scholarly journals Secondary aerosol formation promotes water uptake by organic-rich wildfire haze particles in Equatorial Asia

2017 ◽  
Author(s):  
Jing Chen ◽  
Sri Hapsari Budisulistiorini ◽  
Takuma Miyakawa ◽  
Yuichi Komazaki ◽  
Mikinori Kuwata

Abstract. Diameter growth factors (GF) of 100 nm haze particles at 85 % relative humidity and chemical characteristics were simultaneously monitored at Singapore in October 2015 during a pervasive wildfire haze episode, which was caused by peatland burning in Indonesia. Non-refractory submicron particles (NR-PM1) were dominated by organics (approximating 77.1 % in total mass), whereas sulfate was the most abundant inorganic constituent (11.7 % on average). A statistical analysis of the organic mass spectra showed that most of organics (36.0 % of NR-PM1 mass) were highly oxygenated. Diurnal variations of GF, number fraction of highly hygroscopic mode particles, mass fraction of sulfate, and mass fraction of oxygenated organics (OOA) synchronized well, peaking during daytime. The mean hygroscopicity parameter (κ) of haze particles was 0.189 ± 0.087, and mean κ values of organics were 0.157 ± 0.108 (κorg, bulk organics) and 0.287 ± 0.193 (κOOA, OOA), demonstrating the important roles of both sulfate and highly oxygenated organics in hygroscopic growth of wildfire haze particles. κorg was also affected by the water-soluble organic fraction to some extent. These results show the importance of secondary formation processes in promoting water uptake properties of wildfire haze particles, including both inorganic and organic species. Further detailed size-resolved as well as molecular level chemical information of organics will be necessary for more profound exploration of water uptake by wildfire haze particles in Equatorial Asia.

2018 ◽  
Vol 18 (11) ◽  
pp. 7781-7798 ◽  
Author(s):  
Jing Chen ◽  
Sri Hapsari Budisulistiorini ◽  
Takuma Miyakawa ◽  
Yuichi Komazaki ◽  
Mikinori Kuwata

Abstract. The diameter growth factor (GF) of 100 nm haze particles at 85 % relative humidity (RH) and their chemical characteristics were simultaneously monitored at Singapore in October 2015 during a pervasive wildfire haze episode that was caused by peatland burning in Indonesia. Non-refractory submicron particles (NR-PM1) were dominated by organics (OA; approximating 77.1 % in total mass), whereas sulfate was the most abundant inorganic constituent (11.7 % on average). A statistical analysis of the organic mass spectra showed that most organics (36.0 % of NR-PM1 mass) were highly oxygenated. Diurnal variations of GF, number fractions of more hygroscopic mode particles, mass fractions of sulfate, and mass fractions of oxygenated organics (OOA) synchronized well, peaking during the day. The mean hygroscopicity parameter (κ) of the haze particles was 0.189 ± 0.087, and the mean κ values of organics were 0.157 ± 0.108 (κorg, bulk organics) and 0.266 ± 0.184 (κOOA, OOA), demonstrating the important roles of both sulfate and highly oxygenated organics in the hygroscopic growth of organics-dominated wildfire haze particles. κorg correlated with the water-soluble organic fraction insignificantly, but it positively correlated with f44 (fraction of the ion fragment at m∕z 44 in total organics) (R = 0.70), implying the oxygenation degree of organics could be more critical for the water uptake of organic compounds. These results further suggest the importance of sulfate and secondary organic aerosol formation in promoting the hygroscopic growth of wildfire haze particles. Further detailed size-resolved as well as molecular-level chemical information about organics is necessary for the profound exploration of water uptake by wildfire haze particles in equatorial Asia.


2015 ◽  
Vol 15 (15) ◽  
pp. 8847-8869 ◽  
Author(s):  
E. F. Mikhailov ◽  
G. N. Mironov ◽  
C. Pöhlker ◽  
X. Chi ◽  
M. L. Krüger ◽  
...  

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


2015 ◽  
Vol 15 (6) ◽  
pp. 7837-7893
Author(s):  
E. F. Mikhailov ◽  
G. N. Mironov ◽  
C. Pöhlker ◽  
X. Chi ◽  
M. L. Krüger ◽  
...  

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


2017 ◽  
Vol 10 (3) ◽  
pp. 1269-1280 ◽  
Author(s):  
Sergey S. Vlasenko ◽  
Hang Su ◽  
Ulrich Pöschl ◽  
Meinrat O. Andreae ◽  
Eugene F. Mikhailov

Abstract. A tandem arrangement of Differential Mobility Analyser and Humidified Centrifugal Particle Mass Analyser (DMA-HCPMA) was developed to measure the deliquescence and efflorescence thresholds and the water uptake of submicron particles over the relative humidity (RH) range from 10 to 95 %. The hygroscopic growth curves obtained for ammonium sulfate and sodium chloride test aerosols are consistent with thermodynamic model predictions and literature data. The DMA-HCPMA system was applied to measure the hygroscopic properties of urban aerosol particles, and the kappa mass interaction model (KIM) was used to characterize and parameterize the concentration-dependent water uptake observed in the 50–95 % RH range. For DMA-selected 160 nm dry particles (modal mass of 3.5 fg), we obtained a volume-based hygroscopicity parameter, κv ≈  0.2, which is consistent with literature data for freshly emitted urban aerosols.Overall, our results show that the DMA-HCPMA system can be used to measure size-resolved mass growth factors of atmospheric aerosol particles upon hydration and dehydration up to 95 % RH. Direct measurements of particle mass avoid the typical complications associated with the commonly used mobility-diameter-based HTDMA technique (mainly due to poorly defined or unknown morphology and density).


