Particle Hygroscopic Growth Research Articles

Direct radiative forcing of urban aerosols over Pretoria (25.75°S, 28.28°E) using AERONET Sunphotometer data: First scientific results and environmental impact

The present study uses the data collected from Cimel Sunphotometer of Aerosol Robotic Network (AERONET) for the period from January to December, 2012 over an urban site, Pretoria (PTR; 25.75°S, 28.28°E, 1449mabove sea level), South Africa. We found that monthly mean aerosol optical depth (AOD, τa) exhibits two maxima that occurred in summer (February) and winter (August) having values of 0.36±0.19 and 0.25±0.14, respectively, high-to-moderate values in spring and thereafter, decreases from autumn with a minima in early winter (June) 0.12±0.07. The Angstrom exponents (α440–870) likewise, have its peak in summer (January) 1.70±0.21 and lowest in early winter (June) 1.38±0.26, while the columnar water vapor (CWV) followed AOD pattern with high values (summer) at the beginning of the year (February, 2.10±0.37cm) and low values (winter) in the middle of the year (July, 0.66±0.21cm). The volume size distribution (VSD) in the fine-mode is higher in the summer and spring seasons, whereas in the coarse mode the VSD is higher in the winter and lower in the summer due to the hygroscopic growth of aerosol particles. The single scattering albedo (SSA) ranged from 0.85 to 0.96 at 440nm over PTR for the entire study period. The averaged aerosol radiative forcing (ARF) computed using SBDART model at the top of the atmosphere (TOA) was −8.78±3.1W/m2, while at the surface it was −25.69±8.1W/m2 leading to an atmospheric forcing of +16.91±6.8W/m2, indicating significant heating of the atmosphere with a mean of 0.47K/day.

Effects of meteorology and secondary particle formation on visibility during heavy haze events in Beijing, China

The causes of haze formation in Beijing, China were analyzed based on a comprehensive measurement, including PBL (planetary boundary layer), aerosol composition and concentrations, and several important meteorological parameters such as visibility, RH (relative humidity), and wind speed/direction. The measurement was conducted in an urban location from Nov. 16, 2012 to Jan. 15, 2013. During the period, the visibility varied from >20km to less than a kilometer, with a minimum visibility of 667m, causing 16 haze occurrences. During the haze occurrences, the wind speeds were less than 1m/s, and the concentrations of PM2.5 (particle matter with radius less than 2.5μm) were often exceeded 200μg/m3. The correlation between PM2.5 concentration and visibility under different RH values shows that visibility was exponentially decreased with the increase of PM2.5 concentrations when RH was less than 80%. However, when RH was higher than 80%, the relationship was no longer to follow the exponentially decreasing trend, and the visibility maintained in very low values, even with low PM2.5 concentrations. Under this condition, the hygroscopic growth of particles played important roles, and a large amount of water vapor acted as particle matter (PM) for the reduction of visibility. The variations of meteorological parameters (RH, PBL heights, and WS (wind speed)), chemical species in gas-phase (CO, O3, SO2, and NOx), and gas-phase to particle-phase conversions under different visibility ranges were analyzed. The results show that from high visibility (>20km) to low visibility (<2km), the averaged PBL decreased from 1.24km to 0.53km; wind speeds reduced from 1m/s to 0.5m/s; and CO increased from 0.5ppmv to 4.0ppmv, suggesting that weaker transport/diffusion caused the haze occurrences. This study also found that the formation of SPM (secondary particle matter) was accelerated in the haze events. The conversions between SO2 and SO4 as well as NOx to NO3− increased, especially under high humidity conditions. When the averaged RH was 70%, the conversions between SO2 and SO4 accounted for about 20% concentration of PM2.5, indicating that formation of secondary particle matter had important contribution for the haze occurrences in Beijing.

