Showing papers in "Atmospheric Chemistry and Physics in 2007"

An Asian emission inventory of anthropogenic emission sources for the period 1980-2020

Abstract: . We developed a new emission inventory for Asia (Regional Emission inventory in ASia (REAS) Version 1.1) for the period 1980–2020. REAS is the first inventory to integrate historical, present, and future emissions in Asia on the basis of a consistent methodology. We present here emissions in 2000, historical emissions for 1980–2003, and projected emissions for 2010 and 2020 of SO2, NOx, CO, NMVOC, black carbon (BC), and organic carbon (OC) from fuel combustion and industrial sources. Total energy consumption in Asia more than doubled between 1980 and 2003, causing a rapid growth in Asian emissions, by 28% for BC, 30% for OC, 64% for CO, 108% for NMVOC, 119% for SO2, and 176% for NOx. In particular, Chinese NOx emissions showed a marked increase of 280% over 1980 levels, and growth in emissions since 2000 has been extremely high. These increases in China were mainly caused by increases in coal combustion in the power plants and industrial sectors. NMVOC emissions also rapidly increased because of growth in the use of automobiles, solvents, and paints. By contrast, BC, OC, and CO emissions in China showed decreasing trends from 1996 to 2000 because of a reduction in the use of biofuels and coal in the domestic and industry sectors. However, since 2000, Chinese emissions of these species have begun to increase. Thus, the emissions of air pollutants in Asian countries (especially China) showed large temporal variations from 1980–2003. Future emissions in 2010 and 2020 in Asian countries were projected by emission scenarios and from emissions in 2000. For China, we developed three emission scenarios: PSC (policy success case), REF (reference case), and PFC (policy failure case). In the 2020 REF scenario, Asian total emissions of SO2, NOx, and NMVOC were projected to increase substantially by 22%, 44%, and 99%, respectively, over 2000 levels. The 2020 REF scenario showed a modest increase in CO (12%), a lesser increase in BC (1%), and a slight decrease in OC (−5%) compared with 2000 levels. However, it should be noted that Asian total emissions are strongly influenced by the emission scenarios for China.

ISORROPIA II: a computationally efficient thermodynamic equilibrium model for K + –Ca 2+ –Mg 2+ –NH 4 + –Na + –SO 4 2− –NO 3 − –Cl − –H 2 O aerosols

Abstract: . This study presents ISORROPIA II, a thermodynamic equilibrium model for the K+–Ca2+–Mg2+–NH4+–Na+–SO42−–NO3−–Cl−–H2O aerosol system. A comprehensive evaluation of its performance is conducted against water uptake measurements for laboratory aerosol and predictions of the SCAPE2 thermodynamic module over a wide range of atmospherically relevant conditions. The two models agree well, to within 13% for aerosol water content and total PM mass, 16% for aerosol nitrate and 6% for aerosol chloride and ammonium. Largest discrepancies were found under conditions of low RH, primarily from differences in the treatment of water uptake and solid state composition. In terms of computational speed, ISORROPIA II was more than an order of magnitude faster than SCAPE2, with robust and rapid convergence under all conditions. The addition of crustal species does not slow down the thermodynamic calculations (compared to the older ISORROPIA code) because of optimizations in the activity coefficient calculation algorithm. Based on its computational rigor and performance, ISORROPIA II appears to be a highly attractive alternative for use in large scale air quality and atmospheric transport models.

Secondary organic aerosol formation from m-xylene, toluene, and benzene

Abstract: Secondary organic aerosol (SOA) formation from the photooxidation of m-xylene, toluene, and benzene is investigated in the Caltech environmental chambers. Experiments are performed under two limiting NOx conditions; under high-NOx conditions the peroxy radicals (RO2) react only with NO, while under low-NOx conditions they react only with HO2. For all three aromatics studied (m-xylene, toluene, and benzene), the SOA yields (defined as the ratio of the mass of organic aerosol formed to the mass of parent hydrocarbon reacted) under low-NOx conditions substantially exceed those under high-NOx conditions, suggesting the importance of peroxy radical chemistry in SOA formation. Under low-NOx conditions, the SOA yields for m-xylene, toluene, and benzene are constant (36%, 30%, and 37%, respectively), indicating that the SOA formed is essentially nonvolatile. Under high-NOx conditions, aerosol growth occurs essentially immediately, even when NO concentration is high. The SOA yield curves exhibit behavior similar to that observed by Odum et al. (1996, 1997a, b), although the values are somewhat higher than in the earlier study. The yields measured under high-NOx conditions are higher than previous measurements, suggesting a "rate effect" in SOA formation, in which SOA yields are higher when the oxidation rate is faster. Experiments carried out in the presence of acidic seed aerosol reveal no change of SOA yields from the aromatics as compared with those using neutral seed aerosol.

Source apportionment of submicron organic aerosols at an urban site by factor analytical modelling of aerosol mass spectra

Abstract: Submicron ambient aerosol was characterized in summer 2005 at an urban background site in Zurich, Switzer- land, during a three-week measurement campaign Highly time-resolved samples of non-refractory aerosol components were analyzed with an Aerodyne aerosol mass spectrometer (AMS) Positive matrix factorization (PMF) was used for the first time for aerosol mass spectra to identify the main com- ponents of the total organic aerosol and their sources The PMF retrieved factors were compared to measured reference mass spectra and were correlated with tracer species of the aerosol and gas phase measurements from collocated instru- ments Six factors were found to explain virtually all vari- ance in the data and could be assigned either to sources or to aerosol components such as oxygenated organic aerosol (OOA) Our analysis suggests that at the measurement site only a small (<10%) fraction of organic PM1 originates from freshly emitted fossil fuel combustion Other primary sources identified to be of similar or even higher importance are charbroiling (10-15%) and wood burning ( 10%) The fraction of all identified primary sources is considered as pri- mary organic aerosol (POA) This interpretation is supported by calculated ratios of the modelled POA and measured pri- mary pollutants such as elemental carbon (EC), NOx, and CO, which are in good agreement to literature values A high fraction (60-69%) of the measured organic aerosol mass is OOA which is interpreted mostly as secondary organic aerosol (SOA) This oxygenated organic aerosol can be sepa- rated into a highly aged fraction, OOA I, (40-50%) with low volatility and a mass spectrum similar to fulvic acid, and a more volatile and probably less processed fraction, OOA II (on average 20%) This is the first publication of a multiple component analysis technique to AMS organic spectral data and also the first report of the OOA II component

