Changes in black carbon and PM2.5 in Tokyo in 2003-2017.

Black carbon (BC) particles cause adverse health effects and contribute to the heating of the atmosphere by absorbing visible solar radiation. Efforts have been made to reduce BC emissions, especially in urban areas; however, long-term measurements of BC mass concentration (MBC) are very limited in Japan. We report MBC measurements conducted in Tokyo from 2003 to 2017, showing that MBC decreased by a factor of 3 from 2003 to 2010 and was stable from 2010 to 2017. Fine particulate concentrations (PM2.5) decreased by a much smaller factor during 2003-2010. The diurnal variations of BC size distributions suggest that the BC in Tokyo originates mainly from local sources, even after 2010. Our three-dimensional model calculations show that BC from the Asian continent contributes a small portion (about 20%) of the annual average MBC in the Kanto region of Japan, which includes Tokyo. This indicates that continued reduction of BC emissions inside Japan should be effective in further decreasing MBC.

The Origin of Capacity Fade in the Li2MnO3·LiMO2 (M = Li, Ni, Co, Mn) Microsphere Positive Electrode: An Operando Neutron Diffraction and Transmission X-ray Microscopy Study.

The mechanism of capacity fade of the Li2MnO3·LiMO2 (M = Li, Ni, Co, Mn) composite positive electrode within a full cell was investigated using a combination of operando neutron powder diffraction and transmission X-ray microscopy methods, enabling the phase, crystallographic, and morphological evolution of the material during electrochemical cycling to be understood. The electrode was shown to initially consist of 73(1) wt % R3̅m LiMO2 with the remaining 27(1) wt % C2/m Li2MnO3 likely existing as an intergrowth. Cracking in the Li2MnO3·LiMO2 electrode particle under operando microscopy observation was revealed to be initiated by the solid-solution reaction of the LiMO2 phase on charge to 4.55 V vs Li(+)/Li and intensified during further charge to 4.7 V vs Li(+)/Li during the concurrent two-phase reaction of the LiMO2 phase, involving the largest lattice change of any phase, and oxygen evolution from the Li2MnO3 phase. Notably, significant healing of the generated cracks in the Li2MnO3·LiMO2 electrode particle occurred during subsequent lithiation on discharge, with this rehealing being principally associated with the solid-solution reaction of the LiMO2 phase. This work reveals that while it is the reduction of lattice size of electrode phases during charge that results in cracking of the Li2MnO3·LiMO2 electrode particle, with the extent of cracking correlated to the magnitude of the size change, crack healing is possible in the reverse solid-solution reaction occurring during discharge. Importantly, it is the phase separation during the two-phase reaction of the LiMO2 phase that prevents the complete healing of the electrode particle, leading to pulverization over extended cycling. This work points to the minimization of behavior leading to phase separation, such as two-phase and oxygen evolution, as a key strategy in preventing capacity fade of the electrode.

Source contribution of black carbon aerosol during 2020-2022 at an urban site in Indo-Gangetic Plain.

The extensive emissions of black carbon (BC) from the Indo-Gangetic Plain (IGP) region of India have been well recognized. Particularly, biomass emissions from month-specific crop-residue burning (April, May, October, November) and heating activities (December-February) are considered substantial contributors to BC emissions in the IGP. However, their precise contribution to ambient BC aerosol has not been quantified yet and remains an issue of debate. Therefore, this study aims to fill this gap by quantifying the contribution of these month-specific biomass emissions to ambient BC at an urban site in IGP. This study presents the analysis of BC mass concentrations (MBC) measured for 3 years (2020-2022) in Delhi using an optical photometer i.e., continuous soot monitoring system (COSMOS). A statistical analysis of monthly mean MBC and factors affecting the MBC (ventilation coefficients, air mass back trajectories, fire counts) is performed to derive month-wise contribution due to background concentration, conventional emission, regional transport, crop-residue burning, and heating activities. The yearly mean MBC (5.3 ± 4.7, 5.6 ± 5.0, and 5.3 ± 3.5 µg m-3 during 2020, 2021, and 2022, respectively) remained relatively consistent with repetitive monthly patterns in each year. The peak concentrations were observed from November to January and low concentrations from June to September. Anthropogenic activities contributed significantly to MBC over Delhi with background concentration contributing only 30 % of observed MBC. The percentage contribution of emissions from crop-residue burning varied from 15 % (May) to 37 % (November), while the contribution from heating activities ranged from 25 % (December) to 39 % (January). This source quantification study highlights the significant impact of month-specific biomass emissions in the IGP and can play a vital role in better management and control of these emissions in the region.

Physical and chemical properties of PM1 in Delhi: A comparison between clean and polluted days.