Seasonal variation of aerosol water uptake and its impact on the direct radiative effect at Ny-Ålesund, Svalbard

Abstract. In this study we investigated the impact of water uptake by aerosol particles in ambient atmosphere on their optical properties and their direct radiative effect (ADRE, W m−2) in the Arctic at Ny-Ålesund, Svalbard, during 2008. To achieve this, we combined three models, a hygroscopic growth model, a Mie model and a radiative transfer model, with an extensive set of observational data. We found that the seasonal variation of dry aerosol scattering coefficients showed minimum values during the summer season and the beginning of fall (July-August-September), when small particles (&lt; 100 nm in diameter) dominate the aerosol number size distribution. The maximum scattering by dry particles was observed during the Arctic haze period (March-April-May) when the average size of the particles was larger. Considering the hygroscopic growth of aerosol particles in the ambient atmosphere had a significant impact on the aerosol scattering coefficients: the aerosol scattering coefficients were enhanced by on average a factor of 4.30 ± 2.26 (mean ± standard deviation), with lower values during the haze period (March-April-May) as compared to summer and fall. Hygroscopic growth of aerosol particles was found to cause 1.6 to 3.7 times more negative ADRE at the surface, with the smallest effect during the haze period (March-April-May) and the highest during late summer and beginning of fall (July-August-September).

Hygroscopic growth of submicron and supermicron aerosols in the marine boundary layer

We investigate hygroscopic growth of marine aerosols from three research cruises: TexAQS-GoMACCS 2006, ICEALOT 2008 and CalNex 2010. Particle hygroscopic growth was characterized by measuring the effect of water uptake under sub-saturated conditions on the aerosol light extinction at 532 nm. Mie theory calculations were utilized to convert the observed optical growth factors (fext(RH)) into physical growth factors (GF) at 85% RH. GF is found to be a more robust measure of aerosol hygroscopic growth than fext(RH), which can be biased by changes in aerosol dry size. Consistent with previous observations, the overall GF(85%) for submicron aerosol depended on the fraction of organics. The submicron GFOM(85%) specifically was found to range from 1.0-1.3 for all three campaigns. A robust positive linear dependence of the overall supermicron GF(85%) on the mass fraction of sea salt was observed. During TexAQS, two types of dust particles with distinct hygroscopic properties were identified in the supermicron mode; one that originated from the Sahara desert was moderately hygroscopic (GFdust(85%) = ~1.4) and the other from continental sources was nearly hydrophobic. The GF(85%) of supermicron organics was estimated through hygroscopicity closure calculations. Supermicron organics that originated from marine sources were found to be substantially more hygroscopic than those from continental sources, with the latter having a GF(85%) similar to that of the submicron organics. This study demonstrates the potential of using aerosol optical measurements to retrieve hygroscopic growth factor and underlines the importance and need for future investigations on the hygroscopic properties of marine supermicron aerosols.

Growth of sulphuric acid nanoparticles under wet and dry conditions

Abstract. New particle formation, which greatly influences the number concentrations and size distributions of an atmospheric aerosol, is often followed by a rapid growth of freshly formed particles. The initial growth of newly formed aerosol is the crucial process determining the fraction of nucleated particles growing to cloud condensation nuclei sizes, which have a significant influence on climate. In this study, we report the laboratory observations of the growth of nanoparticles produced by nucleation of H2SO4 and water in a laminar flow tube at temperatures of 283, 293 and 303 K, under dry (a relative humidity of 1%) and wet conditions (relative humidity of 30%) and residence times of 30, 45, 60 and 90 s. The initial H2SO4 concentration spans the range from 2 × 108 to 1.4 × 1010 molecule cm−3 and the calculated wall losses of H2SO4 were assumed to be diffusion limited. The detected particle number concentrations, measured by the Ultrafine Condensation Particle Counter (UCPC) and Differential Mobility Particle Sizer (DMPS), were found to depend strongly on the residence time. Hygroscopic particle growth, presented by growth factors, was found to be in good agreement with the previously reported studies. The experimental growth rates ranged from 20 nm h−1 to 890 nm h−1 at relative humidity (RH) 1% and from 7 nm h−1 to 980 nm h−1 at RH 30% and were found to increase significantly with the increasing concentration of H2SO4. Increases in the nucleation temperature had a slight enhancing effect on the growth rates under dry conditions. The influence of relative humidity on growth was not consistent – at lower H2SO4 concentrations, the growth rates were higher under dry conditions while at H2SO4 concentrations greater than 1 × 1010 molecule cm−3, the growth rates were higher under wet conditions. The growth rates show only a weak dependence on the residence time. The experimental observations were compared with predictions made using a numerical model, which investigates the growth of particles with three different extents of neutralization by ammonia, NH3: (1) pure H2SO4 – H2O particles; (2) particles formed by ammonium bisulphate, (NH4)HSO4; (3) particles formed by ammonium sulphate, (NH4)2SO4. The highest growth rates were found for ammonium sulphate particles. Since the model accounting for the initial H2SO4 concentration predicted the experimental growth rates correctly, our results suggest that the commonly presumed diffusional wall losses of H2SO4 in case of long-lasting experiments are not so significant. We therefore assume that there are not only losses of H2SO4 on the wall, but also a flux of H2SO4 molecules from the wall into the flow tube, the effect being more profound under dry conditions and at higher temperatures of the tube wall. Based on a comparison with the atmospheric observations, our results indicate that sulphuric acid alone cannot explain the growth rates of particles formed in the atmosphere.

