scholarly journals Interactions of organosulfates with water vapor under sub- and supersaturated conditions

2021 ◽  
Author(s):  
Chao Peng ◽  
Patricia N. Razafindrambinina ◽  
Kotiba A. Malek ◽  
Lanxiadi Chen ◽  
Weigang Wang ◽  
...  

Abstract. Organosulfates (OS) are important constituents of secondary organic aerosols, but their hygroscopic properties and cloud condensation nucleation (CCN) activities have not been well understood. In this work we employed three complementary techniques to characterize interactions of several OS with water vapor under sub- and supersaturated conditions. A vapor sorption analyzer was used to measure mass changes of OS samples with RH (0–90 %); among the 11 organosulfates examined, only sodium methyl sulfate (methyl-OS), sodium ethyl sulfate (ethyl-OS), sodium octyl sulfate (octyl-OS) and potassium hydroxyacetone sulfate were found to deliquesce as RH increased, and their mass growth factors at 90 % RH were determined to be 3.652 ± 0.064, 3.575 ± 0.024, 1.591 ± 0.004 and 2.202 ± 0.031. Hygroscopic growth of methyl-, ethyl- and octyl-OS aerosols was also studied using a humidity tandem differential mobility analyzer (H-TDMA); continuous hygroscopic growth was observed, and their growth factors at 90 % RH were determined to be 1.83 ± 0.03, 1.79 ± 0.02 and 1.21 ± 0.02. We further investigated CCN activities of methyl-, ethyl- and octyl-OS aerosols, and their single hygroscopicity parameters (κccn) were determined to be 0.459 ± 0.021, 0.397 ± 0.010 and 0.206 ± 0.008. For methyl- and ethyl-OS aerosols, κccn values agree reasonably well with those derived from H-TDMA measurements (κgf), whereas κccn was found to be significantly larger than κgf for octyl-OS, likely due to both solubility limit and surface tension reduction.

2021 ◽  
Vol 21 (9) ◽  
pp. 7135-7148
Author(s):  
Chao Peng ◽  
Patricia N. Razafindrambinina ◽  
Kotiba A. Malek ◽  
Lanxiadi Chen ◽  
Weigang Wang ◽  
...  

Abstract. Organosulfates (OSs) are important constituents of secondary organic aerosols, but their hygroscopic properties and cloud condensation nucleation (CCN) activities have not been well understood. In this work we employed three complementary techniques to characterize interactions of several OSs with water vapor under sub- and supersaturated conditions. A vapor sorption analyzer was used to measure mass changes in OS samples with relative humidity (RH, 0 %–90 %); among the 11 organosulfates examined, only sodium methyl sulfate (methyl-OS), sodium ethyl sulfate (ethyl-OS), sodium octyl sulfate (octyl-OS) and potassium hydroxyacetone sulfate were found to deliquesce as RH increased, and their mass growth factors at 90 % RH were determined to be 3.65 ± 0.06, 3.58 ± 0.02, 1.59 ± 0.01 and 2.20 ± 0.03. Hygroscopic growth of methyl-, ethyl- and octyl-OS aerosols was also studied using a humidity tandem differential mobility analyzer (H-TDMA); continuous hygroscopic growth was observed, and their growth factors at 90 % RH were determined to be 1.83 ± 0.03, 1.79 ± 0.02 and 1.21 ± 0.02. We further investigated CCN activities of methyl-, ethyl- and octyl-OS aerosols, and their single hygroscopicity parameters (κccn) were determined to be 0.459 ± 0.021, 0.397 ± 0.010 and 0.206 ± 0.008. For methyl- and ethyl-OS aerosols, κccn values agree reasonably well with those derived from H-TDMA measurements (κgf) with relative differences being < 25 %, whereas κccn was found to be ∼ 2.4 times larger than κgf for octyl-OS, likely due to both the solubility limit and surface tension reduction.


2013 ◽  
Vol 13 (3) ◽  
pp. 5805-5841 ◽  
Author(s):  
S. Bezantakos ◽  
K. Barmpounis ◽  
M. Giamarelou ◽  
E. Bossioli ◽  
M. Tombrou ◽  
...  

