scholarly journals Overview of the field measurement campaign in Hyytiälä, August 2001 in the framework of the EU project OSOA

2004 ◽  
Vol 4 (3) ◽  
pp. 657-678 ◽  
Author(s):  
M. Boy ◽  
T. Petäjä ◽  
M. Dal Maso ◽  
Ü. Rannik ◽  
J. Rinne ◽  
...  

Abstract. As part of the OSOA (Origin and formation of Secondary Organic Aerosols) project, two intensive field campaigns were conducted in Melpitz, Germany and Hyytiälä, Finland. This paper gives an overview of the measurements made during the Hyytiälä campaign, which was held between 1 and 16 August 2001. Various instrumental techniques were used to achieve physical and chemical characterisation of aerosols and to investigate possible precursor gases. During the OSOA campaign in Hyytiälä, particle formation was observed on three consecutive days at the beginning of the campaign (1 to 3 August 2001) and on three days later on. The investigation of the meteorological situation divided the campaign into two parts. During the first three days of August, relatively cold and clean air masses from northwest passed over the station (condensation sink – CS: <0.002 s-1, NOx: <0.5 ppb). Daily particle bursts of one fraction of the nucleation mode aerosols (3–10 nm) with number concentrations between 600–1200 particles cm-3 were observed. After this period, warmer and more polluted air from south-west to south-east arrived at the station (CS: 0.002–0.01 s-1, NOx: 0.5–4 ppb) and during these 13 days only three events were observed. These events were not as apparent as those that occurred during the earlier period of the campaign. The chemical analyses from different institutes of PM2, PM2.5 and PM10 particles confirmed the assumption that organic matter from the oxidation of various terpenes contributed to the formation of secondary organic aerosols (SOA). Concerning these conclusions among others, the ratio between formic (oxidation product of isoprene and monoterpenes by ozone) and acetic acid (increased by anthropogenic emissions) (ratio=1 to 1.5) and concentration of different carboxylic acids (up to 62 ngm-3) were investigated. Gas/particle partitioning of five photo-oxidation products from α- and β-pinene resulted in higher concentrations of pinonic, nor pinonic and pinic acids in the particle phase than in the gas phase, which indicates a preference to the particle phase for these compounds. The average growth factors (GF) from 100 nm particles in water vapour gave a diurnal pattern with a maximum during daytime and values between 1.2 and 1.7. On average, the amount of secondary organic carbon reached values around 19% of the sampled aerosols and we speculate that formation of SOA with the influence of photo-oxidation products from terpenes was the reason for the observed particle bursts during the campaign. However, correlations between the precursor gases or the favourable condensing species with the monitored nucleation mode particles were not found. For the investigated time period other factors like the condensation sink of newly formed particles to the pre-existing aerosols, temperature and solar irradiance seem to be more important steering parameters for the production of new aerosols. Another open question concerns the vertical distribution of the formation of SOA. For this reason measurements were conducted at different altitudes using a tethered balloon platform with particle sampling and particle counting equipment. They were incorporated with eddy covariance (EC) flux measurements made at 23 m above ground level. The results give first indications that production of new aerosols happens throughout the planetary boundary layer (PBL), whereby different parameters e.g. temperature, CS, solar irradiance or concentration of monoterpenes are responsible for the location of the vertical maximum.

2003 ◽  
Vol 3 (4) ◽  
pp. 3769-3831 ◽  
Author(s):  
M. Boy ◽  
T. Petäja ◽  
M. Dal Maso ◽  
Ü. Rannik ◽  
J. Rinne ◽  
...  