Atmosphere ◽  
2019 ◽  
Vol 10 (7) ◽  
pp. 397 ◽  
Author(s):  
Zhengxu Gao ◽  
Xiaoling Wang ◽  
Lijuan Shen ◽  
Hua Xiang ◽  
Honglei Wang

As the new core region of the haze pollution, the terrain effect of sub-basin and water networks over the Twin-Hu Basin (THB) in the Yangtze River Middle-Reach (YRMR) had great impacts on the variations and distributions of air pollutants. In this study, trace gases (NH3, HNO3, and HCl), water-soluble ions (WSIs), organic carbon (OC), and elemental carbon (EC) were measured in PM2.5 from 9 January to 27 January 2018, in Wuhan using monitoring for aerosols and gases (MARGA) and a semi-continuous OC/EC analyzer (Model RT-4). The characteristics of air pollutants during a haze episode were discussed, and the PM2.5 sources were quantitatively analyzed on haze and non-haze days using the principal component analysis/absolute principal component scores (PCA/APCS) model. The average PM2.5 concentration was 122.61 μg·m−3 on haze days, which was 2.20 times greater than it was on non-haze days. The concentrations of secondary water soluble ions (WSIs) including NO3−, SO42−, and NH4+ increased sharply on haze days, which accounted for 91.61% of the total WSIs and were 2.43 times larger than the values on non-haze days. The heterogeneous oxidation reactions of NO2 and SO2 during haze episodes were proven to be the major sources of sulfate and nitrate in PM2.5. On haze days, the concentrations of EC, primary organic carbon (POC), and secondary organic carbon (SOC) were 1.68, 1.69, and 1.34 times larger than those on non-haze days, the CO, HNO3, and NH3 concentrations enhanced and relatively low SO2, O3, and HNO2 levels were observed on haze days. The diurnal variations of different pollutants distinctly varied on haze days. The PM2.5 in Wuhan primarily originated from the secondary formation, combustion, dust, industry, and vehicle exhaust sources. The source contributions of the secondary formation + combustion sources to PM2.5 on haze days were 2.79 times larger than the level on non-haze days. The contribution of the vehicle exhaust + combustion source on haze days were 0.59 times the value on non-haze days. This description is supported by a summary of how pollutant concentrations and patterns vary in the THB compared to the variations in other pollution regions in China, which have been more completely described.


2009 ◽  
Vol 9 (14) ◽  
pp. 4841-4854 ◽  
Author(s):  
T. Anttila ◽  
P. Vaattovaara ◽  
M. Komppula ◽  
A.-P. Hyvärinen ◽  
H. Lihavainen ◽  
...  

Abstract. In situ measurements of aerosol water uptake and activation of aerosols into cloud droplets provide information on how aerosols influence the microphysical properties of clouds. Here we present a computational scheme that can be used in connection with such measurements to assess the influence of the particle hygroscopicity and mixing state (in terms of the water uptake) on the cloud nucleating ability of particles. Additionally, it provides an estimate for the peak supersaturation of water vapour reached during the formation of the observed cloud(s). The method was applied in interpreting results of a measurement campaign that focused on aerosol-cloud interactions taking place at a subarctic background site located in Northern Finland (second Pallas Cloud Experiment, 2nd PaCE). A set of case studies was conducted, and the observed activation behavior could be successfully explained by a maximum supersaturation that varied between 0.18 and 0.26% depending on the case. In these cases, the diameter corresponding to the activated fraction of 50% was in the range of 110–140 nm, and the particles were only moderately water soluble with hygroscopic growth factors varying between 1.1 and 1.4. The conducted analysis showed that the activated fractions and the total number of particles acting as CCN are expected to be highly sensitive to the particle hygroscopic growth properties. For example, the latter quantity varied over a factor between 1.8 and 3.1, depending on the case, when the mean hygroscopic growth factors were varied by 10%. Another important conclusion is that size-dependent activation profiles carries information on the mixing state of particles.


