Thermodenuder Research Articles

Volatility and chemical composition of secondary organic aerosol derived from acenaphthylene and acenaphthene under various oxidant conditions

Acenaphthene (ACE) and acenaphthylene (ACY), distinguished by their unique structures, exhibit high reactivity among polycyclic aromatic hydrocarbons (PAHs). Particularly, the rapid ozonolysis of the carbon-carbon double bond in ACY and the swift oxidation of the fused cyclopenta ring in both ACE and ACY by NO3 underscore their distinct atmospheric fate. Through the utilization of a thermo denuder and high-resolution mass spectrometry, the chemical composition and volatility of four types of secondary organic aerosols (SOA) derived from ACE and ACY are investigated. The chemical composition of SOA formed by ACY ozonolysis is characterized by low O: C ratios and high unsaturation, suggesting the retention of aromatic structures. This leads to measured high SOA volatility and is consistent with the low reactivity of O3 with aromatic compounds. In contrast to ozonolysis, the reaction of NO3 with ACY could yield SOA with very low volatility, characterized by abundant dimers and highly oxidized products. Furthermore, the prevalence of compounds with 11 carbon atoms suggests the presence of complex mechanisms in the ACY oxidation process initiated by NO3, where dealkylation reactions and cleavage reactions may be pivotal. The diverse chemical composition and volatility of SOA from ACE and ACY reacting with NO3 radicals highlight the substantial impact of precursor structure on SOA chemical composition, particularly concerning the presence of active carbon-carbon double bonds. The higher O: C ratio of SOA from OH-initiated oxidation of ACE indicates the significant role of OH in the oxidation of PAHs. These findings offer valuable insights into the atmospheric fate of these PAHs, underscoring the necessity for a comprehensive understanding of their degradation processes and the formation of SOA.

Quantitative Characterization of the Volatility Distribution of Organic Aerosols in a Polluted Urban Area: Intercomparison Between Thermodenuder and Molecular Measurements

AbstractTo quantify the volatility of organic aerosols (OA), a comprehensive campaign was conducted in the Chinese megacity. Volatility distributions of OA and particle‐phase organic nitrate (pON) were estimated based on five methods: (a) empirical method and (b) kinetic model based on the measurement of a thermodenuder (TD) coupled with an aerosol mass spectrometer; (c) Formula‐based SIMPOL model‐driven method; (d) Element‐based estimations using molecular formula measurements of OA; and (e) gas/particle partitioning. Our results demonstrate that the ambient OA volatility distribution shows good agreement between the two heating methods and the formula‐based method when assuming ambient OA was mainly composed of organic nitrate (pON), organic sulfate and acid groups using the SIMPOL model. However, the element‐based method tends to overestimate the volatility of OA compared to the above three methods, suggesting large uncertainties in the parameterizations or in the representativeness of the molecular measurements that need further refinement. The volatility of ambient OA is generally lower than that of the laboratory‐derived secondary OA, emphasizing the impact of aging. A large fraction at the higher and lower volatility ranges (approximately log C* ≤ −9 and ≥2 μg m−3) was found for pON, implying the importance of both extremely low volatile and semi‐volatile species. Overall, this study evaluates different methods for volatility estimation and gives new insight into the volatility of OA and pON in urban areas.

Influences of meteorology on emission sources and physicochemical properties of particulate matter in Seoul, Korea during the heating period

