ALBERT

Description: As part of the 2008 Campaign of Air Quality Research in Beijing and Surrounding Regions (CAREBeijing 2008), measurements of gaseous sulfuric acid (H2SO4) have been conducted at an urban site in Beijing, China from 7 July to 25 September 2008 using atmospheric pressure ion drift – chemical ionization mass spectrometry (AP-ID-CIMS). This represents the first gaseous H2SO4 measurements in China. Diurnal profile of sulfuric acid is strongly dependent on the actinic flux, reaching a daily maximum around noontime and with an hourly average concentration of 5 × 106 molecules cm−3. Simulation of sulfuric acid on the basis of the measured sulfur dioxide concentration, photolysis rates of ozone and nitrogen dioxide, and aerosol surface areas captures the trend of the measured H2SO4 diurnal variation within the uncertainties, indicating that photochemical production and condensation onto preexisting particle surface dominate the observed diurnal H2SO4 profile. The frequency of the peak H2SO4 concentration exceeding 5 × 106 molecules cm−3 increases by 16 % during the period of the summer Olympic Games (8–24 August 2008), because of the implementation of air quality control regulations. Using a multivariate statistical method, the critical nucleus during nucleation events is inferred, containing two H2SO4 molecules (R2 = 0.85). The calculated condensation rate of H2SO4 can only account for 10–25 % of PM1 sulfate formation, indicating that either much stronger sulfate production exists at the SO2 source region or other sulfate production mechanisms are responsible for the sulfate production.

Description: Aerosol particles in the atmosphere are important participants in the formation of cloud droplets and have significant impact on cloud albedo and global climate. According to the Köhler theory which describes the nucleation and the equilibrium growth of cloud droplets, the surface tension of an aerosol droplet is one of the most important factors that determine the critical supersaturation of droplet activation. In this paper, with specific interest to remote marine aerosol, we predict the surface tension of aerosol droplets by performing molecular dynamics simulations on two model systems, the pure water droplets and glycine in water droplets. The curvature dependence of the surface tension is interpolated by a quadratic polynomial over the nano-sized droplets and the limiting case of a planar interface, so that the so-called Aitken mode particles which are critical for droplet formation could be covered and the Köhler equation could be improved by incorporating surface tension corrections.

Description: We performed MAX-DOAS measurements during the PRiDe-PRD2006 campaign in the Pearl River Delta region 50 km north of Guangzhou, China, for 4 weeks in June 2006. We used an instrument sampling at 7 different elevation angles between 3° and 90°. During 9 cloud-free days, differential slant column densities (DSCDs) of O4 (O2 dimer) absorptions between 351 nm and 389 nm were evaluated for 6 elevation angles. Here, we show that radiative transfer modeling of the DSCDS can be used to retrieve the aerosol extinction and the height of the boundary layer. A comparison of the aerosol extinction with simultaneously recorded, ground based nephelometer data shows excellent agreement.

Description: The Project of Atmospheric Combined Pollution Monitoring over Beijing and its Surrounding Areas, was an intensive field campaign conducted over Northern China between June 2009 and August 2011 to provide a comprehensive record of ozone (O3) and nitrogen oxides (NOx) and contribute to an in-depth understanding of air pollution in Northern China and its driving forces. In this campaign, 25 stations in an air-quality monitoring network provided regional-scale spatial coverage. In this study, we analyzed the data on O3 and NOx levels obtained at 22 sites (out of 25 sites due to data availability) over Northern China between 1 September 2009 and 31 August 2010. Our goal was to investigate the O3 spatial-temporal variations and control strategy in this area. Significant diurnal and seasonal variations were noted, with the highest concentrations typically found at around 03:00 p.m. (local time) and in June. The lowest concentrations were generally found during early morning hours (around 06:00 a.m.) and in December. Compared with July and August, June has increased photochemical production due to decreased cloud cover coupled with reduced O3 loss due to less dry deposition, inducing an O3 peak appearing in June. The averaged O3 concentrations were lower in the plains area compared with the mountainous area due to the titration effects of high NOx emissions in urban areas. When the characteristics of O3 pollution in different regions were distinguished by factor analysis, we found high levels of O3 that exceeded China's National Standard throughout the plains, especially over Beijing and the surrounding areas. An integrated analysis with emissions data, meteorological data, and topography over Northern China found that the meteorological conditions were the main factors that dominated the spatial variations of O3, with the presence of abundant emissions of precursors in this area. The smog production algorithm and space-based HCHO/NO2 column ratio were used to show the O3-NOx-VOCs sensitivity and examine the control strategy of O3 over Northern China. The results show that summer O3 production in the plains and northern mountainous areas was sensitive to VOCs and NOx, respectively. The presented results are intended to provide guidance for redefining government strategies to control the photochemical formation of air pollutants over Northern China and are relevant for developing urban agglomerations worldwide.