Halogens and their role in polar boundary-layer ozone depletion

Abstract: . During springtime in the polar regions, unique photochemistry converts inert halide salt ions (e.g. Br−) into reactive halogen species (e.g. Br atoms and BrO) that deplete ozone in the boundary layer to near zero levels. Since their discovery in the late 1980s, research on ozone depletion events (ODEs) has made great advances; however many key processes remain poorly understood. In this article we review the history, chemistry, dependence on environmental conditions, and impacts of ODEs. This research has shown the central role of bromine photochemistry, but how salts are transported from the ocean and are oxidized to become reactive halogen species in the air is still not fully understood. Halogens other than bromine (chlorine and iodine) are also activated through incompletely understood mechanisms that are probably coupled to bromine chemistry. The main consequence of halogen activation is chemical destruction of ozone, which removes the primary precursor of atmospheric oxidation, and generation of reactive halogen atoms/oxides that become the primary oxidizing species. The different reactivity of halogens as compared to OH and ozone has broad impacts on atmospheric chemistry, including near complete removal and deposition of mercury, alteration of oxidation fates for organic gases, and export of bromine into the free troposphere. Recent changes in the climate of the Arctic and state of the Arctic sea ice cover are likely to have strong effects on halogen activation and ODEs; however, more research is needed to make meaningful predictions of these changes.

The global lightning-induced nitrogen oxides source

Abstract: . The knowledge of the lightning-induced nitrogen oxides (LNOx) source is important for understanding and predicting the nitrogen oxides and ozone distributions in the troposphere and their trends, the oxidising capacity of the atmosphere, and the lifetime of trace gases destroyed by reactions with OH. This knowledge is further required for the assessment of other important NOx sources, in particular from aviation emissions, the stratosphere, and from surface sources, and for understanding the possible feedback between climate changes and lightning. This paper reviews more than 3 decades of research. The review includes laboratory studies as well as surface, airborne and satellite-based observations of lightning and of NOx and related species in the atmosphere. Relevant data available from measurements in regions with strong LNOx influence are identified, including recent observations at midlatitudes and over tropical continents where most lightning occurs. Various methods to model LNOx at cloud scales or globally are described. Previous estimates are re-evaluated using the global annual mean flash frequency of 44±5 s−1 reported from OTD satellite data. From the review, mainly of airborne measurements near thunderstorms and cloud-resolving models, we conclude that a "typical" thunderstorm flash produces 15 (2–40)×1025 NO molecules per flash, equivalent to 250 mol NOx or 3.5 kg of N mass per flash with uncertainty factor from 0.13 to 2.7. Mainly as a result of global model studies for various LNOx parameterisations tested with related observations, the best estimate of the annual global LNOx nitrogen mass source and its uncertainty range is (5±3) Tg a−1 in this study. In spite of a smaller global flash rate, the best estimate is essentially the same as in some earlier reviews, implying larger flash-specific NOx emissions. The paper estimates the LNOx accuracy required for various applications and lays out strategies for improving estimates in the future. An accuracy of about 1 Tg a−1 or 20%, as necessary in particular for understanding tropical tropospheric chemistry, is still a challenging goal.

An overview of snow photochemistry: evidence, mechanisms and impacts

Abstract: It has been shown that sunlit snow and ice plays an important role in processing atmospheric species. Photochemical production of a variety of chemicals has recently been reported to occur in snow/ice and the release of these photochemically generated species may significantly impact the chemistry of the overlying atmosphere. Nitrogen oxide and oxidant precursor fluxes have been measured in a number of snow covered environments, where in some cases the emissions significantly impact the overlying boundary layer. For example, photochemical ozone production (such as that occurring in polluted mid-latitudes) of 3–4 ppbv/day has been observed at South Pole, due to high OH and NO levels present in a relatively shallow boundary layer. Field and laboratory experiments have determined that the origin of the observed NOx flux is the photochemistry of nitrate within the snowpack, however some details of the mechanism have not yet been elucidated. A variety of low molecular weight organic compounds have been shown to be emitted from sunlit snowpacks, the source of which has been proposed to be either direct or indirect photo-oxidation of natural organic materials present in the snow. Although myriad studies have observed active processing of species within irradiated snowpacks, the fundamental chemistry occurring remains poorly understood. Here we consider the nature of snow at a fundamental, physical level; photochemical processes within snow and the caveats needed for comparison to atmospheric photochemistry; our current understanding of nitrogen, oxidant, halogen and organic photochemistry within snow; the current limitations faced by the field and implications for the future.

Spectral absorption properties of atmospheric aerosols

Abstract: We have determined the solar spectral absorption optical depth of atmospheric aerosols for specific case studies during several field programs (three cases have been reported previously; two are new results). We combined airborne measurements of the solar net radiant flux density and the aerosol optical depth with a detailed radiative transfer model for all but one of the cases. The field programs (SAFARI 2000, ACE Asia, PRIDE, TARFOX, INTEX-A) contained aerosols representing the major absorbing aerosol types: pollution, biomass burning, desert dust and mixtures. In all cases the spectral absorption optical depth decreases with wavelength and can be approximated with a power-law wavelength dependence (Absorption Angstrom Exponent or AAE). We compare our results with other recent spectral absorption measurements and attempt to briefly summarize the state of knowledge of aerosol absorption spectra in the atmosphere. We discuss the limitations in using the AAE for calculating the solar absorption. We also discuss the resulting spectral single scattering albedo for these cases.

