ALBERT

Beschreibung: The heterogeneous hydrolysis of dinitrogen pentoxide (N2O5) has a significant impact on both nocturnal particulate nitrate formation and photochemistry on the following day through the photolysis of nitryl chloride (ClNO2), yet these processes in highly polluted urban areas remain poorly understood. Here we present measurements of gas-phase N2O5 and ClNO2 by high-resolution time-of-flight chemical ionization mass spectrometer (ToF-CIMS) during summer in urban Beijing, China as part of the Air Pollution and Human Health (APHH) campaign. N2O5 and ClNO2 show large day-to-day variations with average (±1σ) mixing ratios of 79.2±157.1 and 174.3±262.0 pptv, respectively. High reactivity of N2O5, with τ (N2O5)−1 ranging from 0.20 × 10−2 to 1.46 × 10−2 s−1, suggests active nocturnal chemistry and a large nocturnal nitrate formation potential via N2O5 heterogeneous uptake. The lifetime of N2O5, τ (N2O5), decreases rapidly with the increase in aerosol surface area, yet it varies differently as a function of relative humidity with the highest value peaking at ∼ 40 %. The N2O5 uptake coefficients estimated from the product formation rates of ClNO2 and particulate nitrate are in the range of 0.017–0.19, corresponding to direct N2O5 loss rates of 0.00044–0.0034 s−1. Further analysis indicates that the fast N2O5 loss in the nocturnal boundary layer in urban Beijing is mainly attributed to its indirect loss via NO3, for example through the reactions with volatile organic compounds and NO, while the contribution of the heterogeneous uptake of N2O5 is comparably small (7–33 %). High ClNO2 yields ranging from 0.10 to 0.35 were also observed, which might have important implications for air quality by affecting nitrate and ozone formation.

Beschreibung: High concentration of fine particles (PM2.5), the primary concern about air quality in China, is believed to closely relate to China's large consumption of coal. In order to quantitatively identify the contributions of coal combustion in different sectors to ambient PM2. 5, we developed an emission inventory for the year 2013 using up-to-date information on energy consumption and emission controls, and we conducted standard and sensitivity simulations using the chemical transport model GEOS-Chem. According to the simulation, coal combustion contributes 22 µg m−3 (40 %) to the total PM2. 5 concentration at national level (averaged in 74 major cities) and up to 37 µg m−3 (50 %) in the Sichuan Basin. Among major coal-burning sectors, industrial coal burning is the dominant contributor, with a national average contribution of 10 µg m−3 (17 %), followed by coal combustion in power plants and the domestic sector. The national average contribution due to coal combustion is estimated to be 18 µg m−3 (46 %) in summer and 28 µg m−3 (35 %) in winter. While the contribution of domestic coal burning shows an obvious reduction from winter to summer, contributions of coal combustion in power plants and the industrial sector remain at relatively constant levels throughout the year.

Beschreibung: Despite extensive efforts toward the characterization of submicron aerosols at ground level in the megacity of Beijing, our understanding of aerosol sources and processes at high altitudes remains low. Here we conducted a 3-month real-time measurement of non-refractory submicron aerosol (NR-PM1) species at a height of 260 m from 10 October 2014 to 18 January 2015 using an aerosol chemical speciation monitor. Our results showed a significant change in aerosol composition from the non-heating period (NHP) to the heating period (HP). Organics and chloride showed clear increases during HP due to coal combustion emissions, while nitrate showed substantial decreases from 28 to 15–18 %. We also found that NR-PM1 species in the heating season can have average mass differences of 30–44 % under similar emission sources yet different meteorological conditions. Multi-linear engine 2 (ME-2) using three primary organic aerosol (OA) factors as constraints, i.e., fossil-fuel-related OA (FFOA) dominantly from coal combustion emissions, cooking OA (COA), and biomass burning OA (BBOA) resolved from ground high-resolution aerosol mass spectrometer measurements, was applied to OA mass spectra of ACSM. Two types of secondary OA (SOA) that were well correlated with nitrate and chloride–CO, respectively, were identified. SOA played a dominant role in OA during all periods at 260 m although the contributions were decreased from 72 % during NHP to 58–64 % during HP. The SOA composition also changed significantly from NHP to HP. While the contribution of oxygenated OA (OOA) was decreased from 56–63 to 32–40 %, less oxidized OOA (LO-OOA) showed a large increase from 9–16 to 24–26 %. COA contributed a considerable fraction of OA at high altitude, and the contribution was relatively similar across different periods (10–13 %). In contrast, FFOA showed a large increase during HP due to the influences of coal combustion emissions. We also observed very different OA composition between ground level and 260 m. Particularly, the contributions of COA and BBOA at the ground site were nearly twice those at 260 m, while SOA at 260 m was ∼ 15–34 % higher than that at ground level. Bivariate polar plots and back-trajectory analysis further illustrated the different source regions of OA factors in different seasons.