Abstract. The chemical composition and water uptake characteristics of sub-micrometer atmospheric particles in the region of the Aegean Sea were measured between 25 August and 11 September 2011 in the framework of the Aegean-Game campaign. High time-resolution measurements of the chemical composition of the particles were conducted using an airborne compact Time-Of-Flight Aerosol Mass Spectrometer (cTOF-AMS). These measurements involved two flights from the island of Crete to the island of Lemnos and back. A Hygroscopic Tandem Differential Mobility Analyzer (HTDMA) located on the island of Lemnos was used to measure the ability of the particles to take up water. The HTDMA measurements showed that the particles were internally mixed, having hygroscopic growth factors that ranged from 1.00 to 1.59 when exposed to 85% relative humidity. When the aircraft flew near the ground station on Lemnos, the cTOF-AMS measurements showed that the organic volume fraction of the particles ranged from 43 to 56%. These measurements corroborate the range of hygroscopic growth factors measured by the HTDMA during that time. Good closure between HTDMA and cTOF-AMS measurements was achieved when assuming that the organic species were hydrophobic and had an average density that corresponds to aged organic species. Using the results from the closure study, the cTOF-AMS measurements were employed to determine a representative aerosol hygroscopic parameter κmix for the whole path of the two flights. Calculated κmix values ranged from 0.17 to 1.03 during the first flight and from 0.15 to 0.93 during the second flight. Air masses of different origin as determined by back trajectory calculations can explain the spatial variation in the chemical composition and κmix values of the particles observed in the region.


2014 ◽  
Vol 14 (6) ◽  
pp. 8257-8285
Author(s):  
J. Jung ◽  
K. Kawamura

Abstract. To investigate the hygroscopic property of ultrafine particles during the new particle formation event, hygroscopic growth factors (g(RH)) of size-segregated atmospheric particles were measured at an urban site in Sapporo, northern Japan, during the summer of 2011. Hygroscopic growth factors at 85% RH (g(85%)) of freshly formed nucleation mode particles were measured at a dry particle diameter (Dp) centered at 20 nm to be 1.11 to 1.28 (average 1.16 ± 0.06), which are equivalent to 1.17 to 1.35 (1.23 ± 0.06) for a dry Dp centered at 100 nm after considering the Kelvin effect. These values are comparable with those of secondary organic aerosols, suggesting that low-volatility organic vapors are important to the burst of nucleation mode particles at the measurement site surrounded by a deciduous forest. Gradual increases in mode diameter after the burst of nucleation mode particles were obtained under southerly wind condition with a dominant contribution of intermediately-hygroscopic particles. However, sharp increases in mode diameter were obtained when wind direction shifted to northwesterly or northeasterly with a sharp increase in highly-hygroscopic particle faction in the Aitken mode particles, indicating that local wind direction is an important factor controlling the growth of newly formed particles and their hygroscopic properties. Higher g(85%) values (1.27 ± 0.05) were obtained at a dry Dp of 120 nm when the air masses originated from the Asian Continent, whereas lower g(85%) values (1.19 ± 0.06) were obtained when clean marine air masses arrived at the urban site. These results indicate that the hygroscopic property of large Aitken and small accumulation mode particles (80–165 nm) is highly influenced by the long-range atmospheric transport of particles and their precursors.


2019 ◽  
Vol 19 (4) ◽  
pp. 2115-2133 ◽  
Author(s):  
Liya Guo ◽  
Wenjun Gu ◽  
Chao Peng ◽  
Weigang Wang ◽  
Yong Jie Li ◽  
...  

