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Black carbon (BC) particles in the Arctic contribute to rapid warming of the Arctic by heating the atmosphere and snow and ice surfaces. Understanding the source contributions to Arctic BC is therefore important, but they are not well understood, especially those for atmospheric and snow radiative effects. Here we estimate simultaneously the source contributions of Arctic BC to near-surface and vertically integrated atmospheric BC mass concentrations (MBC_SRF and MBC_COL), BC deposition flux (MBC_DEP), and BC radiative effects at the top of the atmosphere and snow surface (REBC_TOA and REBC_SNOW), and show that the source contributions to these five variables are highly different. In our estimates, Siberia makes the largest contribution to MBC_SRF, MBC_DEP, and REBC_SNOW in the Arctic (defined as > 70° N), accounting for 70 %, 53 %, and 43 %, respectively. In contrast, Asia’s contributions to MBC_COL and REBC_TOA are largest, accounting for 38 % and 45 %, respectively. In addition, the contributions of biomass burning sources are larger (24−34 %) to MBC_DEP, REBC_TOA, and REBC_SNOW, which are highest from late spring to summer, and smaller (4.2−14 %) to MBC_SRF and MBC_COL, whose concentrations are highest from winter to spring. These differences in source contributions to these five variables are due to seasonal variations in BC emission, transport, and removal processes and solar radiation, as well as to differences in radiative effect efficiency (radiative effect per unit BC mass) among sources. Radiative effect efficiency varies by a factor of up to 4 among sources (1465−5439 W g–1) depending on lifetimes, mixing states, and heights of BC and seasonal variations of emissions and solar radiation. As a result, source contributions to radiative effects and mass concentrations (i.e., REBC_TOA and MBC_COL, respectively) are substantially different. The results of this study demonstrate the importance of considering differences in the source contributions of Arctic BC among mass concentrations, deposition, and atmospheric and snow radiative effects for accurate understanding of Arctic BC and its climate impacts.

The terminal velocity of cloud drops and raindrops used in numerical model calculations can significantly affect weather predictions. Current formulations rely on laboratory experiments made in the 1940s and 1960s. Because these experiments were performed only at typical environmental conditions of 20°C and 1013 hPa, parameterizations have been introduced to deduce the terminal velocity aloft without rigorous evaluation. In this study, an incompressible two-phase flow direct numerical simulation model is used to calculate the free-falling motion of axisymmetric drops with diameters between 0.025 and 0.5 mm to study the terminal fall velocity. Simulated terminal fall velocities of free-falling drops at 20°C and 1013 hPa agree within 3.2% with the previous empirical parameterization (Beard formula), and 4.5% with existing laboratory data in the diameter range between 0.3 and 0.5 mm. The velocities converge to the analytic Hadamard–Rybczynski solution within 2% for small Reynolds numbers, demonstrating the robustness of our simulations. Simulations under various atmospheric conditions show that existing empirical parameterizations that account for the air density dependence of the terminal velocity have errors up to 11.8% under the conditions examined in this study. We propose a new empirical formula that describes the air density dependence of the terminal velocity. It is also shown that the falling speed of a small drop is not sensitive to shape oscillation, and the terminal velocity decreases by only less than 1.3% when the axis ratio increases by 12% with reduced surface tension. Internal circulation within falling drops is also presented and compared with previous studies.

The Arctic region is sensitive to climate change and is warming faster than the global average. Aerosol particles change cloud properties by acting as cloud condensation nuclei and ice-nucleating particles, thus influencing the Arctic climate system. Therefore, understanding the aerosol particle properties in the Arctic is needed to interpret and simulate their influences on climate. In this study, we collected ambient aerosol particles using whole-air and PM10 inlets and residual particles of cloud droplets and ice crystals from Arctic low-level clouds (typically, all-liquid or mixed-phase clouds) using a counterflow virtual impactor inlet at the Zeppelin Observatory near Ny-Ålesund, Svalbard, within a time frame of 4 years. We measured the composition and mixing state of individual fine-mode particles in 239 samples using transmission electron microscopy. On the basis of their composition, the aerosol and cloud residual particles were classified as mineral dust, sea salt, K-bearing, sulfate, and carbonaceous particles. The number fraction of aerosol particles showed seasonal changes, with sulfate dominating in summer and sea salt increasing in winter. There was no measurable difference in the fractions between ambient aerosol and cloud residual particles collected at ambient temperatures above 0 ∘C. On the other hand, cloud residual samples collected at ambient temperatures below 0 ∘C had several times more sea salt and mineral dust particles and fewer sulfates than ambient aerosol samples, suggesting that sea spray and mineral dust particles may influence the formation of cloud particles in Arctic mixed-phase clouds. We also found that 43 % of mineral dust particles from cloud residual samples were mixed with sea salt, whereas only 18 % of mineral dust particles in ambient aerosol samples were mixed with sea salt. This study highlights the variety in aerosol compositions and mixing states that influence or are influenced by aerosol–cloud interactions in Arctic low-level clouds.

Key Points: • First ever measurements with a high‐accuracy single‐particle soot photometer of black carbon (BC) concentrations in Arctic snowpack • Topography and BC emission flux strongly influenced latitudinal variations of mass concentrations and size distributions of BC • Measured BC mass concentrations 2–25 times lower than previously reported show the importance of revalidating climate models Black carbon (BC) deposited on snow lowers its albedo, potentially contributing to warming in the Arctic. Atmospheric distributions of BC and inorganic aerosols, which contribute directly and indirectly to radiative forcing, are also greatly influenced by depositions. To quantify these effects, accurate measurement of the spatial distributions of BC and ionic species representative of inorganic aerosols (ionic species hereafter) in snowpack in various regions of the Arctic is needed, but few such measurements are available. We measured mass concentrations of size-resolved BC (CMBC) and ionic species in snowpack by using a single-particle soot photometer and ion chromatography, respectively, over Finland, Alaska, Siberia, Greenland, and Spitsbergen during early spring in 2012–2016. Total BC mass deposited per unit area (DEPMBC) during snow accumulation periods was derived from CMBC and snow water equivalent (SWE). Our analyses showed that the spatial distributions of anthropogenic BC emission flux, total precipitable water, and topography strongly influenced latitudinal variations of CMBC, BC size distributions, SWE, and DEPMBC. The average size distributions of BC in Arctic snowpack shifted to smaller sizes with decreasing CMBC due to an increase in the removal efficiency of larger BC particles during transport from major sources. Our measurements of CMBC were lower by a factor of ~13 than previous measurements made with an Integrating Sphere/Integrating Sandwich spectrophotometer due mainly to interference from coexisting non-BC particles such as mineral dust. The SP2 data presented here will be useful for constraining climate models that estimate the effects of BC on the Arctic climate. Plain Language Summary Black carbon (BC) particles, commonly known as soot, are emitted from incomplete combustion of fossil fuels and biomass. They efficiently absorb solar radiation and thus heat the atmosphere. BC particles emitted at midlatitudes and in the Arctic are deposited onto snow in the Arctic, accelerating snowmelt in early spring by absorbing solar radiation. These processes contribute to warming in the Arctic. Calculations of this warming effect by using numerical models need to be validated by comparison with observed BC concentrations in snowpack. However, there are very few accurate records of concentrations of BC in snow because of technical difficulties in making these measurements. We developed a new laser-induced incandescence technique to measure BC concentrations in snowpack and applied it for the first time in six Arctic regions (Finland, Alaska, North and South Siberia, Greenland, and Spitsbergen). The BC concentrations we measured were highest in Finland and South Siberia, which are closer to large anthropogenic BC sources than the other regions, where our measured BC concentrations were much lower. On average, our BC concentrations were much lower than those previously measured by different techniques. Therefore, previous comparisons of modeled and observed BC concentrations need to be re-evaluated using the present data.

