ALBERT

Description: In this study we describe the hygroscopic properties of accumulation- and coarse-mode aerosol particles sampled at the Zotino Tall Tower Observatory (ZOTTO) in Central Siberia (61° N; 89° E) from 16 to 21 June 2013. The hygroscopic growth measurements were supplemented with chemical analyses of the samples, including inorganic ions and organic/elemental carbon. In addition, the microstructure and chemical composition of aerosol particles were analyzed by X-ray micro-spectroscopy (STXM-NEXAFS) and transmission electron microscopy (TEM). A mass closure analysis indicates that organic carbon accounted for 61 and 38% of PM in the accumulation mode and coarse mode, respectively. The water soluble fraction of organic matter was estimated to be 52 and 8% of PM in these modes. Sulfate, predominantly in the form of ammoniated sulfate, was the dominant inorganic component in both size modes: ∼34% in the accumulation vs. ∼47% in the coarse mode. The hygroscopic growth measurements were conducted with a filter-based differential hygroscopicity analyzer (FDHA) over the range of 5–99.4% RH in the hydration and dehydration operation modes. The FDHA study indicates that both accumulation and coarse modes exhibit pronounced water uptake approximately at the same RH, starting at ∼70%, while efflorescence occurred at different humidities, i.e., at ∼35% RH for submicron particles vs. ∼50% RH for supermicron particles. This ∼15% RH difference was attributed to higher content of organic material in the submicron particles, which suppresses water release in the dehydration experiments. The kappa mass interaction model (KIM) was applied to characterize and parameterize non-ideal solution behavior and concentration-dependent water uptake by atmospheric aerosol samples in the 5–99.4% RH range. Based on KIM, the volume-based hygroscopicity parameter, κv, was calculated. The κv, ws value related to the water soluble (ws) fraction was estimated to be ∼0.15 for the accumulation mode and ∼0.36 for the coarse mode, respectively. The obtained κv, ws for the accumulation mode is in good agreement with earlier data reported for remote sites in the Amazon rain forest (κv ≈ 0.15) and a Colorado boreal forest (κv ≈ 0.16). We used the Zdanovskii–Stokes–Robinson (ZSR) mixing rule to predict the chemical composition dependent hygroscopicity, κv, p. The obtained κv, p values overestimate the experimental FDHA-KIM-derived κv, ws by factors of 1.8 and 1.5 for the accumulation and coarse modes, respectively. This divergence can be partly explained by incomplete dissolution of the hygroscopic inorganic compounds resulting from kinetic limitations due to a sparingly soluble organic coating. The TEM and STXM-NEXAFS results indicate that aged submicron (〉300 nm) and supermicron aerosol particles possess core-shell structures with an inorganic core, and are enriched in organic carbon at the mixed particle surface. The direct FDHA kinetic studies provide a bulk diffusion coefficient of water of ∼10−12 cm2 s−1 indicating a semi-solid state of the organic-rich phase leading to kinetic limitations of water uptake and release during hydration and dehydration cycles. Overall the present ZOTTO data set, obtained in the growing season, has revealed a strong influence of organic carbon on the hygroscopic properties of the ambient aerosols. The sparingly soluble organic coating controls hygroscopic growth, phase transitions, and microstructural rearrangement processes. The observed kinetic limitations can strongly influence the outcome of experiments performed on multi-second time scales, such as the commonly applied HTDMA (Hygroscopicity Tandem Differential Mobility Analyzer) and CCNC (Cloud Condensation Nuclei Counter) measurements.

