Sensitivity analysis of source regions to PM2.5 concentration at Fukue Island, Japan.

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.

Eliminating the interference of water for direct sensing of submerged plastics using hyperspectral near-infrared imager.

Interference from water in the reflectance spectra of plastics is a major obstacle to optical sensing of plastics in aquatic environments. Here we present evidence of the feasibility of sensing plastics in water using hyperspectral near-infrared to shortwave-infrared imaging techniques. We captured hyperspectral images of nine polymers submerged to four depths (2.5-15 mm) in water using a hyperspectral imaging system that utilizes near-infrared to shortwave-infrared light sources. We also developed algorithms to predict the reflectance spectra of each polymer in water using the spectra of the dry plastics and water as independent variables in a multiple linear regression model after a logarithmic transformation. A narrow 1100-1300 nm wavelength range was advantageous for detection of polyethylene, polystyrene, and polyvinyl chloride in water down to the 160-320 µm size range, while a wider 970-1670 nm wavelength range was beneficial for polypropylene reflectance spectrum prediction in water. Furthermore, we found that the spectra of the other five polymers, comprising polycarbonate, acrylonitrile butadiene styrene, phenol formaldehyde, polyacetal, and polymethyl methacrylate, could also be predicted within their respective optimized wavelength ranges. Our findings provide fundamental information for direct sensing of plastics in water on both benchtop and airborne platforms.

The worldwide COVID-19 lockdown impacts on global secondary inorganic aerosols and radiative budget.

Global lockdown measures to prevent the spread of the coronavirus disease 2019 (COVID-19) led to air pollutant emission reductions. While the COVID-19 lockdown impacts on both trace gas and total particulate pollutants have been widely investigated, secondary aerosol formation from trace gases remains unclear. To that end, we quantify the COVID-19 lockdown impacts on NOx and SO2 emissions and sulfate-nitrate-ammonium aerosols using multiconstituent satellite data assimilation and model simulations. We find that anthropogenic emissions over major polluted regions were reduced by 19 to 25% for NOx and 14 to 20% for SO2 during April 2020. These emission reductions led to 8 to 21% decreases in sulfate and nitrate aerosols over highly polluted areas, corresponding to >34% of the observed aerosol optical depth declines and a global aerosol radiative forcing of +0.14 watts per square meter relative to business-as-usual scenario. These results point to the critical importance of secondary aerosol pollutants in quantifying climate impacts of future mitigation measures.

Characteristics of atmospheric black carbon and other aerosol particles over the Arctic Ocean in early autumn 2016: Influence from biomass burning as assessed with observed microphysical properties and model simulations.

We conducted ship-based measurements of marine aerosol particles (number concentration, size distribution, black carbon (BC), autofluorescence property, and PM2.5 composition) and trace gases (ozone (O3) 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/m3, confirming the validity of our previously-reported observations (~1 ng/m3) 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 (Utqiagvik), 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/m3/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.

Optimization of a hyperspectral imaging system for rapid detection of microplastics down to 100 µm.

Plastic pollution has become one of the most emergent issues threating aquatic and terrestrial ecosystems. However, it is still challenging to rapidly detect small microplastics. Here, we present a method to rapidly detect microplastics using hyperspectral imaging in which we optimized a commercially available hyperspectral imaging system (Pika NIR-640, Resonon Inc., USA). The optimizations included: (1) changing the four-lamp assembly to a symmetrical set of converged-light near-infrared lamps that are placed sideways instead of above the sample stage; (2) adopting a macro-photography technique by applying an extension tube between the camera and the lens, and moving the lens of the hyperspectral camera to the imaging target (working distance of ~3 cm); (3) adjusting the exposure and aspect ratio by tuning the frame rate and scan speed of the imaging system. After optimization, the detection resolution of each pixel improved from 250 µm to 14.8 µm. With the optimized system, microplastics down to 100 µm in size were rapidly detected. This result is promising for the application of our new method in the accelerated detection of microplastics and will contribute to a better understanding of the microplastic pollution situation.

Light-absorption properties of brown carbon aerosols in the Asian outflow: Implications of a combination of filter and ground remote-sensing observations at Fukue Island, Japan.

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 (rs = 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.

Dominance of the residential sector in Chinese black carbon emissions as identified from downwind atmospheric observations during the COVID-19 pandemic.

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.

Development of robust models for rapid classification of microplastic polymer types based on near infrared hyperspectral images.