Surface organic monolayers control the hygroscopic growth of submicrometer particles at high relative humidity.

Although many organic molecules commonly found in the atmosphere are known to be surface-active in macroscopic aqueous solutions, the impact of surface partitioning of organic molecules to a microscopic aqueous droplet interface remains unclear. Here we measure the droplet size formed, at a relative humidity (∼99.9%) just below saturation, on submicrometer particles containing an ammonium sulfate core and an organic layer of a model compound of varying thickness. The 12 model organic compounds are a series of dicarboxylic acids (C3 to C10), cis-pinonic, oleic, lauric, and myristic acids, which represent a broad range in solubility from miscible (malonic acid) to insoluble. The variation in droplet size with increasing organic aerosol fraction cannot be explained by assuming the organic material is dissolved in the bulk droplet. Instead, the wet droplet diameters exhibit a complex and nonlinear dependence on organic aerosol volume fraction, leading to hygroscopic growth that is in some cases smaller and in others larger than that predicted by bulk solubility alone. For palmitic and stearic acid, small droplets at or below the detection limit of the instrument are observed, indicating significant kinetic limitations for water uptake, which are consistent with mass accommodation coefficients on the order of 10(-4). A model based on the two-dimensional van der Waals equation of state is used to explain the complex droplet growth with organic aerosol fraction and dry diameter. The model suggests that mono- and dicarboxylic acids with limited water solubility partition to the droplet surface and reduce surface tension only after a two-dimensional condensed monolayer is formed. Two relatively soluble compounds, malonic and glutaric acid, also appear to form surface phases, which increase hygroscopicity. There is a clear alternation in the threshold for droplet growth observed for odd and even carbon number diacids, which is explained in the model by differences in the excluded molecular areas of even (∼40 Å(2)/molecule) and odd (∼20 Å(2)/molecule) diacids. These differences are consistent with the odd diacids arranged at the droplet interface in "end-to-end" configurations with only one acid group in contact with the aqueous phase, which is in contrast to even carbon numbered diacids forming "folded" films with both acid groups in contact with the bulk phase. Organic matter produced by the ozonolysis of α-pinene forms surface films that exhibit similar behavior and become thinner with oxidation, allowing for greater water uptake. These results reveal a new and complex relationship between the composition of an organic aerosol and its hygroscopicity, suggesting that organic surface films might strongly influence cloud droplet formation as well as the multiphase chemistry of organic aerosols.

Aqueous-phase photochemical oxidation and direct photolysis of vanillin – a model compound of methoxy phenols from biomass burning

Abstract. We present here experimental results on aqueous-phase (A) photochemical oxidation (with UV and OH radicals generated from H2O2 photolysis) and (B) direct photolysis (with only UV irradiation) of a methoxy phenol, vanillin (VL), as a model compound from biomass burning. Both on-line aerosol mass spectrometric (AMS) characterization and off-line chemical analyses were performed. AMS analyses of dried atomized droplets of the bulk reacting mixtures showed that VL almost entirely evaporates during the drying process. Large amounts of organic mass remained in the particle phase after reactions under both conditions. Under condition (A), AMS measured organic mass first increased rapidly and then decreased, attributable to the formation of non-volatile products and subsequent formation of smaller and volatile products, respectively. The oxygen-to-carbon (O : C) ratio of the products reached 1.5 after about 80 min, but dropped substantially thereafter. In contrast, organic mass increased slowly under condition (B). The O : C ratio reached 1.0 after 180 min. In off-line analyses, small oxygenates were detected under condition (A), while hydroxylated products and dimers of VL were detected under condition (B). Particle hygroscopic growth factor (GF) and cloud condensation nuclei (CCN) activity of the reacting mixtures were found to depend on both organic volume fraction and the degree of oxygenation of organics. Results show that (1) aqueous-phase processes can lead to the retention of a large portion of the organic mass in the particle phase; (2) once retained, this portion of organic mass significantly changes the hygroscopicity and CCN activity of the aerosol particles; (3) intensive photochemical oxidation gave rise to an O : C ratio as high as 1.5 but the ratio decreased as further oxidation led to smaller and more volatile products; and (4) polymerization occurred with direct photolysis, resulting in high-molecular-weight products of a yellowish color. This study demonstrates that aqueous-phase reactions of a methoxy phenol can lead to substantial amount of secondary organic aerosol (SOA) formation. Given the vast amount of biomass burning input globally, model representation of either the SOA budget or their subsequent effects would not be adequate if the contribution of SOA formation from aqueous-phase reactions of methoxy phenols is not considered.