Description: New particle formation (NPF) has been investigated intensively during the last two decades because of its influence on aerosol population and the possible contribution to cloud condensation nuclei. However, intensive measurements and modelling activities on this topic in urban metropolitans in China with frequently high pollution episodes are still very limited. This study provides results from a comprehensive modelling study on the occurrence of new particle formation events in the western part of the Yangtze River Delta region (YRD), China. The comprehensive modelling system, which combines regional chemical transport model WRF-Chem (the Weather Research and Forecasting model coupled with Chemistry) and the sectional box model MALTE-BOX (the model to predict new aerosol formation in the lower troposphere), was shown to be capable of simulating atmospheric nucleation and subsequent growth. Here we present a detailed discussion of three typical NPF days, during which the measured air masses were notably influenced by either anthropogenic activities, biogenic emissions, or mixed ocean and continental sources. Overall, simulated NPF events were generally in good agreement with the corresponding measurements, enabling us to get further insights into NPF processes in the YRD region. Based on the simulations, we conclude that besides gas-phase sulphuric acid, biogenic organic compounds, particularly monoterpenes, play an essential role in condensational growth of newly formed clusters and probably also in the particle formation process through their low volatile oxidation products. Although some uncertainties remain in this modelling system, this method provides a possibility to better understand the NPF processes.

Description: Aerosol particles play important roles in regional air quality and global climate change. In this study, we analyzed two-year (2011–2013) of measurements of submicron particles (6–800 nm) at a suburban site in western Yangtze River delta (YRD) of East China. The number concentrations (NCs) of particles in the nucleation, Aitken and accumulation modes were 5300 ± 5500, 8000 ± 4400, 5800 ± 3200 cm-3, respectively. Number concentrations and size distributions of submicron particles were also influenced by long-range and regional transport of air masses. The highest and lowest accumulation mode particle number concentrations were observed in air masses from YRD and coastal region, respectively. Continental air masses from inland had the highest concentrations of nucleation mode particles. New particle formation (NPF) events, apparent in 44% of the effective measurement days, occurred frequently in all the seasons except winter. Radiation and pre-existing particles were found to be the main factors influencing the occurrence of NPF events. The particle formation rate was the highest in spring (3.6 ± 2.4 cm-3 s-1), whereas the particle growth rate had the highest values in summer (12.8 ± 4.4 nm h-1). The formation rate was typically high in relatively clean air masses, whereas the growth rate tended to be high in the polluted YRD air masses. The frequency of NPF events and the growth rate showed a strong year-to-year difference. In the summer of 2013, associated with a multi-week heat wave and photochemical pollution, NPF events occurred more frequently and the growth rate was much higher than in the same period of 2012. The difference in the location and strength of sub-tropical High, which influences the air mass transport pathways and solar radiation, seems to be the driving cause for year-to-year differences. This study reported the longest continuous measurement records of submicron particles in the East China and gained a comprehensive understanding of the main factors controlling the seasonal and year-to-year variation of the aerosol size distribution and NPF in the East China. The work highlights the importance and need for long-term measurements in understanding the atmosphere system and the impact by human activities.

Description: The Amazon Basin plays key roles in the carbon and water cycles, climate change, atmospheric chemistry, and biodiversity. It already has been changed significantly by human activities, and more pervasive change is expected to occur in the next decades. It is therefore essential to establish long-term measurement sites that provide a baseline record of present-day climatic, biogeochemical, and atmospheric conditions and that will be operated over coming decades to monitor change in the Amazon region as human perturbations increase in the future. The Amazon Tall Tower Observatory (ATTO) has been set up in a pristine rain forest region in the central Amazon Basin, about 150 km northeast of the city of Manaus. An ecological survey including a biodiversity assessment has been conducted in the forest region surrounding the site. Two 80 m towers have been operated at the site since 2012, and a 325 m tower is nearing completion in mid-2015. Measurements of micrometeorological and atmospheric chemical variables were initiated in 2012, and their range has continued to broaden over the last few years. The meteorological and micrometeorological measurements include temperature and wind profiles, precipitation, water and energy fluxes, turbulence components, soil temperature profiles and soil heat fluxes, radiation fluxes, and visibility. A tree has been instrumented to measure stem profiles of temperature, light intensity, and water content in cryptogamic covers. The trace gas measurements comprise continuous monitoring of carbon dioxide, carbon monoxide, methane, and ozone at 5 to 8 different heights, complemented by a variety of additional species measured during intensive campaigns (e.g., VOC, NO, NO2, and OH reactivity). Aerosol optical, microphysical, and chemical measurements are made above the canopy as well as in the canopy space. They include light scattering and absorption, aerosol fluorescence, number and volume size distributions, chemical composition, cloud condensation nuclei (CCN) concentrations, and hygroscopicity. Initial results from ecological, meteorological, and chemical studies at the ATTO site are presented in this paper.