Beschreibung: Aerosol particles are of importance in the Earth's radiation budget since they scatter and absorb sunlight. While extensive studies of aerosol optical properties have been conducted at ground sites, vertical measurements and characterization are very limited in megacities. In this work, we present simultaneous real-time online measurements of aerosol optical properties at ground level and at 260 m on a meteorological tower from 16 November to 13 December in 2016 in Beijing along with measurements of continuous vertical profiles during two haze episodes. The average (±1σ) scattering and absorption coefficients (bsca and babs; λ=630 nm) were 337.6 (±356.0) and 36.6 (±33.9) Mm−1 at 260 m, which were 26.5 % and 22.5 % lower than those at ground level. Single scattering albedo (SSA), however, was comparable between the two heights, with slightly higher values at ground level (0.89±0.04). Although bsca and babs showed overall similar temporal variations between ground level and 260 m, the ratios of 260 m to ground varied substantially from less than 0.4 during the clean stages of haze episodes to 〉 0.8 in the late afternoon. A more detailed analysis indicates that vertical profiles of bsca, babs, and SSA in the low atmosphere were closely related to the changes in meteorological conditions and mixing layer height. The mass absorption cross section (MAC) of equivalent black carbon (eBC, λ=630 nm) varied substantially from 9.5 to 13.2 m2 g−1 in winter in Beijing, and it was strongly associated with the mass ratio of coating materials on refractory BC (rBC) to rBC (MR), and also the oxidation degree of organics in rBC-containing particles. Our results show that the increases in MAC of eBC in winter were mainly caused by photochemically produced secondary materials. Light absorption of organic carbon (brown carbon, BrC) was also important in winter, which on average accounted for 46 (±8.5) % and 48 (±9.3) % of the total absorption at 370 nm at ground level and 260 m, respectively. A linear regression model combined with positive matrix factorization analysis was used to show that coal combustion was the dominant source contribution of BrC (48 %–55 %) followed by biomass burning (17 %) and photochemically processed secondary organic aerosol (∼20 %) in winter in Beijing.

Beschreibung: Aerosol liquid water (ALW) is ubiquitous in ambient aerosol and plays an important role in the formation of both aerosol organics and inorganics. To investigate the interactions between ALW and aerosol organics during haze formation and evolution, ALW was modelled based on long-term measurement of submicron aerosol composition in different seasons in Beijing. ALW contributed by aerosol inorganics (ALWinorg) was modelled by ISORROPIA II, and ALW contributed by organics (ALWorg) was estimated with κ-Köhler theory, where the real-time hygroscopicity parameter of the organics (κorg) was calculated from the real-time organic oxygen-to-carbon ratio (O∕C). Overall particle hygroscopicity (κtotal) was computed by weighting component hygroscopicity parameters based on their volume fractions in the mixture. We found that ALWorg, which is often neglected in traditional ALW modelling, contributes a significant fraction (18 %–32 %) to the total ALW in Beijing. The ALWorg fraction is largest on the cleanest days when both the organic fraction and κorg are relatively high. The large variation in O∕C, from 0.2 to 1.3, indicates the wide variety of organic components. This emphasizes the necessity of using real-time κorg, instead of fixed κorg, to calculate ALWorg in Beijing. The significant variation in κorg (calculated from O∕C), together with highly variable organic or inorganic volume fractions, leads to a wide range of κtotal (between 0.20 and 0.45), which has a great impact on water uptake. The variation in organic O∕C, or derived κorg, was found to be influenced by temperature (T), ALW, and aerosol mass concentrations, among which T and ALW both have promoting effects on O∕C. During high-ALW haze episodes, although the organic fraction decreases rapidly, O∕C and derived κorg increase with the increase in ALW, suggesting the formation of more soluble organics via heterogeneous uptake or aqueous processes. A positive feedback loop is thus formed: during high-ALW episodes, increasing κorg, together with decreasing particle organic fraction (or increasing particle inorganic fraction), increases κtotal, and thus further promotes the ability of particles to uptake water.