Observed poleward expansion of the Hadley circulation since 1979

Abstract: Using three meteorological reanalyses and three outgoing long-wave radiation (OLR) datasets, we show that the Hadley circulation has a significant expansion of about 2 to 4.5 degrees of latitude since 1979. The three reanalyses all indicate that the poleward expansion of the Hadley circulation in each hemisphere occurs during its summer and fall seasons. Results from the OLR datasets do not have such seasonality. The expansion of the Hadley circulation implies a poleward expansion of the band of subtropical subsidence, leading to enhanced mid-latitude tropospheric warming and poleward shifts of the subtropical dry zone. This would contribute to an increased frequency of midlatitude droughts in both hemispheres.

Contribution of fungi to primary biogenic aerosols in the atmosphere: wet and dry discharged spores, carbohydrates, and inorganic ions

Abstract: Biogenic aerosols play important roles in atmospheric chemistry physics, the biosphere, climate, and public health. Here, we show that fungi which actively discharge their spores with liquids into the air, in particular actively wet spore discharging Ascomycota (AAM) and actively wet spore discharging Basidiomycota (ABM), are a major source of primary biogenic aerosol particles and components. We present the first estimates for the global average emission rates of fungal spores. Measurement results and budget calculations based on investigations in Amazonia (Balbina, Brazil, July 2001) indicate that the spores of AAM and ABM may account for a large proportion of coarse particulate matter in tropical rainforest regions during the wet season (0.7–2.3 μg m^−3). For the particle diameter range of 1–10 μm, the estimated proportions are ~25% during day-time, ~45% at night, and ~35% on average. For the sugar alcohol mannitol, the budget calculations indicate that it is suitable for use as a molecular tracer for actively wet discharged basidiospores (ABS). ABM emissions seem to account for most of the atmospheric abundance of mannitol (10–68 ng m^−3), and can explain the observed diurnal cycle (higher abundance at night). ABM emissions of hexose carbohydrates might also account for a significant proportion of glucose and fructose in air particulate matter (7–49 ng m^−3), but the literature-derived ratios are not consistent with the observed diurnal cycle (lower abundance at night). AAM emissions appear to account for a large proportion of potassium in air particulate matter over tropical rainforest regions during the wet season (17–43 ng m^−3), and they can also explain the observed diurnal cycle (higher abundance at night). The results of our investigations and budget calculations for tropical rainforest aerosols are consistent with measurements performed at other locations. Based on the average abundance of mannitol reported for extratropical continental boundary layer air (~25 ng m^−3), we have also calculated a value of ~17 Tg yr^−1 as a first estimate for the global average emission rate of ABS over land surfaces, which is consistent with the typically observed concentrations of ABS (~10³–10^4 m^−3; ~0.1–1 μg m^−3). The global average atmospheric abundance and emission rate of total fungal spores, including wet and dry discharged species, are estimated to be higher by a factor of about three, i.e. 1 μg m^−3 and ~50 Tg yr^−1. Comparisons with estimated rates of emission and formation of other major types of organic aerosol (~47 Tg yr^−1 of anthropogenic primary organic aerosol; 12–70 Tg yr^−1 of secondary organic aerosol) indicate that emissions from fungi should be taken into account as a significant global source of organic aerosol. The effects of fungal spores and related chemical components might be particularly important in tropical regions, where both physicochemical processes in the atmosphere and biological activity at the Earth's surface are particularly intense, and where the abundance of fungal spores and related chemical compounds are typically higher than in extratropical regions.

Effect of NO x level on secondary organic aerosol (SOA) formation from the photooxidation of terpenes

Abstract: Secondary organic aerosol (SOA) formation from the photooxidation of one monoterpene (α-pinene) and two sesquiterpenes (longifolene and aromadendrene) is investigated in the Caltech environmental chambers. The effect of NOx on SOA formation for these biogenic hydrocarbons is evaluated by performing photooxidation experiments under varying NOx conditions. The NOx dependence of α-pinene SOA formation follows the same trend as that observed previously for a number of SOA precursors, including isoprene, in which SOA yield (defined as the ratio of the mass of organic aerosol formed to the mass of parent hydrocarbon reacted) decreases as NOx level increases. The NOx dependence of SOA yield for the sesquiterpenes, longifolene and aromadendrene, however, differs from that determined for isoprene and α-pinene; the aerosol yield under high-NOx conditions substantially exceeds that under low-NOx conditions. The reversal of the NOx dependence of SOA formation for the sesquiterpenes is consistent with formation of relatively low-volatility organic nitrates, and/or the isomerization of large alkoxy radicals leading to less volatile products. Analysis of the aerosol chemical composition for longifolene confirms the presence of organic nitrates under high-NOx conditions. Consequently the formation of SOA from certain biogenic hydrocarbons such as sesquiterpenes (and possibly large anthropogenic hydrocarbons as well) may be more efficient in polluted air.

Arctic smoke – record high air pollution levels in the European Arctic due to agricultural fires in Eastern Europe in spring 2006

Abstract: . In spring 2006, the European Arctic was abnormally warm, setting new historical temperature records. During this warm period, smoke from agricultural fires in Eastern Europe intruded into the European Arctic and caused the most severe air pollution episodes ever recorded there. This paper confirms that biomass burning (BB) was indeed the source of the observed air pollution, studies the transport of the smoke into the Arctic, and presents an overview of the observations taken during the episode. Fire detections from the MODIS instruments aboard the Aqua and Terra satellites were used to estimate the BB emissions. The FLEXPART particle dispersion model was used to show that the smoke was transported to Spitsbergen and Iceland, which was confirmed by MODIS retrievals of the aerosol optical depth (AOD) and AIRS retrievals of carbon monoxide (CO) total columns. Concentrations of halocarbons, carbon dioxide and CO, as well as levoglucosan and potassium, measured at Zeppelin mountain near Ny Alesund, were used to further corroborate the BB source of the smoke at Spitsbergen. The ozone (O3) and CO concentrations were the highest ever observed at the Zeppelin station, and gaseous elemental mercury was also elevated. A new O3 record was also set at a station on Iceland. The smoke was strongly absorbing – black carbon concentrations were the highest ever recorded at Zeppelin – and strongly perturbed the radiation transmission in the atmosphere: aerosol optical depths were the highest ever measured at Ny Alesund. We furthermore discuss the aerosol chemical composition, obtained from filter samples, as well as the aerosol size distribution during the smoke event. Photographs show that the snow at a glacier on Spitsbergen became discolored during the episode and, thus, the snow albedo was reduced. Samples of this polluted snow contained strongly elevated levels of potassium, sulphate, nitrate and ammonium ions, thus relating the discoloration to the deposition of the smoke aerosols. This paper shows that, to date, BB has been underestimated as a source of aerosol and air pollution for the Arctic, relative to emissions from fossil fuel combustion. Given its significant impact on air quality over large spatial scales and on radiative processes, the practice of agricultural waste burning should be banned in the future.

