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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.

Nitrous acid (HONO) is an important atmospheric gas given its contribution to the cycles of NOx and HOx, but its role in global atmospheric photochemistry is not fully understood. This study implemented three pathways of HONO formation in the chemistry–climate model CHASER (MIROC-ESM) to explore three physical phenomena: gas-phase kinetic reactions (GRs), direct emission (EM), and heterogeneous reactions on cloud and aerosol particles (HRs). We evaluated the simulations by the atmospheric aircraft-based measurements from EMeRGe-Asia-2018 (Effect of Megacities on the Transport and Transformation of Pollutants on the Regional to Global Scales), ATom-1 (atmospheric tomography), observations from the ship R/V Mirai, EANET (Acid Deposition Monitoring Network in eastern Asia)/EMEP (European Monitoring and Evaluation Programme) ground-based stationary observations, and the OMI (Ozone Monitoring Instrument). We showed that the inclusion of the HONO chemistry in the modelling process reduced the model bias against the measurements for PM2.5, NO3-/HNO3, NO2, OH, HO2, O3, and CO, especially in the lower troposphere and the North Pacific (NP) region. We found that the retrieved global abundance of tropospheric HONO was 1.4 TgN. Of the three source pathways, HRs and EM contributed 63 % and 26 % to the net HONO production, respectively. We also observed that reactions on the aerosol surfaces contributed larger amounts of HONO (51 %) than those on the cloud surfaces (12 %). The model exhibited significant negative biases for daytime HONO in the Asian off-the-coast region, compared with the airborne measurements by EMeRGe-Asia-2018, indicating the existence of unknown daytime HONO sources. Strengthening of aerosol uptake of NO2 near the surface and in the middle troposphere, cloud uptake, and direct HONO emission were all potential yet-unknown HONO sources. The most promising daytime source for HONO found in this study was the combination of enhanced aerosol uptake of NO2 and surface-catalysed HNO3 photolysis (maxST+JANO3-B case), which could also remedy the model bias for NO2 and O3 during EMeRGe. We also found that the simulated HONO abundance and its impact on NOx–O3 chemistry were sensitive to the yield of the heterogeneous conversion of NO2 to HONO (vs. HNO3). Inclusion of HONO reduced global tropospheric NOx (NO + NO2) levels by 20.4 %, thereby weakening the tropospheric oxidizing capacity (OH, O3) occurring for NOx-deficit environments (remote regions and upper altitudes), which in turn increased CH4 lifetime (13 %) and tropospheric CO abundance (8 %). The calculated reduction effect on the global ozone level reduced the model overestimates for tropospheric column ozone against OMI spaceborne observations for a large portion of the North Hemisphere. HRs on the surfaces of cloud particles, which have been neglected in previous modelling studies, were the main drivers of these impacts. This effect was particularly salient for the substantial reductions of levels of OH (40 %–67 %) and O3 (30 %–45 %) in the NP region during summer, given the significant reduction of the NOx level (50 %–95 %). In contrast, HRs on aerosol surfaces in China (Beijing) enhanced OH and O3 winter mean levels by 600 %–1700 % and 10 %–33 %, respectively, with regards to their minima in winter. Furthermore, sensitivity simulations revealed that the heterogeneous formation of HONO from NO2 and heterogenous photolysis of HNO3 coincided in the real atmosphere. Nevertheless, the global effects calculated in the combined case (enhancing aerosol uptakes of NO2 and implementing heterogeneous photolysis of HNO3), which most captured the measured daytime HONO level, still reduced the global tropospheric oxidizing capacity. Overall, our findings suggest that a global model that does not consider HONO heterogeneous mechanisms (especially photochemical heterogeneous formations) may erroneously predict the effect of HONO in remote areas and polluted regions.

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 cloud particle sensor (CPS) sonde is an observing system attached with a radiosonde sensor to observe the vertical structure of cloud properties. The signals obtained from CPS sondes are related to the phase, size, and number of cloud particles. The system offers economic advantages including human resource and simple operation costs compared with aircraft measurements and land-/satellite-based remote sensing. However, the observed information should be appropriately corrected because of several uncertainties. Here we made field experiments in the Arctic region by launching approximately 40 CPS sondes between 2018 and 2020. Using these data sets, a better practical correction method was proposed to exclude unreliable data, estimate the effective cloud water droplet radius, and determine a correction factor for the total cloud particle count. We apply this method to data obtained in October 2019 over the Arctic Ocean and March 2020 at Ny-Ålesund, Svalbard, Norway, to compare with a particle counter aboard a tethered balloon and liquid water content retrieved by a microwave radiometer. The estimated total particle count and liquid water content from the CPS sondes generally agree with those data. Although further development and validation of CPS sondes based on dedicated laboratory experiments would be required, the practical correction approach proposed here would offer better advantages in retrieving quantitative information on the vertical distribution of cloud microphysics under the condition of a lower number concentration.