2016 ◽  
Author(s):  
Sergey S. Vlasenko ◽  
Hang Su ◽  
Ulrich Pöschl ◽  
Meinrat O. Andreae ◽  
Eugene F. Mikhailov

Abstract. A tandem arrangement of Differential Mobility Analyzer and Humidified Centrifugal Particle Mass Analyzer (DMA-HCPMA) was developed to measure the deliquescence and efflorescence thresholds and the water uptake of submicron particles over the relative humidity (RH) range from 10 % to 95 %. The hygroscopic growth curves obtained for Ammonium sulfate and sodium chloride test aerosols are consistent with thermodynamic model predictions and literature data. The DMA-HCPMA system was applied to measure the hygroscopic properties of urban aerosol particles, and the kappa mass interaction model (KIM) was used to characterize and parameterize the concentration-dependent water uptake observed in the 50–95 % RH range. For DMA-selected 160 nm dry particles (mass of 3.5 fg), we obtained a volume-based hygroscopicity parameter κv ≈ 0.2, which is consistent with literature data for freshly emitted urban aerosols. Overall, our results show that the DMA-HCPMA system can be used to measure size-resolved mass growth factors of atmospheric aerosol particles upon hydration and dehydration up to 95 % RH. The direct measurements of humidified particle mass allow avoiding complications that occur in the commonly used mobility-diameter-based HTDMA technique due to poorly defined particle morphology and density.


2008 ◽  
Vol 8 (4) ◽  
pp. 16789-16817
Author(s):  
S. P. Hersey ◽  
A. Sorooshian ◽  
S. M. Murphy ◽  
R. C. Flagan ◽  
J. H. Seinfeld

Abstract. We have conducted the first closure study to couple high-resolution aerosol mass spectrometer (AMS) composition data with size-resolved, multiple-RH, high-time-resolution hygroscopic growth factor (GF) measurements from the differential aerosol sizing and hygroscopicity spectrometer probe (DASH-SP). These data were collected off the coast of Central California during seven of the 16 flights carried out during the MASE-II field campaign in July 2007. Two of the seven flights were conducted in airmasses that originated over the continental United States. These flights exhibited elevated organic volume fractions (VForganic=0.46±0.22, as opposed to 0.24±0.18 for all other flights), corresponding to significantly suppressed GFs at high RH (1.61±0.14 at 92% RH, as compared with 1.91±0.07 for all other flights), more moderate GF suppression at intermediate RH (1.53±0.10 at 85%, compared with 1.58±0.08 for all other flights, and no measurable GF suppression at low RH (1.31±0.06 at 74%, compared with 1.31±0.07 for all other flights). Organic loadings were slightly elevated in above-cloud aerosols, as compared with below-cloud aerosols, and corresponded to a similar trend of significantly suppressed GF at high RH, but more moderate impacts at lower values of RH. A hygroscopic closure based on a volume-weighted mixing rule provided excellent agreement with DASH-SP measurements (R2=0.79). Minimization of root mean square error between observations and predictions indicated mission-averaged organic GFs of 1.20, 1.43, and 1.46 at 74, 85, and 92% RH, respectively. These values agree with previously reported values for water-soluble organics such as dicarboxylic and multifunctional acids, and correspond to a highly oxidized, presumably water-soluble, organic fraction (O:C=0.92±0.33). Finally, a backward stepwise linear regression revealed that, other than RH, the most important predictor for GF is VForganic, indicating that a simple emperical model relating GF, RH, and the relative abundance of organic material can provide accurate predictions of hygroscopic growth in the marine atmosphere.


2019 ◽  
Vol 214 ◽  
pp. 116760 ◽  
Author(s):  
Simon L. Clegg ◽  
Lynn R. Mazzoleni ◽  
Vera Samburova ◽  
Nathan F. Taylor ◽  
Don R. Collins ◽  
...  

2013 ◽  
Vol 13 (19) ◽  
pp. 9819-9835 ◽  
Author(s):  
A. Wonaschütz ◽  
M. Coggon ◽  
A. Sorooshian ◽  
R. Modini ◽  
A. A. Frossard ◽  
...  

Abstract. During the Eastern Pacific Emitted Aerosol Cloud Experiment (E-PEACE), a plume of organic aerosol was produced by a smoke generator and emitted into the marine atmosphere from aboard the R/V Point Sur. In this study, the hygroscopic properties and the chemical composition of the plume were studied at plume ages between 0 and 4 h in different meteorological conditions. In sunny conditions, the plume particles had very low hygroscopic growth factors (GFs): between 1.05 and 1.09 for 30 nm and between 1.02 and 1.1 for 150 nm dry size at a relative humidity (RH) of 92%, contrasted by an average marine background GF of 1.6. New particles were produced in large quantities (several 10 000 cm−3), which lead to substantially increased cloud condensation nuclei (CCN) concentrations at supersaturations between 0.07 and 0.88%. Ratios of oxygen to carbon (O : C) and water-soluble organic mass (WSOM) increased with plume age: from < 0.001 to 0.2, and from 2.42 to 4.96 μg m−3, respectively, while organic mass fractions decreased slightly (~ 0.97 to ~ 0.94). High-resolution aerosol mass spectrometer (AMS) spectra show that the organic fragment m/z 43 was dominated by C2H3O+ in the small, new particle mode and by C3H7+ in the large particle mode. In the marine background aerosol, GFs for 150 nm particles at 40% RH were found to be enhanced at higher organic mass fractions: an average GF of 1.06 was observed for aerosols with an organic mass fraction of 0.53, and a GF of 1.04 for an organic mass fraction of 0.35.


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