Abstract. Calcium- and magnesium-containing salts are important components for mineral dust and sea salt aerosols, but their physicochemical properties are not well understood yet. In this study, hygroscopic properties of eight Ca- and Mg-containing salts, including Ca(NO3)2⚫4H2O, Mg(NO3)2⚫6H2O, MgCl2⚫6H2O, CaCl2⚫6H2O, Ca(HCOO)2, Mg(HCOO)2⚫2H2O, Ca(CH3COO)2⚫H2O and Mg(CH3COO)2⚫4H2O, were investigated using two complementary techniques. A vapor sorption analyzer was used to measure the change of sample mass with relative humidity (RH) under isotherm conditions, and the deliquescence relative humidities (DRHs) for temperature in the range of 5–30 ∘C as well as water-to-solute ratios as a function of RH at 5 and 25 ∘C were reported for these eight compounds. DRH values showed large variation for these compounds; for example, at 25 ∘C DRHs were measured to be ∼ 28.5 % for CaCl2⚫6H2O and >95 % for Ca(HCOO)2 and Mg(HCOO)2⚫2H2O. We further found that the dependence of DRH on temperature can be approximated by the Clausius–Clapeyron equation. In addition, a humidity tandem differential mobility analyzer was used to measure the change in mobility diameter with RH (up to 90 %) at room temperature, in order to determine hygroscopic growth factors of aerosol particles generated by atomizing water solutions of these eight compounds. All the aerosol particles studied in this work, very likely to be amorphous under dry conditions, started to grow at very low RH (as low as 10 %) and showed continuous growth with RH. Hygroscopic growth factors at 90 % RH were found to range from 1.26 ± 0.04 for Ca(HCOO)2 to 1.79 ± 0.03 for Ca(NO3)2, and the single hygroscopicity parameter ranged from 0.09–0.13 for Ca(CH3COO)2 to 0.49–0.56 for Ca(NO3)2. Overall, our work provides a comprehensive investigation of hygroscopic properties of these Ca- and Mg-containing salts, largely improving our knowledge of the physicochemical properties of mineral dust and sea salt aerosols.


2004 ◽  
Vol 4 (1) ◽  
pp. 35-50 ◽  
Author(s):  
M. Gysel ◽  
E. Weingartner ◽  
S. Nyeki ◽  
D. Paulsen ◽  
U. Baltensperger ◽  
...  

Abstract. Ambient continental-rural fine aerosol (K-puszta, Hungary, PM1.5) was sampled on quartz fibre filters in winter and summer 2001. Water-soluble matter (WSM) was extracted in MilliQ-water, and, in a second step, solid phase extraction was used to isolate the less hydrophilic fraction (ISOM) of the water-soluble organic matter (WSOM) from remaining inorganic salts and "most" hydrophilic organic matter (MHOM). This approach allowed ISOM, which constitutes the major fraction of WSOM, to be isolated from ambient aerosols and investigated in pure form. Hygroscopic properties of both WSM and ISOM extracts as well as of aquatic reference fulvic and humic acids were investigated using a Hygroscopicity Tandem Differential Mobility Analyser (H-TDMA). ISOM deliquesced between 30% and 60% relative humidity (RH), and hygroscopic growth factors at 90% RH ranged from 1.08 to 1.17. The hygroscopicity of ISOM is comparable to secondary organic aerosols obtained in smog chamber experiments, but lower than the hygroscopicity of highly soluble organic acids. The hygroscopic behaviour of investigated fulvic and humic acids had similarities to ISOM, but hygroscopic growth factors were slightly smaller and deliquescence was observed at higher RH (75-85% and 85-95% RH for fulvic acid and humic acid, respectively). These differences probably originate from larger average molecular mass and lower solubility of fulvic and humic acids. Inorganic composition data, measured ISOM hygroscopicity, and a presumed value for the hygroscopicity of the small remaining MHOM fraction were used to predict hygroscopic growth of WSM extracts. Good agreement between model prediction and measured water uptake was observed with differences (by volume) ranging from +1% to -18%. While deliquescence properties of WSM extracts were mainly determined by the inorganic salts (42-53 wt % of WSM), the WSOM accounted for a significant fraction of particulate water. At 90% RH, according to model predictions and measurements, about 80-62% of particulate water in the samples are associated with inorganic salts and about 20-38% with WSOM. The relative contributions of both distinguished WSOM fractions, ISOM and MHOM, remains uncertain since MHOM was not available in isolated form, but the results suggest that the less abundant MHOM is also important due to its presumably larger hygroscopicity.


