1970, however, it increases the overestimate of the post 1970 warming. In contrast the older generation coupled atmosphere-ocean general circulation models Canadian CanCM3 and NCAR/LANL CCSM3, used in the IPCC 2007 climate change assessment report, overestimate the rate of the 20th century Arctic warming by factor of two to three and they are unable to reproduce the observed 20th century Arctic climate variability.

Sources of carbonaceous aerosols and deposited black carbon in the Arctic in winter-spring: implications for radiative forcing

Abstract: . We use a global chemical transport model (GEOS-Chem CTM) to interpret observations of black carbon (BC) and organic aerosol (OA) from the NASA ARCTAS aircraft campaign over the North American Arctic in April 2008, as well as longer-term records in surface air and in snow (2007–2009). BC emission inventories for North America, Europe, and Asia in the model are tested by comparison with surface air observations over these source regions. Russian open fires were the dominant source of OA in the Arctic troposphere during ARCTAS but we find that BC was of prevailingly anthropogenic (fossil fuel and biofuel) origin, particularly in surface air. This source attribution is confirmed by correlation of BC and OA with acetonitrile and sulfate in the model and in the observations. Asian emissions are the main anthropogenic source of BC in the free troposphere but European, Russian and North American sources are also important in surface air. Russian anthropogenic emissions appear to dominate the source of BC in Arctic surface air in winter. Model simulations for 2007–2009 (to account for interannual variability of fires) show much higher BC snow content in the Eurasian than the North American Arctic, consistent with the limited observations. We find that anthropogenic sources contribute 90% of BC deposited to Arctic snow in January-March and 60% in April–May 2007–2009. The mean decrease in Arctic snow albedo from BC deposition is estimated to be 0.6% in spring, resulting in a regional surface radiative forcing consistent with previous estimates.

Relating hygroscopicity and composition of organic aerosol particulate matter

Abstract: . A hygroscopicity tandem differential mobility analyzer (HTDMA) was used to measure the water uptake (hygroscopicity) of secondary organic aerosol (SOA) formed during the chemical and photochemical oxidation of several organic precursors in a smog chamber. Electron ionization mass spectra of the non-refractory submicron aerosol were simultaneously determined with an aerosol mass spectrometer (AMS), and correlations between the two different signals were investigated. SOA hygroscopicity was found to strongly correlate with the relative abundance of the ion signal m/z 44 expressed as a fraction of total organic signal ( f 44 ). m/z 44 is due mostly to the ion fragment CO 2 + for all types of SOA systems studied, and has been previously shown to strongly correlate with organic O/C for ambient and chamber OA. The analysis was also performed on ambient OA from two field experiments at the remote site Jungfraujoch, and the megacity Mexico City, where similar results were found. A simple empirical linear relation between the hygroscopicity of OA at subsaturated RH, as given by the hygroscopic growth factor (GF) or "ϰ org " parameter, and f 44 was determined and is given by ϰ org = 2.2 × f 44 − 0.13. This approximation can be further verified and refined as the database for AMS and HTDMA measurements is constantly being expanded around the world. The use of this approximation could introduce an important simplification in the parameterization of hygroscopicity of OA in atmospheric models, since f 44 is correlated with the photochemical age of an air mass.

Ozone database in support of CMIP5 simulations: results and corresponding radiative forcing

