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Forest wildfires in interior Alaska represent an important black carbon (BC) source for the Arctic and sub-Arctic. However, BC observations in interior Alaska have not been sufficient to constrain the range of existing emissions. Here, we show our observations of BC mass concentrations and carbon monoxide (CO) mixing ratios in the Poker Flat Research Range (65.12° N, 147.43° W), located in central Alaska, from April 2016 to December 2020. The medians, 10th percentile ranges, and 90th percentile ranges of the hourly BC mass concentration and CO mixing ratio throughout the observation period were 13, 2.9, and 56 ng m−3 and 124.7, 98.7, and 148.3 ppb, respectively. Sporadically large peaks in the BC mass concentration and CO mixing ratio were observed at the same time, indicating influences from common sources. These BC peaks coincided with peaks at other comparative sites in Alaska, indicating large BC emissions in interior Alaska. Source estimation by FLEXPART-WRF (Flexible Particle Dispersion–Weather Research and Forecast) confirmed a contribution of boreal forest wildfires in Alaska and western Canada when high BC mass concentrations were observed. For these cases, we found a positive correlation (r=0.44) between the observed BC/ΔCO ratio and fire radiative power (FRP) observed in Alaska and Canada. This finding implies that the variability of the BC and CO emission ratio is associated with the intensity and time progress of forest wildfires and suggests that the BC emission factor and/or inventory could be potentially improved by FRP. We recommend that FRP be integrated into future bottom-up emission inventories to achieve a better understanding of the dynamics of pollutants from frequently occurring forest wildfires under the rapidly changing climate in the Arctic.

We investigated the association of marine biological indicators (polysaccharides, protein-like gel particles, and chl a) with the formation of fluorescent aerosol particles, cloud condensation nuclei (CCNs), and ice-nucleating particles (INPs) over the North Pacific Ocean, Bering Sea, and Arctic Ocean during September–November 2019. The abundance of bioindicators was high in the North Pacific Ocean and the Bering Sea (e.g., up to 1.3 mg m−3 of chl a), suggesting high biological activity due to a phytoplankton bloom. In the North Pacific Ocean, particles were characterized by high mass fractions of organics and sulfate with a predominance of terrestrial air masses. Conversely, in the Bering Sea and the Arctic Ocean, particles were characterized by high mass fractions of sea salt and sulfate with a predominance of maritime air masses. The averaged range/value of the CCN concentration at 0.4 % supersaturation were 99–151, 43–139, and 36 cm−3 over the North Pacific Ocean with terrestrial influences, over the Bering Sea with marine biogenic influences, and over the Arctic Ocean with marine influences, respectively, and the corresponding range/value of the hygroscopicity parameter κ were 0.17–0.59, 0.42–0.68, and 0.66, respectively. The averaged INP concentration (NINP) measured at temperatures of −18 and −24 ∘C with marine sources in the North Pacific and Bering Sea was 0.01–0.09 and 0.1–2.5 L−1, respectively, and that over the Arctic Ocean was 0.001–0.016 and 0.012–0.27 L−1, respectively. When marine sources were dominant, fluorescent bioaerosols in the fine mode were strongly correlated with all bioindicator types (R: 0.81–0.88) when the effect of wind-induced uplift from the sea surface to the atmosphere was considered. Correlations between NINP measured at −18 and −24 ∘C and all bioindicator types (R: 0.58–0.95 and 0.79–0.93, respectively) were positive, even when the extreme outlier point was omitted, as were those between NINP and fluorescent bioaerosols (R: 0.50 and 0.60, respectively), suggesting that marine bioindicators contributed substantially as sources of bioaerosols and to cloud formation.