Chemical properties of particulate matter (PM), organic aerosol (OA) properties, sources and the volatility distribution were investigated during autumn in Seoul, Korea using aerodyne high resolution time of flight aerosol mass spectrometer (HR-ToF-AMS) with a thermodenuder (TD) combined system (TD-AMS). Overall, the average PM1 + black carbon (BC) concentration was 21.49 μg/m3, ranging from 7.85 μg/m3 to 48.36 μg/m3, and the largest proportion of PM1 components was organic (54%), followed by NO3− (17%), SO42− (12%), NH4+ (9%) and BC (6%). During this period, the O/C and H/C ratios were similar to those in other studies (0.45 and 1.70, respectively), but the N/C ratio was slightly higher than that in other studies. Five organic aerosol (OA) sources were identified through positive matrix factorization (PMF) analysis, where four POAs (HOA, COA, SFOA1 and SFOA2) and one SOA (LVOOA) were identified. A distinct feature during this study was that two different combustion-related sources, SFOA1 and SFOA2 were observed. Two different SFOAs showed time-dependent features and different chemical compositions. SFOA2, which was dominant during the higher-temperature period (16.3 °C (5.1–26.6)) showed less O/C (0.41 vs 0.57) and N/C (0.033 vs 0.059) and more volatile feature than the one of SFOA1 during colder period (10.1 °C (−1.8-19.4)). It might be due to different heating activities and more intensive gas to particle parting and oxidizing processing under colder condition. Haze is also influenced by heating activities. When stagnant conditions occur with high heating activities, enhanced emission sources (SFOA1), enhanced gas-to-particle partitioning (nitrate) and the accumulation of primary OA result in severe haze conditions in urban air. This result suggests that controlling emission sources during heating seasons is still required for haze control in urban environments.

Volatility distribution of primary organic aerosol emissions from household crop waste combustion in China

Biomass-burning emissions are a significant source of primary organic aerosol (POA). Volatility is one of the most important physical properties of organic aerosol (OA). Dilution and thermodenuder (TD) measurements were used to investigate the volatility of POA from household crop waste combustion in China. Between 10% and 30% of the POA desorbed when diluted from 20:1 to 120:1, while 10%–40% of POA evaporated in the TD when heated to 150 °C. Thus, a considerable proportion of the POA emissions were volatile. A dynamic mass transfer model was applied to derived volatility distributions of POA based on TD data. A best fit volatility distributions for POA and associated mass accommodation coefficients (α), and the enthalpy of vaporization (ΔHvap) were presented. The emissions factors and volatility distribution of POA emission from household crop waste combustion in this study can be used to improve emission inventories and simulate gas-particle partitioning of organic aerosol in chemical transport models.

Impact of aging on the sources, volatility, and viscosity of organic aerosols in Chinese outflows

Abstract. To investigate the impact of aging on the sources, volatility, and viscosity of organic aerosol (OA) in Chinese outflows, a high-resolution time-of-flight aerosol mass spectrometer (HR-AMS) coupled with a thermodenuder (TD) was deployed in the spring of 2018 in Dongying, which is a regional receptor site of metropolitan emissions in the North China Plain (NCP). The average mass concentration of PM1 is 31.5±22.7 µg m−3, which is mainly composed of nitrate (33 %) and OA (25 %). The source apportionment results show that the OA is mainly contributed by oxygenated OA (OOA) from secondary sources, including background-OOA (33 %) representing a background concentration of OA (2.6 µg m−3) in the NCP area, and transported-OOA (33 %) oxidized from urban emissions. The other two factors include aged hydrocarbon-liked OA (aged-HOA, 28 %) from transported vehicle emissions and biomass burning OA (BBOA, 5 %) from local open burning. The volatility of total OA (average C*=3.2×10-4 µg m−3) in this study is generally lower than that reported in previous field studies, which is mainly due to the high OA oxidation level resulting from aging processes during transport. The volatilities of OA factors follow the order of background-OOA (average C*=2.7×10-5 µg m−3) < transported-OOA (3.7×10-4µgm-3)< aged-HOA (8.1×10-4µgm-3)< BBOA (0.012 µg m−3). Extremely low volatilities in ambient air indicate that oligomers may exist in aged plumes. The viscosity estimation suggests that the majority of ambient OA in this study behaves as semisolid (60 %), liquifies at higher relative humidity (RH) (21 %), and solidifies (19 %) during noon when the RH is low and the oxidation level is high. Finally, the estimated mixing time of molecules in 200 nm OA varies dramatically from minutes at night to years in the afternoon, emphasizing the need to consider its dynamic kinetic limits when modeling OA. In general, the overall results of this study improve our understanding of the impact of aging on OA volatility and viscosity.