Abstract. As one part of the OSOA (Origin and formation of Secondary Organic Aerosols) project, two intensive field campaigns were conducted in Melpitz, Germany and Hyytiälä, Finland. This paper gives an overview of the measurements made during the Hyytiälä campaign, which was held between the 1st and 16th of August 2001. Various instrumental techniques were used to achieve physical and chemical characterisation of aerosols and to investigate possible precursor gases. During the OSOA campaign in Hyytiälä, particle formation was observed on three consecutive days at the beginning of the campaign (1 to 3 August 2001) and on three days later on. The investigation of the meteorological situation divided the campaign into two parts. During the first three days of August, relatively cold and clean air masses from northwest passed over the station (condensation sink – CS: <0.002 s−1, NOx: < 0.5 ppb). Daily particle bursts of one fraction of the nucleation mode aerosols (3–10\\,nm) with number concentrations between 600–1200 particles cm-3 were observed. After this period, warmer and more polluted air from south-west to south-east arrived at the station (CS: 0.002-0.01 s−1, NOx: 0.5–4 ppb) and during these 13 days only three events were observed. These events were not as apparent as those that occurred during the earlier period of the campaign. The chemical analyses from different institutes of PM2, PM2.5 and PM10 particles confirmed the assumption that organic matter from the oxidation of various terpenes contributed to the formation of secondary organic aerosols (SOA). Concerning these conclusions among others, the ratio between formic (oxidation product of isoprene and monoterpenes by ozone) and acetic acid (increased by anthropogenic emissions) (ratio=1 to 1.5) and concentration of different carboxylic acids (up to 62 ng m−3) were investigated. Gas/particle partitioning of five photo-oxidation products from α- and β-pinene resulted in higher concentrations for pinonic, nor pinonic and pinic acids in the particle phase than in the gas phase, which indicates preference to the particle phase for these compounds. The average growth factors (GF) from 100 nm particles in water vapour gave a diurnal pattern with a maximum during daytime and values between 1.2 and 1.7. On average, the amount of secondary organic carbon reached values around of 19% of the sampled aerosols and the results indicate that formation of SOA with the influence of photo-oxidation products from terpenes was the reason for the observed particle bursts during the campaign. However, correlations between the precursor gases or the favourable condensing species with the monitored nucleation mode particles were not found. For the investigated time period other factors like the condensation sink of newly formed particles to the pre-existing aerosols, temperature and solar irradiance seem to be more important steering parameters for the production of new aerosols. Another open question concerns the vertical distribution of the formation of SOA. For this reason measurements were conducted at different altitudes using a tethered balloon platform with particle sampling and particle counting equipment. They were incorporated with eddy covariance (EC) flux measurements made at 23 m above ground level. The results give first indications that the process of the production of new aerosols happens throughout the planetary boundary layer (PBL), whereby different parameters e.g. temperature, CS, solar irradiance or concentration of monoterpenes are responsible for the location of the vertical maximum.


2019 ◽  
Author(s):  
Ying Li ◽  
Manabu Shiraiwa

Abstract. Secondary organic aerosols (SOA) account for a substantial fraction of air particulate matter and SOA formation is often modeled assuming rapid establishment of gas-particle equilibrium. Here, we estimate the characteristic timescale for SOA to achieve gas−particle equilibrium under a wide range of temperatures and relative humidities using a state-of-the-art kinetic flux model. Equilibration timescales were calculated by varying particle phase state, size, mass loadings, and volatility of organic compounds. Model simulations suggest that the equilibration timescale for semi-volatile compounds is on the order of seconds or minutes for most conditions in the planetary boundary layer, but it can be longer than one hour if particles adopt glassy or amorphous solid states with high glass transition temperature at low relative humidity. In the free troposphere with lower temperatures it can be longer than hours or days even at moderate or relatively high RH due to kinetic limitations of bulk diffusion in highly viscous particles. The timescale of partitioning of low-volatile compounds is shorter compared to semi-volatile compounds, as it is largely determined by condensation sink due to very slow re-evaporation. These results provide critical insights into thermodynamic or kinetic treatments of SOA partitioning for accurate predictions of gas- and particle-phase concentrations of semi-volatile compounds in regional and global chemical transport models.


2004 ◽  
Vol 38 (25) ◽  
pp. 4093-4098 ◽  
Author(s):  
Magda Claeys ◽  
Wu Wang ◽  
Alina C Ion ◽  
Ivan Kourtchev ◽  
András Gelencsér ◽  
...  

2013 ◽  
Vol 13 (22) ◽  
pp. 11535-11549 ◽  
Author(s):  
J. J. Li ◽  
G. H. Wang ◽  
J. J. Cao ◽  
X. M. Wang ◽  
R. J. Zhang