This study uses a chemistry–climate model CHASER (MIROC) to explore the roles of heterogeneous reactions (HRs) in global tropospheric chemistry. Three distinct HRs of N2O5, HO2, and RO2 are considered for surfaces of aerosols and cloud particles. The model simulation is verified with EANET and EMEP stationary observations; R/V Mirai ship-based data; ATom1 aircraft measurements; satellite observations by OMI, ISCCP, and CALIPSO-GOCCP; and reanalysis data JRA55. The heterogeneous chemistry facilitates improvement of model performance with respect to observations for NO2, OH, CO, and O3, especially in the lower troposphere. The calculated effects of heterogeneous reactions cause marked changes in global abundances of O3 (−2.96 %), NOx (−2.19 %), CO (+3.28 %), and global mean CH4 lifetime (+5.91 %). These global effects were contributed mostly by N2O5 uptake onto aerosols in the middle troposphere. At the surface, HO2 uptake gives the largest contributions, with a particularly significant effect in the North Pacific region (−24 % O3, +68 % NOx, +8 % CO, and −70 % OH), mainly attributable to its uptake onto clouds. The RO2 reaction has a small contribution, but its global mean negative effects on O3 and CO are not negligible. In general, the uptakes onto ice crystals and cloud droplets that occur mainly by HO2 and RO2 radicals cause smaller global effects than the aerosol-uptake effects by N2O5 radicals (+1.34 % CH4 lifetime, +1.71 % NOx, −0.56 % O3, +0.63 % CO abundances). Nonlinear responses of tropospheric O3, NOx, and OH to the N2O5 and HO2 uptakes are found in the same modeling framework of this study (R>0.93). Although all HRs showed negative tendencies for OH and O3 levels, the effects of HR(HO2) on the tropospheric abundance of O3 showed a small increment with an increasing loss rate. However, this positive tendency turns to reduction at higher rates (>5 times). Our results demonstrate that the HRs affect not only polluted areas but also remote areas such as the mid-latitude sea boundary layer and upper troposphere. Furthermore, HR(HO2) can bring challenges to pollution reduction efforts because it causes opposite effects between NOx (increase) and surface O3 (decrease).

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.

Iron availability limits marine ecosystem activities in large areas of the ocean. However, the sources and seasonal supply of iron, critically important for controlling surface ocean biogeochemistry and carbon cycling, are poorly understood. The western subarctic Pacific is a high-nutrient and low-chlorophyll region, and despite high concentrations of macronutrients, iron limits phytoplankton production in summer. Here, we determine the seasonal deposition flux of Asian dust using scanning electron microscope-cathodoluminescence analysis of single quartz particles derived from the western subarctic Pacific during 2003-2022 to trace provenance. We found a high (up to 6.9 mg m -2  day -1 ) deposition flux of Asian dust in May, June, and early July, with an annual average of 1.0 ± 0.2 mg m -2  day -1 . The supply of dissolved-iron flux calculated from Asian dust was 0.9 ± 0.3 µg m -2  day -1 during the high productivity season (April-July), which is approximately half that from the deeper part of the ocean, calculated from vertical profiles of dissolved iron. Our study provides a reliable approach for estimating iron supply from dust to the surface ocean that may be critical for sustaining biological productivity under future ocean stratification, which suppresses nutrient supply from the subsurface ocean., (© 2023. Springer Nature Limited.)

We conducted ship-based measurements of marine aerosol particles (number concentration, size distribution, black carbon (BC), autofluorescence property, and PM 2.5 composition) and trace gases (ozone (O 3 ) and carbon monoxide (CO)) during a cruise of the R/V Mirai (23 August to 4 October 2016) over the Arctic Ocean, Northwest Pacific Ocean, and Bering Sea. Over the Arctic Ocean at latitudes >70°N, the averaged BC mass concentration was 0.7 ± 1.8 ng/m 3 , confirming the validity of our previously-reported observations (~1 ng/m 3 ) over the same region during September 2014 and September 2015. The observed levels over the Arctic Ocean need to be used as a benchmark when testing the atmospheric transport models over the ocean, while they are substantially lower than those reported at Barrow (Utqiaġvik), a nearby ground-based station. We identified events with elevated BC mass concentrations and CO mixing ratios over the Arctic Ocean and Bering Sea as influenced by biomass burnings, with evidences from elevated levoglucosan levels, mixing states of BC particles, and particle size distributions. With WRF-Chem model simulations, we confirmed Siberian Forest fire plumes traveled over thousands of kilometers and produced substantially high BC and CO levels over the Bering Sea. The ΔBC/ΔCO ratios during these periods were estimated as ~1 ng/m 3 /ppbv, which are lower than those values reported, indicating that the results might have been affected by the wet removal process during transportation and/or by emission in smoldering conditions., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 Elsevier B.V. All rights reserved.)