Hyperspectral data in the near infrared range were examined for nine common types of plastic particles of 1 mm and 100-500 µm sizes on dry and wet glass fiber filters. Weaker peak intensities were detected for small particles compared to large particles, and the reflectances were weaker at longer wavelengths when the particles were measured on a wet filter. These phenomena are explainable due to the effect of the correlation between the particle size and the absorption of infrared light by water. We constructed robust classification models that are capable of classifying polymer types, regardless of particle size or filter conditions (wet vs. dry), based on hyperspectral data for small particles measured on wet filters. Using the models, we also successfully classified the polymer type of polystyrene beads covered with microalgae, which simulates the natural conditions of microplastics in the ocean. This study suggests that hyperspectral imaging techniques with appropriate classification models allow the identification of microplastics without the time- and labor-consuming procedures of drying samples and removing biofilms, thus enabling more rapid analyses.

Characterization of microplastics on filter substrates based on hyperspectral imaging: Laboratory assessments.

Microplastic pollution has become an urgent issue because it adversely affects ecosystems. However, efficient methods to detect and characterize microplastic particles are still in development. By conducting a series of laboratory assessments based on near-infrared hyperspectral imaging in the wavelength range of 900-1700 nm, we report the fundamental spectral features of (i) 11 authentic plastics and (ii) 11 filter substrate materials. We found that different plastic polymers showed distinct spectral features at 1150-1250 nm, 1350-1450 nm and 1600-1700 nm, enabling their automatic recognition and identification with spectral separation algorithms. Using an improved hyperspectral imaging system, we demonstrated the detection of three types of microplastic particles, polyethylene, polypropylene and polystyrene, down to 100 µm in diameter. As a filter substrate, a gold-coated polycarbonate filter (GPC0847-BA) showed constant reflectance over 900-1700 nm and a large radiative contrast against loaded plastic particles. Glass fiber filters (GF10 and GF/F) would also be suitable substrates due to their low cost and easy commercial availability. This study provides key parameters for applying hyperspectral imaging techniques for the detection of microplastics.

Sources of atmospheric black carbon and related carbonaceous components at Rishiri Island, Japan: The roles of Siberian wildfires and of crop residue burning in China.

A field study was conducted to clarify sources of atmospheric black carbon and related carbonaceous components at Rishiri Island, Japan. We quantified equivalent black carbon (eBC) particle mass and the absorption Ångström exponent (AAE), atmospheric CO and CH4, in addition to levoglucosan in total suspended particles, a typical tracer of biomass burning. Sixteen high eBC events were identified attributable to either anthropogenic sources or biomass burning in Siberia/China. These events were often accompanied by increases of co-emitted gases such as CH4 and CO. Specifically, we observed pollution events with elevated eBC, AAE, levoglucosan, and CH4CO slope in late July 2014, which were attributed to forest fires in Siberia by reference to the FLEXPART model footprint and fire hotspots. In autumn, drastic increases of eBC, AAE, and levoglucosan were observed, accompanied by an eBC-CO slope of >15 ng m-3/ppb, resulting from long-range transport of emissions from extensive burning of crop residue on the Northeast China Plain. Other than the sources of fossil fuel combustion in China and forest fires in Siberia, we report for the first time that pollution events in northern Japan are caused by crop residue burning in China. This study elucidated valuable information that will improve understanding of the effects of biomass burning in East Asia on atmospheric carbonaceous components.

Kinetics of heterogeneous reactions of HO2 radical at ambient concentration levels with (NH4)2SO4 and NaCl aerosol particles.

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.

Seasonal Response of North Western Pacific Marine Ecosystems to Deposition of Atmospheric Inorganic Nitrogen Compounds from East Asia.

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 (HNO3 and NH3) and aerosol particles (NO3- and NH4+), 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/m3. Similarly, the gross primary productivity, integrated over sea depths of 0-200 m, increased from 85 to 147 mg C/m2/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.

Diurnal variations in H2O2, O3, PAN, HNO3 and aldehyde concentrations and NO/NO2 ratios at Rishiri Island, Japan: potential influence from iodine chemistry.