Black carbon (BC) aerosol deposited in and onto Arctic snow increases the snow's absorption of solar radiation and accelerates snowmelt. Concentrations of BC in the Arctic atmosphere and snow are controlled by wet deposition; however, details of this process are poorly understood owing to the scarcity of time-resolved measurements of BC in hydrometeors. We measured mass concentrations of BC in hydrometeors (CMBC) and in air (MBC) with 16% and 15% accuracies, respectively, at Ny-Ålesund, Svalbard during 2012–2019. Median monthly MBC and CMBC values showed similar seasonal variations, being high in winter-spring and low in summer. Median monthly BC wet deposition mass flux (FMBC) was highest in winter and lowest in summer, associated with seasonal patterns of CMBC and precipitation. Seasonally averaged BC size distributions in hydrometeors were similar except for summer. Measurements of MBC and CMBC in spring 2017 showed a size-independent removal efficiency, indicating that BC-containing particles were efficiently activated into cloud droplets. These observations at Ny-Ålesund were compared with observations at Barrow, Alaska, during 2013–2017. The near-surface MBC at Ny-Ålesund and Barrow had similar seasonal patterns; however, the two sites differed in CMBC and FMBC. In summer, CMBC was low at Ny-Ålesund but moderate at Barrow, likely reflecting differences in MBC in the lower troposphere. Seasonally averaged BC size distributions in hydrometeors were similar at both sites, suggesting that average BC size distributions are similar in the Arctic lower troposphere. The efficiency of BC removal tends to be size-independent during transport, leading to the observed similarity.

Long-term measurements of the light absorption coefficient (b(abs)) obtained with a particle soot absorption photometer (PSAP), b(abs) (PSAP), have been previously reported for Barrow, Alaska, and ...

We quantify the responses of aerosols to changes in emissions (sulfur dioxide, black carbon (BC), primary organic aerosol, nitrogen oxides (NOx), and volatile organic compounds) over East Asia by using simulations including gas-oxidant-aerosol coupling, organic aerosol (OA) formation, and BC aging processes. The responses of aerosols to NOx emissions are complex and are dramatically changed by simulating gas-phase chemistry and aerosol processes online. Reduction of NOx emissions by 50% causes a 30–40% reduction of oxidant (hydroxyl radical and ozone) concentrations and slows the formation of sulfate and OA by 20–30%. Because the response of OA to changes in NOx emissions is sensitive to the treatment of emission and oxidation of semivolatile and intermediate volatility organic compounds, reduction of the uncertainty in these processes is necessary to evaluate gas-oxidant-aerosol coupling accurately. Our simulations also show that the sensitivity of aerosols to changes in emissions is enhanced by 50–100% when OA formation and BC aging processes are resolved in the model. Sensitivity simulations show that the increase of NOx emissions from 1850 to 2000 explains 70% (40%) of the enhancement of aerosol mass concentrations (direct radiative effects) over East Asia during that period through enhancement of oxidant concentrations and that this estimation is sensitive to the representation of OA formation and BC aging processes. Our results demonstrate the importance of simultaneous simulation of gas-oxidant-aerosol coupling and detailed aerosol processes. The impact of NOx emissions on aerosol formation will be a key to formulating effective emission reduction strategies such as BC mitigation and aerosol reduction policies in East Asia.

An improved understanding of the variations in the mass concentration and size distribution of black carbon (BC) in the free troposphere (FT) over East Asia, where BC emissions are very high, is needed to reliably estimate the radiative forcing of BC in climate models. We measured these parameters and the carbon monoxide (CO) concentration by conducting the Aerosol Radiative Forcing in East Asia (A-FORCE) 2013W aircraft campaign in East Asia in winter 2013 and compared these data with measurements made in the same region in spring 2009. The median BC concentrations in the FT originating from North China (NC) and South China (SC) showed different seasonal variations, which were primarily caused by variations in meteorological conditions. CO concentrations above the background were much higher in SC than in NC in both seasons, suggesting a more active upward transport of CO. In SC, precipitation greatly increased from winter to spring, leading to an increased wet deposition of BC. As a result, the median BC concentration in the FT was highest in SC air in winter. This season and region were optimal for the effective transport of BC from the planetary boundary layer to the FT. The count median diameters of the BC size distributions generally decreased with altitude via wet removal during upward transport. The altitude dependence of the BC size distributions was similar in winter and spring, in accord with the similarity in the BC mixing state. The observed BC concentrations and microphysical properties will be useful for evaluating the performance of climate models.

Two years of continuous in situ measurements of Arctic low‐level clouds have been made at the Mount Zeppelin Observatory (78°56′N, 11°53′E), in Ny‐Alesund, Spitsbergen. The monthly median value of the cloud particle number concentration (Nc) showed a clear seasonal variation: Its maximum appeared in May–July (65 ± 8 cm−3), and it remained low between October and March (8 ± 7 cm−3). At temperatures warmer than 0 °C, a clear correlation was found between the hourly Nc values and the number concentrations of aerosols with dry diameters larger than 70 nm (N70), which are proxies for cloud condensation nuclei (CCN). When clouds were detected at temperatures colder than 0 °C, some of the data followed the summertime Nc to N70 relationship, while other data showed systematically lower Nc values. The lidar‐derived depolarization ratios suggested that the former (CCN‐controlled) and latter (CCN‐uncontrolled) data generally corresponded to clouds consisting of supercooled water droplets and those containing ice particles, respectively. The CCN‐controlled data persistently appeared throughout the year at Zeppelin. The aerosol‐cloud interaction index (ACI = dlnNc/(3dlnN70)) for the CCN‐controlled data showed high sensitivities to aerosols both in the summer (clean air) and winter–spring (Arctic haze) seasons (0.22 ± 0.03 and 0.25 ± 0.02, respectively). The air parcel model calculations generally reproduced these values. The threshold diameters of aerosol activation (Dact), which account for the Nc of the CCN‐controlled data, were as low as 30–50 nm when N70 was less than 30 cm−3, suggesting that new particle formation can affect Arctic cloud microphysics.

Black carbon (BC) aerosols become internally mixed with non-BC compounds (BC coatings) during aging in the atmosphere. In this study, we measured the hygroscopicity parameter κ on a single-particle basis for both BC-coating materials (κBC-coat) and BC-free particles (κBC-free) in the urban atmosphere of Tokyo, using a single-particle soot photometer (SP2). In our measurement system, dry ambient particles were first mass selected by an aerosol particle mass analyzer, then humidified, and then passed to the SP2 for detection of their refractory BC mass content and optical diameter. A quadrupole aerosol mass spectrometer was also employed to interpret the hygroscopicity data. During the observation period, the measured κBC-coat generally agreed with κBC-free to within ±25% and was usually in typical range for inorganic and organic aerosols. These results indicate that BC-coating materials and BC-free particles in Tokyo usually had similar chemical compositions, internal mixtures of inorganic and organic compounds, even in a source region. However, occasionally κBC-coat was much higher than κBC-free values, when the mass concentrations of BC and organic aerosols were poorly correlated. This indicates external mixing of BC-containing and BC-free particles from different sources. These findings improve our understanding of the cloud condensation nuclei activity of BC-containing particles, which strongly influences their wet removal, and optical properties in the ambient air.

