ALBERT

Description: China has experienced dramatic changes in emissions since 2010, which accelerated following the implementation of the Clean Air Action program in 2013. These changes have resulted in significant air quality improvements that are reflected in observations from both surface networks and satellite observations. Air pollutants, such as PM2.5, surface ozone, and their precursors, have long enough lifetimes in the troposphere to be easily transported downwind. Emission changes in China will thus not only change the domestic air quality but will also affect the air quality in other regions. In this study, we use a global chemistry transport model (CAM-chem) to simulate the influence of Chinese emission changes from 2010 to 2017 on both domestic and foreign air quality. We then quantify the changes in air-pollution-associated (including both PM2.5 and O3) premature mortality burdens at regional and global scales. Within our simulation period, the population-weighted annual PM2.5 concentration in China peaks in 2011 (94.1 µg m−3) and decreases to 69.8 µg m−3 by 2017. These estimated national PM2.5 concentration changes in China are comparable with previous studies using fine-resolution regional models, though our model tends to overestimate PM2.5 from 2013 to 2017 when evaluated with surface observations. Relative to 2010, emission changes in China increased the global PM2.5-associated premature mortality burdens through 2013, among which a majority of the changes (∼ 93 %) occurred in China. The sharp emission decreases after 2013 generated significant benefits for human health. By 2017, emission changes in China reduced premature deaths associated with PM2.5 by 108 800 (92 800–124 800) deaths per year globally, relative to 2010, among which 92 % were realized in China. In contrast, the population-weighted, annually averaged maximum daily 8 h ozone concentration peaked in 2014 and did not reach 2010 levels by 2017. As such, O3 generated nearly 8500 (6500–9900) more premature deaths per year in 2017 compared to 2010. Downwind regions, such as South Korea, Japan, and the United States, generally experienced O3 improvements following 2013 due to the decreased export of ozone and its precursors. Overall, we conclude that the sharp emission reductions in China over the past decade have generated substantial benefits for air quality that have reduced premature deaths associated with air pollution at a global scale.

Description: The photo-oxidation of myrcene, a monoterpene species emitted by plants, was investigated at atmospheric conditions in the outdoor simulation chamber SAPHIR (Simulation of Atmospheric PHotochemistry In a Large Reaction Chamber). The chemical structure of myrcene consists of one moiety that is a conjugated π system (similar to isoprene) and another moiety that is a triple-substituted olefinic unit (similar to 2-methyl-2-butene). Hydrogen shift reactions of organic peroxy radicals (RO2) formed in the reaction of isoprene with atmospheric OH radicals are known to be of importance for the regeneration of OH. Structure–activity relationships (SARs) suggest that similar hydrogen shift reactions like in isoprene may apply to the isoprenyl part of RO2 radicals formed during the OH oxidation of myrcene. In addition, SAR predicts further isomerization reactions that would be competitive with bimolecular RO2 reactions for chemical conditions that are typical for forested environments with low concentrations of nitric oxide. Assuming that OH peroxy radicals can rapidly interconvert by addition and elimination of O2 like in isoprene, bulk isomerization rate constants of 0.21 and 0.097 s−1 (T=298 K) for the three isomers resulting from the 3′-OH and 1-OH addition, respectively, can be derived from SAR. Measurements of radicals and trace gases in the experiments allowed us to calculate radical production and destruction rates, which are expected to be balanced. The largest discrepancies between production and destruction rates were found for RO2. Additional loss of organic peroxy radicals due to isomerization reactions could explain the observed discrepancies. The uncertainty of the total radical (ROx=OH+HO2+RO2) production rates was high due to the uncertainty in the yield of radicals from myrcene ozonolysis. However, results indicate that radical production can only be balanced if the reaction rate constant of the reaction between hydroperoxy (HO2) and RO2 radicals derived from myrcene is lower (0.9 to 1.6×10-11 cm3 s−1) than predicted by SAR. Another explanation of the discrepancies would be that a significant fraction of products (yield: 0.3 to 0.6) from these reactions include OH and HO2 radicals instead of radical-terminating organic peroxides. Experiments also allowed us to determine the yields of organic oxidation products acetone (yield: 0.45±0.08) and formaldehyde (yield: 0.35±0.08). Acetone and formaldehyde are produced from different oxidation pathways, so that yields of these compounds reflect the branching ratios of the initial OH addition to myrcene. Yields determined in the experiments are consistent with branching ratios expected from SAR. The yield of organic nitrate was determined from the gas-phase budget analysis of reactive oxidized nitrogen in the chamber, giving a value of 0.13±0.03. In addition, the reaction rate constant for myrcene + OH was determined from the measured myrcene concentration, yielding a value of (2.3±0.3)×10-10 cm3 s−1.