The presence of iodine chemistry, hypothesized due to the overprediction of HO(2) levels by a photochemical box model at Rishiri Island in June 2000, was quantitatively tested against the observed NO/NO(2) ratios and the net production rates of ozone. The observed NO/NO(2) ratios were reproduced reasonably well by considering the conversion of NO to NO(2) by IO, whose amount was calculated so as to reproduce the observed HO(2) levels. However, the net production rates of ozone were calculated to be negative when such high mixing ratios of IO were considered, which was inconsistent with the observed buildup of ozone during daytime. These results suggest that iodine chemistry may not be the sole mechanism for the reduced mixing ratios of HO(2), or that "hot spots" for iodine chemistry were present. Diurnal variations in the mixing ratios of HCHO, CH(3)CHO, peroxy acetyl nitrate (PAN) and HNO(3) observed during the study are presented along with the simulated ones. The box model simulations suggest that the effect of iodine chemistry on these concentrations is small and that important sources of CH(3)CHO and sinks of PAN are probably missing from our current understanding of the tropospheric chemistry mechanism.

Size-dependent validation of MODIS MCD64A1 burned area over six vegetation types in boreal Eurasia: Large underestimation in croplands.

Pollutants emitted from wildfires in boreal Eurasia can be transported to the Arctic, and their subsequent deposition could accelerate global warming. The Moderate Resolution Imaging Spectroradiometer (MODIS) MCD64A1 burned area product is the basis of fire emission products. However, uncertainties due to the "moderate resolution" (500 m) characteristic of the MODIS sensor could be introduced. Here, we present a size-dependent validation of MCD64A1 with reference to higher resolution (better than 30 m) satellite products (Landsat 7 ETM+, RapidEye, WorldView-2, and GeoEye-1) for six ecotypes over 12 regions of boreal Eurasia. We considered the 2012 boreal Eurasia burning season when severe wildfires occurred and when Arctic sea ice extent was historically low. Among the six ecotypes, we found MCD64A1 burned areas comprised only 13% of the reference products in croplands because of inadequate detection of small fires (<100 ha). Our results indicate that over all ecotypes, the actual burned area in boreal Eurasia (15,256 km2) could have been ~16% greater than suggested by MCD64A1 (13,187 km2) when applying the correction factors proposed in this study. This implies the effects of wildfire emissions in boreal Eurasia on Arctic warming could be greater than currently estimated.

Gating a channel photomultiplier with a fast high-voltage switch: reduction of afterpulse rates in a laser-induced fluorescence instrument for measurement of atmospheric OH radical concentrations.

By employing a commercially available high-voltage switch in a time-gating circuit to drive a channel photomultiplier (CPM), the afterpulse rates are significantly reduced in the time window to collect fluorescence >200 ns after the pulsed laser excitation. The CPM, kept deactivated under normal conditions (normally off), is turned on immediately after the passage of the laser pulse by shifting the voltage applied to the photocathode by 150 V to collect the fluorescence. When the detection system is used as part of a laser-induced fluorescence instrument to measure atmospheric OH radicals with the photon-counting method, the background signal is reduced by more than a factor of 10 as compared with our previous case where a conventional dynode-gated photomultiplier tube (PMT) is used, while the sensitivity toward the fluorescence is almost unchanged. A detection limit as low as 2 x 10(5) radicals cm-3 or 0.008 parts per trillion by volume is achieved for OH, with an integration time of 1 min and a signal-to-noise ratio of 2, enabling sensitive detection of the important radical in the atmosphere. This system is a superior choice with higher sensitivity and cost effectiveness as compared with the gated PMITs utilizing a microchannel plate as an electron multiplier, and could also be used effectively in light detection and ranging (lidar) instruments, where a delayed scattering signal would be efficiently discriminated from afterpulses.

Direct measurements of HOx radicals in the marine boundary layer: testing the current tropospheric chemistry mechanism.

OH and HO(2) radicals, atmospheric detergents, and the reservoir thereof, play central roles in tropospheric chemistry. In spite of their importance, we had no choice but to trust their concentrations predicted by modeling studies based on known chemical processes. However, recent direct measurements of these radicals have enabled us to test and revise our knowledge of the processes by comparing the predicted and observed values of the radical concentrations. We developed a laser-induced fluorescence (LIF) instrument and successfully observed OH and HO(2) at three remote islands of Japan (Oki Island, Okinawa Island, and Rishiri Island). At Okinawa Island, the observed daytime level of HO(2) agreed closely with the model estimates, suggesting that the photochemistry at Okinawa is well described by the current chemistry mechanism. At Rishiri Island, in contrast, the observed daytime level of HO(2) was consistently much lower than the calculated values. We proposed that iodine chemistry, usually not incorporated into the mechanism, is at least partly responsible for the discrepancy in the results. At night, HO(2) was detected at levels greater than 1 pptv at all three islands, suggesting the presence of processes in the dark that produce radicals. We showed that ozone reactions with unsaturated hydrocarbons, including monoterpenes, could significantly contribute to radical production.