Description: Concentrations of leaf nitrogen (N) and phosphorus (P) are key leaf traits in ecosystem functioning and dynamics. Foliar stoichiometry varies remarkably among life forms. However, previous studies have focused on trees and grasses, leaving the knowledge gap for the stoichiometric patterns of shrubs. In this study, we explored the intra- and interspecific variations of leaf N and P concentration in relation to climate, soil property and evolutionary history based on 1486 samples composed of 163 shrub species from 361 shrubland sites in northern China expanding 46.1° (86.7–132.8° E) in longitude and 19.8° (32.6–52.4° N) in latitude. The results showed that leaf N concentration decreased with precipitation, leaf P concentration decreased with temperature and increased with precipitation and soil P concentration. Both leaf N and P concentrations were phylogenetically conserved, but leaf P concentration was less conserved than leaf N concentration. At community level, climates explained more interspecific, while soil nutrient explained more intraspecific, variation of leaf nutrient concentrations. These results suggested that leaf N and P concentrations responded to climate, soil, and phylogeny in different ways. Climate influenced the community chemical traits through the shift in species composition, whereas soil directly influenced the community chemical traits.

Description: Aerosol optical properties were measured with a seven-wavelength aethalometer and a three-wavelength nephelometer at the suburban site SORPES in Nanjing, China, in September 2013–January 2015. The aethalometer compensation parameter k, calculated with the Virkkula et al. (2007) method depended on the backscatter fraction, measured with an independent method, the integrating nephelometer. At λ = 660 nm the daily averaged compensation parameter k ≈ 0.0017 ± 0.0002 and 0.0042 ± 0.0013 when backscatter fraction at λ = 635 nm was in the ranges of 0.100 ± 0.005 and 0.160 ± 0.005, respectively. Also, the wavelength dependency of the compensation parameter depended on the backscatter fraction: when b(λ = 525 nm) was less than approximately 0.13 the compensation parameter decreased with wavelength and at larger b it increased with wavelength. This dependency has not been considered in any of the algorithms that are currently used for processing aethalometer data. The compensation parameter also depended on the single-scattering albedo ω0 so that k decreased with increasing ω0. For the green light (λ = 520 nm) in the ω0 range 0.870 ± 0.005, the average (± standard deviation) k ≈ 0.0047 ± 0.006 and in the ω0 range 0.960 ± 0.005, k ≈ 0.0028 ± 0.0007. This difference was larger for the near-infrared light (λ = 880 nm): in the ω0 range 0.860 ± 0.005, k ≈ 0.0055 ± 0.0023 and in the ω0 range 0.960 ± 0.005, k ≈ 0.0019 ± 0.0011. The negative dependence of k on ω0 was also shown with a simple theoretical analysis.