Atmospheric transport of iron (Fe) in fine anthropogenic aerosol particles is an important route of soluble Fe supply from continental areas to remote oceans. To elucidate Fe properties of aerosol particles over remote oceans, we collected atmospheric aerosol particles over the Indian Ocean during the RV Hakuho Maru KH-18-6 cruise. After aerosol particles were collected using a cascade impactor, particles of 0.3–0.9 µm aerodynamic diameter on the sample stage were analyzed using transmission electron microscopy (TEM) with an energy-dispersive X-ray spectrometry analyzer. The particle shape and composition indicated that most particles collected north of the Equator were composed mainly of ammonium sulfate. Regarding the particle number fraction, 0.6 %–3.0 % of particles contained Fe, which mostly co-existed with sulfate. Of those particles, 26 % of Fe occurred as metal spheres, often co-existing with Al or Si, regarded as fly ash; 14 % as mineral dust; and 7 % as iron oxide aggregates. Water dialysis analyses of TEM samples indicated Fe in spherical fly ash as being almost entirely insoluble and Fe in other morphological-type particles as being partly soluble (65 % Fe mass on average). Global model simulations mostly reproduced observed Fe mass concentrations in particulate matter with a diameter of less than 2.5 µm (PM2.5) collected using a high-volume air sampler, including their north–south contrast during the cruise. In contrast, a marked difference was found between the simulated mass fractions of Fe mineral sources and the observed Fe types. For instance, the model underestimated anthropogenic aluminosilicate (illite and kaolinite) Fe contained in matter such as fly ash from coal combustion. Our observations revealed multiple shapes and compositions of Fe minerals in particles over remote ocean areas and further suggested that their solubilities after aging processes differ depending on their morphological and mineral types. Proper consideration of such Fe types at their sources is necessary for accurately estimating atmospheric Fe effects on marine biological activity.

While carbon dioxide is the main cause for global warming, modeling short-lived climate forcers (SLCFs) such as methane, ozone, and particles in the Arctic allows us to simulate near-term climate and health impacts for a sensitive, pristine region that is warming at 3 times the global rate. Atmospheric modeling is critical for understanding the long-range transport of pollutants to the Arctic, as well as the abundance and distribution of SLCFs throughout the Arctic atmosphere. Modeling is also used as a tool to determine SLCF impacts on climate and health in the present and in future emissions scenarios. In this study, we evaluate 18 state-of-the-art atmospheric and Earth system models by assessing their representation of Arctic and Northern Hemisphere atmospheric SLCF distributions, considering a wide range of different chemical species (methane, tropospheric ozone and its precursors, black carbon, sulfate, organic aerosol, and particulate matter) and multiple observational datasets. Model simulations over 4 years (2008–2009 and 2014–2015) conducted for the 2022 Arctic Monitoring and Assessment Programme (AMAP) SLCF assessment report are thoroughly evaluated against satellite, ground, ship, and aircraft-based observations. The annual means, seasonal cycles, and 3-D distributions of SLCFs were evaluated using several metrics, such as absolute and percent model biases and correlation coefficients. The results show a large range in model performance, with no one particular model or model type performing well for all regions and all SLCF species. The multi-model mean (mmm) was able to represent the general features of SLCFs in the Arctic and had the best overall performance. For the SLCFs with the greatest radiative impact (CH4, O3, BC, and SO42-), the mmm was within ±25 % of the measurements across the Northern Hemisphere. Therefore, we recommend a multi-model ensemble be used for simulating climate and health impacts of SLCFs. Of the SLCFs in our study, model biases were smallest for CH4 and greatest for OA. For most SLCFs, model biases skewed from positive to negative with increasing latitude. Our analysis suggests that vertical mixing, long-range transport, deposition, and wildfires remain highly uncertain processes. These processes need better representation within atmospheric models to improve their simulation of SLCFs in the Arctic environment. As model development proceeds in these areas, we highly recommend that the vertical and 3-D distribution of SLCFs be evaluated, as that information is critical to improving the uncertain processes in models.

Iodine compounds destroy ozone (O3) in the global troposphere and form new aerosols, thereby affecting the global radiative balance. However, few reports have described the latitudinal distribution of atmospheric iodine compounds. This work reports iodine monoxide (IO) measurements taken over unprecedented sampling areas from the Arctic to the Southern Hemisphere and spanning sea surface temperatures (SSTs) of approximately 0 to 31.5 ∘C. The highest IO concentrations were observed over the Western Pacific warm pool (WPWP), where O3 minima were also measured. There, a negative correlation was found between O3 and IO mixing ratios at extremely low O3 concentrations. This correlation is not explained readily by the O3-dependent oceanic fluxes of photolabile inorganic iodine compounds, which is the dominant source in recent global-scale chemistry transport models representing iodine chemistry. Actually, the correlation rather implies that O3-independent pathways can be similarly important in the WPWP. The O3-independent fluxes result in a 15 % greater O3 loss than that estimated for O3-dependent processes alone. The daily O3 loss rate related to iodine over the WPWP is as high as approximately 2 ppbv (parts per billion by volume) despite low O3 concentrations of approximately 10 ppbv, with the loss being up to 100 % greater than that without iodine. This finding suggests that warming SST driven by climate change might affect the marine atmospheric chemical balance through iodine–ozone chemistry.