Aerosol hygroscopicity derived from size-segregated chemical composition and its parameterization in the North China Plain

Abstract. Hygroscopic growth of aerosol particles is of significant importance in quantifying the aerosol radiative effect in the atmosphere. In this study, hygroscopic properties of ambient particles are investigated based on particle chemical composition at a suburban site in the North China Plain during the HaChi campaign (Haze in China) in summer 2009. The size-segregated aerosol particulate mass concentration as well as the particle components such as inorganic ions, organic carbon and water-soluble organic carbon (WSOC) are identified from aerosol particle samples collected with a ten-stage impactor. An iterative algorithm is developed to evaluate the hygroscopicity parameter κ from the measured chemical composition of particles. During the HaChi summer campaign, almost half of the mass concentration of particles between 150 nm and 1 μm is contributed by inorganic species. Organic matter (OM) is abundant in ultrafine particles, and 77% of the particulate mass with diameter (Dp) of around 30 nm is composed of OM. A large fraction of coarse particle mass is undetermined and is assumed to be insoluble mineral dust and liquid water. The campaign's average size distribution of κ values shows three distinct modes: a less hygroscopic mode (Dp &lt; 150 nm) with κ slightly above 0.2, a highly hygroscopic mode (150 nm &lt; Dp &lt; 1 μm) with κ greater than 0.3 and a nearly hydrophobic mode (Dp &gt; 1 μm) with κ of about 0.1. The peak of the κ curve appears around 450 nm with a maximum value of 0.35. The derived κ values are consistent with results measured with a high humidity tandem differential mobility analyzer within the size range of 50–250 nm. Inorganics are the predominant species contributing to particle hygroscopicity, especially for particles between 150 nm and 1 μm. For example, NH4NO3, H2SO4, NH4HSO4 and (NH4)2SO4 account for nearly 90% of κ for particles of around 900 nm. For ultrafine particles, WSOC plays a critical role in particle hygroscopicity due to the predominant mass fraction of OM in ultrafine particles. WSOC for particles of around 30 nm contribute 52% of κ. Aerosol hygroscopicity is related to synoptic transport patterns. When southerly wind dominates, particles are more hygroscopic; when northerly wind dominates, particles are less hygroscopic. Aerosol hygroscopicity also has a diurnal variation, which can be explained by the diurnal evolution of planetary boundary layer, photochemical aging processes during daytime and enhanced black carbon emission at night. κ is highly correlated with mass fractions of SO42−, NO3− and NH4+ for all sampled particles as well as with the mass fraction of WSOC for particles of less than 100 nm. A parameterization scheme for κ is developed using mass fractions of SO42−, NO3−, NH4+ and WSOC due to their high correlations with κ, and κ calculated from the parameterization agrees well with κ derived from the particle's chemical composition. Further analysis shows that the parameterization scheme is applicable to other aerosol studies in China.