Real-time detection of vehicle-originated condensable particulate matter through thermodenuder integrated aerosol measurement method at tailpipes

Condensable particulate matter (CPM) corresponds to primary particulate matter ≤2.5 μm (PM2.5) obtained through the condensation of gaseous air pollutants caused by temperature drops in the atmosphere. The internal combustion of vehicle engines can produce CPM because of the condensable compounds in the exhaust gas. Conventional CPM measurement methods have been developed for coal-fired power plants with stable emissions through sampling and off-site analyses. They are therefore unsuitable for detecting the rapidly changing vehicle-originated CPM. In addition, the current system for evaluating PM2.5 from vehicles, based on the particle measurement program (PMP) protocol, provides only the emission factors of total PM2.5 (and not CPM separately) at a fixed temperature (∼25 °C) and dilution ratio (∼ × 35). This study reports, for the first time, the development of a real-time detection method for vehicle-originated CPM through a thermodenuder (TD) integrated with real-time aerosol instruments. This method was designed to reduce the loss of CPM due to condensation and diffusion while sampling the exhaust gas. It permits the investigation of the effects of dilution gas temperature (5–45 °C) and dilution ratio (up to × 30) on the formation of CPM. During the feasibility test of this method using a diesel vehicle (Euro-4), the real-time total particle number concentrations (PNs) matched well with those obtained by a PMP protocol-based evaluation system. Moreover, this method detected PNs concentrations ten times higher than the detection limit (4 × 106 particles/cm3) of the PMP-based system. The emission factors of the total PM2.5 with a bulk density (1 g/cm3) measured by this method also showed consistency with the results of the PMP protocol. The mass emission factor of CPM determined by deploying the TD was ∼14.57 mg/km (∼63% contribution to the total PM2.5).

Aqueous aging of secondary organic aerosol coating onto black carbon: Insights from simultaneous L-ToF-AMS and SP-AMS measurements at an urban site in southern China

Secondary organic aerosol (SOA) in the atmosphere can be formed from the gas phase precursors and evolve in the particle phase. Compared to numerous studies on gas phase oxidation of volatile organic compounds (VOCs), the evolution of OA and corresponding mechanisms in the particle phase are still unclear. In this study, a thermodenuder (TD) was coupled with both a long time-of-flight aerosol mass spectrometer (L-ToF-AMS) and a soot particle aerosol mass spectrometer (SP-AMS) at an urban site in southern China during wintertime of 2018, to explore whether there is significant difference for OA evolution on black carbon (BC) aerosols. The OA measured by L-ToF-AMS and SP-AMS were resolved into different primary and secondary factors, with the OA factors on BC particles showed different volatilities to that on the bulk aerosol. The more-oxidized oxygenated OA (MO-OOA, an agent of aged SOA) exhibited a unique preference on BC particles compared to other OA components. The abundant transition metals detected on BC particles was possibly the catalyser for the transformation from less oxidized OOA (LO-OOA, an agent of fresh SOA) to MO-OOA in aerosol aqueous-phase on BC particles and thus facilitates SOA formation. More studies are needed to further explore the potential role of BC and transition metals as catalysers for OA aging and the co-benefit of BC and transition metals pollution control on SOA reduction in the atmosphere.

Summertime aerosol volatility measurements in Beijing, China

Abstract. Volatility plays a key role in affecting mass concentrations and the lifetime of aerosol particles in the atmosphere, yet our knowledge of aerosol volatility in relatively polluted environment, e.g., north China, remains poor. Here aerosol volatility in Beijing in summer 2017 and 2018 was measured using a thermodenuder (TD) coupled with an Aerodyne high-resolution aerosol mass spectrometer (AMS) and a soot particle AMS. Our results showed overall similar thermograms for most non-refractory aerosol species compared with those reported in previous studies. However, high mass fraction remaining and NO+/NO2+ ratio for chloride and nitrate, each above 200 ∘C, indicated the presence of considerable metallic salts and organic nitrates in Beijing. The volatility distributions of organic aerosol (OA) and four OA factors that were resolved from positive matrix factorization were estimated using a mass transfer model. The ambient OA comprised mainly semi-volatile organic compounds (SVOCs; 63 %) with an average effective saturation concentration (C*) of 0.55 µg m−3, suggesting overall more volatile properties than OA in megacities of Europe and the US. Further analysis showed that the freshly oxidized secondary OA was the most volatile OA factor (SVOC = 70 %) followed by hydrocarbon-like OA (HOA). In contrast, the volatility of more oxidized oxygenated OA (MO-OOA) was comparable to that of cooking OA with SVOC on average accounting for 60.2 %. We also compared the volatility of ambient and black-carbon-containing OA. Our results showed that the BC-containing primary OA (POA) was much more volatile than ambient POA (C*=0.69 µg m−3 vs. 0.37 µg m−3), while the BC-containing SOA was much less volatile, highlighting the very different composition and properties between BC-containing and ambient aerosol particles.