Combining wideband integrated bioaerosol sensors and DNA-staining techniques, online and offline shipboard observations of fluorescent aerosol particles in the atmosphere were carried out over the central Pacific Ocean during March 2019 to identify bioaerosols and determine their spatiotemporal distribution. To understand the origins of and processes associated with bioaerosols, we conducted correlation analyses of fluorescent particle number concentration, wind speed, and a variety of chemical and biological indicators, including concentrations of chlorophyll a, bacteria, and marine organic gel particles such as transparent exopolymer particles (TEPs) and Coomassie stainable particles (CSPs). Five-day backward trajectory analysis indicated that oceanic air masses were dominant between 6 and 18 March, after which the influence of long-range transport from the continent of Asia was prominent. For the first period, we identified certain types of fluorescent particles as bioaerosols with marine origins, because their number concentrations were highly correlated with concentrations of TEPs and bacteria (R: 0.80–0.92) after considering the wind speed effect. For the second period, there was strong correlation between another type of fluorescent particles and CSPs irrespective of wind speed, implying that the fluorescent particles advected from land were mixed with those of marine origins. From the results of our correlation analysis, we developed equations to derive atmospheric bioaerosol number density in the marine atmosphere over the central Pacific Ocean from a combination of biogenic proxy quantities (chlorophyll a, TEPs, and bacteria) and wind speed. We conclude that it is likely that TEPs were transported from the sea surface to the atmosphere together with bacteria to form fluorescent bioaerosols.

A long-term, robust observational record of atmospheric black carbon (BC) concentrations at Fukue Island for 2009–2019 was produced by unifying the data from a continuous soot monitoring system (COSMOS) and a Multi-Angle Absorption Photometer (MAAP). This record was then used to analyze emission trends from China. We identified a rapid reduction in BC concentrations of (-5.8±1.5) % yr−1 or −48 % from 2010 to 2018. We concluded that an emission change of (-5.3±0.7) % yr−1, related to changes in China of as much as −4.6 % yr−1, was the main underlying driver. This evaluation was made after correcting for the interannual meteorological variability (IAV) by using the regional atmospheric chemistry model simulations from the Weather Research and Forecasting (WRF) and Community Multiscale Air Quality (CMAQ) models (collectively WRF/CMAQ) with the constant emissions. This resolves the current fundamental disagreements about the sign of the BC emissions trend from China over the past decade as assessed from bottom-up emission inventories. Our analysis supports inventories reflecting the governmental clean air actions after 2010 (e.g., MEIC1.3, ECLIPSE versions 5a and 6b, and the Regional Emission inventory in ASia (REAS) version 3.1) and recommends revisions to those that do not (e.g., Community Emissions Data System – CEDS). Our estimated emission trends were fairly uniform across seasons but diverse among air mass origins. Stronger BC reductions, accompanied by a reduction in carbon monoxide (CO) emissions, occurred in regions of south-central East China, while weaker BC reductions occurred in north-central East China and northeastern China. Prior to 2017, the BC and CO emissions trends were both unexpectedly positive in northeastern China during winter months, which possibly influenced the climate at higher latitudes. The pace of the estimated emissions reduction over China surpasses the Shared Socioeconomic Pathways (SSPs with reference to SSP1, specifically) scenarios for 2015–2030, which suggests highly successful emission control policies. At Fukue Island, the BC fraction of fine particulate matter (PM2.5) also steadily decreased over the last decade. This suggests that reductions in BC emissions started without significant delay when compared to other pollutants such as NOx and SO2, which are among the key precursors of scattering PM2.5.