Abstract: . A continuous tropospheric and stratospheric vertically resolved ozone time series, from 1850 to 2099, has been generated to be used as forcing in global climate models that do not include interactive chemistry. A multiple linear regression analysis of SAGE I+II satellite observations and polar ozonesonde measurements is used for the stratospheric zonal mean dataset during the well-observed period from 1979 to 2009. In addition to terms describing the mean annual cycle, the regression includes terms representing equivalent effective stratospheric chlorine (EESC) and the 11-yr solar cycle variability. The EESC regression fit coefficients, together with pre-1979 EESC values, are used to extrapolate the stratospheric ozone time series backward to 1850. While a similar procedure could be used to extrapolate into the future, coupled chemistry climate model (CCM) simulations indicate that future stratospheric ozone abundances are likely to be significantly affected by climate change, and capturing such effects through a regression model approach is not feasible. Therefore, the stratospheric ozone dataset is extended into the future (merged in 2009) with multi-model mean projections from 13 CCMs that performed a simulation until 2099 under the SRES (Special Report on Emission Scenarios) A1B greenhouse gas scenario and the A1 adjusted halogen scenario in the second round of the Chemistry-Climate Model Validation (CCMVal-2) Activity. The stratospheric zonal mean ozone time series is merged with a three-dimensional tropospheric data set extracted from simulations of the past by two CCMs (CAM3.5 and GISS-PUCCINI) and of the future by one CCM (CAM3.5). The future tropospheric ozone time series continues the historical CAM3.5 simulation until 2099 following the four different Representative Concentration Pathways (RCPs). Generally good agreement is found between the historical segment of the ozone database and satellite observations, although it should be noted that total column ozone is overestimated in the southern polar latitudes during spring and tropospheric column ozone is slightly underestimated. Vertical profiles of tropospheric ozone are broadly consistent with ozonesondes and in-situ measurements, with some deviations in regions of biomass burning. The tropospheric ozone radiative forcing (RF) from the 1850s to the 2000s is 0.23 W m−2, lower than previous results. The lower value is mainly due to (i) a smaller increase in biomass burning emissions; (ii) a larger influence of stratospheric ozone depletion on upper tropospheric ozone at high southern latitudes; and possibly (iii) a larger influence of clouds (which act to reduce the net forcing) compared to previous radiative forcing calculations. Over the same period, decreases in stratospheric ozone, mainly at high latitudes, produce a RF of −0.08 W m−2, which is more negative than the central Intergovernmental Panel on Climate Change (IPCC) Fourth Assessment Report (AR4) value of −0.05 W m−2, but which is within the stated range of −0.15 to +0.05 W m−2. The more negative value is explained by the fact that the regression model simulates significant ozone depletion prior to 1979, in line with the increase in EESC and as confirmed by CCMs, while the AR4 assumed no change in stratospheric RF prior to 1979. A negative RF of similar magnitude persists into the future, although its location shifts from high latitudes to the tropics. This shift is due to increases in polar stratospheric ozone, but decreases in tropical lower stratospheric ozone, related to a strengthening of the Brewer-Dobson circulation, particularly through the latter half of the 21st century. Differences in trends in tropospheric ozone among the four RCPs are mainly driven by different methane concentrations, resulting in a range of tropospheric ozone RFs between 0.4 and 0.1 W m−2 by 2100. The ozone dataset described here has been released for the Coupled Model Intercomparison Project (CMIP5) model simulations in netCDF Climate and Forecast (CF) Metadata Convention at the PCMDI website ( http://cmip-pcmdi.llnl.gov/ ).

Predicting the relative humidities of liquid-liquid phase separation, efflorescence, and deliquescence of mixed particles of ammonium sulfate, organic material, and water using the organic-to-sulfate mass ratio of the particle and the oxygen-to-carbon elemental ratio of the organic component

Abstract: . Individual particles that on a mass basis consist dominantly of the components ammonium sulfate, oxygenated organic material, and water are a common class of submicron particles found in today's atmosphere. Here we use (1) the organic-to-sulfate (org:sulf) mass ratio of the overall particle and (2) the oxygen-to-carbon (O:C) elemental ratio of the organic component as input variables in parameterisations that predict the critical relative humidity of several different types of particle phase transitions. Specifically these variables were used to predict the critical relative humidity of liquid-liquid phase separation (SRH), efflorescence (ERH), and deliquescence (DRH). Experiments were conducted by optical microscopy for 11 different oxygenated organic-ammonium sulfate systems covering the range 0.1

A review of the anthropogenic influence on biogenic secondary organic aerosol

Abstract: . Because of the climate and air quality effects of organic aerosol, it is important to quantify the influence of anthropogenic emissions on the aerosol burden, both globally and regionally, and both in terms of mass and number. Methods exist with which the fractions of organic aerosol resulting directly from anthropogenic and biogenic processes can be estimated. However, anthropogenic emissions can also lead to an enhancement in secondary organic aerosol formation from naturally emitted precursors. We term this enhanced biogenic secondary organic aerosol (eBSOA). Here, we review the mechanisms through which such an effect may occur in the atmosphere and describe a work flow via which it may be quantified, using existing measurement techniques. An examination of published data reveals support for the existence of the enhancement effect.