Number concentrations, size distributions, and mixing states of aerosols are essential parameters for accurate estimations of aerosol direct and indirect effects. In this study, we develop an aerosol module, designated the Aerosol Two-dimensional bin module for foRmation and Aging Simulation (ATRAS), that can explicitly represent these parameters by considering new particle formation (NPF), black carbon (BC) aging, and secondary organic aerosol (SOA) processes. A two-dimensional bin representation is used for particles with dry diameters from 40 nm to 10 μm to resolve both aerosol sizes (12 bins) and BC mixing states (10 bins) for a total of 120 bins. The particles with diameters between 1 and 40 nm are resolved using additional eight size bins to calculate NPF. The ATRAS module is implemented in the WRF-Chem model and applied to examine the sensitivity of simulated mass, number, size distributions, and optical and radiative parameters of aerosols to NPF, BC aging, and SOA processes over East Asia during the spring of 2009. The BC absorption enhancement by coating materials is about 50% over East Asia during the spring, and the contribution of SOA processes to the absorption enhancement is estimated to be 10–20% over northern East Asia and 20–35% over southern East Asia. A clear north–south contrast is also found between the impacts of NPF and SOA processes on cloud condensation nuclei (CCN) concentrations: NPF increases CCN concentrations at higher supersaturations (smaller particles) over northern East Asia, whereas SOA increases CCN concentrations at lower supersaturations (larger particles) over southern East Asia. The application of ATRAS in East Asia also shows that the impact of each process on each optical and radiative parameter depends strongly on the process and the parameter in question. The module can be used in the future as a benchmark model to evaluate the accuracy of simpler aerosol models and examine interactions between NPF, BC aging, and SOA processes under different meteorological conditions and emissions.

Organic aerosol (OA) simulations using the volatility basis-set approach were made for East Asia and its outflow region. Model simulations were evaluated through comparisons with OA measured by aerosol mass spectrometers in and around Tokyo (at Komaba and Kisai in summer 2003 and 2004) and over the outflow region in East Asia (at Fukue and Hedo in spring 2009). The simulations with aging processes of organic vapors reproduced the mass concentrations, temporal variations, and formation efficiencies of observed OA at all of the sites reasonably well. As OA mass was severely underestimated in the simulations without the aging processes, the oxidations of organic vapors are essential for reasonable OA simulations over East Asia. By considering the aging processes, simulated OA concentrations increased from 0.24 to 1.28 μg m−3 in the boundary layer over the whole of East Asia. OA formed from the interaction of anthropogenic and biogenic sources was also enhanced by the aging processes. The fraction of controllable OA was estimated to be 87% of total OA over the whole of East Asia, which indicated that most of the OA in our simulations were formed anthropogenically (from controllable combustion sources). A large portion of biogenic secondary OA (78% of biogenic secondary OA) was formed through the influence of anthropogenic sources. These fractions were higher than the fraction of anthropogenic emissions. An important reason for these higher controllable fractions was higher oxidant concentrations and the resulting faster oxidation rates of OA precursors by considering anthropogenic sources. Both the amounts (from 0.18 to 1.12 μg m−3) and the fraction (from 75 to 87%) of controllable OA were increased by aging processes of organic vapors over East Asia.

[1] Absorption aerosol optical depth (AAOD) measurements made by sun-sky photometers are currently the only constraint available for estimates of the global radiative forcing of black carbon (BC), but their validation studies are limited. In this paper, we report the first attempt to compare AAODs derived from single-particle soot photometer (SP2) and ground-based sun-sky photometer (sky radiometer, SKYNET) measurements. During the Aerosol Radiative Forcing in East Asia (A-FORCE) experiments, BC size distribution and mixing state vertical profiles were measured using an SP2 on board a research aircraft near the Fukue Observatory (32.8°N, 128.7°E) over the East China Sea in spring 2009 and late winter 2013. The aerosol extinction coefficients (bext) and single scattering albedo (SSA) at 500 nm were calculated based on aerosol size distribution and detailed BC mixing state information. The calculated aerosol optical depth (AOD) agreed well with the sky radiometer measurements (2 ± 6%) when dust loadings were low (lidar-derived nonspherical particle contribution to AOD less than 20%). However, under these low-dust conditions, the AAODs obtained from sky radiometer measurements were only half of the in situ estimates. When dust loadings were high, the sky radiometer measurements showed systematically higher AAODs even when all coarse particles were assumed to be dust for in situ measurements. These results indicate that there are considerable uncertainties in AAOD measurements. Uncertainties in the BC refractive index, optical calculations from in situ data, and sky radiometer retrieval analyses are discussed.

[1] The Community Multiscale Air Quality model with a source and process tagged method (CMAQ/PASCAL) was used to understand source regions and types (anthropogenic (AN) and biomass burning (BB)) of Asian black carbon (BC) outflow to the Pacific during 2008–2010. The model simulations generally reproduced absolute concentrations and temporal (seasonal, monthly, and day-to-day) variations of BC mass concentrations, observed by both surface and aircraft measurements in outflow regions in East Asia. These model simulations show that both the total eastward flux and transport efficiency (fractions transported from sources) of BC are highest during spring (26 kg s−1 and 33% at 150°E) and lowest during summer (8 kg s−1 and 20% at 150°E). These seasonal variations of Asian BC outflow are generally controlled by transport patterns (monsoons, frontal passages, and convection) and emissions from the following three sources: (1) AN emissions from China (China AN), (2) BB emissions from Southeast Asia and South China (SEA BB) during February–April, and (3) BB emissions from Siberia and Kazakhstan (Siberia BB) during April–July. In our simulations, China AN dominates the total eastward BC flux on a 3 year average (61%, 17%, and 6% from China AN, Siberia BB, and SEA BB, respectively, at 150°E). In contrast, SEA and Siberia BB account for 30–50% of the total eastward BC flux (150°E and 175°E) during spring and summer, and they increase the seasonal variability of the Asian BC outflow flux. BC from Siberia BB is also found to be transported to the Pacific more efficiently than BC from other sources. Although the magnitudes of BB emissions are highly uncertain, our results suggest that the control of Siberia BB will be important in terms of the transboundary transport of BC to the Pacific, North America, and the Arctic.

[1] The emission of black carbon (BC) from East Asia and its long-range transport strongly influence the mass concentration of BC (MBC) over the western Pacific. However, reliable and long-term BC data are still limited in this region, especially at elevated altitudes. In this study, we present accurate measurements of MBC using a continuous soot monitoring system at Happo, a remote mountain site at an altitude of about 1.8 km in Japan, from August 2007 to August 2009. The annual average MBC at Happo was about 0.26 ± 0.18 (1σ) µg m−3. The monthly average MBC values exhibited similar seasonal variations during both years, with minimum values in winter. Around 40% of the air sampled at the site was of free tropospheric (FT) origin, with about 10% originating in North China (NC) origin, respectively. The MBC values for FT (0.24 µg m−3) and NC (0.23 µg m−3) air were representative of the MBC values (0.26 µg m−3) at 1.8 km height in the western Pacific, which are strongly influenced by BC emissions in North China. The MBC values calculated using a regional-scale model reproduced well the MBC observed at Happo. The model predicted that BC transported from northern China alone contributed ~53% to the measured MBC, consistent with trajectory analysis. The comparison of model-calculated and observed MBC values indicates that the minimum values of MBC in winter were caused by the suppressed upward transport of BC over the Asian continent. Biomass burning in Siberia substantially increased MBC in the spring of 2008.