Description: The source apportionment of aerosol iron (Fe), including natural and combustion Fe, is an important issue because aerosol Fe can enhance oceanic primary production in the surface ocean. Based on our previous finding that combustion Fe emitted by evaporation processes has Fe isotope ratios (δ56Fe) that are approximately 4 ‰ lower than those of natural Fe, this study aimed to distinguish aerosol Fe sources over the northwestern Pacific using two size-fractionated marine aerosols. The δ56Fe values of fine and coarse particles from the eastern or northern Pacific were found to be similar to each other, ranging from 0.0 ‰ to 0.4 ‰. Most of them were close to the crustal average, suggesting the dominance of natural Fe. On the other hand, particles from the direction of East Asia demonstrated lower δ56Fe values in fine particles (−0.5 ‰ to −2.2 ‰) than in coarse particles (on average −0.02 ± 0.12 ‰). The correlations between the δ56Fe values and the enrichment factors of lead and vanadium suggested that the low δ56Fe values obtained were due to the presence of combustion Fe. The δ56Fe values of the soluble component of fine particles in this region were lower than the total, indicating the preferential dissolution of combustion Fe. In addition, we found a negative correlation between the δ56Fe value and the fractional Fe solubility in air masses from the direction of East Asia. These results suggest that the presence of combustion Fe is an important factor in controlling the fractional Fe solubility in air masses from the direction of East Asia, whereas other factors are more important in the other areas. By assuming typical δ56Fe values for combustion and natural Fe, the contribution of combustion Fe to the total (acid-digested) Fe in aerosols was estimated to reach up to 50 % of fine and 21 % of bulk (coarse + fine) particles in air masses from the direction of East Asia, whereas its contribution was small in the other areas. The contribution of combustion Fe to the soluble Fe component estimated for one sample was approximately twice as large as the total, indicating the importance of combustion Fe as a soluble Fe source despite lower emissions than the natural. These isotope-based estimates were compared with those estimated using an atmospheric chemical transport model (IMPACT), in which the fractions of combustion Fe in fine particles, especially in air masses from the direction of East Asia, were consistent with each other. In contrast, the model estimated a relatively large contribution from combustion Fe in coarse particles, probably because of the different characteristics of combustion Fe that are included in the model calculation and the isotope-based estimation. This highlights the importance of observational data on δ56Fe for size-fractionated aerosols to scale the combustion Fe emission by the model. The average deposition fluxes of soluble Fe to the surface ocean were 1.4 and 2.9 nmol m−2 d−1 from combustion and natural aerosols, respectively, in air masses from the direction of East Asia, which suggests that combustion Fe could be an important Fe source to the surface seawater among other Fe sources. Distinguishing Fe sources using the δ56Fe values of marine aerosols and seawater is anticipated to lead to a more quantitative understanding of the Fe cycle in the atmosphere and surface ocean.

Description: Free tropospheric ozone (O3) trends in the Central East China (CEC) and export regions are investigated for 2008–2017 using the IASI (Infrared Atmospheric Sounding Interferometer) O3 observations and the LMDZ-OR-INCA model simulations, including the most recent Chinese emission inventory. The observed and modelled trends in the CEC region are −0.07 ± 0.02 and −0.08 ± 0.02 DU yr−1, respectively, for the lower free troposphere (3–6 km column) and −0.05 ± 0.02 and −0.06 ± 0.02 DU yr−1, respectively, for the upper free troposphere (6–9 km column). The statistical p value is smaller to 0.01 for all the derived trends. A good agreement between the observations and the model is also observed in the region, including the Korean Peninsula and Japan and corresponding to the region of pollution export from China. Based on sensitivity studies conducted with the model, we evaluate, at 60 % and 52 %, the contribution of the Chinese anthropogenic emissions to the trend in the lower and upper free troposphere, respectively. The second main contribution to the trend is the meteorological variability (34 % and 50 %, respectively). These results suggest that the reduction in NOx anthropogenic emissions that has occurred since 2013 in China led to a decrease in ozone in the Chinese free troposphere, contrary to the increase in ozone at the surface. We designed some tests to compare the trends derived by the IASI observations and the model to independent measurements, such as the In-service Aircraft for a Global Observing System (IAGOS) or other satellite measurements (Ozone Monitoring Instrument (OMI)/Microwave Limb Sounder (MLS)). These comparisons do not confirm the O3 decrease and stress the difficulty in analysing short-term trends using multiple data sets with various sampling and the risk of overinterpreting the results.