2014 ◽  
Vol 14 (2) ◽  
pp. 737-749 ◽  
Author(s):  
K. A. Kamilli ◽  
L. Poulain ◽  
A. Held ◽  
A. Nowak ◽  
W. Birmili ◽  
...  

Abstract. Aerosol hygroscopic growth factors and chemical properties were measured as part of the MEGAPOLI "Megacities Plume Case Study" at the urban site Laboratoire d'Hygiène de la Ville de Paris (LHVP) in the city center of Paris from June to August 2009, and from January to February 2010. Descriptive hygroscopic growth factors (DGF) were derived in the diameter range from 25 to 350 nm at relative humidities of 30, 55, 75, and 90% by applying the summation method on humidified and dry aerosol size distributions measured simultaneously with a humidified differential mobility particle sizer (HDMPS) and a twin differential mobility particle sizer (TDMPS). For 90% relative humidity, the DGF varied from 1.06 to 1.46 in summer, and from 1.06 to 1.66 in winter. Temporal variations in the observed mean DGF could be well explained with a simple growth model based on the aerosol chemical composition measured by aerosol mass spectrometry (AMS) and black carbon photometry (MAAP). In particular, good agreement was observed when sulfate was the predominant inorganic factor. A clear overestimation of the predicted growth factor was found when the nitrate mass concentration exceeded values of 10 μg m−3, e.g., during winter.


2006 ◽  
Vol 6 (2) ◽  
pp. 471-491 ◽  
Author(s):  
J. Rissler ◽  
A. Vestin ◽  
E. Swietlicki ◽  
G. Fisch ◽  
J. Zhou ◽  
...  

Abstract. Aerosol particle number size distributions and hygroscopic properties were measured at a pasture site in the southwestern Amazon region (Rondonia). The measurements were performed 11 September-14 November 2002 as part of LBA-SMOCC (Large scale Biosphere atmosphere experiment in Amazonia - SMOke aerosols, Clouds, rainfall and Climate), and cover the later part of the dry season (with heavy biomass burning), a transition period, and the onset of the wet period. Particle number size distributions were measured with a DMPS (Differential Mobility Particle Sizer, 3-850nm) and an APS (Aerodynamic Particle Sizer), extending the distributions up to 3.3 µm in diameter. An H-TDMA (Hygroscopic Tandem Differential Mobility Analyzer) measured the hygroscopic diameter growth factors (Gf) at 90% relative humidity (RH), for particles with dry diameters (dp) between 20-440 nm, and at several occasions RH scans (30-90% RH) were performed for 165nm particles. These data provide the most extensive characterization of Amazonian biomass burning aerosol, with respect to particle number size distributions and hygroscopic properties, presented until now. The evolution of the convective boundary layer over the course of the day causes a distinct diel variation in the aerosol physical properties, which was used to get information about the properties of the aerosol at higher altitudes. The number size distributions averaged over the three defined time periods showed three modes; a nucleation mode with geometrical median diameters (GMD) of ~12 nm, an Aitken mode (GMD=61-92 nm) and an accumulation mode (GMD=128-190 nm). The two larger modes were shifted towards larger GMD with increasing influence from biomass burning. The hygroscopic growth at 90% RH revealed a somewhat external mixture with two groups of particles; here denoted nearly hydrophobic (Gf~1.09 for 100 nm particles) and moderately hygroscopic (Gf~1.26). While the hygroscopic growth factors were surprisingly similar over the periods, the number fraction of particles belonging to each hygroscopic group varied more, with the dry period aerosol being more dominated by nearly hydrophobic particles. As a result the total particle water uptake rose going into the cleaner period. The fraction of moderately hygroscopic particles was consistently larger for particles in the accumulation mode compared to the Aitken mode for all periods. Scanning the H-TDMA over RH (30-90% RH) showed no deliquescence behavior. A parameterization of both Gf(RH) and Gf(dp), is given.


