Hygroscopicity Of Aerosol Particles Research Articles

A broad supersaturation scanning (BS2) approach for rapid measurement of aerosol particle hygroscopicity and cloud condensation nuclei activity

Abstract. The activation and hygroscopicity of cloud condensation nuclei (CCN) are key to the understanding of aerosol–cloud interactions and their impact on climate. They can be measured by scanning the particle size and supersaturation in CCN measurements. The scanning of supersaturation is often time-consuming and limits the temporal resolution and performance of CCN measurements. Here we present a new approach, termed the broad supersaturation scanning (BS2) method, in which a range of supersaturation is simultaneously scanned, reducing the time interval between different supersaturation scans. The practical applicability of the BS2 approach is demonstrated with nano-CCN measurements of laboratory-generated aerosol particles. Model simulations show that the BS2 approach may also be applicable for measuring CCN activation of ambient mixed particles. Due to its fast response and technical simplicity, the BS2 approach may be well suited for aircraft and long-term measurements. Since hygroscopicity is closely related to the fraction of organics/inorganics in aerosol particles, a BS2-CCN counter can also serve as a complementary sensor for fast detection/estimation of aerosol chemical compositions.

Linking variations in sea spray aerosol particle hygroscopicity to composition during two microcosm experiments

Abstract. The extent to which water uptake influences the light scattering ability of marine sea spray aerosol (SSA) particles depends critically on SSA chemical composition. The organic fraction of SSA can increase during phytoplankton blooms, decreasing the salt content and therefore the hygroscopicity of the particles. In this study, subsaturated hygroscopic growth factors at 85 % relative humidity (GF(85 %)) of predominately submicron SSA particles were quantified during two induced phytoplankton blooms in marine aerosol reference tanks (MARTs). One MART was illuminated with fluorescent lights and the other was illuminated with sunlight, referred to as the "indoor" and "outdoor" MARTs, respectively. Optically weighted GF(85 %) values for SSA particles were derived from measurements of light scattering and particle size distributions. The mean optically weighted SSA diameters were 530 and 570 nm for the indoor and outdoor MARTs, respectively. The GF(85 %) measurements were made concurrently with online particle composition measurements, including bulk composition (using an Aerodyne high-resolution aerosol mass spectrometer) and single particle (using an aerosol time-of-flight mass spectrometer) measurement, and a variety of water-composition measurements. During both microcosm experiments, the observed optically weighted GF(85 %) values were depressed substantially relative to pure inorganic sea salt by 5 to 15 %. There was also a time lag between GF(85 %) depression and the peak chlorophyll a (Chl a) concentrations by either 1 (indoor MART) or 3-to-6 (outdoor MART) days. The fraction of organic matter in the SSA particles generally increased after the Chl a peaked, also with a time lag, and ranged from about 0.25 to 0.5 by volume. The observed depression in the GF(85 %) values (relative to pure sea salt) is consistent with the large observed volume fractions of non-refractory organic matter (NR-OM) comprising the SSA. The GF(85 %) values exhibited a reasonable negative correlation with the SSA NR-OM volume fractions after the peak of the blooms (i.e., Chl a maxima); i.e., the GF(85 %) values generally decreased when the NR-OM volume fractions increased. The GF(85 %) vs. NR-OM volume fraction relationship was interpreted using the Zdanovskii–Stokes–Robinson (ZSR) mixing rule and used to estimate the GF(85 %) of the organic matter in the nascent SSA. The estimated pure NR-OM GF(85 %) values were 1.16 ± 0.09 and 1.23 ± 0.10 for the indoor and outdoor MARTS, respectively. These measurements demonstrate a clear relationship between SSA particle composition and the sensitivity of light scattering to variations in relative humidity. The implications of these observations to the direct climate effects of SSA particles are discussed.