Beschreibung: We applied an Ensemble Optimal Interpolation (EnOI) data assimilation method in the BCC_CSM1.1 to investigate the impact of ocean data assimilations on seasonal forecasts in an idealized twin-experiment framework. Pseudo-observations of sea surface temperature (SST), sea surface height (SSH), sea surface salinity (SSS), temperature and salinity (T/S) profiles were first generated in a free model run. Then, a series of sensitivity tests initialized with predefined bias were conducted for a one-year period; this involved a free run (CTR) and seven assimilation runs. These tests allowed us to check the analysis field accuracy against the truth. As expected, data assimilation improved all investigated quantities; the joint assimilation of all variables gave more improved results than assimilating them separately. One-year predictions initialized from the seven runs and CTR were then conducted and compared. The forecasts initialized from joint assimilation of surface data produced comparable SST root mean square errors to that from assimilation of T/S profiles, but the assimilation of T/S profiles is crucial to reduce subsurface deficiencies. The ocean surface currents in the tropics were better predicted when initial conditions produced by assimilating T/S profiles, while surface data assimilation became more important at higher latitudes, particularly near the western boundary currents. The predictions of ocean heat content and mixed layer depth are significantly improved initialized from the joint assimilation of all the variables. Finally, a central Pacific El Niño was well predicted from the joint assimilation of surface data, indicating the importance of joint assimilation of SST, SSH, and SSS for ENSO predictions.

Beschreibung: Volatility plays a key role in affecting mass concentrations and lifetime of aerosol particles in the atmosphere, yet our knowledge of aerosol volatility in relatively polluted environment, e.g., north China remains poor. Here aerosol volatility in Beijing in summer 2017 and 2018 was measured using a thermodenuder (TD) coupled with an Aerodyne high-resolution aerosol mass spectrometer (AMS) and a soot particle AMS. Our results showed overall similar thermograms for most non-refractory aerosol species compared with those reported in previous studies. However, high mass fraction remaining and NO+/NO2+ ratio for chloride and nitrate, respectively above 200 °C indicated the presence of considerable metallic salts and organic nitrates in Beijing. The volatility distributions of organic aerosol (OA) and four OA factors that were resolved from positive matrix factorization were estimated using a mass transfer model. The ambient OA comprised mainly semi-volatile organic compounds (SVOC, 63 %) with an average effective saturation concentration (C*) of 0.55 µg m−3, suggesting overall more volatile properties than OA in megacities of Europe and US. Further analysis showed that the freshly oxidized secondary OA (LO-OOA) was the most volatile OA factor (SVOC = 70 %) followed by hydrocarbon-like OA (HOA). In contrast, the volatility of more oxidized SOA (MO-OOA) was comparable to that of cooking OA with SVOC on average accounting for 60.2 %. We also compared the volatility of ambient and black carbon–containing OA. Our results showed that the BC-containing primary OA (POA) was much more volatile than ambient POA (C*= 0.69 µg m−3 vs. 0.37 µg m−3), while the BC-containing SOA was much less volatile, highlighting the very different composition and properties between BC-containing and ambient aerosol particles.

Beschreibung: High concentration of fine particles (PM2.5), the primary concern about air quality in China, is believed to closely relate to China’s large consumption of coal. In order to quantitatively identify the contributions of coal combustion in different sectors to ambient PM2.5, we developed an emission inventory for the year 2013 using up-to-date information on energy consumption and emission controls, and conducted standard and sensitivity simulations using the chemical transport model GEOS-Chem. According to the simulation, coal combustion contributes 22 μg m−3 (40 %) to the total PM2.5 concentration at national level (averaged in 74 major cities), and up to 37 μg m−3 (50 %) in Sichuan Basin. Among major coal-burning sectors, industrial coal burning is the dominant contributor with a national average contribution of 10 μg m−3 (17 %), followed by coal combustion in power plants and domestic sector. The national average contribution due to coal combustion is estimated to be 18 μg m−3 (46 %) in summer and 28 μg m−3 (35 %) in winter. While the contribution of domestic coal burning shows an obvious reduction from winter to summer, contributions of coal combustion in power plants and industrial sector remain at relatively constant levels through out the year.