Cloud microphysics and aerosol indirect effects in the global climate model ECHAM5-HAM

Abstract: The double-moment cloud microphysics scheme from ECHAM4 that predicts both the mass mixing ratios and number concentrations of cloud droplets and ice crystals has been coupled to the size-resolved aerosol scheme ECHAM5-HAM. ECHAM5-HAM predicts the aerosol mass, number concentrations and mixing state. The simulated liquid, ice and total water content and the cloud droplet and ice crystal number concentrations as a function of temperature in stratiform mixed-phase clouds between 0 and −35° C agree much better with aircraft observations in the ECHAM5 simulations. ECHAM5 performs better because more realistic aerosol concentrations are available for cloud droplet nucleation and because the Bergeron-Findeisen process is parameterized as being more efficient. The total anthropogenic aerosol effect includes the direct, semi-direct and indirect effects and is defined as the difference in the top-of-the-atmosphere net radiation between present-day and pre-industrial times. It amounts to −1.9 W m^−2 in ECHAM5, when a relative humidity dependent cloud cover scheme and aerosol emissions representative for the years 1750 and 2000 from the AeroCom emission inventory are used. The contribution of the cloud albedo effect amounts to −0.7 W m^−2. The total anthropogenic aerosol effect is larger when either a statistical cloud cover scheme or a different aerosol emission inventory are employed because the cloud lifetime effect increases.

Twenty-five years of continuous sulphur dioxide emission reduction in Europe

Abstract: During the last twenty-five years European emission data have been compiled and reported under the Cooperative Programme for Monitoring and Evaluation of the Long-range Transmission of Air Pollutants in Europe (EMEP) as part of the work under the UNECE Convention on Long-range Transboundary Air Pollution (LRTAP). This paper presents emission trends of SO 2 reported to EMEP and validated within the programme for the period 1980–2004. These European anthropogenic sulphur emissions have been steadily decreasing over the last twenty-five years, amounting from about 55 Tg SO 2 in 1980 to 15 Tg SO 2 in 2004. The uncertainty in sulphur emission estimates for individual countries and years are documented to range between 3% and 25%. The relative contribution of European emissions to global anthropogenic sulphur emissions has been halved during this period. Based on annual emission reports from European countries, three emission reduction regimes have been identified. The period 1980–1989 is characterized by low annual emission reductions (below 5% reduction per year and 20% for the whole period) and is dominated by emission reductions in Western Europe. The period 1990–1999 is characterised by high annual emission reductions (up to 11% reduction per year and 54% for the whole period), most pronounced in Central and Eastern Europe. The annual emission reductions in the period 2000–2004 are medium to low (below 6% reduction per year and 17% for the whole period) and reflect the unified Europe, with equally large reductions in both East and West. The sulphur emission reduction has been largest in the sector Combustion in energy and transformation industries , but substantial decreases are also seen in the Non-industrial combustion plants together with the sectors Industrial combustion and Industrial production processes . The majority of European countries have reduced their emissions by more than 60% between 1990 and 2004, and one quarter have already achieved sulphur emission reductions higher than 80%. At European level, the total sulphur target for 2010 set in the Gothenburg Protocol (16 Tg) has apparently already been met by 2004. However, still half of the Parties to the Gothenburg Protocol have to reduce further their sulphur emissions in order to attain their individual country total emission targets for 2010. It is also noteworthy that, contrasting the Gothenburg Protocol requirements, a growing number of countries have recently been reporting increasing sulphur emissions, while others report only minor further decreases. The emission trends presented here are supported by different studies of air concentrations and depositions carried out within and outside the framework of the LRTAP Convention.

Evaluation of nitrogen dioxide chemiluminescence monitors in a polluted urban environment

Abstract: Data from a recent field campaign in Mexico City are used to evaluate the performance of the EPA Federal Ref- erence Method for monitoring the ambient concentrations of NO2. Measurements of NO2 from standard chemilumines- cence monitors equipped with molybdenum oxide converters are compared with those from Tunable Infrared Laser Differ- ential Absorption Spectroscopy (TILDAS) and Differential Optical Absorption Spectroscopy (DOAS) instruments. A significant interference in the chemiluminescence measure- ment is shown to account for up to 50% of ambient NO2 con- centration during afternoon hours. As expected, this interfer- ence correlates well with non-NOx reactive nitrogen species (NOz) as well as with ambient O3 concentrations, indicat- ing a photochemical source for the interfering species. A combination of ambient gas phase nitric acid and alkyl and multifunctional alkyl nitrates is deduced to be the primary cause of the interference. Observations at four locations at varying proximities to emission sources indicate that the per- centage contribution of HNO3 to the interference decreases with time as the air parcel ages. Alkyl and multifunctional alkyl nitrate concentrations are calculated to reach concen-