Description: We performed measurements of nitrous acid (HONO) during the PRIDE-PRD2006 campaign in the Pearl River Delta region 60 km north of Guangzhou, China, for 4 weeks in June 2006. HONO was measured by a LOPAP in-situ instrument which was setup in one of the campaign supersites along with a variety of instruments measuring hydroxyl radicals, trace gases, aerosols, and meteorological parameters. Maximum diurnal HONO mixing ratios of 1–5 ppb were observed during the nights. We found that the nighttime build-up of HONO can be attributed to the heterogeneous NO2 to HONO conversion on ground surfaces and the OH + NO reaction. In addition to elevated nighttime mixing ratios, measured noontime values of ≈200 ppt indicate the existence of a daytime source higher than the OH + NO→HONO reaction. Using the simultaneously recorded OH, NO, and HONO photolysis frequency, a daytime additional source strength of HONO (PM) was calculated to be 0.77 ppb h−1 on average. This value compares well to previous measurements in other environments. Our analysis of PM provides evidence that the photolysis of HNO3 adsorbed on ground surfaces contributes to the HONO formation.

Description: As part of the 2008 Campaign of Air Quality Research in Beijing and Surrounding Regions (CAREBeijing 2008), measurements of gaseous sulfuric acid (H2SO4) have been conducted at an urban site in Beijing, China from 7 July to 25 September 2008 using atmospheric pressure ion drift – chemical ionization mass spectrometry (AP-ID-CIMS). This represents the first gaseous H2SO4 measurements in China. Diurnal profile of sulfuric acid is strongly dependent on the actinic flux, reaching a daily maximum around noontime and with an hourly average concentration of 5 × 106 molecule cm−3. Simulation of sulfuric acid on the basis of the measured sulfur dioxide concentration, photolysis rates of ozone and nitrogen dioxide, and aerosol surface areas captures the trend of the measured H2SO4 diurnal variation within the uncertainties, indicating that photochemical production and condensation onto preexisting particle surface dominate the observed diurnal H2SO4 profile. The frequency of the peak H2SO4 concentration exceeding 5 × 106 molecule cm−3 increases by 16% during the period of the summer Olympic Games (8–23 August 2008), because of the implementation of air quality control regulations. Using a multivariate statistical method, the critical nucleus during nucleation events is inferred, containing two H2SO4 molecules (R2 = 0.85). When neither nucleation nor precipitation occurs, the condensation rate of H2SO4 correlates with the daytime sulfate mass concentration of the Aitken mode, but not with that of the accumulation mode aerosols.

Description: Atmospheric amino acids constitute an important fraction of the water-soluble organic nitrogen compounds in both marine and continental aerosols, and have been confirmed as effective cloud condensation nuclei materials in laboratory tests. We here present a molecular dynamics study of amino acids representative for the remote marine atmospheric aerosol-cloud system, in order to investigate molecular distributions, orientations and induced changes in surface tension, and to evaluate their indirect effects on optical properties of clouds. These L-amino acids, including serine, glycine, alanine, valine, methionine and phenylalanine, are categorized as hydrophilic and hydrophobic according to their affinities to water. Different amino acids show distinct effects on the surface tension; even the same amino acid has different influence on the surface tension for planar and spherical interfaces. The curvature dependence of the surface tension is modelled by a quadratic polynomial function of the inverse of droplet radius, and such relationship is used to improve the Köhler equation in predicting the critical water vapour supersaturation of the droplet activation.