[1] A new two-dimensional aerosol bin scheme, which resolves both aerosol size and black carbon (BC) mixing state for BC aging processes (e.g., condensation and coagulation) with 12 size × 10 mixing state bins, has been developed and implemented into the WRF-chem model (MS-resolved WRF-chem). The mixing state of BC simulated by this model is compared with direct measurements over the East Asian region in spring 2009. Model simulations generally reproduce the observed features of the BC mixing state, such as the size-dependent number fractions of BC-containing and BC-free particles and the coating thickness of BC-containing particles. This result shows that the model can simulate realistic BC mixing states in the atmosphere if condensation and coagulation processes are calculated explicitly with the detailed treatment of BC mixing state. Sensitivity simulations show that the condensation process is dominant for the growth of thinly coated BC particles, while the coagulation process is necessary to produce thickly coated BC particles. Off-line optical and radiative calculations assuming an average mixing state for each size bin show that the domain- and period-averaged absorption coefficient and heating rate by aerosols are overestimated by 30–40% in the boundary layer, compared with a benchmark simulation with the detailed treatment of mixing state. The absolute value of aerosol radiative forcing is also overestimated (10%, 3 W m–2) at the surface. However, these overestimations are reduced considerably when all the parameters (including mass and number concentration) are calculated with the simple treatment of mixing state. This is because the overestimation of radiative parameters due to higher absorption efficiency (compared with the benchmark simulation) is largely canceled by the underestimation of BC concentrations due to efficient wet removal processes. The overall errors in radiative forcing can be much smaller because of this cancellation, but for the wrong reasons.

We have developed a new source and process apportionment method, the Process, Age, and Source region Chasing ALgorithm (PASCAL), and implemented it in a three-dimensional chemical transport model, the Community Multiscale Air Quality (CMAQ) model. By adding new variables (tagged species), PASCAL traces 1) the source region of emissions (source apportionment), 2) the age of individual species (elapsed time from emissions), 3) net and gross production and loss amounts from individual physical and chemical processes during transport (Lagrangian way), and 4) local production and loss rates at individual grid cells (Eulerian way) for primary and secondary aerosols and their precursor gases. The main advantage of PASCAL is the third one, which can trace accumulated production and loss amounts of individual processes during transport from source regions to each grid cell (Lagrangian type of integration) for both gross (production and loss) and net (gross production − loss) concentrations. Currently the method is applied for mixing ratios of CO and SO 2 and mass concentrations of black carbon and sulfate aerosols. This algorithm is not impacted by the non-linearity of chemical reactions and is computationally efficient. CMAQ/PASCAL model calculations were conducted over the East Asian region to test its performance. The overall validity of PASCAL calculations is confirmed for all species, periods, altitudes, and regions. This algorithm will be a useful tool in evaluating source regions as well as formation and loss processes of aerosols in the atmosphere in order to make effective strategies for emissions reduction.

Large amounts of reactive gases and aerosols are emitted from urban areas. Megacities, including the Tokyo Metropolitan Area (TMA), are very large, concentrated sources of these species affecting local, regional, and global ozone (O3) and aerosol levels. Emissions strongly influence air quality and climate on these scales. In 2003-2004, we made intensive measurements of O3 and chemical composition of aerosol particles with diameters less than 1 µm (PM1 aerosol) together with their precursors for the first time in Tokyo, Japan, as a part of the series of Integrated Measurement Program for Aerosol and Oxidant Chemistry in Tokyo (IMPACT) campaigns. Using these data, we investigated the formation and transport processes of O3 and PM1 aerosols through the analysis of their temporal variations near the urban center of Tokyo and regions downwind. Key findings obtained in these studies are reviewed in this paper.

Ambient measurements of hydrocarbons, carbon monoxide and nitrogen oxides from three mega-cities (Beijing, Mexico City, Tokyo) are compared with similar measurements from US cities in the mid-1980s and the early 2000s. The common hydrocarbon pattern seen in all data sets suggests that emissions associated with gasoline-fueled vehicles dominate in all of these cities. This commonality suggests that it will be efficient and, ultimately, cost effective to proceed with vehicular emission controls in most emerging mega-cities, while proceeding with development of more locally appropriate air quality control strategies through emissions inventory development and ambient air monitoring. Over the three decades covered by the US data sets, the hydrocarbon emissions decreased by a significant factor (something like an order of magnitude), which is greater than suggested by emission inventories, particularly the EDGAR international inventory. The ambient hydrocarbon and CO concentrations reported for the three non-US mega-cities are higher than present US ambient concentrations, but lower than those observed in the 1980s in the US. The one exception to the preceding statement is the high concentrations of CO observed in Beijing, which apparently have a large regional contribution.

In our previous aircraft observations, the possible influence of high sea surface temperature (SST) along the Kuroshio Current on aerosol-cloud interactions over the western North Pacific was revealed. The cloud droplet number concentration (Nc) was found to increase with decreasing near-surface static stability (NSS), which was evaluated locally as the difference between the SST and surface air temperature (SAT). To explore the spatial and temporal extent to which this warm SST influence can be operative, the present study analyzed Nc values estimated from Moderate Resolution Imaging Spectroradiometer (MODIS) satellite measurements. The comparison of the local Nc values between the high and low SST – SAT days revealed a marked increase in Nc (up to a factor of 1.8) along the Kuroshio Current in the southern East China Sea, where particularly high SST – SAT values (up to 8 K) were observed in winter under monsoonal cold air outflows from the Asian Continent. This cold airflow destabilizes the atmospheric boundary layer, which leads to enhanced updraft velocities within the well-developed mixed layer and thus greater Nc. The monsoonal northwesterlies also bring a large amount of anthropogenic aerosols from the Asian continent that increase Nc in the first place. These results suggest that the same modulations of cloud microphysics can occur over other warm western boundary currents, including the Gulf Stream, under polluted cool continental airflows. Possibilities of influencing the cloud liquid water path (CLWP) are also discussed.

Vertical profiles of HNO 3 , N 2 O, O 3 , and the aerosol extinction coefficient at 780 nm were observed by the Improved Limb Atmospheric Spectrometer (ILAS) on board the Advanced Earth Observing Satellite (ADEOS) during the Arctic winter of 1996-1997. Irreversible redistribution of HNO 3 is evaluated using HNO 3 -N 2 O and HNO 3 -O 3 correlations. Denitrification and nitrification started to be observed just after the Arctic vortex cooled to below the ice frost point (T ICE ) on February 10. Trajectory analyses show that denitrification occurred only in air masses, which were once cooled to near T ICE and were kept at temperatures below the nitric acid trihydrate saturation threshold continuously for more than 4 days. Such a temperature history provides the necessary conditions for nucleation and growth of particles causing denitrification. The average extent of denitrification at 19 km reached 43% at the center of the vortex, suggesting that stratospheric ozone could be affected by denitrification deep inside the vortex. Denitrification (>2 ppbv) and nitrification (> 1 ppbv) covered 40±10% and 35±10% of the vortex area, respectively. Redistributed numbers of HNO 3 molecules at each altitude were calculated by integrating the area-weighted changes in the HNO 3 concentration. The decreases in total HNO 3 concentration at 17-21 km in late February and early March agreed with the increases at 12-15 km to within 25%, confirming conservation of HNO 3 during sedimentation and evaporation of HNO 3 -containing polar stratospheric cloud particles.