Abstract. Secondary organic aerosols (SOA) derived from isoprene, pinene and caryophyllene were determined for PM10 and size-segregated (9-stages) aerosols collected at the summit (2060 m a.s.l.) of Mt. Hua, central China during the summer of 2009. Estimated concentrations of isoprene, α-/β-pinene and β-caryophyllene derived secondary organic carbon (SOC) are 81 ± 53, 29 ± 14 and 98 ± 53 ng m−3, accounting for 2.7 ± 1.0%, 0.8 ± 0.2% and 2.1 ± 1.0% of OC, respectively. Concentrations of biogenic (BSOA, the isoprene/pinene/caryophyllene oxidation products) and anthropogenic (ASOA, mainly aromatic acids) SOA positively correlated with temperature (R=0.57–0.90). However, a decreasing trend of BSOA concentration with an increase in relative humidity (RH) was observed during the sampling period, although a clear trend between ASOA and RH was not found. Based on the AIM Model calculation, we found that during the sampling period an increase in RH resulted in a decrease in the aerosol acidity and thus reduced the effect of acid-catalysis on BSOA formation. There was no significant correlation observed for the BSOA products and anthropogenic parameters (e.g. EC, SO42− and NO4−). Size distribution measurements showed that most of the determined BSOA are formed in the aerosol phase and enriched in the fine mode (<2.1 μm) except for cis-pinonic acid, which is formed in the gas phase and subsequently partitioned into aerosol phase and thus presents a bimodal pattern with a small peak in the fine mode and a large peak in the coarse mode (>2.1 μm).


2013 ◽  
Vol 13 (7) ◽  
pp. 17643-17674 ◽  
Author(s):  
J. J. Li ◽  
G. H. Wang ◽  
J. J. Cao ◽  
X. M. Wang ◽  
R. J. Zhang

Abstract. Secondary organic aerosols (SOA) derived from isoprene, pinene and caryophyllene were determined for PM10 and size-segregated (9-stage) aerosols collected at the summit (2060 m, a.s.l.) of Mt. Hua, central China during the summer of 2009. Concentrations of estimated isoprene, α-/β-pinene and β-caryophyllene derived SOC are 81± 53, 29 ± 14 and 98 ± 53 ng m−3, accounting for 2.7± 1.0%, 0.8 ± 0.2% and 2.1 ± 1.0% of OC, respectively. Concentrations of biogenic (BSOA, the isoprene/pinene/caryophyllene oxidation products) and anthropogenic (ASOA, mainly aromatic acids) SOA positively correlated with temperature (R=0.57–0.90). However, a decreasing trend of BSOA concentration with an increase in relative humidity (RH) was observed during the sampling period, although a clear trend between ASOA and RH was not found. Based on the AIM Model calculation, we found that during the sampling period an increase in RH resulted in a decrease in the aerosol acidity and thus reduced the effect of acid-catalysis on BSOA formation. Size distribution measurement showed that most of the determined isoprene derived SOA may form in aerosol phase and enriched in the fine mode (<2.1μm). 3-Hydroxyglutaric acid, 3-methyl-1,2,3-butanetricarboxylic acid and β-caryophyllinic acid are only presented in fine particles. However, cis-pinonic acid presents a large peak in the coarse mode (>2.1 μm) due to its highly volatile nature.


2021 ◽  
Author(s):  
Chao Qin ◽  
Yafeng Gou ◽  
Yuhang Wang ◽  
Yuhao Mao ◽  
Hong Liao ◽  
...  

Abstract. Gas-particle partitioning of water-soluble organic compounds plays a significant role in the formation and source apportionment of organic aerosols, but is poorly characterized. In this work, gas- and particle-phase concentrations of isoprene oxidation products (C5-alkene triols and 2-methylterols), levoglucosan, and sugar polyols were measured simultaneously at a suburban site of the western Yangtze River Delta in east China. All target polyols were primarily distributed into the particle phase (85.9–99.8 %), and their average particle-phase fractions were not strictly dependent on vapor pressures. Moreover, the measurement-based partitioning coefficients (Kp,OM) of isoprene oxidation products and levoglucosan were 102 to 104 times larger than their predicted Kp,OM based on the equilibrium absorptive partitioning model. These are likely attributed to the hygroscopic properties of polyol tracers and high aerosol liquid water (ALW) concentrations (~20 µg m−3) of the study location. Due to the large gaps (up to 107) between measurement-based effective Henry's law coefficients (KH,e) and predicted values in pure water (KH,w), the gas-particle partitioning of polyol tracers could not be depicted using Henry's law alone either. The regressions of log (KH,w/KH,e) versus molality of major water-soluble components in ALW indicated that sulfate ions (salting-in effect) and water-soluble organic carbon can promote the partitioning of polyol tracers into the aqueous phase. These results suggest a partitioning mechanism of enhanced aqueous-phase uptake for polyol tracers, which partly reveals the discrepancy between observation and modeling of secondary organic aerosols.