Hygroscopicity of aerosol particles and CCN activity of nearly hydrophobic particles in the urban atmosphere over Japan during summer

AbstractWe investigated the hygroscopicity of 150 nm particles and the number‐size distributions and the cloud condensation nuclei (CCN) activity of nearly hydrophobic particles in aerosols over Nagoya, Japan, during summer. We analyzed the correlations between the number concentrations of particles in specific hygroscopic growth factor (g) ranges and the mass concentrations of chemical components. This analysis suggests the association of nearly hydrophobic particles with hydrocarbon‐like organic aerosol, elemental carbon and semivolatile oxygenated organic aerosol (SV‐OOA), that of less hygroscopic particles with SV‐OOA and nitrate and that of more hygroscopic particles with low‐volatile oxygenated organic aerosol (LV‐OOA) and sulfate. The hygroscopicity parameter (κ) of organics was derived based on the g distributions and chemical composition of 150 nm particles. The κ of the organics correlated positively with the fraction of the total organic mass spectral signal at m/z 44 and the volume fraction of the LV‐OOA to the organics, indicating that organics with highly oxygenated structures including carboxylic acid groups contribute to the water uptake. The number‐size distributions of the nearly hydrophobic particles with g around 1.0 and 1.1 correlated with the mass concentrations of chemical components. The results show that the chemical composition of the particles with g around 1.0 was different between the Aitken mode and the accumulation mode size ranges. An analysis for a parameter Fmax of the curves fitted to the CCN efficiency spectra of the particles with g around 1.0 suggests that the coating by organics associated with SV‐OOA elevated the CCN activity of these particles.

A synthesis of cloud condensation nuclei counter (CCNC) measurements within the EUCAARI network

Abstract. Cloud condensation nuclei counter (CCNC) measurements performed at 14 locations around the world within the European Integrated project on Aerosol Cloud Climate and Air Quality interactions (EUCAARI) framework have been analysed and discussed with respect to the cloud condensation nuclei (CCN) activation and hygroscopic properties of the atmospheric aerosol. The annual mean ratio of activated cloud condensation nuclei (NCCN) to the total number concentration of particles (NCN), known as the activated fraction A, shows a similar functional dependence on supersaturation S at many locations – exceptions to this being certain marine locations, a free troposphere site and background sites in south-west Germany and northern Finland. The use of total number concentration of particles above 50 and 100 nm diameter when calculating the activated fractions (A50 and A100, respectively) renders a much more stable dependence of A on S; A50 and A100 also reveal the effect of the size distribution on CCN activation. With respect to chemical composition, it was found that the hygroscopicity of aerosol particles as a function of size differs among locations. The hygroscopicity parameter κ decreased with an increasing size at a continental site in south-west Germany and fluctuated without any particular size dependence across the observed size range in the remote tropical North Atlantic and rural central Hungary. At all other locations κ increased with size. In fact, in Hyytiälä, Vavihill, Jungfraujoch and Pallas the difference in hygroscopicity between Aitken and accumulation mode aerosol was statistically significant at the 5 % significance level. In a boreal environment the assumption of a size-independent κ can lead to a potentially substantial overestimation of NCCN at S levels above 0.6 %. The same is true for other locations where κ was found to increase with size. While detailed information about aerosol hygroscopicity can significantly improve the prediction of NCCN, total aerosol number concentration and aerosol size distribution remain more important parameters. The seasonal and diurnal patterns of CCN activation and hygroscopic properties vary among three long-term locations, highlighting the spatial and temporal variability of potential aerosol–cloud interactions in various environments.

Structural Change of Aerosol Particle Aggregates with Exposure to Elevated Relative Humidity

Structural changes of aggregates composed of inorganic salts exposed to relative humidity (RH) between 0 and 80% after formation at selected RH between 0 and 60% were investigated using a tandem differential mobility analyzer (TDMA) and fluorescence microscopy. The TDMA was used to measure a shift in peak mobility diameter for 100-700 nm aggregates of hygroscopic aerosol particles composed of NaCl, Na2SO4, (NH4)2SO4, and nonhygroscopic Al2O3 as the RH was increased. Aggregates of hygroscopic particles were found to shrink when exposed to RH greater than that during the aggregation process. The degree of aggregate restructuring is greater for larger aggregates and greater increases in RH. Growth factors (GF) calculated from mobility diameter measurements as low as 0.77 were seen for NaCl before deliquescence. The GF subsequently increased to 1.23 at 80% RH, indicating growth after deliquescence. Exposure to RH lower than that experienced during aggregation did not result in structural changes. Fluorescent microscopy confirmed that aggregates formed on wire surfaces undergo an irreversible change in structure when exposed to elevated RH. Analysis of 2D movement of aggregates shows a displacement of 5-13% compared to projected length of initial aggregate from a wire surface. Surface tension due to water adsorption within the aggregate structure is a potential cause of the structural changes.