Emissions of black carbon (BC) particles from anthropogenic and natural sources contribute to climate change and human health impacts. Therefore, they need to be accurately quantified to develop an effective mitigation strategy. Although the spread of the emission flux estimates for China have recently narrowed under the constraints of atmospheric observations, consensus has not been reached regarding the dominant emission sector. Here, we quantified the contribution of the residential sector, as 64% (44-82%) in 2019, using the response of the observed atmospheric concentration in the outflowing air during Feb-Mar 2020, with the prevalence of the COVID-19 pandemic and restricted human activities over China. In detail, the BC emission fluxes, estimated after removing effects from meteorological variability, dropped only slightly (- 18%) during Feb-Mar 2020 from the levels in the previous year for selected air masses of Chinese origin, suggesting the contributions from the transport and industry sectors (36%) were smaller than the rest from the residential sector (64%). Carbon monoxide (CO) behaved differently, with larger emission reductions (- 35%) in the period Feb-Mar 2020, suggesting dominance of non-residential (i.e., transport and industry) sectors, which contributed 70% (48-100%) emission during 2019. The estimated BC/CO emission ratio for these sectors will help to further constrain bottom-up emission inventories. We comprehensively provide a clear scientific evidence supporting mitigation policies targeting reduction in residential BC emissions from China by demonstrating the economic feasibility using marginal abatement cost curves., (© 2021. The Author(s).)

Brown carbon (BrC) aerosols have important warming effects on Earth's radiative forcing. However, information on the evolution of the light-absorption properties of BrC aerosols in the Asian outflow region is limited. In this study, we evaluated the light-absorption properties of BrC using in-situ filter measurements and sky radiometer observations of the ground-based remote sensing network SKYradiometer NETwork (SKYNET) made on Fukue Island, western Japan in 2018. The light-absorption coefficient of BrC obtained from filter measurements had a temporal trend similar to that of the ambient concentration of black carbon (BC), indicating that BrC and BC have common combustion sources. The absorption Angstrom exponent in the wavelength range of 340-870 nm derived from the SKYNET observations was 15% higher in spring (1.81 ± 0.30) than through the whole year (1.53 ± 0.50), suggesting that the Asian outflow carries light-absorbing aerosols to Fukue Island and the western North Pacific. After eliminating the contributions of BC, the absorption Angstrom exponent of BrC alone obtained from filter observations had a positive Spearman correlation (r s = 0.77, p < 0.1) with that derived from SKYNET observations but 33% higher values, indicating that the light-absorption properties of BrC were successfully captured using the two methods. Using the atmospheric transport model FLEXPART and fire hotspots obtained from the Visible Infrared Imaging Radiometer Suite product, we identified a high-BrC event related to an air mass originating from regions with consistent fossil fuel combustion and sporadic open biomass burning in central East China. The results of the study may help to clarify the dynamics and climatic effects of BrC aerosols in East Asia., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2021 Elsevier B.V. All rights reserved.)

The contribution of the atmospheric deposition of inorganic nitrogen compounds produced in East Asia to the marine ecosystems of the North Western Pacific Ocean (NWPO) was investigated in this study using a 3-D lower trophic-marine ecosystem model (NEMURO) combined with an atmospheric regional chemical transport model (WRF-CMAQ). The monthly mean values for the wet and dry deposition of nitrogen compounds, including gases (HNO 3 and NH 3 ) and aerosol particles (NO 3 - and NH 4 + ), were determined using the WRF-CMAQ for the NWPO from 2009-2016. These values were input into the NEMURO as an additional nitrogen source. The NEMURO indicated that the annual average chlorophyll mass concentration at the surface in the subtropical region (20°N-30°N; 125°E-150°E) of the NWPO increased from 0.04 to 0.10 mg/m 3 . Similarly, the gross primary productivity, integrated over sea depths of 0-200 m, increased from 85 to 147 mg C/m 2 /day because of this deposition. This study indicates that the supply of atmospheric inorganic nitrogen compounds from East Asia to the NWPO could have a high nutrient impact on the marine ecosystem in the subtropical region.