Secondary aerosol formation from atmospheric reactions of aliphatic amines

Abstract: Although aliphatic amines have been detected in both urban and rural atmospheric aerosols, little is known about the chemistry leading to particle formation or the potential aerosol yields from reactions of gas-phase amines. We present here the first systematic study of aerosol formation from the atmospheric reactions of amines. Based on laboratory chamber experiments and theoretical calculations, we evaluate aerosol formation from reaction of OH, ozone, and nitric acid with trimethylamine, methylamine, triethylamine, diethylamine, ethylamine, and ethanolamine. Entropies of formation for alkylammonium nitrate salts are estimated by molecular dynamics calculations enabling us to estimate equilibrium constants for the reactions of amines with nitric acid. Though subject to significant uncertainty, the calculated dissociation equilibrium constant for diethylammonium nitrate is found to be sufficiently small to allow for its atmospheric formation, even in the presence of ammonia which competes for available nitric acid. Experimental chamber studies indicate that the dissociation equilibrium constant for triethylammonium nitrate is of the same order of magnitude as that for ammonium nitrate. All amines studied form aerosol when photooxidized in the presence of NOx with the majority of the aerosol mass present at the peak of aerosol growth consisting of aminium (R3NH+) nitrate salts, which repartition back to the gas phase as the parent amine is consumed. Only the two tertiary amines studied, trimethylamine and triethylamine, are found to form significant non-salt organic aerosol when oxidized by OH or ozone; calculated organic mass yields for the experiments conducted are similar for ozonolysis (15% and 5% respectively) and photooxidation (23% and 8% respectively). The non-salt organic aerosol formed appears to be more stable than the nitrate salts and does not quickly repartition back to the gas phase.

Dangerous human-made interference with climate: a GISS modelE study

Abstract: . We investigate the issue of "dangerous human-made interference with climate" using simulations with GISS modelE driven by measured or estimated forcings for 1880–2003 and extended to 2100 for IPCC greenhouse gas scenarios as well as the "alternative" scenario of Hansen and Sato (2004). Identification of "dangerous" effects is partly subjective, but we find evidence that added global warming of more than 1°C above the level in 2000 has effects that may be highly disruptive. The alternative scenario, with peak added forcing ~1.5 W/m2 in 2100, keeps further global warming under 1°C if climate sensitivity is ~3°C or less for doubled CO2. The alternative scenario keeps mean regional seasonal warming within 2σ (standard deviations) of 20th century variability, but other scenarios yield regional changes of 5–10σ, i.e. mean conditions outside the range of local experience. We conclude that a CO2 level exceeding about 450 ppm is "dangerous", but reduction of non-CO2 forcings can provide modest relief on the CO2 constraint. We discuss three specific sub-global topics: Arctic climate change, tropical storm intensification, and ice sheet stability. We suggest that Arctic climate change has been driven as much by pollutants (O3, its precursor CH4, and soot) as by CO2, offering hope that dual efforts to reduce pollutants and slow CO2 growth could minimize Arctic change. Simulated recent ocean warming in the region of Atlantic hurricane formation is comparable to observations, suggesting that greenhouse gases (GHGs) may have contributed to a trend toward greater hurricane intensities. Increasing GHGs cause significant warming in our model in submarine regions of ice shelves and shallow methane hydrates, raising concern about the potential for accelerating sea level rise and future positive feedback from methane release. Growth of non-CO2 forcings has slowed in recent years, but CO2 emissions are now surging well above the alternative scenario. Prompt actions to slow CO2 emissions and decrease non-CO2 forcings are required to achieve the low forcing of the alternative scenario.

Introducing the concept of Potential Aerosol Mass (PAM)

Abstract: Potential Aerosol Mass (PAM) can be defined as the maximum aerosol mass that the oxidation of precursor gases produces. In the measurement, all precursor gases are rapidly oxidized with extreme amounts of oxidants to low volatility compounds, resulting in the aerosol formation. Oxidation occurs in a small, simple, flow-through chamber that has a short residence time and is irradiated with ultraviolet light. The amount of the oxidants ozone (O3), hydroxyl (OH), and hydroperoxyl (HO2) were measured directly and can be controlled by varying the UV light and the relative humidity. Maximum values were 40 ppmv for O3, 500 pptv for OH, and 4 ppbv for HO2. The oxidant amounts are 100 to 1000 times troposphere values, but the ratios OH/O3 and HO2/OH are similar to troposphere values. The aerosol production mechanism and the aerosol mass yield were studied for several controlling variables, such as temperature, relative humidity, oxidant concentration, presence of nitrogen oxides (NOx), precursor gas composition and amount, and the presence of acidic seed aerosol. The measured secondary organic aerosol (SOA) yield of several natural and anthropogenic volatile organic compounds and a mixture of hydrocarbons in the PAM chamber were similar to those obtained in large, batch-style environmental chambers. This PAM method is being developed for measuring potential aerosol mass in the atmosphere, but is also useful for examining SOA processes in the laboratory and in environmental chambers.

Air quality in North America's most populous city - overview of the MCMA-2003 campaign

Abstract: Exploratory field measurements in the Mexico City Metropolitan Area (MCMA) in February 2002 set the stage for a major air quality field measurement campaign in the spring of 2003 (MCMA-2003). Involving over 100 scientists from more than 30 institutions in Mexico, the United States and Europe, MCMA-2003 revealed important new insights into the meteorology, primary pollutant emissions, ambient secondary pollutant precursor concentrations, photochemical oxidant production and secondary aerosol particle formation in North America's most populated and polluted megacity. A description of meteorological and atmospheric chemistry and aerosol microphysics measurements performed during MCMA-2003 is presented. More than 40 published or submitted MCMA-2003 research papers are reviewed and key discoveries pertinent to understanding and improving air quality in Mexico City and similar megacities in the developing world are summarized.