The Arctic environment is undergoing rapid changes such as faster warming than the global average and exceptional melting of glaciers in Greenland. Black carbon (BC) particles, which are a short-lived climate pollutant, are one cause of Arctic warming and glacier melting. However, the sources of BC particles are still uncertain. We simulated the potential emission sensitivity of atmospheric BC present over the Arctic (north of 66∘ N) using the FLEXPART (FLEXible PARTicle) Lagrangian transport model (version 10.1). This version includes a new aerosol wet removal scheme, which better represents particle-scavenging processes than older versions did. Arctic BC at the surface (0–500 m) and high altitudes (4750–5250 m) is sensitive to emissions in high latitude (north of 60∘ N) and mid-latitude (30–60∘ N) regions, respectively. Geospatial sources of Arctic BC were quantified, with a focus on emissions from anthropogenic activities (including domestic biofuel burning) and open biomass burning (including agricultural burning in the open field) in 2010. We found that anthropogenic sources contributed 82 % and 83 % of annual Arctic BC at the surface and high altitudes, respectively. Arctic surface BC comes predominantly from anthropogenic emissions in Russia (56 %), with gas flaring from the Yamalo-Nenets Autonomous Okrug and Komi Republic being the main source (31 % of Arctic surface BC). These results highlight the need for regulations to control BC emissions from gas flaring to mitigate the rapid changes in the Arctic environment. In summer, combined open biomass burning in Siberia, Alaska, and Canada contributes 56 %–85 % (75 % on average) and 40 %–72 % (57 %) of Arctic BC at the surface and high altitudes, respectively. A large fraction (40 %) of BC in the Arctic at high altitudes comes from anthropogenic emissions in East Asia, which suggests that the rapidly growing economies of developing countries could have a non-negligible effect on the Arctic. To our knowledge, this is the first year-round evaluation of Arctic BC sources that has been performed using the new wet deposition scheme in FLEXPART. The study provides a scientific basis for actions to mitigate the rapidly changing Arctic environment.

Constraints from ozone (O3) observations over oceans are needed in addition to those from terrestrial regions to fully understand global tropospheric chemistry and its impact on the climate. Here, we provide a large data set of ozone and carbon monoxide (CO) levels observed (for 11 666 and 10 681 h, respectively) over oceans. The data set is derived from observations made during 24 research cruise legs of R/V Mirai during 2012 to 2017, in the Southern, Indian, Pacific, and Arctic oceans, covering the region from 67∘ S to 75∘ N. The data are suitable for critical evaluation of the over-ocean distribution of ozone derived from global atmospheric chemistry models. We first give an overview of the statistics in the data set and highlight key features in terms of geographical distribution and air mass type. We then use the data set to evaluate ozone mixing ratio fields from the tropospheric chemistry reanalysis version 2 (TCR-2), produced by assimilating a suite of satellite observations of multiple species into a global atmospheric chemistry model, namely CHASER. For long-range transport of polluted air masses from continents to the oceans, during which the effects of forest fires and fossil fuel combustion were recognized, TCR-2 gave an excellent performance in reproducing the observed temporal variations and photochemical buildup of O3 when assessed from ΔO3∕ΔCO ratios. For clean marine conditions with low and stable CO mixing ratios, two focused analyses were performed. The first was in the Arctic (> 70∘ N) in September every year from 2013 to 2016; TCR-2 underpredicted O3 levels by 6.7 ppbv (21 %) on average. The observed vertical profiles from O3 soundings from R/V Mirai during September 2014 had less steep vertical gradients at low altitudes (> 850 hPa) than those obtained by TCR-2. This suggests the possibility of a more efficient descent of the O3-rich air from above than assumed in the models. For TCR-2 (CHASER), dry deposition on the Arctic ocean surface might also have been overestimated. In the second analysis, over the western Pacific equatorial region (125–165∘ E, 10∘ S to 25∘ N), the observed O3 level more frequently decreased to less than 10 ppbv in comparison to that obtained with TCR-2 and also those obtained in most of the Atmospheric Chemistry Climate Model Intercomparison Project (ACCMIP) model runs for the decade from 2000. These results imply loss processes that are unaccounted for in the models. We found that the model's positive bias positively correlated with the daytime residence times of air masses over a particular grid, namely 165–180∘ E and 15–30∘ N; an additional loss rate of 0.25 ppbv h−1 in the grid best explained the gap. Halogen chemistry, which is commonly omitted from currently used models, might be active in this region and could have contributed to additional losses. Our open data set covering wide ocean regions is complementary to the Tropospheric Ozone Assessment Report data set, which basically comprises ground-based observations and enables a fully global study of the behavior of O3.