Unlabelled: The authors analyze the sensitivities of source regions in East Asia to PM2.5 (particulate matter with an aerodynamic diameter of < or = 2.5 microm) concentration at Fukue Island located in the western part of Japan by using a regional chemical transport model with emission sensitivity simulations for the year 2010. The temporal variations in PM2.5 concentration are generally reproduced, but the absolute concentration is underestimated by the model. Chemical composition of PM2.5 in the model is compared with filter sampling data in spring; simulated sulfate, ammonium, and elemental carbon are consistent with observations, but mass concentration of particulate organic matters is underestimated. The relative contribution from each source region shows the seasonal variation, especially in summer. The contribution from central north China (105 degrees E-124 degrees E, 34 degrees N-42 degrees N) accounts for 50-60% of PM2.5 at Fukue Island except in summer; it significantly decreases in summer (18%). Central south China (105 degrees E-123 degrees E, 26 degrees N-34 degrees N) has the relative contribution of 15-30%. The contribution from the Korean Peninsula is estimated at about 10% except in summer. The domestic contribution accounts for about 7% in spring and autumn and increases to 19% in summer. We also estimate the relative contribution to daily average concentration in high PM2.5 days (> 35 microg m(-3)). Central north China has a significant contribution of 60-70% except in summer. The relative contribution from central south China is estimated at 46% in summer and about 30% in the other seasons. The contributions from central north and south China on high PM2.5 days are generally larger than those of their seasonal mean contributions. The domestic contribution is smaller than the seasonal mean value in every season; it is less than 10% even in summer. These model results suggest that foreign anthropogenic sources have a substantial impact on attainment of the atmospheric environmental standard of Japan at Fukue Island., Implications: The contribution from several source regions in East Asia to PM2.5 concentration at Fukue Island, a remote island located in the western part of Japan and close to the Asian continent, is estimated using a three-dimensional chemical transport model. The model results suggest that PM2.5 that is attributed to foreign anthropogenic sources have a larger contribution than that of domestic pollution and have a substantial impact on attainment of the atmospheric environmental standard of Japan at Fukue Island.

Carbon monoxide (CO) is of great interest as a restriction factor for pollutants related to incomplete combustions. This study attempted to evaluate CO emission in East China using the analytical Bayesian inverse method and observations at Mount Hua in springtime. The mixing ratio of CO at the receptor was calculated using 5-day source-receptor relationship (SRR) simulated by a Lagrangian Particle Dispersion Model (FLEXPART) and CO emission flux. The stability of the inversion solution was evaluated on the basis of repeated random sampling simulations. The inversion results demonstrated that there were two city cluster regions (the Beijing-Tianjin-Hebei region and the low reaches of the Yangtze River Delta) where the difference between a priori (Intercontinental Chemical Transport Experiment-Phase B, INTEX-B) and a posteriori was statistically significant and the a priori might underestimate the CO emission flux by 37 %. A correction factor (a posteriori/a priori) of 1.26 was suggested for CO emission in China in spring. The spatial distribution and magnitude of the CO emission flux were comparable to the latest regional emission inventory in Asia (REAS2.0). Nevertheless, further evaluation is still necessary in view of the larger uncertainties for both the analytical inversion and the bottom-up statistical approaches.

Purpose: To determine the amplitude of pseudoaccommodation and higher-order aberrations with three types of implanted monofocal intraocular lenses (IOLs): aspheric yellow (IQ); spheric yellow (NT); and spheric clear (AT)., Setting: Department of Ophthalmology, Nara Medical University, Nara, Japan., Methods: We studied 60 patients who underwent small incision phacoemulsification with the implantation of a monofocal IQ, NT, or AT IOL. The pseudoaccommodation was measured by the lens-loading method, and the postoperative ocular higher-order aberrations were measured with a Hartmann-Shack wavefront analyzer through natural and 4 mm pupils., Results: Sixty eyes of 60 patients were studied. The average amplitude of the pseudoaccommodation was 0.45±0.24 D with the IQ IOL, which was significantly lower than that with the AT IOL at 0.81±0.37 D (Tukey's test; P<0.01). The differences in the amplitude of the pseudoaccommodation between the IQ and the NT IOLs, and between the NT and the AT IOLs were not significant (Tukey's test; P>0.05). The degree of spherical aberration was significantly different for the IQ, NT, and AT lenses (analysis of variance, P=0.016). The spherical aberration through the IQ IOL was significantly lower than that through the NT and the AT IOLs (Tukey's test; P<0.01). The fourth-order RMS (root mean square) aberration of the IQ lens was also significantly lower than that of the NT and AT IOLs (Tukey's test; P<0.01)., Conclusion: Our results suggest that the spherical aberration and selective spectral transmission of IOLs may work together to increase the amplitude of the pseudoaccommodation.