Intercontinental transport of pollution and dust aerosols: implications for regional air quality

Abstract: We use the global model GOCART to examine the impact of pollution and dust aerosols emitted from their ma- jor sources on surface fine particulate matter concentrations at regional and hemispheric scales. Focusing on the North America region in 2001, we use measurements from the IM- PROVE network in the United States to evaluate the model- simulated surface concentrations of the "reconstructed fine mass" (RCFM) and its components of ammonium sulfate, black carbon (BC), organic matter (OM), and fine mode dust. We then quantify the RCFM budget in terms of the RCFM chemical composition, source type, and region of origin to find that in the eastern U.S., ammonium sulfate is the domi- nant RCFM component ( 60%) whereas in the western U.S., dust and OM are just as important as sulfate but have con- siderable seasonal variations, especially in the NW. On an annual average, pollution aerosol (defined as aerosols from fuel combustion for industrial and transportation uses) from North America accounts for 65-70% of the surface RCFM in the eastern U.S. and for a lower proportion of 30-40% in the western U.S.; by contrast, pollution from outside of North America contributes to just 2-6% ( 0.2µg m 3 ) of the total RCFM over the U.S. In comparison, long-range transport of dust brings 3 to 4 times more fine particles than the transport of pollution to the U.S. (0.5-0.8 µg m 3 on an annual aver- age) with a maximum influence in spring and over the NW. Of the major pollution regions, Europe has the largest poten- tial to affect the surface aerosol concentrations in other con- tinents due to its shorter distance from receptor continents and its larger fraction of sulfate-producing precursor gas in the outflow. With the IPCC emission scenario for the year 2000, we find that European emissions increase levels of am- monium sulfate by 1-5µg m 3 over the surface of northern Africa and western Asia, and its contribution to eastern Asia

Sensitivity of PM 2.5 to climate in the Eastern US: a modeling case study

Abstract: . The individual effects of various meteorological parameters on PM2.5 concentrations in the Eastern US are examined using the PMCAMx chemical transport model so that these effects and their relative magnitudes can be better understood. A suite of perturbations in temperature, wind speed, absolute humidity, mixing height, cloud cover, and precipitation are imposed individually on base case conditions corresponding to periods in July 2001 and January 2002 in order to determine the sensitivities of PM2.5 concentrations and composition to these separate meteorological parameters. Temperature had a major effect on average PM2.5 in January (−170 ng m−3 K−1) due largely to the evaporation of ammonium nitrate and organic aerosol at higher temperatures; increases in sulfate production with increased temperature counteracted much of this decrease in July. Changes in mixing height also had major effects on PM2.5 concentrations: 73 ng m−3 (100 m)−1 in January and 210 ng m−3 (100 m)−1 in July. Changes in wind speed (30 to 55 ng m−3 %−1) and absolute humidity (15 to 20 ng m−3 %−1) also had appreciable effects on average PM2.5 concentrations. Precipitation changes had large impacts on parts of the domain (a consequence of the base case meteorology), with sensitivities to changing area of precipitation in July up to 100 ng m−3 %−1. Perturbations in cloud cover had the smallest effects on average PM2.5 concentrations. The changes in PM2.5 concentrations resulting from changing all eight meteorological parameters simultaneously were approximately within 25% or so of the sum of the changes to the eight individual perturbations. The sensitivities of PM2.5 concentrations to changes in these meteorological parameters indicate that changes in climate could potentially have important impacts on PM2.5 concentrations.

Emission rate and chemical state estimation by 4-dimensional variational inversion

Abstract: This study aims to assess the potential and limits of an advanced inversion method to estimate pollutant pre- cursor sources mainly from observations. Ozone, sulphur dioxide, and partly nitrogen oxides observations are taken to infer source strength estimates. As methodology, the four- dimensional variational data assimilation technique has been generalised and employed to include emission rate optimisa- tion, in addition to chemical state estimates as usual objective of data assimilation. To this end, the optimisation space of the variational assimilation system has been complemented by emission rate correction factors of 19 emitted species at each emitting grid point, involving the University of Cologne mesoscale EURAD model. For validation, predictive skills were assessed for an August 1997 ozone episode, comparing forecast performances of pure initial value optimisation, pure emission rate optimisation, and joint emission rate/initial value optimisation. Validation procedures rest on both measurements withheld from data assimilation and prediction skill evaluation of fore- casts after the inversion procedures. Results show that excel- lent improvements can be claimed for sulphur dioxide fore- casts, after emission rate optimisation. Significant improve- ments can be claimed for ozone forecasts after initial value and joint emission rate/initial value optimisation of precursor constituents. The additional benefits applying joint emission rate/initial value optimisation are moderate, and very useful in typical cases, where upwind emission rate optimisation is essential. In consequence of the coarse horizontal model grid resolution of 54 km, applied in this study, comparisons indi- cate that the inversion improvements can rest on assimilat- ing ozone observations only, as the inclusion of NOx obser- vations does not provide additional forecast skill. Emission estimates were found to be largely independent from initial guesses from emission inventories, demonstrating the poten- tial of the 4D-var method to infer emission rate improve- ments. The study also points to the need for improved hori- zontal model resolution to more efficient use of NO x obser- vations.

Civil Aircraft for the regular investigation of the atmosphere based on an instrumented container: The new CARIBIC system

Abstract: An airfreight container with automated instruments for measurement of atmospheric gases and trace compounds was operated on a monthly basis onboard a Boeing 767-300 ER of LTU International Airways during long-distance flights from 1997 to 2002 (CARIBIC, Civil Aircraft for Regular Investigation of the Atmosphere Based on an Instrument Container, http://www.caribic-atmospheric.com). Subsequently a more advanced system has been developed, using a larger capacity container with additional equipment and an improved inlet system. CARIBIC phase #2 was implemented on a new long-range aircraft type Airbus A340-600 of the Lufthansa German Airlines (Star Alliance) in December 2004, creating a powerful flying observatory. The instrument package comprises detectors for the measurement of O3, total and gaseous H2O, NO and NOy, CO, CO2, O2, Hg, and number concentrations of sub-micrometer particles (>4 nm, >12 nm, and >18 nm diameter). Furthermore, an optical particle counter (OPC) and a proton transfer mass spectrometer (PTR-MS) are incorporated. Aerosol samples are collected for analysis of elemental composition and particle morphology after flight. Air samples are taken in glass containers for laboratory analyses of hydrocarbons, halocarbons and greenhouse gases (including isotopic composition of CO2) in several laboratories. Absorption tubes collect oxygenated volatile organic compounds. Three differential optical absorption spectrometers (DOAS) with their telescopes mounted in the inlet system measure atmospheric trace gases such as BrO, HONO, and NO2. A video camera mounted in the inlet provides information about clouds along the flight track. The flying observatory, its equipment and examples of measurement results are reported.