Description: Nitryl chloride (ClNO2) is an important chlorine reservoir in the atmosphere that affects the oxidation of volatile organic compounds (VOCs) and the production of ROx radicals and ozone (O3). This study presents measurements of ClNO2 and related compounds at urban, polluted rural, and polluted lower tropospheric (mountaintop) sites in the winter of 2017–2018 over the North China Plain (NCP). The nocturnal concentrations of ClNO2 were lower at the urban and polluted rural sites but higher at the polluted lower tropospheric site. The winter concentrations of ClNO2 were generally lower than the summer concentrations that were previously observed at these sites, which was due to the lower nitrate radical (NO3) production rate (P(NO3)) and the smaller N2O5 uptake coefficients (γ(N2O5)) in winter, despite the higher ratios of dinitrogen pentoxide (N2O5) to NO3 in winter. Significant daytime peaks of ClNO2 were observed at all the sites during the winter campaigns, with ClNO2 mixing ratios of up to 1.3 ppbv. Vertical transport of ClNO2 from the residual layers and prolonged photochemical lifetime of ClNO2 in winter may explain the elevated daytime concentrations. The daytime-averaged chlorine radical (Cl) production rates (P(Cl)) from the daytime ClNO2 were 0.17, 0.11, and 0.12 ppbv h−1 at the polluted rural, urban, and polluted lower tropospheric sites, respectively, which were approximately 3–4 times higher than the campaign-averaged conditions. Box model calculations showed that the Cl atoms liberated during the daytime peaks of ClNO2 increased the ROx levels by up to 27 %–37 % and increased the daily O3 productions by up to 13 %–18 %. Our results provide new insights into the ClNO2 processes in the lower troposphere impacted by fresh and intense anthropogenic emissions and reveal that ClNO2 can be an important daytime source of Cl radicals under certain conditions in winter.

Description: 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.

Description: Lake breezes are proved by downdrafts and the divergence flows of zonal wind in the source region of the Yellow River (SRYR) in the daytime based on ERA-Interim reanalysis data. In order to depict the effect of the circulations induced by surface anomaly heating (patches) on the boundary-layer turbulence, the UK Met Office Large Eddy Model was used to produce a set of 1D strip-like surface heat flux distributions based on observations, which were obtained by a field campaign in the Ngoring Lake basin in the summer of 2012. The simulations show that for the cases without background wind, patch-induced circulations (SCs) promote the growth of convective boundary layer (CBL), enhance the turbulent kinetic energy (TKE), and then modify the spatial distribution of TKE. Based on phase-averaged analysis, which separates the attribution from the SCs and the background turbulence, the SCs contribute no more than 10 % to the vertical turbulent intensity, but their contributions to the heat flux can be up to 80 %. The thermal internal boundary layer (TIBL) reduces the wind speed and forms the stable stratification, which produces the obvious change of turbulent momentum flux and heat flux over the heterogeneous surfaces. The increased downdrafts, which mainly occur over the lake patches, carry more warm, dry air down from the free atmosphere. The background wind inhibits the SCs and the development of the CBL; it also weakens the patch-induced turbulent intensity, heat flux, and convective intensity.