Description: Aerosol particles play important roles in regional air quality and global climate change. In this study, we analyzed 2 years (2011–2013) of measurements of submicron particles (6–800 nm) at a suburban site in the western Yangtze River Delta (YRD) of eastern China. The number concentrations (NCs) of particles in the nucleation, Aitken and accumulation modes were 5300 ± 5500, 8000 ± 4400, 5800 ± 3200 cm−3, respectively. The NCs of total particles are comparable to those at urban/suburban sites in other Chinese megacities, such as Beijing, but about 10 times higher than in the remote western China. Long-range and regional transport largely influenced number concentrations and size distributions of submicron particles. The highest and lowest accumulation-mode particle number concentrations were observed in air masses from the YRD and coastal regions, respectively. Continental air masses from inland brought the highest concentrations of nucleation-mode particles. New particle formation (NPF) events, apparent in 44 % of the effective measurement days, occurred frequently in all the seasons except winter. The frequency of NPF in spring, summer and autumn is much higher than other measurement sites in China. Sulfuric acid was found to be the main driver of NPF events. The particle formation rate was the highest in spring (3.6 ± 2.4 cm−3 s−1), whereas the particle growth rate had the highest values in summer (12.8 ± 4.4 nm h−1). The formation rate was typically high in relatively clean air masses, whereas the growth rate tended to be high in the polluted YRD air masses. The frequency of NPF events and the particle growth rates showed a strong year-to-year difference. In the summer of 2013, associated with a multi-week heat wave and strong photochemical processes, NPF events occurred with larger frequency and higher growth rates compared with the same period in 2012. The difference in the location and strength of the subtropical high pressure system, which influences the air mass transport pathways and solar radiation, seems to be the cause for year-to-year differences. This study reports, up to now, the longest continuous measurement records of submicron particles in eastern China and helps to achieve a comprehensive understanding of the main factors controlling the seasonal and year-to-year variation of the aerosol size distribution and NPF in this region.

Description: The Amazon Basin plays key roles in the carbon and water cycles, climate change, atmospheric chemistry, and biodiversity. It has already been changed significantly by human activities, and more pervasive change is expected to occur in the coming decades. It is therefore essential to establish long-term measurement sites that provide a baseline record of present-day climatic, biogeochemical, and atmospheric conditions and that will be operated over coming decades to monitor change in the Amazon region, as human perturbations increase in the future. The Amazon Tall Tower Observatory (ATTO) has been set up in a pristine rain forest region in the central Amazon Basin, about 150 km northeast of the city of Manaus. Two 80 m towers have been operated at the site since 2012, and a 325 m tower is nearing completion in mid-2015. An ecological survey including a biodiversity assessment has been conducted in the forest region surrounding the site. Measurements of micrometeorological and atmospheric chemical variables were initiated in 2012, and their range has continued to broaden over the last few years. The meteorological and micrometeorological measurements include temperature and wind profiles, precipitation, water and energy fluxes, turbulence components, soil temperature profiles and soil heat fluxes, radiation fluxes, and visibility. A tree has been instrumented to measure stem profiles of temperature, light intensity, and water content in cryptogamic covers. The trace gas measurements comprise continuous monitoring of carbon dioxide, carbon monoxide, methane, and ozone at five to eight different heights, complemented by a variety of additional species measured during intensive campaigns (e.g., VOC, NO, NO2, and OH reactivity). Aerosol optical, microphysical, and chemical measurements are being made above the canopy as well as in the canopy space. They include aerosol light scattering and absorption, fluorescence, number and volume size distributions, chemical composition, cloud condensation nuclei (CCN) concentrations, and hygroscopicity. In this paper, we discuss the scientific context of the ATTO observatory and present an overview of results from ecological, meteorological, and chemical pilot studies at the ATTO site.