2021 ◽  
Vol 21 (3) ◽  
pp. 1565-1580
Author(s):  
Manabu Shiraiwa ◽  
Ulrich Pöschl

Abstract. Mass accommodation is an essential process for gas–particle partitioning of organic compounds in secondary organic aerosols (SOA). The mass accommodation coefficient is commonly described as the probability of a gas molecule colliding with the surface to enter the particle phase. It is often applied, however, without specifying if and how deep a molecule has to penetrate beneath the surface to be regarded as being incorporated into the condensed phase (adsorption vs. absorption). While this aspect is usually not critical for liquid particles with rapid surface–bulk exchange, it can be important for viscous semi-solid or glassy solid particles to distinguish and resolve the kinetics of accommodation at the surface, transfer across the gas–particle interface, and further transport into the particle bulk. For this purpose, we introduce a novel parameter: an effective mass accommodation coefficient αeff that depends on penetration depth and is a function of surface accommodation coefficient, volatility, bulk diffusivity, and particle-phase reaction rate coefficient. Application of αeff in the traditional Fuchs–Sutugin approximation of mass-transport kinetics at the gas–particle interface yields SOA partitioning results that are consistent with a detailed kinetic multilayer model (kinetic multilayer model of gas–particle interactions in aerosols and clouds, KM-GAP; Shiraiwa et al., 2012) and two-film model solutions (Model for Simulating Aerosol Interactions and Chemistry, MOSAIC; Zaveri et al., 2014) but deviate substantially from earlier modeling approaches not considering the influence of penetration depth and related parameters. For highly viscous or semi-solid particles, we show that the effective mass accommodation coefficient remains similar to the surface accommodation coefficient in the case of low-volatility compounds, whereas it can decrease by several orders of magnitude in the case of semi-volatile compounds. Such effects can explain apparent inconsistencies between earlier studies deriving mass accommodation coefficients from experimental data or from molecular dynamics simulations. Our findings challenge the approach of traditional SOA models using the Fuchs–Sutugin approximation of mass transfer kinetics with a fixed mass accommodation coefficient, regardless of particle phase state and penetration depth. The effective mass accommodation coefficient introduced in this study provides an efficient new way of accounting for the influence of volatility, diffusivity, and particle-phase reactions on SOA partitioning in process models as well as in regional and global air quality models. While kinetic limitations may not be critical for partitioning into liquid SOA particles in the planetary boundary layer (PBL), the effects are likely important for amorphous semi-solid or glassy SOA in the free and upper troposphere (FT–UT) as well as in the PBL at low relative humidity and low temperature.


2016 ◽  
Author(s):  
Wei Deng ◽  
Qihou Hu ◽  
Tengyu Liu ◽  
Xinming Wang ◽  
Yanli Zhang ◽  
...  

Abstract. In China primary particulate matter emission from on-road vehicles is predominantly coming from diesels, yet secondary organic aerosols (SOA) formed from diesel emission may be also of greater significance due to more intermediate volatile organic compounds (IVOC) in the exhaust. Here we introduced exhaust from in-use diesel vehicles under warm idling condition directly into an indoor smog chamber with a 30 m3 Teflon reactor, and investigated the SOA formation as well as chemical aging of organic aerosols during photo-oxidation. The emission factors of primary organic aerosol (POA) and black carbon (BC) for the three typical Chinese diesel vehicles ranged 0.18–0.91 and 0.15–0.51 g kg-fuel−1, respectively; and the SOA production factors ranged 0.50–1.8 g kg-fuel−1 with an average SOA/POA ratio of 1.6. Aromatic hydrocarbons could only explain less than 3 % of SOA formed during aging, and IVOC and oxygenated VOC might contribute substantially to SOA formation. High resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS) resolved that POA dominated by CH classes (alkanes, cycloalkanes and alkenes) with high abundances of the CnH2n+1 and CnH2n-1 fragments, and after photo-oxidation the fraction of CH classes and the H/C ratios decreased, while the fraction of CHO, as well as the ratios of O/C and of organic matter to organic carbon (OM/OC), all increased. The plot of f44 (ratio of m/z 44 to the total signal in a mass spectrum) versus f43 indicated that diesel SOA were semi-volatile oxygenated organic aerosols (SV-OOA). The slopes of O:C versus H:C element ratios in the Van Krevelen diagram ranged from −0.47 to −0.68, suggesting a combination of carboxylic acid and alcohols/peroxides formed during the aging of diesel exhaust.


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