Description: Aerosol-induced absorption of shortwave radiation can modify the climate through local atmospheric heating, which affects lapse rates, precipitation, and cloud formation. Presently, the total amount of aerosol absorption is poorly constrained, and the main absorbing aerosol species (black carbon (BC), organic aerosols (OA), and mineral dust) are diversely quantified in global climate models. As part of the third phase of the Aerosol Comparisons between Observations and Models (AeroCom) intercomparison initiative (AeroCom phase III), we here document the distribution and magnitude of aerosol absorption in current global aerosol models and quantify the sources of intermodel spread, highlighting the difficulties of attributing absorption to different species. In total, 15 models have provided total present-day absorption at 550 nm (using year 2010 emissions), 11 of which have provided absorption per absorbing species. The multi-model global annual mean total absorption aerosol optical depth (AAOD) is 0.0054 (0.0020 to 0.0098; 550 nm), with the range given as the minimum and maximum model values. This is 28 % higher compared to the 0.0042 (0.0021 to 0.0076) multi-model mean in AeroCom phase II (using year 2000 emissions), but the difference is within 1 standard deviation, which, in this study, is 0.0023 (0.0019 in Phase II). Of the summed component AAOD, 60 % (range 36 %–84 %) is estimated to be due to BC, 31 % (12 %–49 %) is due to dust, and 11 % (0 %–24 %) is due to OA; however, the components are not independent in terms of their absorbing efficiency. In models with internal mixtures of absorbing aerosols, a major challenge is the lack of a common and simple method to attribute absorption to the different absorbing species. Therefore, when possible, the models with internally mixed aerosols in the present study have performed simulations using the same method for estimating absorption due to BC, OA, and dust, namely by removing it and comparing runs with and without the absorbing species. We discuss the challenges of attributing absorption to different species; we compare burden, refractive indices, and density; and we contrast models with internal mixing to models with external mixing. The model mean BC mass absorption coefficient (MAC) value is 10.1 (3.1 to 17.7) m2 g−1 (550 nm), and the model mean BC AAOD is 0.0030 (0.0007 to 0.0077). The difference in lifetime (and burden) in the models explains as much of the BC AAOD spread as the difference in BC MAC values. The difference in the spectral dependency between the models is striking. Several models have an absorption Ångstrøm exponent (AAE) close to 1, which likely is too low given current knowledge of spectral aerosol optical properties. Most models do not account for brown carbon and underestimate the spectral dependency for OA.

Description: Ammonium nitrate is a major aerosol constituent over many land regions and contributes to air pollution episodes, ecosystem destruction, regional haze, and aerosol-induced climate forcing. Many climate models that represent ammonium nitrate assume that the ammonium–sulfate–nitrate chemistry reaches thermodynamic equilibrium instantaneously without considering kinetic limitations on condensation rates. The Met Office's Unified Model (UM) is employed to investigate the sensitivity of ammonium nitrate concentrations to the nitric acid uptake coefficient (γ) in a newly developed nitrate scheme in which first-order condensation theory is utilised to limit the rate at which thermodynamic equilibrium is attained. Two values of γ representing fast (γ=0.193) and slow (γ=0.001) uptake rates are tested in 20-year global UM integrations. The global burden of nitrate associated with ammonium in the “fast” simulation (0.11 Tg[N]) is twice as great as in the “slow” simulation (0.05 Tg[N]), while the top-of-the-atmosphere radiative impact of representing nitrate is −0.19 W m−2 in the fast simulation and −0.07 W m−2 in the slow simulation. In general, the fast simulation exhibits better spatial correlation with observed nitrate concentrations, while the slow simulation better resolves the magnitude of concentrations. Local near-surface nitrate concentrations are found to be highly correlated with seasonal ammonia emissions, suggesting that ammonia is the predominant limiting factor controlling nitrate prevalence. This study highlights the high sensitivity of ammonium nitrate concentrations to nitric acid uptake rates and provides a novel mechanism for reducing nitrate concentration biases in climate model simulations. The new UM nitrate scheme represents a step change in aerosol modelling capability in the UK across weather and climate timescales.

Description: To understand the ambient levels and sources of atmospheric mercury (Hg) in the Tibetan Plateau, a full-year continuous measurement of speciated atmospheric mercury was conducted at the Waliguan (WLG) Baseline Observatory (3816 m a.s.l.) from May 2012 to April 2013. Mean concentrations (± 1 SD) of gaseous elemental mercury (GEM), gaseous oxidized mercury (GOM) and particulate bound mercury (PBM) during the whole study period were 1.90±0.80 ng m−3, 12.0±10.6 and 65.4±63.2 pg m−3, respectively. Seasonal variations of GEM were very small, while those of PBM were quite large with mean values being 4 times higher in the cold (102.3±66.7 pg m−3) than warm (22.8±14.6 pg m−3) season. Anthropogenic emissions to the east of the Tibetan Plateau contributed significantly to GEM pollution at WLG, while dust particles originating from desert and Gobi regions in Xinjiang province and the Tibetan Plateau to the west of WLG were responsible for PBM pollution at WLG. This finding is also supported by the significant positive correlation between daily PBM concentration and daily cumulative absorbing aerosol index (AAI) in air masses transported during the preceding 2 d.