2003 ◽  
Vol 3 (5) ◽  
pp. 4879-4925 ◽  
Author(s):  
M. Gysel ◽  
E. Weingartner ◽  
S. Nyeki ◽  
D. Paulsen ◽  
U. Baltensperger ◽  
...  

Abstract. Ambient continental-rural fine aerosol (K-puszta, Hungary, PM1.5) was sampled on quartz fibre filters in winter and summer 2001. Water-soluble matter (WSM) was extracted in MilliQ-water, and, in a second step, solid phase extraction was used to isolate the less hydrophilic fraction (ISOM) of the water-soluble organic matter (WSOM) from inorganic salts and remaining most hydrophilic organic matter (MHOM). This approach allowed to investigate a major fraction of WSOM isolated in pure form from ambient aerosols. Hygroscopic properties of both WSM and ISOM extracts as well as of aquatic reference fulvic and humic acids were investigated using a Hygroscopicity Tandem Differential Mobility Analyser (H-TDMA). ISOM deliquesced between 40–60% and 30–55% relative humidity (RH), in winter and summer, respectively, and hygroscopic growth factors at 90% RH were 1.08–1.11 and 1.16–1.17. The hygroscopicity of ISOM is comparable to secondary organic aerosols obtained in smog chamber experiments, but lower than the hygroscopicity of highly soluble organic acids. Hygroscopic behaviour of investigated fulvic and humic acids had similarities to ISOM, but hygroscopic growth factors were slightly smaller and deliquescence was observed at higher RH (75–85% and 85–95% RH for fulvic acid and humic acid, respectively). These differences probably originate from larger average molecular weight and lower solubility of fulvic and humic acids. Inorganic composition data, measured ISOM hygroscopicity, and a presumable value for the hygroscopicity of the small remaining MHOM fraction were used to predict hygroscopic growth of WSM extracts. Good agreement between model prediction and measured water uptake was observed with differences (by volume) of +1% and −5% in winter, and −18% and −12% in summer. While deliquescence properties of WSM extracts were mainly determined by the inorganic salts (42–53 wt \\% of WSM), the WSOM accounted for a significant fraction of particulate water. At 90% RH, according to model predictions and measurements, about 80% (62%) of particulate water in winter (summer) samples are associated with inorganic salts and about 20% (38%) with WSOM. The relative contributions of both distinguished WSOM fractions, ISOM and MHOM, remains uncertain since MHOM was not available in isolated form, but the results suggest that the less abundant MHOM is also important due to its presumably larger hygroscopicity.


2011 ◽  
Vol 11 (9) ◽  
pp. 4251-4271 ◽  
Author(s):  
M. Stock ◽  
Y. F. Cheng ◽  
W. Birmili ◽  
A. Massling ◽  
B. Wehner ◽  
...  