The emission characteristics of refractory black carbon (rBC) from biomass burning are essential information for numerical simulations of regional pollution and climate effects. We conducted combustion experiments in the laboratory to investigate the emission ratio and mixing state of rBC from the burning of wheat straw and rapeseed plants, which are the main crops cultivated in the Yangtze River Delta region of China. A single particle soot photometer (SP2) was used to measure rBC-containing particles at high temporal resolution and with high accuracy. The combustion state of each burning case was indicated by the modified combustion efficiency (MCE), which is calculated using the integrated enhancement of carbon dioxide and carbon monoxide concentrations relative to their background values. The mass size distribution of the rBC particles showed a lognormal shape with a mode mass equivalent diameter (MED) of 189 nm (ranging from 152 to 215 nm), assuming an rBC density of 1.8 g cm−3. rBC particles less than 80 nm in size (the lower detection limit of the SP2) accounted for ∼ 5 % of the total rBC mass, on average. The emission ratios, which are expressed as ΔrBC ∕ ΔCO (Δ indicates the difference between the observed and background values), displayed a significant positive correlation with the MCE values and varied between 1.8 and 34 ng m−3 ppbv−1. Multi-peak fitting analysis of the delay time (Δt, or the time of occurrence of the scattering peak minus that of the incandescence peak) distribution showed that rBC-containing particles with rBC MED = 200 ± 10 nm displayed two peaks at Δt = 1.7 µs and Δt = 3.2 µs, which could be attributed to the contributions from both flaming and smoldering combustion in each burning case. Both the Δt values and the shell / core ratios of the rBC-containing particles clearly increased as the MCE decreased from 0.98 (smoldering-dominant combustion) to 0.86 (flaming-dominant combustion), implying the great importance of the rapid condensation of semi-volatile organics. This laboratory study found that the mixing state of rBC particles from biomass burning strongly depends on its combustion processes, and overall MCE should be taken carefully into consideration while the climate effect of rBC particles from open biomass burning is simulated.

We implemented a tagged tracer method of black carbon (BC) into a global chemistry transport model, GEOS-Chem, examined the pathways and efficiency of long-range transport from a variety of anthropogenic and biomass burning emission sources to the Arctic, and quantified the source contributions of individual emissions. Firstly, we evaluated the simulated BC by comparing it with observations at the Arctic sites and examined the sensitivity of an aging parameterization and wet scavenging rate by ice clouds. For tagging BC, we added BC tracers distinguished by source types (anthropogenic and biomass burning) and regions; the global domain was divided into 16 and 27 regions for anthropogenic and biomass burning emissions, respectively. Our simulations showed that BC emitted from Europe and Russia was transported to the Arctic mainly in the lower troposphere during winter and spring. In particular, BC transported from Russia was widely spread over the Arctic in winter and spring, leading to a dominant contribution of 62 % to the Arctic BC near the surface as the annual mean. In contrast, BC emitted from East Asia was found to be transported in the middle troposphere into the Arctic mainly over the Sea of Okhotsk and eastern Siberia during winter and spring. We identified an important window area, which allowed a strong incoming of East Asian BC to the Arctic (130–180° E and 3–8 km of altitude at 66° N). The model demonstrated that the contribution from East Asia to the Arctic had a maximum at about 5 km of altitude due to uplifting during long-range transport in early spring. The efficiency of BC transport from East Asia to the Arctic was lower than that from other large source regions such as Europe, Russia, and North America. However, the East Asian contribution was the most important for BC in the middle troposphere (41 %) and the BC burden over the Arctic (27 %) because of the large emissions from this region. These results suggested that the main sources of Arctic BC differed with altitude. The contribution of all the anthropogenic sources to Arctic BC concentrations near the surface was dominant (90 %) on an annual basis. The contributions of biomass burning in boreal regions (Siberia, Alaska, and Canada) to the annual total BC deposition onto the Arctic were estimated to be 12–15 %, which became the maximum during summer.

Ground-based measurements of black carbon (BC) were performed near an industrial source region in the early summer of 2014 and at a remote island in Japan in the spring of 2015. Here, we report the temporal variations in the transport, size distributions, and mixing states of the BC-containing particles. These particles were characterized using a continuous soot monitoring system, a single particle soot photometer, and an aerosol chemical speciation monitor. The effects of aging on the growth of BC-containing particles were examined by comparing the ground-based observations between the near-source and remote island sites. Secondary formation of sulfate and organic aerosols strongly affected the increases in BC coating (i.e., enhancement of cloud condensation nuclei activity) with air mass aging from the source to the outflow regions. The effects of wet removal on BC microphysics were elucidated by classifying the continental outflow air masses depending on the enhancement ratios of BC to CO (ΔBC ∕ ΔCO), which were used as an indicator of the transport efficiency of BC. It was found that ΔBC ∕ ΔCO ratios were controlled mainly by the wet removal during transport in the planetary boundary layer (PBL) on the timescale of 1–2 days. The meteorological conditions and backward trajectory analyses suggested that air masses strongly affected by wet removal originated mainly from a region in southern China (20–35° N) in the spring of 2015. Removal of large and thickly coated BC-containing particles was detected in the air masses that were substantially affected by the wet removal in the PBL, as predicted by Köhler theory. The size and water solubility of BC-containing particles in the PBL can be altered by the wet removal as well as the condensation of non-BC materials.