Simultaneous measurements of the oxides of hydrogen and nitrogen made during the NASA Subsonic Assessment, Ozone and Nitrogen Oxide Experiment (SONEX) afforded an opportunity to study the coupling between these two important families throughout the free troposphere and lowermost stratosphere. Moreover, the suite of measurements made during the campaign was unprecedented in its completeness, thus providing a uniquely detailed picture of the radical photochemistry that drives oxidation and ozone production in this part of the atmosphere. On average, observed hydrogen oxides (HOx = OH + HO2) agree well with both instantaneous and diel steady-state models; however, there is a persistent deviation of the observations that correlates with the abundance of nitrogen oxides (NOx = NO + NO2) in the sampled air mass. Specifically, the observed HOx tends to exceed the model predictions in the presence of high NOx concentrations, by as much as a factor of 5 (> 500 pptv NOx), and is sometimes as little as half that expected by steady state at lower NOx levels. While many possibilities for these discrepancies are discussed, it is argued that an instrumental artifact is not probable and that the discrepancy may bespeak a shortcoming of our understanding of HOx chemistry. The consistently elevated HOx in the presence of elevated NOx leads directly to greater ozone production than expected, thereby extending the NOx-limited regime of the upper troposphere. These results could thus have bearing on the predicted impacts of increasing NOx emissions into this region of the atmosphere from, for example, the growth of global air traffic.

A chemical ionization mass spectrometer (CIMS) was used for rapid detection of HNO3 in air traffic corridors, primarily over the North Atlantic region, during the NASA Subsonic Assessment Ozone and Nitrogen Oxide Experiment (SONEX) campaign in the fall of 1997. The sensitivity of the CIMS instrument approaches 1 ion count per second for each 106 molecules cm−3, under ideal conditions. During the SONEX mission the precision of the experiment was considerably lower due to inlet fluctuations. Ten-second integration periods were used to obtain a precision of typically 10 parts per trillion by volume. A description is given of the instrument and the technique, including inflight calibration using a permeation tube. Comparisons are made with NOy data and with the University of New Hampshire HNO3 data obtained with a mist chamber method.

Balloon-borne in situ measurements of total reactive nitrogen (NOy), nitric oxide (NO), nitric acid (HNO3), ozone (O3), and aerosols were conducted over Aire sur l'Adour, France (44°N), between October 11 and 12, 1994. NOy and NO were measured by chemiluminescence NO detectors combined with a gold catalytic converter, and HNO3 was measured by ion mass spectrometry. Two independent box models (Goddard Space Flight Center and Atmospheric and Environment Inc.) run on isentropic trajectories were used to interpret the observed partitioning of reactive nitrogen. The NOy partitioning calculated by the two models agreed within 10% of each other. The model-calculated NO/NOy ratios increase by ∼25% when the updated reaction rates of NO2 + OH, HNO3 + OH, and NO2 + O [Portmann et al., 1999] were used instead of those given by DeMore et al. [1997], leading to a better agreement with the observations by the same amount. At 21–25 km the calculated NO/NOy ratios depended sensitively on the estimate of aerosol surface area. Within the uncertainty of the estimate of aerosol surface area the NO/NOy and HNO3/NOy ratios calculated by the models reproduced those observed within 20%. The same trajectory models also reproduced the NO/NOy ratios measured below 25 km under high aerosol loading in October and November 1992 within ±20%, which is the accuracy level of the measurements.

We present an analysis of the impact of heterogeneous chemistry on the partitioning of nitrogen species measured by the Upper Atmosphere Research Satellite (UARS) instruments. The UARS measurements utilized include: N2O, HNO3 and ClONO2 (Cryogen Limb Array Etalon Spectrometer (CLAES), version 7), temperature, methane, ozone, H2O, HCl, NO and NO2 (HALogen Occultation Experiment (HALOE), version 18). The analysis is carried out for the data from January 1992 to September 1994 in the 100-1 mbar (approx.17-47 km) altitude range and over 10 degree latitude bins from 70degS to 70degN. Temporal-spatial evolution of aerosol surface area density (SAD) is adopted according to the Stratospheric Aerosol and Gas Experiment (SAGE) 11 data. A diurnal steady-state photochemical box model, constrained by the temperature, ozone, H2O, CH4, aerosol SAD and columns of O2 and O3 above the point of interest, has been used as the main tool to analyze these data. Total inorganic nitrogen (NO(y)) is obtained by three different methods: (1) as a sum of the UARS measured NO, NO2, HNO3, and ClONO2; (2) from the N2O-NO(y) correlation, and (3) from the CH4-NO(y) correlation. To validate our current understanding of stratospheric heterogeneous chemistry for post-Pinatubo conditions, the model-calculated NO(x)/NO(y) ratios and the NO, NO2, and HNO3 profiles are compared to the UARS-derived data. In general, the UARS-constrained box model captures the main features of nitrogen species partitioning in the post-Pinatubo years. However, the model underestimates the NO2 content, particularly, in the 30-7 mbar (approx. 23-32 km) range. Comparisons of the calculated temporal behavior of the partial columns of NO2 and HNO3 and ground based measurements at 45degS and 45degN are also presented. Our analysis indicates that ground-based and HALOE v. 18 measurements of the NO2 vertical columns are consistent within the range of their uncertainties and are systematically higher (up to 50%) than the model results at mid-latitudes in both hemispheres. Reasonable agreement is obtained for HNO3 columns at 45degS suggesting some problems with nitrogen species partitioning in the model. Outstanding uncertainties are discussed.

The column amounts of nitrogen dioxide (NO2) and ozone (O3) were measured using a visible spectrometer based on the twilight zenith-sky technique at two observatories located at similar latitudes in the northern part of Japan separated by a distance of 150 km. The measurements began in April 1991 at the Moshiri Observatory (44.4°N, 142.3°E) and in April 1994 at the Rikubetsu Observatory (43.5°N, 143.8°E). Since weather conditions and the possible influence from tropospheric pollution were not always identical at these two observatories, the overall accuracy of the measurements was studied comparing these data sets. The first year data obtained at a solar zenith angle of 90 degrees indicated that the NO2 slant column values at sunrise and sunset agreed within 0.36 and 0.54 × 1016 cm-2, respectively, corresponding to 5 % (June) and to 12 % (December) of the columns. The O3 values agreed within 0.76 × 1019 cm-2, corresponding to 4 % (March) ∼6 % (August) of the columns, although a part of the difference was systematic. The O3 column amounts were also compared to those obtained by the Dobson spectrometer at Sapporo (43.5°N, 143.8°E), whose latitude is similar to these observatories. When an air mass factor of 17.5 was used, the two-year Moshiri vertical column values agreed with the Dobson direct sun values to within 15 Dobson Units, or 3 ∼ 6 % of the column. The difference between the two values was found to be due partly to the change in the air mass factor caused by seasonal and day-to-day changes in the shape of the O3 vertical profiles. These results confirm the reliability of the NO2 and O3 measurements by visible spectrometers at these sites for the Network for the Detection of Stratospheric Change (NDSC).

Results of the comparison of carbon monoxide ground-based infrared solar spectroscopic measurements with data obtained during 1994 Measurement of Air Pollution From Space (MAPS) flights are presented. Spectroscopic measurements were performed correlatively with April and October MAPS flights by nine research groups from Belgium, Canada, Germany, Japan, New Zealand, Russia, and the United States. Characterization of the techniques and error analysis were performed. The role of the CO a priori profile used in the retrieval was estimated. In most cases an agreement between spectroscopic and MAPS data is within estimated MAPS accuracy of _+ 10%.