Purpose: To evaluate the spherical aberration in aspheric intraocular lenses (IOLs) using a model eye., Setting: Nara Medical University, Nara, Japan., Design: Experimental study., Methods: This study tested 20.00 diopter (D) and 10.00 to 30.00 D aspheric IOLs in a fluid-filled model constructed to replicate the optical condition of a pseudophakic human eye. Spherical aberration was measured by Hartmann-Shack aberrometry. The 3 IOLs tested were the Acryfold AC60AD (IOL AC), Acrysof IQ SN60WF (IOL IQ), and Tecnis ZA9003 (IOL ZA). The 1-sample t test and Pearson correlation analysis were used for statistical evaluation., Results: The measured spherical aberration in the 20.00 D IOL AC was statistically significantly less than the manufacturer-indicated value (P=.0020); there was no significant difference for the 20.00 D IOL IQ and IOL ZA. The correlation between IOL power and spherical aberration was significant for IOL AC with a 4.0 mm aperture (P=.0007, r = -0.646) and 6.0 mm aperture (P<.0001, r=-0.684), IOL IQ with a 4.0 mm aperture (P=.040, r=-0.390) but not with a 6.0 mm aperture (P=.929), and IOL ZA with a 4.0 mm aperture (P<.0001, r=-0.696) and 6.0 mm aperture (P=.011, r=-0.470)., Conclusions: Negative correlations were found between IOL power and spherical aberration for 3 aspheric IOL models, particularly for IOL AC and IOL ZA. In a clinical setting, aspheric IOL implantation may result in negative spherical aberration that could exceed the manufacturer-indicated value., (Copyright © 2011 ASCRS and ESCRS. Published by Elsevier Inc. All rights reserved.)

We report on the development of a low-cost and compact instrument for quantifying atmospheric NO(2) concentrations by detecting NO(2) fluorescence using a commercial light-emitting diode around 435 nm as a fluorescence excitation light source. The minimum detectable limit of the NO(2) instrument developed has been estimated to be 9.8 parts per billion of volume mixing ratio (ppbv) in a 60 s integration time and with a signal-to-noise ratio of 2.

Purpose: We investigated the long-term clinical effects of a nipradilol ophthalmic solution on normal-tension glaucoma., Methods: Among normal tension glaucoma patients who consulted the Nara Medical University Hospital or 2 affiliated hospitals between November 2001 and August 2002, we prospectively examined intraocular pressure-decreasing effects, the deterioration of visual field defects, and the appearance of side effects in 46 patients who underwent single therapy with a nipradilol ophthalmic solution. We evaluated intraocular pressure at 6-month intervals. The deterioration of visual field defects was assessed based on a 3-dB or more decrease in the mean deviation measured using the Humphrey Field Analyzer 30-2 program., Results: The 60 months intraocular pressure value after administration of nipradilol ophthalmic solution was significantly lower than the pretreatment value. The deterioration of visual field defects was examined using the Kaplan-Meier life table. The survival rate after 60 months was 82.4%. In 4 of the 46 patients, administration of the nipradilol ophthalmic solution was discontinued due to side effects., Conclusion: Long-term therapy with a nipradilol ophthalmic solution may be useful for treating normal-tension glaucoma.

Objectives: We investigated whether visual field defects can be objectively evaluated using multifocal visual evoked potentials (mfVEPs) in patients with intracranial disease complicated by mental disorders., Patients and Methods: First, to determine the normal pattern of mfVEPs, recordings were performed using a VERIS Junior Science recording apparatus (Mayo, Aichi, Japan) in 40 healthy subjects. Responses from 8 sites in each subject were divided into 4 quadrants (superior and inferior temporal quadrants and superior and inferior nasal quadrants). In each quadrant, two response waves were grouped and averaged, and the peak latency and amplitude were used for assessment. mfVEP recordings were also performed in 3 patients with intracranial disease complicated by mental disorders, in whom dynamic or static perimetry was impossible, or in whom reliable data could not be obtained, and quadrants showing abnormalities were compared with the sites of intracranial lesions observed by imaging techniques., Results: In the 40 normal subjects, no significant differences were observed in the peak latency among the 4 quadrants, but the amplitude was significantly higher in the inferior than in the superior semi-field. mfVEPs in the 3 patients revealed abnormal waves, which corresponded to the lesions observed by imaging techniques., Conclusion: The objective evaluation of visual field defects using mfVEPs may be useful in patients with intracranial disease complicated by mental disorders, in whom kinetic/static perimetry as a subjective examination is difficult.