Long-term (2009–2015) observations of atmospheric black carbon (BC) mass concentrations were performed using a continuous soot-monitoring system (COSMOS) at Fukue Island, western Japan, to provide information on wet removal rate constraints and the emission strengths of important source regions in East Asia (China and others). The annual average mass concentration was 0.36 µg m−3, with distinct seasonality; high concentrations were recorded during autumn, winter, and spring and were caused by Asian continental outflows, which reached Fukue Island in 6–46 h. The observed data were categorized into two classes, i.e., with and without a wet removal effect, using the accumulated precipitation along a backward trajectory (APT) for the last 3 days as an index. Statistical analysis of the observed ΔBC ∕ ΔCO ratios was performed to obtain information on the emission ratios (from data with zero APT only) and wet removal rates (including data with nonzero APTs). The estimated emission ratios (5.2–6.9 ng m−3 ppb−1) varied over the six air mass origin areas; the higher ratios for south-central East China (30–35° N) than for north-central East China (35–40° N) indicated the relative importance of domestic emissions and/or biomass burning sectors. The significantly higher BC ∕ CO emission ratios adopted in the bottom-up Regional Emission inventory in Asia (REAS) version 2 (8.3–23 ng m−3 ppb−1) over central East China and Korea needed to be reduced at least by factors of 1.3 and 2.8 for central East China and Korea, respectively, but the ratio for Japan was reasonable. The wintertime enhancement of the BC emission from China, predicted by REAS2, was verified for air masses from south-central East China but not for those from north-central East China. Wet removal of BC was clearly identified as a decrease in the ΔBC ∕ ΔCO ratio against APT. The transport efficiency (TE), defined as the ratio of the ΔBC ∕ ΔCO ratio with precipitation to that without precipitation, was fitted reasonably well by a stretched exponential decay curve against APT; a single set of fitting parameters was sufficient to represent the results for air masses originating from different areas. An accumulated precipitation of 25.5 ± 6.1 mm reduced the TE to 1∕e. BC-containing particles traveling to Fukue must have already been converted from hydrophobic to hydrophilic particles, because the behavior of TE against APT was similar to that of PM2.5, the major components of which are hydrophilic. Wet loss of BC greatly influenced interannual variations in the ΔBC ∕ ΔCO ratios and BC mass concentrations. This long-term data set will provide a benchmark for testing chemical transport/climate model simulations covering East Asia.

The coating of black carbon (BC) with inorganic salts and organic compounds can enhance the magnitude of light absorption by BC. To elucidate the enhancement of light absorption of aged BC particles and its relation to the mixing state and morphology of individual particles, we conducted observations of particles at an Asian outflow site in Noto Peninsula, Japan, in the spring of 2013. Absorption and scattering coefficients at 405, 532, and 781 nm and mass concentrations/mixing states of refractory BC in PM2.5 were measured using a three-wavelength photoacoustic soot spectrometer and a single-particle soot photometer (SP2), respectively, after passage through a thermodenuder (TD) maintained at 300 or 400 °C or a bypass line maintained at room temperature (25 °C). The average enhancement factor of BC light absorption due to coating was estimated by comparing absorption coefficients at 781 nm for particles that with and without passing through the TD at 300 °C and was found to be 1.22. The largest enhancements (> 1.30) were observed under high absorption coefficient periods when the air mass was long-range transported from urban areas in China. Aerosol samples were also analyzed using a transmission electron microscope (TEM) equipped with an energy dispersive X-ray analyzer. The morphological features and mixing states of soot-containing particles of four samples collected during the high absorption events were analyzed by comparing microphotographs before and after the evaporation of beam-sensitive materials by irradiation with a high-density electron beam. The majority of the soot in all samples was found as mixed particles with sulfate-containing spherules or as clusters of such spherules. For samples showing high enhancement (> 1.30) of BC light absorption, the TEM showed that the internally mixed soot-containing particles tended to have a more spherical shape and to be thickly coated. The SP2 measurements also suggested that the proportion of thickly coated soot was greater. Thus, the observed enhancement of BC light absorption was found to differ according to the mixing states and morphology of soot-containing particles. The enhancement of BC light absorption in our in situ measurements and its relation with individual features of soot-containing particles will be useful to evaluate direct radiative forcing in the downwind areas of large emission sources of BC.