Efficiency of immersion mode ice nucleation on surrogates of mineral dust

Abstract: A differential scanning calorimeter (DSC) was used to explore heterogeneous ice nucleation of emulsified aqueous suspensions of two Arizona test dust (ATD) samples with particle diameters of nominally 0–3 and 0–7 μm, respectively. Aqueous suspensions with ATD concentrations of 0.01–20 wt% have been investigated. The DSC thermograms exhibit a homogeneous and a heterogeneous freezing peak whose intensity ratios vary with the ATD concentration in the aqueous suspensions. Homogeneous freezing temperatures are in good agreement with recent measurements by other techniques. Depending on ATD concentration, heterogeneous ice nucleation occurred at temperatures as high as 256 K or down to the onset of homogeneous ice nucleation (237 K). For ATD-induced ice formation Classical Nucleation Theory (CNT) offers a suitable framework to parameterize nucleation rates as a function of temperature, experimentally determined ATD size, and emulsion droplet volume distributions. The latter two quantities serve to estimate the total heterogeneous surface area present in a droplet, whereas the suitability of an individual heterogeneous site to trigger nucleation is described by the compatibility function (or contact angle) in CNT. The intensity ratio of homogeneous to heterogeneous freezing peaks is in good agreement with the assumption that the ATD particles are randomly distributed amongst the emulsion droplets. The observed dependence of the heterogeneous freezing temperatures on ATD concentrations cannot be described by assuming a constant contact angle for all ATD particles, but requires the ice nucleation efficiency of ATD particles to be (log)normally distributed amongst the particles. Best quantitative agreement is reached when explicitly assuming that high-compatibility sites are rare and that therefore larger particles have on average more and better active sites than smaller ones. This analysis suggests that a particle has to have a diameter of at least 0.1 μm to exhibit on average one active site.

Aerosol absorption and radiative forcing

Abstract: . We present a comprehensive examination of aerosol absorption with a focus on evaluating the sensitivity of the global distribution of aerosol absorption to key uncertainties in the process representation. For this purpose we extended the comprehensive aerosol-climate model ECHAM5-HAM by effective medium approximations for the calculation of aerosol effective refractive indices, updated black carbon refractive indices, new cloud radiative properties considering the effect of aerosol inclusions, as well as by modules for the calculation of long-wave aerosol radiative properties and instantaneous aerosol forcing. The evaluation of the simulated aerosol absorption optical depth with the AERONET sun-photometer network shows a good agreement in the large scale global patterns. On a regional basis it becomes evident that the update of the BC refractive indices to Bond and Bergstrom (2006) significantly improves the previous underestimation of the aerosol absorption optical depth. In the global annual-mean, absorption acts to reduce the short-wave anthropogenic aerosol top-of-atmosphere (TOA) radiative forcing clear-sky from −0.79 to −0.53 W m−2 (33%) and all-sky from −0.47 to −0.13 W m−2 (72%). Our results confirm that basic assumptions about the BC refractive index play a key role for aerosol absorption and radiative forcing. The effect of the usage of more accurate effective medium approximations is comparably small. We demonstrate that the diversity in the AeroCom land-surface albedo fields contributes to the uncertainty in the simulated anthropogenic aerosol radiative forcings: the usage of an upper versus lower bound of the AeroCom land albedos introduces a global annual-mean TOA forcing range of 0.19 W m−2 (36%) clear-sky and of 0.12 W m−2 (92%) all-sky. The consideration of black carbon inclusions on cloud radiative properties results in a small global annual-mean all-sky absorption of 0.05 W m−2 and a positive TOA forcing perturbation of 0.02 W m−2. The long-wave aerosol radiative effects are small for anthropogenic aerosols but become of relevance for the larger natural dust and sea-salt aerosols.

Process-based estimates of terrestrial ecosystem isoprene emissions: incorporating the effects of a direct CO 2 -isoprene interaction

Abstract: In recent years evidence has emerged that the amount of isoprene emitted from a leaf is affected by the CO2 growth environment. Many - though not all - labo- ratory experiments indicate that emissions increase signif- icantly at below-ambient CO2 concentrations and decrease when concentrations are raised to above-ambient. A small number of process-based leaf isoprene emission models can reproduce this CO2 stimulation and inhibition. These mod- els are briefly reviewed, and their performance in standard conditions compared with each other and to an empirical al- gorithm. One of the models was judged particularly useful for incorporation into a dynamic vegetation model frame- work, LPJ-GUESS, yielding a tool that allows the interac- tive effects of climate and increasing CO2 concentration on vegetation distribution, productivity, and leaf and ecosystem isoprene emissions to be explored. The coupled vegetation dynamics-isoprene model is described and used here in a mode particularly suited for the ecosystem scale, but it can be employed at the global level as well. Annual and/or daily isoprene emissions simulated by the model were evaluated against flux measurements (or model estimates that had previously been evaluated with flux data) from a wide range of environments, and agreement between modelled and simulated values was generally good. By us- ing a dynamic vegetation model, effects of canopy composi- tion, disturbance history, or trends in CO 2 concentration can be assessed. We show here for five model test sites that the suggested CO2-inhibition of leaf-isoprene metabolism can be large enough to offset increases in emissions due to CO2- stimulation of vegetation productivity and leaf area growth. When effects of climate change are considered atop the ef- fects of atmospheric composition the interactions between the relevant processes will become even more complex. The CO2-isoprene inhibition may have the potential to signifi- cantly dampen the expected steep increase of ecosystem iso- prene emission in a future, warmer atmosphere with higher CO2 levels; this effect raises important questions for projec- tions of future atmospheric chemistry, and its connection to the terrestrial vegetation and carbon cycle.