Direct measurements of the optical cross sections and refractive indices of individual volatile and hygroscopic aerosol particles.

We present measurements of the evolving extinction cross sections of individual aerosol particles (spanning 700-2500 nm in radius) during the evaporation of volatile components or hygroscopic growth using a combination of a single particle trap formed from a Bessel light beam and cavity ring-down spectroscopy. For single component organic aerosol droplets of 1,2,6-hexanetriol, polyethylene glycol 400, and glycerol, the slow evaporation of the organic component (over time scales of 1000 to 10,000 s) leads to a time-varying size and extinction cross section that can be used to estimate the refractive index of the droplet. Measurements on binary aqueous-inorganic aerosol droplets containing one of the inorganic solutes ammonium bisulfate, ammonium sulfate, sodium nitrate, or sodium chloride (over time scales of 1000 to 15,000 s) under conditions of changing relative humidity show that extinction cross-section measurements are consistent with expectations from accepted models for the variation in droplet refractive index with hygroscopic growth. In addition, we use these systems to establish an experimental protocol for future single particle extinction measurements. The advantages of mapping out the evolving light extinction cross-section of an individual particle over extended time frames accompanied by hygroscopic cycling or component evaporation are discussed.

Numerical investigation of the coagulation mixing between dust and hygroscopic aerosol particles and its impacts

AbstractA statistical‐numerical aerosol parameterization was incorporated into the Community Multiscale Air Quality modeling system to study the coagulation mixing process focusing on a dust storm event that occurred over East Asia. Simulation results show that the coagulation mixing process tends to decrease aerosol mass, surface area, and number concentrations over the dust source areas. Over the downwind oceanic areas, aerosol concentrations generally increased due to enhanced sedimentation as particles became larger upon coagulation. The mixture process can reduce the overall single‐scattering albedo by up to 10% as a result of enhanced core with shell absorption by dust and reduction in the number of scattering particles. The enhanced dry deposition speed also altered the vertical distribution. In addition, the ability of aerosol particles to serve as cloud condensation nuclei (CCN) increased from around 107 m−3 to above 109 m−3 over downwind areas because a large amount of mineral dust particles became effective CCN with solute coating, except over the highly polluted areas where multiple collections of hygroscopic particles by dust in effect reduced CCN number. This CCN effect is much stronger for coagulation mixing than by the uptake of sulfuric acid gas on dust, although the nitric acid gas uptake was not investigated. The ability of dust particles to serve as ice nuclei may decrease or increase at low or high subzero temperatures, respectively, due to the switching from deposition nucleation to immersion freezing or haze freezing.

Composition and hygroscopicity of aerosol particles at Mt. Lu in South China: Implications for acid precipitation

Physicochemical properties of aerosol particles were studied at Mt. Lu, an elevated site (115°59′E, 29°35′N, 1165 m) within the acid precipitation area. Northeast winds transport copious amounts of air pollutants and water vapor from the Yangtze River Delta into this acid precipitation area. NH4+ and SO42− are the dominant ions in PM2.5 and determine aerosol acidity. Individual particle analysis shows abundant S-rich and metals (i.e. Fe-, Zn-, Mn-, and Pb-rich) particles. Unlike aerosol particles in North China and urban areas, there are little soot and mineral particles at Mt. Lu. Lack of mineral particles contributed to the higher acidity in precipitation in the research area. Nano-sized spherical metal particles were observed to be embedded in 37% of S-rich particles. These metal particles were likely originated from heavy industries and fired-power plants. Hygroscopic experiments show that most particles start to deliquesce at 73–76% but organic coating lowers the particle deliquescence relative humidity (DRH) to 63–73%. The DRHs of these aerosol particles are clearly smaller than that of pure ammonium sulfate particles which is 80%. Since RH in ambient air was relatively high, ranging from 65% to 85% during our study period, most particles at our sampling site were in liquid phase. Our results suggest that liquid phase reactions in aerosol particles may contribute to SO2 to sulfuric acid conversion in the acid precipitation area.