Size distribution of vehicle emitted primary particles measured in a traffic tunnel

Total and size-resolved concentrations and emission factors are used to compare fleet-averaged vehicle emissions in Pittsburgh, PA in 2002 and 2014. Winter-time traffic tunnel measurements acquired using dual scanning mobility particle sizers (SMPS) over the size range 3–500 nm form the key input for the analysis. Size-resolved mass emission factors were calculated assuming a nanoparticle aggregate model. The ultrafine particle (<30 nm) emissions of diesel vehicles significantly dropped from 2002 to 2014. In the 2014 study, a thermodenuder (TD) was deployed together with the SMPS to measure emissions of non-volatile particles. After evaporation at 250 °C inside the TD, the median diameter of the number-size distribution shifted from 16 nm to ∼7 nm. The total particle number decreased significantly (69%) after evaporating inside the TD, indicating that vehicle emitted particles may be largely externally mixed and that a large fraction of these particles may be purely composed of volatile components. Based on the SMPS-TD measurements, we report a size-resolved volatile-to-non-volatile-component-ratio for vehicle emitted particles. It shows that smaller particles (10–60 nm) emitted by vehicles are dominantly (over 75%) composed of volatile components. We also apportioned the size-resolved particles and non-volatile particle mass and number emission factors for both gasoline and diesel vehicles. Diesel vehicles emitted significantly more ultrafine particles and non-volatile particles than gasoline vehicles.

Organic aerosol in the summertime southeastern United States: components and their link to volatility distribution, oxidation state and hygroscopicity

Abstract. The volatility distribution of the organic aerosol (OA) and its sources during the Southern Oxidant and Aerosol Study (SOAS; Centreville, Alabama) was constrained using measurements from an Aerodyne high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS) and a thermodenuder (TD). Positive matrix factorization (PMF) analysis was applied on both the ambient and thermodenuded high-resolution mass spectra, leading to four factors: more oxidized oxygenated OA (MO-OOA), less oxidized oxygenated OA (LO-OOA), an isoprene epoxydiol (IEPOX)-related factor (isoprene-OA) and biomass burning OA (BBOA). BBOA had the highest mass fraction remaining (MFR) at 100 ∘C, followed by the isoprene-OA, and the LO-OOA. Surprisingly the MO-OOA evaporated the most in the TD. The estimated effective vaporization enthalpies assuming an evaporation coefficient equal to unity were 58 ± 13 kJ mol−1 for the LO-OOA, 89 ± 10 kJ mol−1 for the MO-OOA, 55 ± 11 kJ mol−1 for the BBOA, and 63 ± 15 kJ mol−1 for the isoprene-OA. The estimated volatility distribution of all factors covered a wide range including both semi-volatile and low-volatility components. BBOA had the lowest average volatility of all factors, even though it had the lowest O : C ratio among all factors. LO-OOA was the more volatile factor and its high MFR was due to its low enthalpy of vaporization according to the model. The isoprene-OA factor had intermediate volatility, quite higher than suggested by a few other studies. The analysis suggests that deducing the volatility of a factor only from its MFR could lead to erroneous conclusions. The oxygen content of the factors can be combined with their estimated volatility and hygroscopicity to provide a better view of their physical properties.