Description: Ambient OH and HO2 concentrations were measured by laser induced fluorescence (LIF) during the PRIDE-PRD2006 (Program of Regional Integrated Experiments of Air Quality over the Pearl River Delta, 2006) campaign at a rural site downwind of the megacity of Guangzhou in Southern China. The observed OH concentrations reached daily peak values of (15–26) × 106 cm−3 which are among the highest values so far reported for urban and suburban areas. The observed OH shows a consistent high correlation with j(O1D) over a broad range of NOx conditions. The correlation cannot be reproduced by model simulations, indicating that OH stabilizing processes are missing in current models. The observed OH exhibited a weak dependence on NOx in contrast to model predictions. While modelled and measured OH agree well at NO mixing ratios above 1 ppb, a continuously increasing underprediction of the observed OH is found towards lower NO concentrations, reaching a factor of 8 at 0.02 ppb NO. A dependence of the modelled-to-measured OH ratio on isoprene cannot be concluded from the PRD data. However, the magnitude of the ratio fits into the isoprene dependent trend that was reported from other campaigns in forested regions. Hofzumahaus et al. (2009) proposed an unknown OH recycling process without NO, in order to explain the high OH levels at PRD in the presence of high VOC reactivity and low NO. Taking a recently discovered interference in the LIF measurement of HO2 into account, the need for an additional HO2 → OH recycling process persists, but the required source strength may be up to 20% larger than previously determined. Recently postulated isoprene mechanisms by Lelieveld et al. (2008) and Peeters and Müller (2010) lead to significant enhancements of OH expected for PRD, but an underprediction of the observed OH by a factor of two remains at low NO (0.1–0.2 ppb). If the photolysis of hydroperoxy aldehydes from isoprene is as efficient as proposed by Peeters and Müller (2010), the corresponding OH formation at PRD would be more important than the primary OH production from ozone and HONO. While the new isoprene mechanisms need to be confirmed by laboratory experiments, there is probably need for other, so far unidentified chemical processes to explain entirely the high OH levels observed in Southern China.

Description: Measurements of ambient OH and HO2 radicals were performed by laser induced fluorescence (LIF) during CAREBeijing2006 (Campaigns of Air Quality Research in Beijing and Surrounding Region 2006) at the suburban site Yufa in the south of Beijing in summer 2006. On most days, local air chemistry was influenced by aged air pollution that was advected by a slow, almost stagnant wind from southern regions. Observed daily maxima of OH and HO2* were in the range of (4–17) × 106 cm−3 and (2–24) × 108 cm−3, respectively. During daytime, OH reactivities were generally high (10–30 s−1) and mainly contributed by VOCs and their oxidation products. The comparison of modelled and measured HOx concentrations reveals a systematic underprediction of OH as a function of NO. A large discrepancy of a factor 2.6 is found at the lowest NO concentration encountered (0.1 ppb), whereas the discrepancy becomes insignificant above 1 ppb NO. This study extends similar observations from the Pearl-River Delta (PRD) in South China to a more urban environment. The OH discrepancy at Yufa can be resolved, if NO-independent additional OH recycling is assumed in the model. The postulated Leuven Isoprene Mechanism (LIM) has the potential to explain the gap between modelled and measured OH at Beijing taking into account conservative error estimates, but still lacks experimental confirmation. This and the hereby unresolved discrepancy at PRD suggest that other VOCs besides isoprene might be involved in the required, additional OH recycling. Fast primary production of ROx radicals up to 7 ppb h−1 was determined at Beijing which was dominated by the photolysis of O3, HONO, HCHO, and dicarbonyls. For a special case, 20 August, when the plume of Beijing city was encountered, a missing primary HOx source (≈ 3 ppb h−1) was determined under high NOx conditions similar to other urban areas like Mexico city. CAREBeijing2006 emphasizes the important role of OVOCs as a radical source and sink, and the need for further investigation of the chemical degradation of VOCs in order to better understand radical chemistry in VOC-rich air.

Description: Microorganisms are continuously blown onto the glacier snow, and thus the glacial depth profiles provide excellent archives of microbial communities and climatic and environmental changes. However, it is uncertain about how aeolian processes that cause climatic changes control the distribution of microorganisms in the glacier ice. In the present study, microbial density, stable isotopic ratios, 18O / 16O in the precipitation, and mineral particle concentrations along the glacial depth profiles were collected from ice cores from the Muztag Ata glacier and the Dunde ice cap. The ice core data showed that microbial abundance was often, but not always associated with high concentrations of particles. Results also revealed clear seasonal patterning with high microbial abundance occurring in both the cooling autumn and warming spring-summer seasons. Microbial comparisons among the neighbouring glaciers display a heterogeneous spatial pattern, with the highest microbial cell density in the glaciers lying adjacent to the central Asian deserts and lowest microbial density in the southwestern margin of the Tibetan Plateau. In conclusion, microbial data of the glaciers indicates the aeolian deposits of microorganisms in the glacier ice and that the spatial patterns of microorgansisms are related to differences in sources of microbial flux and intensity of aeolian activities in the current regions. The results strongly support our hypothesis of aeolian activities being the main agents controlling microbial load in the glacier ice.