Description: In this study we describe the hygroscopic properties of accumulation- and coarse-mode aerosol particles sampled at the Zotino Tall Tower Observatory (ZOTTO) in central Siberia (61° N, 89° E) from 16 to 21 June 2013. The hygroscopic growth measurements were supplemented with chemical analyses of the samples, including inorganic ions and organic/elemental carbon. In addition, the microstructure and chemical compositions of aerosol particles were analyzed by x-ray micro-spectroscopy (STXM-NEXAFS) and transmission electron microscopy (TEM). A mass closure analysis indicates that organic carbon accounted for 61 and 38 % of particulate matter (PM) in the accumulation mode and coarse mode, respectively. The water-soluble fraction of organic matter was estimated to be 52 and 8 % of PM in these modes. Sulfate, predominantly in the form of ammoniated sulfate, was the dominant inorganic component in both size modes: ~ 34 % in the accumulation mode vs. ~ 47 % in the coarse mode. The hygroscopic growth measurements were conducted with a filter-based differential hygroscopicity analyzer (FDHA) over the range of 5–99.4 % RH in the hydration and dehydration operation modes. The FDHA study indicates that both accumulation and coarse modes exhibit pronounced water uptake approximately at the same relative humidity (RH), starting at ~ 70 %, while efflorescence occurred at different humidities, i.e., at ~ 35 % RH for submicron particles vs. ~ 50 % RH for supermicron particles. This ~ 15 % RH difference was attributed to higher content of organic material in the submicron particles, which suppresses water release in the dehydration experiments. The kappa mass interaction model (KIM) was applied to characterize and parameterize non-ideal solution behavior and concentration-dependent water uptake by atmospheric aerosol samples in the 5–99.4 % RH range. Based on KIM, the volume-based hygroscopicity parameter, κv, was calculated. The κv,ws value related to the water-soluble (ws) fraction was estimated to be ~ 0.15 for the accumulation mode and ~ 0.36 for the coarse mode, respectively. The obtained κv,ws for the accumulation mode is in good agreement with earlier data reported for remote sites in the Amazon rain forest (κv ≈ 0.15) and a Colorado mountain forest (κv ≈ 0.16 ). We used the Zdanovskii–Stokes–Robinson (ZSR) mixing rule to predict the chemical composition dependent hygroscopicity, κv,p. The obtained κv,p values overestimate the experimental FDHA-KIM-derived κv,ws by factors of 1.8 and 1.5 for the accumulation and coarse modes, respectively. This divergence can be explained by incomplete dissolution of the hygroscopic inorganic compounds resulting from kinetic limitations due to a sparingly soluble organic coating. The TEM and STXM-NEXAFS results indicate that aged submicron (〉 300 nm) and supermicron aerosol particles possess core–shell structures with an inorganic core, and are enriched in organic carbon at the mixed particle surface. The direct FDHA kinetic studies provide a bulk diffusion coefficient of water of ~ 10−12 cm2 s−1 indicating a semi-solid state of the organic-rich phase leading to kinetic limitations of water uptake and release during hydration and dehydration cycles. Overall, the present ZOTTO data set, obtained in the growing season, has revealed a strong influence of organic carbon on the hygroscopic properties of the ambient aerosols. The sparingly soluble organic coating controls hygroscopic growth, phase transitions, and microstructural rearrangement processes. The observed kinetic limitations can strongly influence the outcome of experiments performed on multi-second timescales, such as the commonly applied HTDMA (Hygroscopicity Tandem Differential Mobility Analyzer) and CCNC (Cloud Condensation Nuclei Counter) measurements.

Description: Aerosol optical properties were measured with a 7-wavelength aethalometer and a 3-wavelength nephelometer at the suburban site SORPES in Nanjing, China, in September 2013–January 2015. The aethalometer compensation parameter k, calculated with the Virkkula et al. (2007) method depended on the backscatter fraction, measured with the independent method, the integrating nephelometer. At λ = 660 nm the daily-averaged compensation parameter k ≈ 0.0017 ± 0.0002 and 0.0042 ± 0.0013 when backscatter fraction at λ = 635 nm was in the ranges of 0.100 ± 0.005 and 0.160 ± 0.005, respectively. Also the wavelength dependency of the compensation parameter depended on the backscatter fraction: when b(λ = 525 nm) was less than approximately 0.13 the compensation parameter decreased with wavelength and at larger b it increased with wavelength. This dependency has not been considered in any of the algorithms that are currently used for processing aethalometer data. The compensation parameter also depended on single-scattering albedo ω0 so that k decreased with increasing ω0. For the green light (λ = 520 nm) in the ω0 range 0.870 ± 0.005 the average (± standard deviation) k ≈ 0.0047 ± 0.006 and in the ω0 range 0.960 ± 0.005 k ≈ 0.0028 ± 0.0007. This difference was larger for the near-infrared light (λ = 880 nm): in the ω0 range 0.860 ± 0.005 k ≈ 0.0055 ± 0.0023 and in the ω0 range 0.960 ± 0.005 k ≈ 0.0019 ± 0.0011. The negative dependence of k on ω0 was also shown with a simple theoretical analysis.