Field Measurements for Quantifying Semi-Volatile Aerosol Influence on Physical and Optical Properties of Ambient Aerosols in the Kathmandu Valley, Nepal

ABSTRACT An intensive field campaign was conducted during the pre-monsoon season of 2015 in the urban atmosphere of the Kathmandu Valley to study the influence of the semi-volatile aerosol fraction on physical and optical properties of aerosols. Ambient air was siphoned through a specific ambient air inlet and then split into two parts. The first part connected directly with an ambient air sample while the second received the air sample through a thermodenuder (TDD). The aerosol properties, such as the aerosol number, size distribution, absorption, and scattering, were studied using Condensation Particle Counters (CPCs), Scanning Mobility Particle Sizers (SMPSs), Aethalometers (AE33) and Nephelometers, respectively. The differences in the properties of the aerosol fraction at room temperature and other TDD set temperatures (50°C, 100°C, 150°C, 200°C, 250°C, and 300°C) were calculated to study the influence of the semi-volatile aerosol fraction on ambient aerosols. The evaporated fraction of the semi-volatile aerosols increased with the TDD set temperature. The semi-volatile fraction of the aerosol number increased from 16% to 49% of ambient aerosol, while the peak mobility diameter of particles shifted from around 60 nm to 40 nm as the temperature increased from 50°C to 300°C. However, increasing the TDD set temperature had no influence on the effective diameter of the aerosol size distribution. Larger aerosol size bins of the SMPS experienced a significantly stronger influence (~70%) from temperature increments compared to smaller size bins (~20%). The semi-volatile aerosol fraction amplified BC absorption by up to 28%, while scattering by the semi-volatile aerosol fraction contributed up to 71% of the total.

Implication of Light Absorption Enhancement and Mixing State of Black Carbon (BC) by Coatings in Hong Kong

Simultaneous measurements of black carbon (BC) and non-refractory PM1 aerosol chemical compositions were performed in autumn 2016 at a suburban site in Hong Kong. A thermodenuder (TD) was employed at different heating temperatures to remove semi-volatile aerosol fractions to varying degrees. The light absorption enhancement (Eabs) of BC due to semi-volatile coatings at seven wavelengths was evaluated, and the coating fractions were further analyzed. Results showed that the overall Eabs ranged from 1.58 ± 0.13 (470 nm) to 1.64 ± 0.16 (660 nm) at 280°C and increased very little from 50°C (1.02–1.04) to 200°C (1.13–1.20). The lensing-effect-related Eabs was probably attributable to the presence of ammonium and sulfate. Furthermore, the ratio of the coating thickness to the BC core radius was around 1.0–2.0 based on Mie calculations. This work evaluated the Eabs from coatings in Hong Kong and implied the BC mixing state, thus providing a critical reference for climate models on the role of aerosol in global warming.

Estimation of the volatility distribution of organic aerosol combining thermodenuder and isothermal dilution measurements

Abstract. A method is developed following the work of Grieshop et al. (2009) for the determination of the organic aerosol (OA) volatility distribution combining thermodenuder (TD) and isothermal dilution measurements. The approach was tested in experiments that were conducted in a smog chamber using organic aerosol (OA) produced during meat charbroiling. A TD was operated at temperatures ranging from 25 to 250 °C with a 14 s centerline residence time coupled to a high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS) and a scanning mobility particle sizer (SMPS). In parallel, a dilution chamber filled with clean air was used to dilute isothermally the aerosol of the larger chamber by approximately a factor of 10. The OA mass fraction remaining was measured as a function of temperature in the TD and as a function of time in the isothermal dilution chamber. These two sets of measurements were used together to estimate the volatility distribution of the OA and its effective vaporization enthalpy and accommodation coefficient. In the isothermal dilution experiments approximately 20 % of the OA evaporated within 15 min. Almost all the OA evaporated in the TD at approximately 200 °C. The resulting volatility distributions suggested that around 60–75 % of the cooking OA (COA) at concentrations around 500 µg m−3 consisted of low-volatility organic compounds (LVOCs), 20–30 % of semivolatile organic compounds (SVOCs), and around 10 % of intermediate-volatility organic compounds (IVOCs). The estimated effective vaporization enthalpy of COA was 100 ± 20 kJ mol−1 and the effective accommodation coefficient was 0.06–0.07. Addition of the dilution measurements to the TD data results in a lower uncertainty of the estimated vaporization enthalpy as well as the SVOC content of the OA.