Balloon-borne in situ measurements of total reactive nitrogen (NO,,) and nitrous oxide (N 2 O) were made from Kiruna (68°N, 21°E), Sweden on February 11, 1995. Ten hours later, N 2 O was again measured by an infrared spectrometer flown on another balloon launched from Kiruna. Both observations were made inside the polar vortex between 380 K (∼14 km) and at least 675 K (∼26 km). In the winter of 1994-1995, temperatures at 475 K (∼19 km) inside the vortex were extremely low, sometimes lower than ice frost point, especially from mid-December to mid-January. The NO y profiles obtained during both the ascent and descent revealed layered structures between 15 and 20 km with mixing ratios ranging from 2.7 to 9.3 parts per billion by volume (ppbv). The observed N 2 O profiles indicate significant downward transport of air due to diabatic cooling in the winter. To quantify the degree of irreversible removal of NO y (denitrification) between 12 and 28 km, the unperturbed values of NO y (i.e., NO * y ) were estimated from the observed N 2 O values using the NO y - N 2 O relationship obtained at midlatitudes by the atmospheric trace molecule spectroscopy ATLAS mission and in situ aircraft and balloon-borne measurements. The largest denitrification was observed at 19± 0.5 km, where the NO y values were lower than the NO * y values by ∼10 ppbv, corresponding to a 70% removal of NO y . In spite of the large uncertainty in NO * y the NO y values generally agreed well with the NO * y values at ∼14 km as well as between 3 and 28 km. The relationship between NO,, and N 2 O measured between 23 and 28 km agreed with that measured above 40 km at northern midlatitudes in fall, indicating that the air masses sampled at 23-28 km over Kiruna were transported from the midlatitude upper stratosphere followed by the descent inside the vortex.

Atmospheric black carbon (BC) absorbs solar radiation, and exacerbates global warming through exerting positive radiative forcing (RF). However, the contribution of BC to ongoing changes in global climate is under debate. Anthropogenic BC emissions, and the resulting distribution of BC concentration, are highly uncertain. In particular, long range transport and processes affecting BC atmospheric lifetime are poorly understood. Here we discuss whether recent assessments may have overestimated present day BC radiative forcing in remote regions. We compare vertical profiles of BC concentration from four recent aircraft measurement campaigns to simulations by 13 aerosol models participating in the AeroCom Phase II intercomparision. An atmospheric lifetime of BC of less than 5 days is shown to be essential for reproducing observations in remote ocean regions, in line with other recent studies. Adjusting model results to measurements in remote regions, and at high altitudes, leads to a 25% reduction in AeroCom Phase II median direct BC forcing, from fossil fuel and biofuel burning, over the industrial era. The sensitivity of modeled forcing to BC vertical profile and lifetime highlights an urgent need for further flight campaigns, close to sources and in remote regions, to provide improved quantification of BC effects for use in climate policy.

Latitudinal distributions of NO, NO(y), O3, CO, CH3I, and H2O mixing ratios at 8.9-12 km were obtained between 30deg N and 1deg S by DC-8 aircraft measurements made in February 1994 during Pacific Exploratory Mission-West B (PEM-West B). Very low NO(y), mixing ratios with a median value of 51 parts per trillion by volume (pptv) were observed at 9.5-12 km at 1deg N-14deg N during two flights made within 3 days. A very low median O3 mixing ratio of 19 parts per billion by volume (ppbv) and high mixing ratios of H2O and CH3I were simultaneously observed, suggesting that the low NO(y), values were probably due to the convective transport of air from the tropical marine boundary layer to this altitude. The median NO(y)/O3 ratio being a factor of 2 smaller than in the air masses in the tropical marine boundary layer might suggest the possibility that the heterogeneous removal of HNO3 during convective transport further reduced NO(y) levels. In addition to the measurements between 9.5 and 12 km, low values of NO(y) and O3 were observed between 4 and 12 km at 1deg N. Divergent wind fields at 200 and 1000 hPa and infrared (IR) cloud images show that there was large scale convection (greater than 1000 km x 1000 km) in the northeast of New Guinea Island centered around Odeg S and 150deg E as part of systematic convective activity of the Intertropical Convergence Zone (ITCZ) and the South Pacific Convergence Zone (SPCZ). This type of large scale convection could have transported air with low levels of NO(y) and O3 to the middle and upper troposphere over a wide area in the tropics. On the other hand, NO mixing ratios of 50-200 pptv and high NQ,/NOY ratios of 0.4-0.6 were observed at 9.5 km between 4deg S and 10deg S. High H2O Mixing ratios of 600-1200 parts per million by volume (ppmv) and low CO mixing ratios of 65 ppbv observed in the air mass indicated that the high NO values were probably due to NO production by lightning. Satellite observations showed relatively frequent lightning flashes over the New Guinea Island for 3 days prior to the aircraft measurements. These results are considered to be consistent with the idea that, in general, marine convection is not accompanied by lightning activity, whereas convection over land is. Because of the large areal extent of the influences from these processes, the convective transport of low NO(y) air and NO production by lightning should play critical roles in controlling the abundance of reactive nitrogen in the equatorial region.

Measurements of NO, NO y , PAN, HNO 3 , O 3 , CO, CH 4 , nonmethane hydrocarbons (NMHCs), and H 2 O were made over the Pacific Ocean in February and March during the Pacific Exploratory Mission West B (PEM-West B). NO x was calculated from NO using a photochemical model. These data were classified according to six air mass categories: western Pacific maritime, tropical, tropical convective, western Pacific continental, high latitude, and stratospheric. It has been found that the mixing ratios of many of the observed species and partitioning of NO varied significantly depending on altitude, air mass, and season. These variations have been interpreted in terms of chemical and transport processes. In the maritime air below 7 km, the mixing ratios of calculated NO x ((NO x ) mc ), PAN, and NO were lower than those in the continental air masses. The lowest values of PAN, HNO 3 , NO y , and O 3 were observed in the tropical region below 5 km. In the continental air, NO y , PAN, CO, and NMHC levels below 4 km were much higher than those obtained in September and October during PEM-West A, due to rapid transport of these species from anthropogenic sources on the continent to the Pacific Ocean by the westerly winds which dominated in early winter and spring. Reduced photochemistry during winter also contributed to the higher values of CO and NMHCs. Above 7 km the values of these species were lower during PEM-West B, possibly due to much weaker convective activity in early spring. In spite of the weaker vertical transport, the median values of (NO x ) mc and the (NO x ) mc /C 3 H 8 ratio at 10 km were 110-140 parts per trillion by volume (pptv) and 2.9-3.4 pptv/pptv, respectively, in the continental and maritime air masses, indicating the importance of in situ NO x production in the upper troposphere. In the continental air the PAN/NO y and HNO 3 /N y ratios ranged between 0.2 and 0.5, showing clear anticorrelation. The PAN/NO y ratio was also anticorrelated with the temperature. In the high-latitude air between 1 and 7 km the PAN/NO y ratio was 0.5-0.8, and the (NO x ) mc /NO y ratio was less than 0.05. Temperature and the concentrations of OH and NMHCs are considered to have strongly influenced the partitioning of NO y at middle and high latitudes. Generally, the sum of (NO x ) mc , PAN, and HNO 3 constituted 90 ± 10% of the observed NO from the boundary layer up to 7 km in all types of air masses. This finding improves our basic understanding on the chemistry and budget of the reactive nitrogen.

Concentrations of nitric oxide (NO), total reactive nitrogen (NO y ), O 3 , and aerosol were measured between 14 and 32 km on balloon platforms launched from Aire sur l'Adour (44°N, 0°W), France, on October 20 and November 6, 1992. Aerosol surface area has been deduced from the observed concentrations of aerosols with radii ranging from 0.18 to 0.7 μm. On these days the surface area was enhanced due to the eruption of Mount Pinatubo, which occurred in June 1991. The data set is used to investigate the effect of heterogeneous reactions on sulfuric acid aerosol reducing NO x . A diurnal photochemical model, which takes into account heterogeneous chemistry, is used to calculate the changes in the partitioning of reactive nitrogen in the altitude region between 18 and 32 km. The observed values of NO and NO x /NO y , ratio are significantly lower than those calculated by the model without taking into account heterogeneous chemistry. The degree of reduction of NO x by heterogeneous reaction was observed to vary sensitively with surface area for values lower than 2 μm 2 cm -3 . The net reduction of NO x by aerosol tended to saturate at surface area larger than 4 μm 2 cm -3 . Observations of NO and NO x /NO y are shown to be in generally good agreement with theoretical values found using the same model but including heterogeneous chemistry, indicating that NO x was reduced primarily by the hydrolysis of N 2 O 5 on sulfuric acid aerosol.