Temperature Effect on Phase-Transition Radiation of Water

Infrared radiation associated with vapor-liquid phase transition of water is investigated using a suspension of cloud droplets and mid-infrared (IR) (3–5 μm) radiation absorption measurements. Recent measurements and Monte Carlo (MC) modeling performed at 60 °C and 1 atm resulted in an interfacial radiative phase-transition probability of 5 × 10−8 and a corresponding surface absorption efficiency of 3–4%, depending on wavelength. In this paper, the measurements and modeling have been extended to 75 °C in order to examine the effect of temperature on water's liquid-vapor phase-change radiation. It was found that the temperature dependence of the previously proposed phase-change absorption theoretical framework by itself was insufficient to account for observed changes in radiation absorption without a change in cloud droplet number density. Therefore, the results suggest a strong temperature dependence of cloud condensation nuclei (CCN) concentration, i.e., CCN increasing approximately a factor of two from 60 °C to 75 °C at near saturation conditions. The new radiative phase-transition probability is decreased slightly to 3 × 10−8. Theoretical results were also calculated at 50 °C in an effort to understand behavior at conditions closer to atmospheric. The results suggest that accounting for multiple interface interactions within a single droplet at wavelengths in atmospheric windows (where anomalous IR radiation is often reported) will be important. Modeling also suggests that phase-change radiation will be most important at wavelengths of low volumetric absorption, i.e., atmospheric windows such as 3–5 μm and 8–10 μm, and for water droplets smaller than stable cloud droplet sizes (<20 μm diameter), where surface effects become relatively more important. This could include unactivated, hygroscopic aerosol particles (not CCN) that have absorbed water and are undergoing dynamic evaporation and condensation. This mechanism may be partly responsible for water vapor's IR continuum absorption in these atmospheric windows.

Study of the relative humidity dependence of aerosol light-scattering in southern Spain

This investigation focuses on the characterisation of the aerosol particle hygroscopicity. Aerosol particle optical properties were measured at Granada, Spain, during winter and spring seasons in 2013. Measured optical properties included particle light-absorption coefficient (σap) and particle light-scattering coefficient (σsp) at dry conditions and at relative humidity (RH) of 85±10%. The scattering enhancement factor, f(RH=85%), had a mean value of 1.5±0.2 and 1.6±0.3 for winter and spring campaigns, respectively. Cases of high scattering enhancement were more frequent during the spring campaign with 27% of the f(RH=85%) values above 1.8, while during the winter campaign only 8% of the data were above 1.8. A Saharan dust event (SDE), which occurred during the spring campaign, was characterised by a predominance of large particles with low hygroscopicity. For the day when the SDE was more intense, a mean daily value of f(RH=85%)=1.3±0.2 was calculated. f(RH=85%) diurnal cycle showed two minima during the morning and afternoon traffic rush hours due to the increase in non-hygroscopic particles such as black carbon and road dust. This was confirmed by small values of the single-scattering albedo and the scattering Ångstrom exponent. A significant correlation between f(RH=85%) and the fraction of particulate organic matter and sulphate was obtained. Finally, the impact of ambient RH in the aerosol radiative forcing was found to be very small due to the low ambient RH. For high RH values, the hygroscopic effect should be taken into account since the aerosol forcing efficiency changed from −13 W/m2 at dry conditions to −17 W/m2 at RH=85%.

Lidar retrievals of cloud droplet number concentration at the cumulus base: A feasibility study

The properties of atmospheric aerosol under a cumulus base were studied using three-wavelength lidar. A growth of hygroscopic aerosol particles in a convective updraft and the activation of cloud condensation nuclei (CCN) were observed. A simple and robust model of droplet formation in a rising parcel was used as a closing assumption to the original approach of cloud droplet number concentration (CDNC) retrieval. The potential to retrieve the vertical profile of the effective radius of droplets near the cloud base and the height of activation and condensation of nuclei is demonstrated.