Abstract. This work examines the effect of direct radiative forcing of aerosols in the eastern Mediterranean troposphere as a function of air mass composition, particle size distribution and hygroscopicity, and relative humidity (RH). During intensive field measurements on the island of Crete, Greece, the hygroscopic properties of atmospheric particles were determined using a Hygroscopicity Tandem Differential Mobility Analyzer (H-TDMA) and a Hygroscopicity Differential Mobility Analyzer-Aerodynamic Particle Sizer (H-DMA-APS). Similar to former studies, the H-TDMA identified three hygroscopic sub-fractions of particles in the sub-μm range: a more hygroscopic group, a less hygroscopic group and a nearly hydrophobic particle group. The average hygroscopic particle growth factors at 90 % RH were a significant function of particle mobility diameter (Dp): 1.42 (± 0.05) at 30 nm compared to 1.63 (± 0.07) at 250 nm. The H-DMA-APS identified up to three hygroscopic sub-fractions at mobility diameters of 1.0 and 1.2 μm. The data recorded between 12 August and 20 October 2005 were classified into four distinct synoptic-scale air mass types distinguishing between different regions of origin (western Mediterranean vs. the Aegean Sea) as well as the degree of continental pollution (marine vs. continentally influenced). The hygroscopic properties of particles with diameter Dp≥150 nm showed the most pronounced dependency on air mass origin, with growth factors in marine air masses exceeding those in continentally influenced air masses. Particle size distributions and hygroscopic growth factors were used to calculate aerosol light scattering coefficients at ambient RH using a Mie model. A main result was the pronounced enhancement of particle scattering over the eastern Mediterranean due to hygroscopic growth, both in the marine and continentally influenced air masses. When RH reached its summer daytime values around 70–80 %, up to 50–70 % of the calculated visibility reduction was due to the hygroscopic growth of the particles by water compared to the effect of the dry particles alone. The estimated aerosol direct radiative forcings for both, marine and continentally influenced air masses were negative indicating a net cooling of the atmosphere due to the aerosol. The radiative forcing ΔFr was nevertheless governed by the total aerosol concentration most of the time: ΔFr was typically more negative for continentally influenced aerosols (ca. −4 W m−2) compared to rather clean marine aerosols (ca. −1.5 W m−2). When RH occasionally reached 90 % in marine air masses, ΔFr even reached values down to −7 W m−2. Our results emphasize, on the basis of explicit particle hygroscopicity measurements, the relevance of ambient RH for the radiative forcing of regional atmospheres.


2010 ◽  
Vol 10 (11) ◽  
pp. 25991-26044
Author(s):  
M. Stock ◽  
Y. F. Cheng ◽  
W. Birmili ◽  
A. Massling ◽  
B. Wehner ◽  
...  

Abstract. This work examines the effect of direct radiative forcing of aerosols in the eastern Mediterranean troposphere as a function of air mass composition, particle size distribution and hygroscopicity, and relative humidity (RH). During intensive field measurements on the island of Crete, Greece, the hygroscopic properties of atmospheric particles were determined using a Hygroscopicity Tandem Differential Mobility Analyzer (H-TDMA) and a Hygroscopicity Differential Mobility Analyzer – Aerodynamic Particle Sizer (H-DMA-APS). Like in several studies before, the H-TDMA identified three hygroscopic sub-fractions of particles in the sub-μm range: a more hygroscopic group, a less hygroscopic group and a nearly hydrophobic particle group. The hygroscopic particle growth factors at 90% RH were a significant function of particle mobility diameter (Dp): 1.42 (± 0.05) at 30 nm compared to 1.63 (± 0.07) at 250 nm. The H-DMA-APS identified up to three hygroscopic sub-fractions at mobility diameters of 1.0 and 1.2 μm. All data recorded between 12 August and 20 October, 2005 were classified into four distinct synoptic-scale air mass types distinguishing between different regions of origin (western Mediterranean vs. the Aegean Sea) as well as the degree of continental pollution (marine vs. continentally influenced). The hygroscopic properties of particles with diameter Dp ≥ 150 nm showed the most pronounced dependency on air mass origin, with growth factors in marine air masses exceeding those in more continentally influenced air masses. Particle size distributions and hygroscopic growth factors were employed to calculate aerosol light scattering coefficients at ambient RH using a Mie model. A main result was the pronounced enhancement of particle scattering over the eastern Mediterranean due to hygroscopic growth, both in the marine and continentally influenced air masses. When RH reached its daytime values around 70–80% in summer, up to 50–70% of the calculated visibility reduction was due to the hygroscopic growth of the particles by water compared to the effect of the dry particles alone. The estimated aerosol direct radiative forcings for both, marine and continentally influenced air masses were negative indicating a net cooling of the atmosphere due to the aerosol. The radiative forcing ΔFr was, nevertheless, dominated by the total aerosol concentration most of the time: ΔFr was typically more negative for continentally influenced aerosols (ca. −4 W m−2) compared to rather clean marine aerosols (ca. −1.5 W m−2). When RH occasionally reached 90% in marine air, ΔFr even reached values down to −7 W m−2. Our results emphasize, on the basis of explicit particle hygroscopicity measurements, the relevance of ambient relative humidity for the radiative forcing of regional atmospheres.


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