NO mixing ratios measured from Kiruna (68°N, 20°E), Sweden, on January 22, 1992, revealed values much smaller than those observed at midlatitude near equinox and had a sharper vertical gradient around 25 km. Location of the measurements was close to the terminator and near the edge of the polar vortex, which is highly distorted from concentric flow by strong planetary wave activities. These conditions necessitate accurate calculation, properly taking into account the transport and photochemical processes, in order to quantitatively explain the observed NO profile. A three-dimensional chemistry and transport model (CTM) and a trajectory model (TM) were used to interpret the profile observations within their larger spatial, temporal, and chemical context. The NOy profile calculated by the CTM is in good agreement with that observed on January 31, 1992. In addition, model NOy profiles show small variabilities depending on latitudes, and they change little between January 22 and 31. The TM uses the observed NOy values. The NO values calculated by the CTM and TM agree with observations up to 27 km. Between 20 and 27 km the NO values calculated by the trajectory model including only gas phase chemistry are much larger than those including heterogeneous chemistry, indicating that NO mixing ratios were reduced significantly by heterogeneous chemistry on sulfuric acid aerosols. Very little sunlight to generate NOx from HNO3 was available, also causing the very low NO values. The good agreement between the observed and modeled NO profiles indicates that models can reproduce the photochemical and transport processes in the region where NO values have a sharp horizontal gradient. Moreover, CTM and TM model results show that even when the NOy gradients are weak, the model NO depends upon accurate calculation of the transport and insolation for several days.

Aircraft measurements of total reactive nitrogen (NOy) and ozone (O3) were made over the sea, south and north of Japan in February and November 1993, respectively. NOy mixing ratios between 1000 and 2000 pptv were observed at altitudes below 1.5 km and 2 km on both days. These values were much higher than those of about 300 pptv in the free troposphere. In the November measurements, the O3 mixing ratios were also high, about 70 ppbv at these low altitudes. These high levels of NOy and O3 extended horizontally for more than 200 km. Back trajectory calculations indicate that the air with these high levels of NOy and O3 in November and February was transported from North Korea and the northeast part of China within about 1 or 1.5 d. Since westerly winds dominate from late autumn to early spring, the large-scale transport of air with high levels of Ny and O3 should have a significant impact on the chemical environment over the western Pacific. The relationship between NOy and O3 shows that the gradient of O3 mixing ratios with respect to the NOy values ( ΔO 3 ΔNO y ) is systematically lower in polluted air at altitudes below 2 km, than those in the relatively clean free troposphere.

Measurements of NO and NO y were carried out during NASA's Pacific Exploratory Mission-West A. In total, 18 aircraft flights were made over the Pacific Ocean, predominantly over the western Pacific Ocean in September and October 1991. NO and NO were measured using a chemiluminescence instrument, and NO x was calculated from NO using a chemical box model. The measurements were carried out from 0.3 to 12 km in altitude. The NO, calculated NO x ((NO x ) mc ), and NO y mixing ratios in continental air were significantly higher than in maritime air. In maritime air, NO increased with altitude. The median values of NO in the boundary layer and the lower, middle, and upper troposphere were 3.7, 5.1, 11.5, and 26.6 parts per trillion by volume (pptv), respectively. In continental air, NO and (NO x ) mc mixing ratios revealed a C-shaped profile. The median NO values observed in the four altitude regions were 37.8, 17.5, 18.2, and 53.2 pptv, respectively. NO did not show any apparent altitude dependence either in maritime or in continental air. In maritime air, median NO y values in the lower, middle, and upper troposphere ranged between 211 and 226 pptv and in continental air between 382 and 401 pptv. The lowest values of NO y , PAN, and O 3 were observed in tropical air masses throughout the entire altitude region. In the middle and upper troposphere of the high-latitude air masses, NO and (NO x ) mc values were the lowest, although NO y mixing ratios were similar to those in continental air masses. PAN, O 3 , CO, CH 4 , and C 2 H 6 data were used to study the budget of reactive nitrogen over the Pacific Ocean. O 3 mixing ratios were found to be correlated with those of (NO x ) mc , NO y , PAN, and CH 4 , although the degree of correlation varied with air mass and altitude. These correlations, together with the profiles of these species, suggest that photochemical production of O 3 from precursor species over the continent is important for the O 3 budget in the troposphere over the western Pacific Ocean.

Monthly and zonal average distributions of ozone in a meridional plane were obtained using the UV spectrometer data on the EXOS-C satellite during March 1984 – September 1987. Individual vertical ozone profiles retrieved from the measured spectral intensities of the backscattered UV was proved to be in general agreement within ±10% with those from ground-based measurements. The EXOS-C meridional ozone distributions are constracted and compared with those of the CIRA model to exhibit an agreement within ±10% on the average in the atmospheric pressure range of 15 – 1.5 mb (altitudes between ∼28 km and ∼45 km). At altitudes above ∼50 km, the EXOS-C ozone volume mixing ratios are systematically smaller than those of the CIRA. This difference can be attributed to a calibration bias. Amplitudes of seasonal variations in ozone volume mixing ratios are also obtained at various latitudes and atmospheric pressure levels and compared with those of the CIRA.

[1] Cloud microphysical properties and aerosol concentrations were measured aboard an aircraft over the East China Sea and Yellow Sea in April 2009 during the Aerosol Radiative Forcing in East Asia (A-FORCE) experiment. We sampled stratocumulus and shallow cumulus clouds over the ocean in 9 cases during 7 flights 500–900 km off the east coast of Mainland China. In this study we report aerosol impacts on cloud microphysical properties by focusing on regional characteristics of two key parameters, namely updraft velocity and aerosol size distribution. First, we show that the cloud droplet number concentration (highest 5%, Nc_max) correlates well with the accumulation-mode aerosol number concentration (Na) below the clouds. We then show that Nc_maxcorrelates partly with near-surface stratification evaluated as the difference between the sea surface temperature (SST) and 950-hPa temperature (SST − T950). Cold air advection from China to the East China Sea was found to bring not only a large number of aerosols but also a dry and cold air mass that destabilized the atmospheric boundary layer, especially over the warm Kuroshio ocean current. Over this high-SST region, greater updraft velocities and hence greater Nc_maxlikely resulted. We hypothesize that the low-level static stability determined by SST and regional-scale airflow modulates both the cloud microphysics (aerosol impact on clouds) and macro-structure of clouds (cloud base and top altitudes, hence cloud liquid water path). Second, we show that not only higher aerosol loading in terms of total aerosol number concentration (NCN, D > 10 nm) but also larger aerosol mode diameters likely contributed to high Ncduring A-FORCE. The mean Nc of 650 ± 240 cm−3was more than a factor of 2 larger than the global average for clouds influenced by continental sources. A crude estimate of the aerosol-induced cloud albedo radiative forcing is also given.