Beschreibung: The heterogeneous hydrolysis of dinitrogen pentoxide (N2O5) has a significant impact on both nocturnal particulate nitrate formation and photochemistry the following day through photolysis of nitryl chloride (ClNO2), yet these processes in highly polluted urban areas remain poorly understood. Here we present measurements of gas-phase N2O5 and ClNO2 by high-resolution time-of-flight chemical ionization mass spectrometers (ToF-CIMS) during summer in urban Beijing, China as part of the Air Pollution and Human Health (APHH) campaign. N2O5 and ClNO2 show large day-to-day variations with average (±1σ) mixing ratios of 79.2±157.1 and 174.3±262.0pptv, respectively. High reactivity of N2O5, with τ (N2O5)−1 ranging from 0.20×10−2 to 1.46×10−2s−1, suggests active nocturnal chemistry and a large nocturnal nitrate formation potential via N2O5 heterogeneous uptake. The life time of N2O5, τ(N2O5), decreases rapidly as the increase of aerosol surface area, yet it varies differently as a function of relative humidity with the highest value peaking at ~40%. The N2O5 uptake coefficients estimated from the product formation rates of ClNO2 and particulate nitrate are in the range of 0.017–0.19, corresponding to direct N2O5 loss rates of 0.00044–0.0034s−1. Further analysis indicates that the fast N2O5 loss in the nocturnal boundary layer in urban Beijing is mainly attributed to its indirect loss via NO3, for example through the reactions with volatile organic compounds and NO, while the contribution of heterogeneous uptake of N2O5 is comparably small (7–33%). High ClNO2 yields ranging from 0.10 to 0.35 were also observed which might have important implications for air quality by affecting nitrate and ozone formation.

Beschreibung: Aerosol liquid water (ALW) is ubiquitous in ambient aerosol and plays an important role in the formation of both aerosol organics and inorganics. To investigate the interactions between ALW and aerosol organics during haze formation and evolution, ALW was modelled based on long-term measurements of submicron aerosol compositions from different seasons in Beijing. ALW contributed by aerosol inorganics (ALWinorg) was modelled by ISORROPIA-II, and ALW contributed by organics (ALWorg) was estimated with κ-Köhler theory, where a real-time hygroscopicity parameter of the organics (κorg) calculated from the real-time organic oxygen-to-carbon (O/C) was used. Particle overall hygroscopicity (κtotal) was computed by weighting component hygroscopicity parameters based on their volume fractions in the mixture. We found that ALWorg, which is often neglected in traditional ALW modelling, contributes a significant fraction (18–32 %) to the total ALW in Beijing. The highest ALWorg fraction appears in the cleanest days when both the organic fraction and κorg are relatively high. The distinct variation of O/C, from 0.2 to 1.3, indicates the wide variety of organic components. This emphasizes the necessity of using real-time κorg, instead of using a fixed κorg, to calculate ALWorg in Beijing. The significant variation of κorg which was calculated from O/C, together with the highly variable organic or inorganic volume fractions, leads to a wide range of κtotal (between 0.20 and 0.45), which exerts great impacts on the water uptake. The variation of organic O/C, or derived κorg, was found to be influenced by T, ALW, and aerosol mass concentrations. Among which, T and ALW both have promoting effects on O/C. During high-ALW haze episodes, although the organic fraction decreases rapidly, O/C, or derived κorg, increases with the increase in ALW, suggesting the formation of more soluble organics via aqueous/heterogeneous-phase process. A positive feedback loop is thus formed: during high-ALW episodes, the ever-increasing κorg, together with the decreasing particle organic fraction (or increasing particle inorganic fraction), increases κtotal, thus further promotes the ability of particles to uptake water.