Laboratory Study on the Hygroscopic Behavior of External and Internal C2–C4Dicarboxylic Acid–NaCl Mixtures

Atmospheric aerosol is usually found to be a mixture of various inorganic and organic components in field measurements, whereas the effect of this mixing state on the hygroscopicity of aerosol particles has remained unknown. In this study, the hygroscopic behavior of mixtures of C2-C4 dicarboxylic acids and NaCl was investigated. For both externally and internally mixed malonic acid-NaCl and succinic acid-NaCl particles, correlation between water content and chemical composition was observed and the water content of these mixtures at relative humidity (RH) above 80% can be well predicted by the Zdanovskii-Stokes-Robinson (ZSR) method. In contrast, a nonlinear relation between the total water content of the mixtures and the water content of each chemical composition separately was found for oxalic acid-NaCl mixtures. Compared to the values predicted by the ZSR method, the dissolution of oxalic acid in external mixtures resulted in an increase in the total water content, whereas the formation of less hygroscopic disodium oxalate in internal mixtures led to a significant decrease in the total water content. Furthermore, we found that the hygroscopicity of the sodium dicarboxylate plays a critical role in determining the aqueous chemistry of dicarboxylic acid-NaCl mixtures during the humidifying and dehumidifying process. It was also found that the hydration of oxalic acid and the deliquescence of NaCl did not change in external oxalic acid-NaCl mixtures. The deliquescence relative humidity (DRHs) for both malonic acid and NaCl decreased in both external and internal mixtures. These results could help in understanding the conversion processes of dicarboxylic acids to dicarboxylate salts, as well as the substitution of Cl by oxalate in the atmosphere. It was demonstrated that the effect of coexisting components on the hygroscopic behavior of mixed aerosols should not be neglected.

Characteristics of aerosol transport and distribution in East Asia

We used daily aerosol simulations for the period from 2001 to 2003 that were generated by the Goddard Chemistry Aerosol Radiation and Transport (GOCART) model to characterize aerosol transport and distributions in East Asia. In comparison with the AERONET, MODIS, and visibility observations, the model can capture the main distribution features of the aerosol optical depth (AOD) and its temporal changes with a correlation coefficient of 0.75 and 0.85, respectively. It was found that high AODs occur in Central China, the Sichuan basin, the Indo-China peninsula, the Indian subcontinent, and the Bay of Bengal because of black carbon, organic matter, and sulfate, whereas in the Taklimakan desert and its adjacent regions, high AODs occur because of dust. The potential effects of the hygroscopicity of aerosol particles on the AOD were mainly observed in the Sichuan basin, the Bay of Bengal, the Indo-China peninsula, and Central and Southern China. The East Asian aerosol transport was distinctly affected by the flux divergence induced by aerosol advection (AFD) and by the flux divergence induced by wind divergence/convergence (WFD). For black carbon, organic matter, and sulfate, the effect of AFD was a factor of 2 or 3 larger than that of WFD in the divergence region, whereas AFD dropped to 70% of WFD in the convergence region. The high AOD of black carbon, organic matter, and sulfate over the Sichuan basin related to the circulation characteristics of convergence in low altitudes and divergence in high altitudes, which can collect aerosol from adjacent regions at altitudes below 300hPa and cause them to diverge easterly at higher altitudes.

我国雾-霾成因及其治理的思考

We assess the relationship among haze-fog, aerosol and meteorological conditions, and analyze the chemical compositions and sources of aerosol particles, as well make some suggestions for aerosol control strategy. Present-day haze and fog in China are both dependent on atmospheric aerosol loading and weather conditions. The secondary aerosol formation and changes, which dominate the total aerosol mass and are highly influenced by meteorological conditions, characterized the regional haze feature in East China. In the Huabei Plain, which suffers from intense haze and fog, secondary organic aerosols are found to have similar role like sulphate, contributing to aerosol mass during both new particle formation and aging stages. The organic aerosol mix with inorganic ones to form hygroscopic particles earlier at ～70% relative humidity (RH), but which have a small hygroscopic growth factor. The hygroscopic aerosol particles would also make the PM2.5 mass monitoring at China exhibiting unrealistic high concentration under high RH stage. About 70% of these particles are internally mixed with two or three different aerosol components. Most mineral particles are covered with visible coatings, including fly ash, soot and metal particles, leading to have more secondary aerosol formed on their surface. This complicates haze formation in China. Under high aerosol particle concentrations, greater numbers of cloud droplets with relative small-size are observed in low clouds relative to high clouds; and the associated aerosol impact on cloud microphysical processe is different in less polluted areas. At low supersaturation most of hygroscopic particles larger than 150 nm form cloud condensation nuclei (CCN), and the impact of aerosol chemical composition on CCN activation is significant. There is a high aerosol concentration in China relative to other areas in the world, except for urban South Asia. These particles form under complex conditions and interact with clouds, resulting that present-day haze and fog in China both are not natural phenomenon. Haze and fog reduces surface radiation, making the atmosphere more stable, resulting in continuous coagulation, condensation, accumulation of aerosol, and more CCN activation, leading to serious and maintained haze-fog events. The heavy and persistent haze-fog between 6 and 16 January 2013 in East China was caused by both high aerosol loading and singular static weather conditions. We need to have adequate scientific judgment on the complexity and expectation of aerosol emission reduction in China. The government needs to make informed decisions and implement laws to maintain the health of its people, but this is not easy when we strive for economic growth. There is no easy solution to control aerosol sources, but the government should spare no effort to cut aerosol and their precursors gas emission. Regional pollution control is also very critical; a strong policy and protocol needs to be enforced by the central government to drive provincial leaders to make the necessary changes to ensure better air quality and quality of life for the population.