We examined the reliability of multifocal visual evoked potentials for evaluating visual-field defects in a child with epilepsy and an arachnoid cyst. Multifocal visual evoked potentials were measured both when perimetry was difficult and several years later, when kinetic perimetry became possible in a child with epilepsy and homonymous hemianopia, as suggested by computed tomography of the brain. The peak latency and amplitude of response waves were used for assessment. The recordings of multifocal visual evoked potentials at both times revealed marked decreases in amplitude in the left visual hemifield. This area of decreased amplitude corresponded to the location of the lesion observed with imaging techniques, and was consistent with the left homonymous hemianopia observed via kinetic perimetry. The objective evaluation of visual-field defects through multifocal visual evoked potentials may be useful in children in whom conventional perimetry is difficult.

The HO2 uptake coefficient (gamma) for inorganic submicrometer wet and dry aerosol particles ((NH4)2SO4 and NaCl) under ambient conditions (760 Torr and 296 +/- 2 K) was measured using an aerosol flow tube (AFT) coupled with a chemical conversion/laser-induced fluorescence (CC/LIF) technique. The CC/LIF technique enabled experiments to be performed at almost the same HO2 radical concentration as that in the atmosphere. HO2 radicals were injected into the AFT through a vertically movable Pyrex tube. Injector position-dependent profiles of LIF intensity were measured as a function of aerosol concentration. Measured gamma values for dry aerosols of (NH4)2SO4 were 0.04 +/- 0.02 and 0.05 +/- 0.02 at 20% and 45% relative humidity (RH), respectively, while those of NaCl were <0.01 and 0.02 +/- 0.01 at 20% and 53% RH, respectively. For wet (NH4)2SO4 aerosols, measured gamma values were 0.11 +/- 0.03, 0.15 +/- 0.03, 0.17 +/- 0.04, and 0.19 +/- 0.04, at 45%, 55%, 65%, and 75% RH, respectively, whereas for wet NaCl aerosols the values were 0.11 +/- 0.03, 0.09 +/- 0.02, and 0.10 +/- 0.02 for 53%, 63%, and 75% RH, respectively. Wet (NH4)2SO4 and NaCl aerosols doped with CuSO4 showed gamma values of 0.53 +/- 0.12 and 0.65 +/- 0.17, respectively. These results suggest that compositions, RH, and phase for aerosol particles are significant to HO2 uptake. Potential HO2 loss processes and their atmospheric contributions are discussed.

We report on the development of a highly sensitive detection system for measuring atmospheric NO(2) by means of a laser-induced fluorescence (LIF) technique at 473 nm using a diode-pumped Nd:YAG laser. A GaN-based laser diode emitting at 410 nm is also used as an alternative fluorescence-excitation source. For laboratory calibrations, standard NO(2) gas is diluted with synthetic air and is introduced into a fluorescence-detection cell. The NO(2) LIF signal is detected by a photomultiplier tube and processed by a photon-counting method. The minimum detectable limits of the NO(2) instrument developed have been estimated to be 0.14 ppbv and 0.39 ppbv (parts per billion, 10(-9), by volume) in 60 s integration time (signal-to-noise ratio of 2) for 473 and 410 nm excitation systems, respectively. Practical performance of the instrument has been demonstrated by the 24 hour continuous measurements of ambient NO(2) in a suburban area.

Purpose: To evaluate the effect of cataract density on the postoperative refractive outcome., Methods: For 59 nuclear cataract eyes, the axial length was preoperatively measured by the IOL Master (Zeiss, Germany) and ultrasound (US; UD-6000, Tomey, Japan) and the cataract density by EAS-1000 (Nidek, Japan). The prediction error was used as evaluation of the accuracy of ocular biometry., Results: There were significant differences between IOL Master and US in the mean error (0.24 +/- 0.63 vs. 0.69 +/- 0.64 dpt, p < 0.001) and the mean absolute error (0.57 +/- 0.36 vs. 0.79 +/- 0.53 dpt, p < 0.001). The cataract density was significantly correlated with the prediction error with IOL Master (r = 0.24, p = 0.03) and US (r = 0.29, p = 0.01)., Conclusions: Measurements with the IOL Master are slightly affected by the cataract density due to the refractive index change, but its accuracy is less affected than US., ((c) 2007 S. Karger AG, Basel.)