[1] The Aerosol Radiative Forcing in East Asia (A-FORCE) aircraft campaign was conducted over East Asia in March–April 2009. During the A-FORCE campaign, 120 vertical profiles of black carbon (BC) and carbon monoxide (CO) were obtained in the planetary boundary layer (PBL) and the free troposphere. This study examines the wet removal of BC in Asian outflow using the A-FORCE data. The concentrations of BC and CO were greatly enhanced in air parcels sampled at 3–6 km in altitude over the Yellow Sea on 30 March 2009, associated with upward transport due to a cyclone with modest amounts of precipitation over northern China. In contrast, high CO concentrations without substantial enhancements of BC concentrations were observed in air parcels sampled at 5–6 km over the East China Sea on 23 April 2009, caused by uplifting due to cumulus convection with large amounts of precipitation over central China. The transport efficiency of BC (TEBC, namely the fraction of BC particles not removed during transport) in air parcels sampled above 2 km during the entire A-FORCE period decreased primarily with the increase in the precipitation amount that air parcels experienced during vertical transport, although their correlation was modest (r2 = 0.43). TEBC also depended on the altitude to which air parcels were transported from the PBL and the latitude where they were uplifted locally over source regions. The median values of TEBC for air parcels originating from northern China (north of 33°N) and sampled at 2–4 km and 4–9 km levels were 86% and 49%, respectively, during the A-FORCE period. These median values were systematically greater than the corresponding median values (69% and 32%, respectively) for air parcels originating from southern China (south of 33°N). Use of the A-FORCE data set will contribute to the reduction of large uncertainties in wet removal process of BC in global- and regional-scale models.

[1] New particle formation (NPF) is one of the most important processes in controlling the concentrations of aerosols (condensation nuclei, CN) and cloud condensation nuclei (CCN) in the atmosphere. In this study, we introduce a new aerosol model representation with 20 size bins between 1 nm and 10 μm and activation-type and kinetic nucleation parameterizations into the WRF-chem model (called NPF-explicit WRF-chem). Model calculations were conducted in the Beijing region in China for the periods during the Campaign of Air Quality Research in Beijing and Surrounding Region 2006 (CARE-Beijing 2006) campaign conducted in August and September 2006. Model calculations successfully reproduced the timing of NPF and no-NPF days in the measurements (21 of 26 days). Model calculations also reproduced the subsequent rapid growth of new particles with a time scale of half a day. These results suggest that once a reasonable nucleation rate at a diameter of 1 nm is given, explicit calculations of condensation and coagulation processes can reproduce the clear contrast between NPF and no-NPF days as well as further growth up to several tens of nanometers. With this reasonable representation of the NPF process, we show that NPF contributed 20%–30% of the CN concentrations (>10 nm in diameter) in and around Beijing on average. We also show that NPF increases CCN concentrations at higher supersaturations (S > 0.2%), while it decreases them at lower supersaturations (S < 0.1%). This is likely because NPF suppresses the increases in both the size and hygroscopicity of preexisting particles through the competition of condensable gases between new particles and preexisting particles. Sensitivity calculations show that a reduction of primary aerosol emissions, such as black carbon (BC), would not necessarily decrease CCN concentrations because of an increase in NPF. Sensitivity calculations also suggest that the reduction ratio of primary aerosol and SO2 emissions will be key in enhancing or damping the BC mitigation effect.

[1] Extensive measurements of black carbon (BC) aerosol were conducted in and near the North American Arctic during the Arctic Research of the Composition of the Troposphere from Aircraft and Satellites (ARCTAS) aircraft campaign in April and June–July 2008. We identify the pathways and mechanisms of transport of BC to the Arctic from the Asian continent using these data. The concentration, transport efficiency, and measured altitude of BC over the North American Arctic were highly dependent on season and origin of air parcels, e.g., biomass burning (BB) in Russia (Russian BB) and anthropogenic (AN) in East Asia (Asian AN). Russian BB air was mainly measured in the middle troposphere and caused maximum BC concentrations at this altitude in spring. The median BC concentration and transport efficiency of the Russian BB air were 270 ng m−3 (at STP) and 80% in spring and 20 ng m−3 and 4% in summer, respectively. Asian AN air was measured most frequently in the upper troposphere, with median values of 20 ng m−3 and 13% in spring and 5 ng m−3 and 0.8% in summer. These distinct differences are explained by differences in the transport mechanisms and accumulated precipitation along trajectories (APT), which is a measure of wet removal processes during transport. The transport of Russian BB air to the Arctic was nearly isentropic with slow ascent (low APT), while Asian AN air underwent strong uplift associated with warm conveyor belts (high APT). The APT values in summer were much larger than those in spring due to the increase in humidity in summer. These results show that the impact of BC emitted from AN sources in East Asia on the Arctic was very limited in both spring and summer. The BB emissions in Russia in spring are demonstrated to be the most important sources of BC transported to the North American Arctic.

Airborne measurements of aerosols were conducted over the western Pacific in the spring of 2009 during the Aerosol Radiative Forcing in East Asia (A-FORCE) aircraft campaign. The A-FORCE flights intensively covered an important vertical-latitudinal range in the outflow region of East Asia (0–9 km altitude; 27°N–38°N). This paper presents the variability of aerosol particle number concentrations obtained by condensation particle counters and a Single-Particle Soot Photometer (SP2), with the focus on those in the free troposphere. The number concentration data include total condensation nuclei with particle diameters (dp) larger than 10 nm (total CN10), PM0.17-CN10 (dp ~10–130 nm), and SP2 black carbon (NBC; dp ~75–850 nm). Large increases in total CN10 that were not associated with NBC were observed in the free troposphere, suggesting influences from new particle formation (NPF). Statistical characteristics of total CN10, PM0.17-CN10, and NBC in the lower troposphere (LT; 0–3 km), middle troposphere (MT; 3–6 km), and upper troposphere (UT; 6–9 km) are investigated. The correlation between total CN10 and NBC, along with the ratio of PM0.17 to total CN10 and carbon monoxide mixing ratio (CO), is used to interpret the observed variability. The median concentrations of total CN10 and PM0.17-CN10 in the UT were higher than those in the MT by a factor of ~1.4 and ~1.6, respectively. We attribute the enhancements of CN10 in the UT to NPF. Possible mechanisms affecting NPF in the free troposphere are discussed.

著者人数: 20名, Accepted: 2010-08-06, 資料番号: SA1005132000

[1] Model calculations were conducted using the Weather Research and Forecasting model coupled with chemistry (WRF-chem) for the region around Beijing, China, in the summer of 2006, when the CAREBeijing-2006 intensive campaign was conducted. In this paper, we interpret aerosol optical properties in terms of aerosol mass concentrations and their chemical compositions by linking model calculations with measurements. The model calculations generally captured the observed variability of various surface and column aerosol optical parameters in and around Beijing. At the surface, the spatial and temporal variations of aerosol absorption and scattering coefficients corresponded well to those of elemental carbon and sulfate mass concentrations, respectively, and were controlled by local-scale (

scale of about 1000 � 1000 km 2 under an anticyclonic pressure system. This air mass was transported northward fromthe high anthropogenic emission area extending south of Beijing with continuous photochemical production. Subsequent cold front passage broughtclean airfromthenorth,andpollutedairaround Beijingwassweptto thesouth of Beijing. This cycle was repeated about once a week and was found to be responsible for observed enhancements/reductions of aerosols at the intensive measurement sites. In contrast to secondary aerosols,the spatial distributions of primary aerosols (EC) reflected those of emissions, resulting in only slight variability despite the changes in synopticscale meteorology. In accordance with these results, source apportionment simulations revealed that primary aerosols around Beijing were controlled by emissions within 100 km around Beijing within the preceding 24 h, while emissions as far as 500 km and within the preceding 3 days were found to affect secondary aerosols.