Cloud condensation nuclei (CCN) from fresh and aged air pollution in the megacity region of Beijing

Abstract. Atmospheric aerosol particles serving as cloud condensation nuclei (CCN) are key elements of the hydrological cycle and climate. CCN properties were measured and characterized during the CAREBeijing-2006 campaign at a regional site south of the megacity of Beijing, China. Size-resolved CCN efficiency spectra recorded for a supersaturation range of S=0.07% to 0.86% yielded average activation diameters in the range of 190 nm to 45 nm. The corresponding effective hygroscopicity parameters (κ) exhibited a strong size dependence ranging from ~0.25 in the Aitken size range to ~0.45 in the accumulation size range. The campaign average value (κ =0.3 ± 0.1) was similar to the values observed and modeled for other populated continental regions. The hygroscopicity parameters derived from the CCN measurements were consistent with chemical composition data recorded by an aerosol mass spectrometer (AMS) and thermo-optical measurements of apparent elemental and organic carbon (EC and OC). The CCN hygroscopicity and its size dependence could be parameterized as a function of only AMS based organic and inorganic mass fractions (forg, finorg) using the simple mixing rule κp ≈ 0.1 · forg + 0.7 · finorg. When the measured air masses originated from the north and passed rapidly over the center of Beijing (fresh city pollution), the average particle hygroscopicity was reduced (κ = 0.2 ± 0.1), which is consistent with enhanced mass fractions of organic compounds (~50%) and EC (~30%) in the fine particulate matter (PM1). Moreover, substantial fractions of externally mixed weakly CCN-active particles were observed at low supersaturation (S=0.07%), which can be explained by the presence of freshly emitted soot particles with very low hygroscopicity (κ < 0.1). Particles in stagnant air from the industrialized region south of Beijing (aged regional pollution) were on average larger and more hygroscopic, which is consistent with enhanced mass fractions (~60%) of soluble inorganic ions (mostly sulfate, ammonium, and nitrate). Accordingly, the number concentration of CCN in aged air from the megacity region was higher than in fresh city outflow ((2.5–9.9) × 103 cm−3 vs. (0.4–8.3) × 103 cm−3 for S=0.07–0.86%) although the total aerosol particle number concentration was lower (1.2 × 104 cm−3 vs. 2.3 × 104 cm−3). A comparison with related studies suggests that the fresh outflow from Chinese urban centers generally may contain more, but smaller and less hygroscopic aerosol particles and thus fewer CCN than the aged outflow from megacity regions.

Shapes of internally mixed hygroscopic aerosol particles after deliquescence, and their effect on light scattering

[1] Hygroscopic aerosol particles change the magnitude of light scattering through condensation and evaporation of water vapor. We collected aerosol particles from two megacities and observed the particle shapes at various values of relative humidity (RH) using an environmental cell within a transmission electron microscope. Many Mexico City samples had sulfate particles that were embedded within weakly hygroscopic organic aerosol, whereas the Los Angeles samples mainly consisted of externally mixed sulfate particles. For the Mexico City samples, when the RH was increased in the microscope, only the sulfate parts deliquesced, but the entire particle did not become spherical, i.e., particles containing deliquescent phases do not necessarily become spherical upon deliquescence. This result conflicts with the assumption used in many models, i.e., that deliquesced particles become spherical. Using a discrete-dipole approximation to calculate light scattering of simulated particles that resemble the observed ones, we show that, for particles >1.0 μm, the spherical-shape assumption used in Mie theory underestimates the light scattering by ∼50%, with the exact value depending on the sizes and relative volumes of the constituent phases.