Objective: This study was conducted to assess dynamic visual acuity (DVA) under pupil dilation., Background: Pupil dilation may negatively affect driving performance., Methods: Thirty healthy young adults (mean age 29.4 years) with pupil dilation participated in this study as the Mydrin P group. In addition to them, 15 healthy young adults (mean age 28.5 years) without pupil dilation were enrolled as the control group. DVA was measured binocularly with free-head viewing at 0, 30, 60, 120, and 360 min after mydriatic drop instillation in both eyes. Pupil size was measured at each time., Results: In the Mydrin P group, DVA significantly improved at 30, 60, and 120 min (ANOVA; p < .01) but returned to the predilation level at 360 min (ANOVA; p = .61). Pupil size changed from 4.1 to 7.8 mm (ANOVA; p < .01) at 30 min after the instillation, and this level was maintained up to 120 min but returned to normal within 360 min. In the control group, DVA did not significantly change at all measured times (ANOVA; p > .9). DVA was significantly (p < .05) correlated with the pupil size at all measured times., Conclusion: The improvement in DVA was related to the enlargement of the pupil. This study suggests that the pupil size is one factor that may affect DVA., Application: Potential applications of this study include useful information to assess the effect of pupil dilation on driving performance.

Purpose: To analyze the effect of total higher-order aberrations (HOAs) on the range of accommodation in pseudophakic eyes and the size of near-vision optotypes., Setting: Department of Ophthalmology, Nara Medical University, Nara, Japan., Methods: The study comprised 30 patients (44 eyes) who were diagnosed with cataract at Nara University of Medical Science Hospital and Municipal Oyodo Hospital. Inclusion criteria included no other eye disorder and a best corrected distance acuity of 20/20 or better 1 month after cataract surgery. All patients had small-incision phacoemulsification followed by in-the-bag implantation of a monofocal intraocular lens (SA60AT, Alcon). All incisions were self-sealing. Accommodation in pseudophakic eyes was measured by the lens-loading method in an examination room under constant illumination. Ocular HOAs were measured using the KR-9000PW Hartmann-Shack wavefront analyzer (Topcon)., Results: The mean patient age was 75.8 years +/- 5.4 (SD) (range 64 to 83 years). The Pearson correlation coefficient (r) showed a significant positive correlation between the range of accommodation and Z7 (vertical coma) for a 4.0 mm pupil using the 1.0 near-vision optotype. There was a significant negative correlation between the range of accommodation and Z12 (spherical aberration) for a 4.0 mm pupil using the 1.0 near-vision optotype (r = .311, P = .040 for Z7;r = -.365, P = .015 for Z12). No other parameter was significantly correlated with the range of accommodation., Conclusions: Measurement of accommodation in pseudophakic eyes by the lens-loading method using the 1.0 near-vision optotype showed that eyes with larger vertical coma aberrations achieved a larger range of accommodation. In contrast, eyes with larger spherical aberrations had smaller amounts of accommodation. The size of the near-vision optotype may affect accommodation analysis in pseudophakic eyes.

Purpose: The purpose of this study was to evaluate the possible injury in the optic pathway by measuring P100 peak latency of pattern-reversal visual evoked potentials (PVEPs) in patients with human T-lymphotropic virus type 1 uveitis (HU)., Methods: The P100 peak latency of PVEP was measured during the period without macular abnormalities observed by fluorescein angiography in 23 patients (46 eyes) with HU and 24 patients (48 eyes) with Vogt-Koyanagi-Harada disease (VKH) with a corrected visual acuity of 20/25 or more. To determine the normal upper limit of P100 peak latency, PVEPs were measured in 31 normal subjects (31 eyes). In addition, in the HU patients, the serum anti-HTLV-1 antibody titer was measured by particle agglutination assay within 3 months of PVEP recording, and the period of HU was retrospectively surveyed., Results: Delayed latency was observed in 4 (7 eyes) of the 23 patients (46 eyes) with HU but none of the 24 patients (48 eyes) with VKH. All four patients with delayed latency showed a serum anti-HTLV-1 antibody titer of more than x4000. The HU period in the HU patients was 0.2-14.0 years, and the HU periods in the four patients with delayed latency were 0.8, 2.7, 4.2, and 14.0 years, respectively., Conclusions: We measured pattern-reversal visual evoked potentials and observed delayed P100 peak latency in 7 of the 46 eyes in 4 (17.4%) of the 23 HU patients. This suggests injury in the optic pathway including the optic nerve by HTLV-1 in some patients with HU. In the future, consideration should also be given to the possible development of optic neuropathy due to HTLV-1.