Considering the significance of PM1 aerosol in assessing health impacts of air pollution, an extensive analysis of PM1 samples collected at an urban site in Delhi is presented in this study. Overall, PM1 contributed to about 50 % of PM2.5 mass which is alarming especially in Delhi where particle mass loadings are usually higher than prescribed limits. Major portion of PM1 consisted of organic matter (OM) that formed nearly 47 % of PM1 mass. Elemental carbon (EC) contributed to about 13 % of PM1 mass, whereas SO42- (16 %), NH4+ (10 %), NO3- (4 %) and Cl- (3 %) were the major inorganic ions present. Sampling was performed in two distinctive campaign periods (in terms of meteorological conditions and heating (fire) activities), during the year 2019, each spanning two-week time, i.e. (i) September 3rd-16th (clean days), and (ii) November 22nd-December 5th (polluted days). Additionally, PM2.5 and black carbon (BC) were measured simultaneously for subsequent analysis. The 24-h averaged mean concentrations of PM2.5 and BC during clean days (polluted days) were 70.6 ± 26.9 and 3.9 ± 1.0 µg m-3 (196 ± 104 and 7.6 ± 4.1 µg m-3), respectively, which were systematically lower (higher) than that of the annual mean (taken from studies conducted at same site in 2019) of 142 and 5.7 µg m-3, respectively. Changes in characteristic ratios (i.e., organic carbon (OC)/elemental carbon (EC) and K+/EC) of chemical species detected in PM1 show an increase in biomass emissions during polluted days. Increase in biomass emission can be attributed to increase in heating practices (burning of biofuels such as wood logs, straw, and cow-dung cake) in- and around- Delhi because of fall in temperature during second campaign. Furthermore, a significant increase in NO3- fraction of PM1 is observed during second campaign which shows fog processing of NOX due to conducive meteorological conditions in winters. Also, comparatively stronger correlation of NO3- with K+ during second campaign (r = 0.98 as compared to r = 0.5 during first campaign) suggests the increased heating practices to be a contributing factor for increased fraction of NO3- in PM1. We observed that during polluted days, meteorological parameters such as dispersion rate also played a major role in intensifying the impact of increased local emissions due to heating activities. Apart from this, change in the direction of regional emission transport to study site and the topology of Delhi are the possible reasons for the elevated pollution level, especially PM1 during winter in Delhi. This study also suggests that black carbon measurement techniques used in current study (optical absorbance with heated inlet and evolved carbon techniques) can be used as reference techniques to determine the site-specific calibration constant of optical photometers for urban aerosol.

Wetting properties of fresh urban soot particles: Evaluation based on critical supersaturation and observation of surface trace materials.

Soot particles strongly absorb solar radiation and contribute to global warming. Also, wetting properties of soot at emission can affect its lifetime. We investigated surface conditions related to wetting and hydrophobic properties of fresh soot using data from measurements taken in Tokyo. A cloud condensation nuclei (CCN) counter was used to clarify surface conditions of particles composed mainly of water-insoluble (WI) materials: total and active particles as CCN around critical supersaturation (Sc) of 203-nm-diameter WI particles. Averaged number fractions of inactivated particles as CCN at 1.05% supersaturation (SS), which is Sc of hydrophilic WI particles, were estimated as 1.4%. Number fractions of inactive particles changed less at 1.78%SS during rush hour and increased at 0.89%SS, implying that most of the WI particles included small amounts of water-soluble (WS) materials rather than being completely hydrophobic. Based on transmission electron microscope (TEM) analysis of samples collected during rush hour, 69% of the mostly bare soot particles had Na or K small domains that are regarded as originating in fossil fuels. Based on water dialysis analysis results, some Na and K on soot were WS. Combination results with CCN measurements suggest that these WS materials decrease the Sc of soot. Moreover, the morphological structure of sulfate covering Na and K domains on the soot surface implicates pre-existing sodium and potassium compounds on soot as a trigger of soot aging. However, inactive particles at Sc at poor-hydrophilic particles and soot particles composed solely of WI materials on TEM samples were also found, although they were minor. Such particles, which are unfavorable for obtaining a wettable surface, might retain non-hygroscopicity for a longer period in the atmosphere. Evaluation of long-range soot transport can benefit from consideration of slight and inhomogeneous differences of chemical compounds on soot that occur along with their emission.

A key process controlling the wet removal of aerosols: new observational evidence.

The lifetime and spatial distributions of accumulation-mode aerosols in a size range of approximately 0.05-1 µm, and thus their global and regional climate impacts, are primarily constrained by their removal via cloud and precipitation (wet removal). However, the microphysical process that predominantly controls the removal efficiency remains unidentified because of observational difficulties. Here, we demonstrate that the activation of aerosols to cloud droplets (nucleation scavenging) predominantly controls the wet removal efficiency of accumulation-mode aerosols, using water-insoluble black carbon as an observable particle tracer during the removal process. From simultaneous ground-based observations of black carbon in air (prior to removal) and in rainwater (after removal) in Tokyo, Japan, we found that the wet removal efficiency depends strongly on particle size, and the size dependence can be explained quantitatively by the observed size-dependent cloud-nucleating ability. Furthermore, our observational method provides an estimate of the effective supersaturation of water vapour in precipitating cloud clusters, a key parameter controlling nucleation scavenging. These novel data firmly indicate the importance of quantitative numerical simulations of the nucleation scavenging process to improve the model's ability to predict the atmospheric aerosol burden and the resultant climate forcings, and enable a new validation of such simulations.