Calculation of hygroscopic particle deposition in the human lung

Context: Inhaled hygroscopic aerosols will absorb water vapor from the warm and humid air of the human lung, thus growing in size and consequently changing their deposition properties.Objective: The objectives of the present study are to study the effect of a stochastic lung structure on individual particle growth and related deposition patterns and to predict local deposition patterns for different hygroscopic aerosols.Materials and methods: The hygroscopic particle growth model proposed by Ferron et al. has been implemented into the stochastic asymmetric lung deposition model IDEAL. Deposition patterns were calculated for sodium chloride (NaCl), cobalt chloride (CoCl2 · 6H2O), and zinc sulfate (ZnSO4 · 7H2O) aerosols, representing high, medium and low hygroscopic growth factors.Results: Hygroscopic growth decreases deposition of submicron particles compared to hydrophobic particles with equivalent diameters due to a less efficient diffusion mechanism, while the more efficient impaction and sedimentation mechanisms increase total deposition for micron-sized particles. Due to the variability and asymmetry of the human airway system, individual trajectories of inhaled particles are associated with individual growth factors, thereby enhancing the variability of the resulting deposition patterns.Discussion and conclusions: Comparisons of model predictions with several experimental data for ultrafine and micrometer-sized particles indicate good agreement, considering intersubject variations of morphometric parameters as well as differences between experimental conditions and modeling assumptions.

Measurements of the Sensitivity of Aerosol Hygroscopicity and the κ Parameter to the O/C Ratio

We report measurements of the subsaturated hygroscopic growth of aerosol particles composed of single organic components of varying oxygen-to-carbon ratio up to relative humidities approaching saturation using the techniques of aerosol optical tweezers and an electrodynamic balance. The variation in the hygroscopicity parameter κ between compounds of even the same O/C ratio is found to be significant with, for example, a range in κ values from 0.12 to 0.38 for compounds with an O/C of 1. The measurements are compared with a review of all of the available literature data for which both the κ value and O/C ratio are reported, and a new parametrization is determined. Critical supersaturations predicted using this parametrization yield values that have associated uncertainties that are comparable to typical uncertainties in experimental measurements of critical supersaturations. However, the systematic variability between κ parametrizations determined from different studies remains large, consistent with the O/C ratio providing only an approximate guide to aerosol hygroscopicity and reflecting significant variations for aerosols of different chemical functionality, composition, and oxidation history.

Size Distribution, Chemical Composition, and Hygroscopicity of Fine Particles Emitted from an Oil-Fired Heating Plant

Heavy fuel oil (HFO) is a commonly used fuel in industrial heating and power generation and for large marine vessels. In this study, the fine particle emissions of a 47 MW oil-fired boiler were studied at 30 MW power and with three different fuels. The studied fuels were HFO, water emulsion of HFO, and water emulsion of HFO mixed with light fuel oil (LFO). With all the fuels, the boiler emitted considerable amounts of particles smaller than 200 nm in diameter. Further, these small particles were quite hygroscopic even as fresh and, in the case of HFO+LFO emulsion, the hygroscopic growth of the particles was dependent on particle size. The use of emulsions and the addition of LFO to the fuel had a reducing effect on the hygroscopic growth of particles. The use of emulsions lowered the sulfate content of the smallest particles but did not affect significantly the sulfate content of particles larger than 42 nm and, further, the addition of LFO considerably increased the black carbon content of particulate matter. The results indicate that even the fine particles emitted from HFO based combustion can have a significant effect on cloud formation, visibility, and air quality.

A study of urban pollution and haze clouds over northern China during the dusty season based on satellite and surface observations

This paper presents a multi-scale study on formation process of urban pollution and haze clouds as well as their interactions over northern China in spring using integrated satellite and surface observations. Several extreme haze events occurred in Beijing area in March 2013, but primary atmospheric pollutants in the urban pollution exhibited inconsistent variations with the widespread haze clouds observed by satellites. Two typical types of haze event were found in Beijing area. Type-1 haze pollution appeared in stagnant weather conditions, during which PM2.5 was <200 μg m−3 with a short duration within 1–2 days. By contrast, strong northwestern winds prevailed in type-2 haze events with durative and intense temperature inversion near surface. Meanwhile, PM2.5 concentration exceeded ∼400 μg m−3 in type-2 pollution, and the heavy pollution can last 3–5 days. Different from urban pollution, our results show that the thick haze clouds were dominated by mixing of floating dust and anthropogenic pollutants in the middle and upper part, accompanied by hygroscopic growth of fine particles. Elevated coarse dust particles were prevalent over northern China, which accounted for a predominant fraction in the columnar optical volume during all the haze events. Furthermore, comparison between satellite and surface observations indicates that haze clouds above surface had no significant direct contribution to the serious urban pollution. In addition, mixing of dust and anthropogenic pollutants at high altitudes regulates regional aerosol optical properties throughout the whole March.