Smog chamber/Fourier transform infrared (FTIR) and laser-induced fluorescence (LIF) spectroscopic techniques were used to study the atmospheric degradation of CH3CHF2. The kinetics and products of the Cl(2P(3/2)) (denoted Cl) atom- and the OH radical-initiated oxidation of CH3CHF2 in 700 Torr of air or N2; diluents at 295 +/- 2 K were studied using smog chamber/FTIR techniques. Relative rate methods were used to measure k(Cl + CH3CHF2) = (2.37 +/- 0.31) x 10(-13) and k(OH + CH3CHF2) = (3.08 +/- 0.62) x 10(-14) cm3 molecule(-1) s(-1). Reaction with Cl atoms gives CH3CF2 radicals in a yield of 99.2 +/- 0.1% and CH2CHF2 radicals in a yield of 0.8 +/- 0.1%. Reaction with OH radicals gives CH3CF2 radicals in a yield >75% and CH2CHF2 radicals in a yield <25%. Absolute rate data for the Cl reaction were measured using quantum-state selective LIF detection of Cl(2P(j)) atoms under pseudo-first-order conditions. The rate constant k(Cl + CH3CHF2) was determined to be (2.54 +/- 0.25) x 10(-13) cm3 molecule(-1) s(-1) by the LIF technique, in good agreement with the relative rate results. The removal rate of spin-orbit excited-state Cl(2P(1/2)) (denoted Cl) in collisions with CH3CHF2 was determined to be k(Cl + CH3CHF2) = (2.21 +/- 0.22) x 10(-10) cm3 molecule(-1) s(-1). The atmospheric photooxidation products were examined in the presence and absence of NO(x). In the absence of NO(x)(), the Cl atom-initiated oxidation of CH3CHF2 in air leads to formation of COF2 in a molar yield of 97 +/- 5%. In the presence of NO(x), the observed oxidation products include COF2 and CH3COF. As [NO] increases, the yield of COF2 decreases while the yield of CH3COF increases, reflecting a competition for CH3CF2O radicals. The simplest explanation for the observed dependence of the CH3COF yield on [NO(x)] is that the atmospheric degradation of CH3CF2H proceeds via OH radical attack to give CH3CF2 radicals which add O2 to give CH3CF2O2 radicals. Reaction of CH3CF2O2 radicals with NO gives a substantial fraction of chemically activated alkoxy radicals, [CH3CF2O]. In 1 atm of air, approximately 30% of the alkoxy radicals produced in the CH3CF2O2 + NO reaction possess sufficient internal excitation to undergo "prompt" (rate >10(10) s(-1)) decomposition to give CH3 radicals and COF2. The remaining approximately 70% become thermalized, CH3CF2O, and undergo decomposition more slowly at a rate of approximately 2 x 10(3) s(-1). At high concentrations (>50 mTorr), NO(x) is an efficient scavenger for CH3CF2O radicals leading to the formation of CH3COF and FNO.

Purpose: To investigate the high-order aberrations (HoAs) in pseudophakia between 2 foldable acrylic intraocular lenses (IOL) with differences in the tilt of IOL., Setting: Department of Ophthalmology, Nara Medical University, Nara, Japan., Method: Sixty-four eyes that had uncomplicated phacoemulsification and IOL implantation were assigned to 1 of 2 groups: Acryfold 60BB (HOYA [n=30 eyes]) and AcrySof MA60AC (Alcon [n=34 eyes]). All patients had best corrected visual acuity better than 20/25. High-order aberrations were measured using the Hartmann-Shack aberrometer at 4.0 mm and 6.0 mm wavefront aperture diameters, and the IOL tilt and decentration were measured using Scheimpflug videophotography., Results: There was a significant difference in the IOL tilt (60BB=2.22 degrees +/- 1.44 (SD), 60AC=3.18 +/- 1.84 degrees; P=.041, Mann-Whitney U test), but no difference in IOL decentration (P>.05). In the cornea, there were no differences between the 2 groups in HoAs at 4.0 mm and 6.0 mm aperture diameters (P>.05, Mann-Whitney U test). In the whole eye, there was no difference between the 2 groups in spherical-like aberrations, coma-like aberrations, and total aberrations at the 4.0 mm and 6.0 mm aperture diameters (P>.05). The compensation of the internal optics with the 60BB group was better than with the 60AC group for coma-like (P=.037) and total aberrations (P=.010) at 6.0 mm aperture diameter., Conclusion: The smaller tilt of the IOL induced more compensation for the coma-like and total aberrations at the 6.0 mm aperture diameter. The IOL tilt should be small, especially in a large pupil, with regard to HoAs.