A new formulation of equivalent effective stratospheric chlorine (EESC)

Abstract: Equivalent effective stratospheric chlorine (EESC) is a convenient parameter to quantify the effects of halogens (chlorine and bromine) on ozone depletion in the stratosphere. We show, discuss, and analyze a new formulation of EESC that now includes the effects of age-of-air dependent fractional release values and an age-of-air spectrum. This EESC can be more appropriately applied to various parts of the stratosphere because of this dependence on mean age-of-air. This new formulation provides quantitative estimates of EESC that can be directly related to inorganic chlorine and bromine throughout the stratosphere. In this paper, we first provide a detailed description of the EESC calculation. We then use this EESC formulation to estimate that human-produced ozone depleting substances will recover to 1980 levels in 2041 in the midlatitudes, and 2067 over Antarctica. These recovery dates are based upon the assumption that the international agreements for regulating ozone-depleting substances are adhered to. In addition to recovery dates, we also estimate the uncertainties and possible problems in the estimated times of recovery. The midlatitude recovery of 2041 has a 95% confidence uncertainty from 2028 to 2049, while the 2067 Antarctic recovery has a 95% confidence uncertainty from 2056 to 2078. The principal uncertainties are from the estimated mean age-of-air and fractional release values, and the assumption that these quantities are time independent. Using other model estimates of age decrease due to climate change, we estimate that midlatitude recovery may be significantly accelerated.

Closure study between chemical composition and hygroscopic growth of aerosol particles during TORCH2

Abstract: Measurements of aerosol properties were made in aged polluted and clean background air masses encountered at the North Norfolk (UK) coastline as part of the TORCH2 field campaign in May 2004. Hygroscopic growth factors (GF) at 90% relative humidity (RH) for D-0=27-217 nm particles and size-resolved chemical composition were simultaneously measured using a Hygroscopicity Tandem Differential Mobility Analyser (HTDMA) and an Aerodyne aerosol mass spectrometer (Q-AMS), respectively. Both hygroscopic properties and chemical composition showed pronounced variability in time and with particles size. With this data set we could demonstrate that the Zdanovskii-Stokes-Robinson (ZSR) mixing rule combined with chemical composition data from the AMS makes accurate quantitative predictions of the mean GF of mixed atmospheric aerosol particles possible. In doing so it is crucial that chemical composition data are acquired with high resolution in both particle size and time, at least matching the actual variability of particle properties. The closure results indicate an ensemble GF of the organic fraction of similar to 1.20 +/- 0.10 at 90% water activity. Thus the organics contribute somewhat to hygroscopic growth, particularly at small sizes, however the inorganic salts still dominate. Furthermore it has been found that most likely substantial evaporation losses of NH4NO3 occurred within the HTDMA instrument, exacerbated by a long residence time of similar to 1 min. Such an artefact is in agreement with our laboratory experiments and literature data for pure NH4NO3, both showing similar evaporation losses within HTDMAs with residence times of similar to 1 min. Short residence times and low temperatures are hence recommended for HTDMAs in order to minimise such evaporation artefacts.

Nitrate aerosols today and in 2030: a global simulation including aerosols and tropospheric ozone

Abstract: Nitrate aerosols are expected to become more important in the future atmosphere due to the expected increase in nitrate precursor emissions and the decline of ammonium-sulphate aerosols in wide regions of this planet. The GISS climate model is used in this study, including atmospheric gas- and aerosol phase chemistry to investigate current and future (2030, following the SRES A1B emission scenario) atmospheric compositions. A set of sensitivity experiments was carried out to quantify the individual impact of emission- and physical climate change on nitrate aerosol formation. We found that future nitrate aerosol loads depend most strongly on changes that may occur in the ammonia sources. Furthermore, microphysical processes that lead to aerosol mixing play a very important role in sulphate and nitrate aerosol formation. The role of nitrate aerosols as climate change driver is analyzed and set in perspective to other aerosol and ozone forcings under pre-industrial, present day and future conditions. In the near future, year 2030, ammonium nitrate radiative forcing is about ?0.14 W/m² and contributes roughly 10% of the net aerosol and ozone forcing. The present day nitrate and pre-industrial nitrate forcings are ?0.11 and ?0.05 W/m², respectively. The steady increase of nitrate aerosols since industrialization increases its role as a non greenhouse gas forcing agent. However, this impact is still small compared to greenhouse gas forcings, therefore the main role nitrate will play in the future atmosphere is as an air pollutant, with annual mean near surface air concentrations, in the fine particle mode, rising above 3 ?g/m³ in China and therefore reaching pollution levels, like sulphate aerosols.

Global trends in visibility: Implications for dust sources

Abstract: . There is a large uncertainty in the relative roles of human land use, climate change and carbon dioxide fertilization in changing desert dust source strength over the past 100 years, and the overall sign of human impacts on dust is not known. We used visibility data from meteorological stations in dusty regions to assess the anthropogenic impact on long term trends in desert dust emissions. We did this by looking at time series of visibility derived variables and their correlations with precipitation, drought, winds, land use and grazing. Visibility data are available at thousands of stations globally from 1900 to the present, but we focused on 357 stations with more than 30 years of data in regions where mineral aerosols play a dominant role in visibility observations. We evaluated the 1974 to 2003 time period because most of these stations have reliable records only during this time. We first evaluated the visibility data against AERONET aerosol optical depth data, and found that only in dusty regions are the two moderately correlated. Correlation coefficients between visibility-derived variables and AERONET optical depths indicate a moderate correlation (0.47), consistent with capturing about 20% of the variability in optical depths. Two visibility-derived variables appear to compare the best with AERONET observations: the fraction of observations with visibility less than 5 km (VIS5) and the surface extinction (EXT). Regional trends show that in many dusty places, VIS5 and EXT are statistically significantly correlated with the Palmer drought severity index (based on precipitation and temperature) or surface wind speeds, consistent with dust temporal variability being largely driven by meteorology. This is especially true for North African and Chinese dust sources, but less true in the Middle East, Australia or South America, where there are not consistent patterns in the correlations. Climate indices such as El Nino or the North Atlantic Oscillation are not correlated with visibility-derived variables in this analysis. There are few stations where visibility measures are correlated with cultivation or grazing estimates on a temporal basis, although this may be a function of the very coarse temporal resolution of the land use datasets. On the other hand, spatial analysis of the visibility data suggests that natural topographic lows are not correlated with VIS5 or EXT, but land use is correlated at a moderate level. This analysis is consistent with land use being important in some regions, but meteorology driving interannual variability during 1974–2003.