Volatility of source apportioned wintertime organic aerosol in the city of Athens

The volatility distribution of ambient organic aerosol (OA) and its components was measured during the winter of 2013 in the city of Athens combining a thermodenuder (TD) and a High Resolution Time-of-Flight Aerosol Mass Spectrometer (HR-ToF-AMS). Positive Matrix Factorization (PMF) analysis of both the ambient and the thermodenuder AMS-spectra resulted in a four-factor solution for the OA, namely: hydrocarbon-like OA (HOA), biomass burning OA (BBOA), cooking OA (COA), and oxygenated OA (OOA). The thermograms of the four factors were analyzed and the corresponding volatility distributions were estimated using the volatility basis set (VBS). All four factors included compounds with a wide range of effective volatilities from 10 to less than 10−4 μg m−3 at 298 K. Almost 40% of the HOA consisted of low-volatility organic compounds (LVOCs) with the semi-volatile compounds (SVOCs) representing roughly 30%, while the remaining 30% consisted of extremely low volatility organic compounds (ELVOCs). BBOA was more volatile than the HOA factor on average, with 10% ELVOCs, 40% LVOCs, and 50% SVOCs. 10% of the COA consisted of ELVOCs, another 65% LVOCs, and 50% SVOCs. Finally, the OOA was the least volatile factor and included 40% ELVOCs, 25% LVOCs, and 35% SVOCs. Combining the volatility distributions and the O:C ratios of the various factors, we placed our results in the 2D-VBS analysis framework of Donahue et al. (2012). HOA and BBOA are in the expected region but also include an ELVOC component. COA is in similar range as HOA, but on average is half an order of magnitude more volatile. The OOA in these wintertime conditions had a moderate O:C ratio and included both semi-volatile and extremely low volatility components. The above results are sensitive to the assumed values of the effective vaporization enthalpy and the accommodation coefficient. A reduction of the accommodation coefficient by an order of magnitude or the reduction of the vaporization enthalpy by 20 kJ mol−1 results in the increase of the average volatility by half an order of magnitude.

Volatility of mixed atmospheric humic-like substances and ammonium sulfate particles

Abstract. The volatility of organic aerosols remains poorly understood due to the complexity of speciation and multiphase processes. In this study, we extracted humic-like substances (HULIS) from four atmospheric aerosol samples collected at the SORPES station in Nanjing, eastern China, and investigated the volatility behavior of particles at different sizes using a Volatility Tandem Differential Mobility Analyzer (VTDMA). In spite of the large differences in particle mass concentrations, the extracted HULIS from the four samples all revealed very high-oxidation states (O : C &gt; 0.95), indicating secondary formation as the major source of HULIS in Yangtze River Delta (YRD). An overall low volatility was identified for the extracted HULIS, with the volume fraction remaining (VFR) higher than 55 % for all the regenerated HULIS particles at the temperature of 280 °C. A kinetic mass transfer model was applied to the thermodenuder (TD) data to interpret the observed evaporation pattern of HULIS, and to derive the mass fractions of semi-volatile (SVOC), low-volatility (LVOC) and extremely low-volatility components (ELVOC). The results showed that LVOC and ELVOC dominated (more than 80 %) the total volume of HULIS. Atomizing processes led to a size-dependent evaporation of regenerated HULIS particles, and resulted in more ELVOC in smaller particles. In order to understand the role of interaction between inorganic salts and atmospheric organic mixtures in the volatility of an organic aerosol, the evaporation of mixed samples of ammonium sulfate (AS) and HULIS was measured. The results showed a significant but nonlinear influence of ammonium sulfate on the volatility of HULIS. The estimated fraction of ELVOC in the organic part of the largest particles (145 nm) increased from 26 %, in pure HULIS samples, to 93 % in 1 : 3 (mass ratio of HULIS : AS) mixed samples, to 45 % in 2 : 2 mixed samples, and to 70 % in 3 : 1 mixed samples, suggesting that the interaction with ammonium sulfate tends to decrease the volatility of atmospheric organic compounds. Our results demonstrate that HULIS are important low-volatility, or even extremely low-volatility, compounds in the organic-aerosol phase. As important formation pathways of atmospheric HULIS, multiphase processes, including oxidation, oligomerization, polymerization and interaction with inorganic salts, are indicated to be important sources of low-volatility and extremely low-volatility species of organic aerosols.