Haze types in Beijing and the influence of agricultural biomass burning

Abstract. Emissions from agricultural biomass burning (ABB) in northern China have a significant impact on the regional and global climate. The monthly average aerosol optical depth (AOD) at 550 nm in northern China in 2007 had a maximum of 0.7 in June. The AOD measurements are consistent with regional brown hazes that occurred at that time, which was a period of severe aerosol pollution. Aerosol particles were collected in urban Beijing from 12 to 30 June 2007, during a period of high haze, and studied using transmission electron microscopy with energy-dispersive X-ray spectrometry. The dominant particle types collected in the fine fraction (diameter <1 μm) were ammonium sulfate, soot, K2SO4, KNO3, and organic matter, except that the K salts were minor between 21 and 30 June. K-rich particles as tracers of biomass burning, together with wildfire maps, show that intense regional ABB in northern China contributed significantly to the regional haze between 12 and 20 June. We therefore grouped the episodes into type-1 and -2 haze, with the former occurring between 12 and 20 June and the latter between 21 and 30 June. After long-range transport, ABB particles in the type-1 haze exhibited marked changes in morphology, composition, and mixing state. KCl particles were absent, presumably having been converted by heterogeneous reactions to K2SO4 and KNO3. Soot particles were mixed with the other particle types. Abundant organic matter and soluble salts emitted by ABB increased their sizes during transport and resulted in more hygroscopic aerosol particles in downwind areas, becoming additional cloud condensation nuclei. The high AOD (average value 2.2) in Beijing during 12 to 20 June is partly explained by the hygroscopic growth of fine aerosol particles and by the strong absorption of internally mixed soot particles, both coming from regional ABB emissions. Therefore, it is important to consider the origins of the haze, which in turn leads to the different particle types.

Cloud condensation nuclei in polluted air and biomass burning smoke near the mega-city Guangzhou, China – Part 1: Size-resolved measurements and implications for the modeling of aerosol particle hygroscopicity and CCN activity

Abstract. Atmospheric aerosol particles serving as Cloud Condensation Nuclei (CCN) are key elements of the hydrological cycle and climate. We measured and characterized CCN in polluted air and biomass burning smoke during the PRIDE-PRD2006 campaign from 1–30 July 2006 at a rural site ~60 km northwest of the mega-city Guangzhou in southeastern China. CCN efficiency spectra (activated fraction vs. dry particle diameter; 20–290 nm) were recorded at water vapor supersaturations (S) in the range of 0.068% to 1.27%. The corresponding effective hygroscopicity parameters describing the influence of particle composition on CCN activity were in the range of κ≈0.1–0.5. The campaign average value of κ=0.3 equals the average value of κ for other continental locations. During a strong local biomass burning event, the average value of κ dropped to 0.2, which can be considered as characteristic for freshly emitted smoke from the burning of agricultural waste. At low S (≤0.27%), the maximum activated fraction remained generally well below one, indicating substantial portions of externally mixed CCN-inactive particles with much lower hygroscopicity – most likely soot particles (up to ~60% at ~250 nm). The mean CCN number concentrations (NCCN,S) ranged from 1000 cm−3 at S=0.068% to 16 000 cm−3 at S=1.27%, which is about two orders of magnitude higher than in pristine air. Nevertheless, the ratios between CCN concentration and total aerosol particle concentration (integral CCN efficiencies) were similar to the ratios observed in pristine continental air (~6% to ~85% at S=0.068% to 1.27%). Based on the measurement data, we have tested different model approaches for the approximation/prediction of NCCN,S. Depending on S and on the model approach, the relative deviations between observed and predicted NCCN,S ranged from a few percent to several hundred percent. The largest deviations occurred at low S with a simple power law. With a Köhler model using variable κ values obtained from individual CCN efficiency spectra, the relative deviations were on average less than ~10% and hardly exceeded 20%, confirming the applicability of the κ-Köhler model approach for efficient description of the CCN activity of atmospheric aerosols. Note, however, that different types of κ-parameters must be distinguished for external mixtures of CCN-active and -inactive aerosol particles (κa, κt, κcut). Using a constant average hygroscopicity parameter (κ=0.3) and variable size distributions as measured, the deviations between observed and predicted CCN concentrations were on average less than 20%. In contrast, model calculations using variable hygroscopicity parameters as measured and constant size distributions led to much higher deviations: ~70% for the campaign average size distribution, ~80% for a generic rural size distribution, and ~140% for a generic urban size distribution. These findings confirm earlier studies suggesting that aerosol particle number and size are the major predictors for the variability of the CCN concentration in continental boundary layer air, followed by particle composition and hygroscopicity as relatively minor modulators. Depending on the required and applicable level of detail, the information and parameterizations presented in this study should enable efficient description of the CCN activity of atmospheric aerosols in detailed process models as well as in large-scale atmospheric and climate models.