Measuring and modeling the hygroscopic growth of two humic substances in mixed aerosol particles of atmospheric relevance

Abstract. The hygroscopic growth of atmospheric particles affects atmospheric chemistry and Earth's climate. Water-soluble organic carbon (WSOC) constitutes a significant fraction of the dry submicron mass of atmospheric aerosols, thus affecting their water uptake properties. Although the WSOC fraction is comprised of many compounds, a set of model substances can be used to describe its behavior. For this study, mixtures of Nordic aquatic fulvic acid reference (NAFA) and Fluka humic acid (HA), with various combinations of inorganic salts (sodium chloride and ammonium sulfate) and other representative organic compounds (levoglucosan and succinic acid), were studied. We measured the equilibrium water vapor pressure over bulk solutions of these mixtures as a function of temperature and solute concentration. New water activity (aw) parameterizations and hygroscopic growth curves at 25 °C were calculated from these data for particles of equivalent composition. We examined the effect of temperature on the water activity and found a maximum variation of 9% in the 0–30 °C range, and 2% in the 20–30 °C range. Five two-component mixtures were studied to understand the effect of adding a humic substance (HS), such as NAFA and HA, to an inorganic salt or a saccharide. The deliquescence point at 25 °C for HS-inorganic mixtures did not change significantly from that of the pure inorganic species. However, the hygroscopic growth of HA / inorganic mixtures was lower than that exhibited by the pure salt, in proportion to the added mass of HA. The addition of NAFA to a highly soluble solute (ammonium sulfate, sodium chloride or levoglucosan) in water had the same effect as the addition of HA to the inorganic species for most of the water activity range studied. Yet, the water uptake of these NAFA mixtures transitioned to match the growth of the pure salt or saccharide at high aw values. The remaining four mixtures were based on chemical composition data for different aerosol types. As expected, the two solutions representing organic aerosols (40% HS/40% succinic acid/20% levoglucosan) showed lower water uptake than the two solutions representing biomass burning aerosols (25% HS/27% succinic acid/18% levoglucosan/30% ammonium sulfate). However, interactions in multicomponent solutions may be responsible for the large variation of the relative water uptake of identical mixtures containing different HSs above a water activity of 0.95. The ZSR (Zdanovskii, Stokes, and Robinson) model was able to predict reasonably well the hygroscopic growth of all the mixtures below aw = 0.95, but produced large deviations for some multicomponent mixtures at higher values.

Relating particle hygroscopicity and CCN activity to chemical composition during the HCCT-2010 field campaign

Abstract. Particle hygroscopic growth at 90% RH (relative humidity), cloud condensation nuclei (CCN) activity, and size-resolved chemical composition were concurrently measured in the Thüringer Wald mid-level mountain range in central Germany in the fall of 2010. The median hygroscopicity parameter values, κ, of 50, 75, 100, 150, 200, and 250 nm particles derived from hygroscopicity measurements are respectively 0.14, 0.14, 0.17, 0.21, 0.24, and 0.28 during the sampling period. The closure between HTDMA (Hygroscopicity Tandem Differential Mobility Analyzers)-measured (κHTDMA) and chemical composition-derived (κchem) hygroscopicity parameters was performed based on the Zdanovskii–Stokes–Robinson (ZSR) mixing rule. Using size-averaged chemical composition, the κ values are substantially overpredicted (30 and 40% for 150 and 100 nm particles). Introducing size-resolved chemical composition substantially improved closure. We found that the evaporation of NH4NO3, which may happen in a HTDMA system, could lead to a discrepancy in predicted and measured particle hygroscopic growth. The hygroscopic parameter of the organic fraction, κorg, is positively correlated with the O : C ratio (κorg = 0.19 × (O : C) − 0.03). Such correlation is helpful to define the κorg value in the closure study. κ derived from CCN measurement was around 30% (varied with particle diameters) higher than that determined from particle hygroscopic growth measurements (here, hydrophilic mode is considered only). This difference might be explained by the surface tension effects, solution non-ideality, gas-particle partitioning of semivolatile compounds, and the partial solubility of constituents or non-dissolved particle matter. Therefore, extrapolating from HTDMA data to properties at the point of activation should be done with great care. Finally, closure study between CCNc (cloud condensation nucleus counter)-measured (κCCN) and chemical composition (κCCN, chem) was performed using CCNc-derived κ values for individual components. The results show that the κCCN can be well predicted using particle size-resolved chemical composition and the ZSR mixing rule.