We conducted an intensive field campaign at the summit of Mt. Tai (36.26° N, 117.11° E, 1534 m above sea level), Shandong Province, located at the center of central East China, during the period 28 May to 30 June 2006, to study seasonal maxima of regional air pollution with respect to ozone (O3) and aerosols. The specific objectives, campaign design, and major findings are summarized. High concentrations of O3 and its precursors, and aerosols, were detected and studied in the context of annual variations. Most importantly, we identified that emissions from regional-scale open crop residue burning after the harvesting of winter wheat, together with photochemical aging, strongly increased the concentrations of O3, aerosols, and primary pollutants in this month of year. Studies of in situ photochemical activity, regional source attribution of O3, O3–aerosol interactions, validation of satellite observations of tropospheric NO2, behaviors of volatile organic compounds and organic/inorganic aerosol species, loss rates of black carbon (BC), and instrument inter-comparisons are also summarized. The observed BC levels must have a strong impact on the regional climate.

HO2 uptake coefficients for ambient aerosol particles, collected on quartz fiber filter using a high-volume air sampler in China, were measured using an aerosol flow tube coupled with a chemical conversion/laser-induced fluorescence technique at 760 Torr and 298 K, with a relative humidity of 75%. Aerosol particles were regenerated with an atomizer using the water extracts from the aerosol particles. Over 10 samples, the measured HO2 uptake coefficients for the aerosol particles at the Mt. Tai site were ranged from 0.13 to 0.34, while those at the Mt. Mang site were in the range of 0.09–0.40. These values are generally larger than those previously reported for single-component particles, suggesting that reactions with the minor components such as metal ions and organics in the particle could contribute to the HO2 uptake. A box model calculation suggested that the heterogeneous loss of HO2 by ambient particles could significantly affect atmospheric HOx concentrations and chemistry.

An observation-based box model approach was undertaken to estimate concentrations of OH, HO2, and RO2 radicals and the net photochemical production rate of ozone at the top of Mount Tai, located in the middle of Central East China, in June 2006. The model calculation was constrained by the measurements of O3, H2O, CO, NO, NO2, hydrocarbon, HCHO, and CH3CHO concentrations, and temperature and J values. The net production rate of ozone was estimated to be 6.4 ppb h−1 as a 6-h average (09:00–15:00 CST), suggesting 58±37 ppb of ozone is produced in one day. Thus the daytime buildup of ozone recorded at the mountain top as ~23 ppb on average is likely affected by in situ photochemistry as well as by the upward transport of polluted air mass in the daytime. On days with high ozone concentrations (hourly values exceeding 100 ppb at least once), in situ photochemistry was more active than it was on low ozone days, suggesting that in situ photochemistry is an important factor controlling ozone concentrations. Sensitivity model runs for which different NOx and hydrocarbon concentrations were assumed suggested that the ozone production occurred normally under NOx-limited conditions, with some exceptional periods (under volatile-organic-compound-limited conditions) in which there was fresh pollution. We also examined the possible influence of the heterogeneous loss of gaseous HO2 radicals in contact with aerosol particle surfaces on the rate and regimes of ozone production.

The formation of formaldehyde via hydrogen atom transfer from the methoxy radical to molecular oxygen is a key step in the atmospheric photochemical oxidation of methane, and in the propagation of deuterium from methane to molecular hydrogen. We report the results of the first investigation of the branching ratio for HCHO and HCDO formation in the CH2DO + O2 reaction. Labeled methoxy radicals (CH2DO) were generated in a photochemical reactor by photolysis of CH2DONO. HCHO and HCDO concentrations were measured using FTIR spectroscopy. Significant deuterium enrichment was seen in the formaldehyde product, from which we derive a branching ratio of 88.2±1.1% for HCDO and 11.8±1.1% for HCHO. The implications of this fractionation on the propagation of deuterium in the atmosphere are discussed.