Hygroscopic growth of urban aerosol particles in Beijing (China) during wintertime: a comparison of three experimental methods

Abstract. The hygroscopic properties of atmospheric aerosols are highly relevant for the quantification of radiative effects in the atmosphere, but also of interest for the assessment of particle health effects upon inhalation. This article reports measurements of aerosol particle hygroscopicity in the highly polluted urban atmosphere of Beijing, China in January 2005. The meteorological conditions corresponded to a relatively cold and dry atmosphere. Three different methods were used: 1) A combination of Humidifying Differential Mobility Particle Sizer (H-DMPS) and Twin Differential Mobility Particle Sizer (TDMPS) measurements, 2) A Hygroscopic Tandem Differential Mobility Analyzer (H-TDMA), and 3) A simplistic solubility model fed by chemical particle composition determined from Micro Orifice Uniform Deposit Impactor (MOUDI) samples. From the H-DMPS and TDMPS particle number size distributions, a size-resolved descriptive hygroscopic growth factor (DHGF) was determined for the relative humidities (RH) 55%, 77% and 90%, and particle diameters between 30 and 400 nm. In Beijing, the highest DHGFs were observed for accumulation mode particles, 1.40 (±0.03) at 90% RH. DHGF decreased significantly with particle size, reaching 1.04 (±0.15) at 30 nm. H-TDMA data also suggest a decrease in growth factor towards the biggest particles investigated (350 nm), associated with an increasing fraction of nearly hydrophobic particles. The agreement between the H-DMPS/TDMPS and H-TDMA methods was satisfactory in the accumulation mode size range (100–400 nm). In the Aitken mode range (<100 nm), the H-DMPS/TDMPS method yielded growth factors lower by up to 0.1 at 90% RH. The application of the solubility model based on measured chemical composition clearly reproduced the size-dependent trend in hygroscopic particle growth observed by the other methods. In the case of aerosol dominated by inorganic ions, the composition-derived growth factors tended to agree (± 0.05) or underestimate (up to 0.1) the values measured by the other two methods. In the case of aerosol dominated by organics, the reverse was true, with an overestimation of up to 0.2. The results shed light on the experimental and methodological uncertainties that are still connected with the determination of hygroscopic growth factors.

Effect of changes in relative humidity on aerosol scattering near clouds

Many investigations using satellite data have determined that aerosol optical depth and cloud cover are correlated and some have interpreted the correlation as evidence of an aerosol indirect effect on clouds. This study uses in situ aircraft observations taken during the Indian Ocean Experiment (INDOEX), February–March 1999, and mostly over the northern Indian Ocean, to show that on average, relative humidity increases as distance to the boundaries of small marine trade cumulus decreases. The increase is sufficient to cause substantial growth of hygroscopic aerosol particles and consequently greatly enhance particle scattering cross sections near clouds. The measured increase is from a relative humidity of about 90% at 1‐km horizontal distance from the cloud to about 94–96% at 100 m from cloud edge. This increase would result in about a 40–80% increase in aerosol scattering cross section based on the composition used to model the aerosol. Observations of scattering in the vicinity of clouds using 30‐m‐resolution imagery from the Multichannel Cloud Radiometer (MCR) indicated that the increase in scattering within 1–2 km of cloud edge was about 50%, comparable to the increase calculated for the particle scattering cross sections. On the basis of these findings, global average estimates of the aerosol direct radiative effect as derived from satellite observations of cloud‐free oceans is estimated to be 35–65% larger than that inferred for large (>20 km) cloud‐free ocean regions. This enhancement is consistent with those derived from satellite observations.