Influence of semi-volatile species on particle hygroscopic growth

In this study, we use a Tandem Differential Mobility Analyser (TDMA) system combining particle volatilization and humidification conditioning (VH-TDMA) to test the effect of the gentle volatilization of a small fraction of the atmospheric particles on the particle hygroscopic growth in several environments (urban to remote). We first give an overview of the Hygroscopic Growth Factors (HGF) in these various environments, showing that in most of them, aerosol particles are externally mixed. We then show that the particle hygroscopicity can either be increased or decreased after thermal conditioning of the particle at moderate temperatures (50–110 °C). The hygroscopic growth factor changes induced by volatilization indicate that some volatile compounds, although present at low concentrations, can significantly influence the hygroscopic growth of particles in a way that can most of time be theoretically explained if simplified assumptions are used. However, simplified assumptions occasionally fail over several hours to explain hygroscopic changes, kinetic/surface effects observed at remote environments are suspected to be important.

Increase of aerosol scattering by hygroscopic growth: Observation, modeling, and implications on visibility

In situ measurements of size-resolved aerosol chemical compositions and its optical properties were concurrently carried out at an urban site in mega-city Beijing from October 24 to November 9, 2007. The main objective was to quantitatively study the relationship between aerosol chemical compositions and its hygroscopic properties, to estimate the influence of relative humidity (RH) on aerosol scattering coefficient and to quantitatively investigate visibility impairment due to particle hygroscopic growth. The hygroscopic factor of aerosol scattering coefficient (f(RH)), which is defined as the ratio of aerosol scattering coefficient at wet condition to that at dry condition (RH≤30%), was calculated with the measured aerosol optical properties at dry and ambient conditions. The relationship between f(RH) and RH was fitted by empirical equation and the fitting parameters were calculated. Meanwhile, f(RH) for externally mixed aerosols or internally mixed aerosols was modeled based on size segregated particulate chemical composition. The modeled f(RH) agreed well with the measured f(RH). Empirical formula for atmospheric visibility based on mass concentration of PM2.5 and f(RH) was proposed. The result of this study is not only proven that RH, in addition to the mass concentration of PM2.5, played an important role on visibility impairment, but also provide practical aid for air quality control to improve the visibility in the megacity region of Beijing.

Model of the Deposition of Aerosol Particles in the Respiratory Tract of the Rat. II. Hygroscopic Particle Deposition

Rats are frequently used to study the pharmacological and toxicological effects of inhaled aerosol particles. The deposition behavior of aerosol particles in airways is affected by their hygroscopic properties, which accordingly influence the results of such studies. A recently published nonhygroscopic aerosol particle deposition model for rat airways was extended with equations for hygroscopic particle growth in humid air and with a model to mimic the temperature and relative humidity conditions in the rat airways transformed from the upper human airways. As there are no experimental data available for hygroscopic deposition in rat lungs, several model assumptions were made for the humidity distribution in the upper rat airways. The total and regional deposition probability of salt particles in the diameter range 0.02 to 5 μm in rat lung was significantly changed by the hygroscopic properties. The maximum ratios of the total deposition of inhaled initially dry sodium chloride, cobalt chloride, and zinc sulfate particles compared with nonhygroscopic particles were 3.28, 2.44, and 2.13, respectively, and the minimum ratios 0.57, 0.63, and 0.70, respectively. The corresponding maximum (and minimum) ratios for the hygroscopic drugs histamine dihydrochloride, carbenicillin disodium, and atropine sulfate were 1.86 (0.65), 1.53 (0.70), and 1.35 (0.76), respectively. Total deposition was about 20% higher in human airways than in rat airways. The flow regime in the rat upper airways influenced total and regional deposition much less than it did in human airways. The hygroscopicity of salt and drug aerosol particles is an important factor in rat lung deposition.

Hygroscopic growth and CCN activity of HULIS from different environments

Humic‐like substances (HULIS) constitute a significant fraction of aerosol particles in different environments. Studies of the role of HULIS in hygroscopic growth and cloud condensation nuclei (CCN) activity of aerosol particles are scarce, and results differ significantly. In this work the hygroscopic growth and CCN activity of water extracts (WE) and HULIS extracted from particulate matter (PM) collected at a polluted urban site (Copenhagen, Denmark), a rural site (Melpitz, Germany) and the remote site Storm Peak Laboratory (Colorado, USA) were investigated. Measurements of inorganic ions, elemental carbon, organic carbon and water soluble organic carbon (WSOC) within the PM confirmed that the sources of aerosol particles most likely differed for the three samples. The hygroscopic properties of the filtered WE were characterized by hygroscopicity parameters for subsaturated conditions (κGF) of 0.25, 0.41 and 0.22, and for supersaturated conditions κCCN were 0.23, 0.29 and 0.22 respectively for the urban, rural and remote WE samples. The measured hygroscopic growth and CCN activity were almost identical for the three HULIS samples and could be well represented by κGF = 0.07 and κCCN = 0.08–0.10 respectively. Small amounts of inorganic ions were present in the HULIS samples so the actual values for pure HULIS are expected to be slightly lower (κGF* = 0.04–0.06 and κCCN* = 0.07–0.08). The HULIS samples are thus less hygroscopic compared to most previous studies. To aid direct comparison of hygroscopic properties of HULIS from different studies, we recommend that the fraction of inorganic species in the HULIS samples always is measured and reported.

Hygroscopic growth of urban aerosol particles during the 2009 Mirage-Shanghai Campaign

The hygroscopic properties of submicrometer urban aerosol particles were studied during the 2009 Mirage-Shanghai Campaign. The urban aerosols were composed of more-hygroscopic and nearly-hydrophobic particles, together with a trace of less-hygroscopic particles. The mean hygroscopicity parameter κ of the more-hygroscopic mode varied in the range of 0.27–0.39 depending on particle size. The relative abundance of the more-hygroscopic particles at any size was ca. 70%, slightly increasing with particle size. The number fraction of the nearly-hydrophobic particles fluctuated between 0.1 and 0.4 daily, in accordance with traffic emissions and atmospheric diffusion. The results from relative humidity dependence on hygroscopic growth and chemical analysis of fine particles indicated that particulate nitrate formation through the homogenous gas-phase reaction was suppressed under ammonia-deficient atmosphere in summer whereas the equilibrium was broken by more available NH3 during adverse meteorological conditions.

Glass formation and unusual hygroscopic growth of iodic acid solution droplets with relevance for iodine mediated particle formation in the marine boundary layer

Abstract. Iodine oxide particles are known to nucleate in the marine boundary layer where gas phase molecular iodine and organoiodine species are produced by macroalgae. These ultra-fine particles may then grow through the condensation of other materials to sizes where they may serve as cloud condensation nuclei. There has been some debate over the chemical identity of the initially nucleated particles. In laboratory simulations, hygroscopic measurements have been used to infer that they are composed of insoluble I2O4, while elemental analysis of laboratory generated particles suggests soluble I2O5 or its hydrated form iodic acid, HIO3 (I2O5·H2O). In this paper we explore the response of super-micron sized aqueous iodic acid solution droplets to varying humidity using both Raman microscopy and single particle electrodynamic traps. These measurements reveal that the propensity of an iodic acid solution droplet to crystallise is negligible on drying to ~0% relative humidity (RH). On applying mechanical pressure to these droplets they shatter in a manner consistent with an ultra-viscous liquid or a brittle glass. Water retention in amorphous material at low RH is important for understanding the hygroscopic growth of aerosol particles and uptake of other condensable material. Subsequent water uptake between 10 and 20% RH causes their viscosity to reduce sufficiently that the cracked droplets flow and merge. The persistence of iodic acid solution in an amorphous state, rather than a crystalline state, suggests they will more readily accommodate other condensable material and are therefore more likely to grow to sizes where they may serve as cloud condensation nuclei. On increasing the humidity to ~90% the mass of the droplets only increases by ~20% with a corresponding increase in radius of only 6%, which is remarkably small for a highly soluble material. We suggest that the small growth factor of aqueous iodic acid solution droplets is consistent with the small aerosol growth factors observed in previous experiments.