Effects of organic aerosol loading and fog processing on organic aerosol volatility

A detailed time-resolved chemical characterization and volatility study of winter time ambient non refractory submicron aerosols (NR-PM1) was conducted at Kanpur, a polluted city of India. Two very distinct, high (HL, ~ 240μg/m3) and low (LL, ~100μg/m3) aerosol loading periods were observed during the campaign, impacted by frequent fog events (n=17). On average, organic aerosols (OA) contributed nearly 60% of the total NR-PM1 mass. Overall, OA volatility, (as measured by mass fraction of OA remaining after passing through a thermo denuder kept at 300°C) decreased significantly (60%) from HL to LL period. OA volatility is anti-correlated to OA loading but much more strongly so in LL compared to HL period. Volatilities of different types of OAs, as identified by positive matrix factorization (PMF) method, showed significant variations (up to 300%) from HL to LL period. This indicates that nature (like oxidation state, molecular structure, functional groups) of the OAs might have changed with variations in loading conditions. The presence of fog had little or no impact on overall OA volatility, in spite of (15–30) % enhancement in the ambinet OA oxidation ratio (O/C ratio) during fog. This study examines combined effects of OA loading and fog aqueous processing on the ambient OA volatility for the first time.

Effects of engine load and dilution conditions on gas-particle partitioning of primary organic aerosol emitted from a light-duty diesel engine

The effects of engine load and dilution conditions on the gas-particle partitioning of primary organic aerosol (POA) emitted from a light-duty diesel engine were investigated in a constant volume container (CVC). A new method was adopted to determine the POA concentration by using the combination of an OC/EC analyzer and a scanning mobility particle sizer (SMPS). A thermodenuder (TD) combined with a gas-chromatography/mass-spectrometry (GC/MS) was further used to study the temperature effect on the POA phase partitioning. Our results indicate that the engine load significantly affects the total organic carbon (OC) emissions while the dilution ratio (DR) influences the phase partitioning. Both sorption and evaporation are observed during the isothermal dilution process. Phase partitioning of the organic aerosol (OA) is dominated by sorption at low dilution condition and by evaporation of the adsorbed/absorbed OA at high dilution condition. A further analysis on the TD experimental data obtained at different engine loads suggests that the OA from the medium load is more sensitive to the temperature while the OA from the high load is hard to evaporate. Two TD kinetic models based on volatility distribution are evaluated and the results are compared with the experimental data. The present study demonstrates the importance of dilution conditions and engine loads on the phase partitioning of diesel POA emitted from light-duty diesel engines at the near tailpipe environment.

Gas-Particle Partitioning of Vehicle Emitted Primary Organic Aerosol Measured in a Traffic Tunnel.

We measured the gas-particle partitioning of vehicle emitted primary organic aerosol (POA) in a traffic tunnel with three independent methods: artifact corrected bare-quartz filters, thermodenuder (TD) measurements, and thermal-desorption gas-chromatography mass-spectrometry (TD-GC-MS). Results from all methods consistently show that vehicle emitted POA measured in the traffic tunnel is semivolatile under a wide range of fleet compositions and ambient conditions. We compared the gas-particle partitioning of POA measured in both tunnel and dynamometer studies and found that volatility distributions measured in the traffic tunnel are similar to volatility distributions measured in the dynamometer studies, and predict similar gas-particle partitioning in the TD. These results suggest that the POA volatility distribution measured in the dynamometer studies can be applied to describe gas-particle partitioning of ambient POA emissions. The POA volatility distribution measured in the tunnel does not have significant diurnal or seasonal variations, which indicate that a single volatility distribution is adequate to describe the gas-particle partitioning of vehicle emitted POA in the urban environment.

Characterisation of diesel particulate emission from engines using commercial diesel and biofuels

In this paper, the number concentration and the size distribution of diluted diesel exhaust particulate matter were measured at three different engine operating points in the speed-load range of the engine as follows: 1600 rpm; 50% load, 1900 rpm; 25% load, 1900 rpm; 75% load, adopted from the UN ECE Vehicle Regulation no. 49 (Revision 2) test protocol using pure diesel and biodiesel fuels, as well as their controlled blends. The emitted particulate assembly had lognormal size distribution in the accumulation mode regardless of the engine operational condition and the type of fuel. The total number and volume concentration emitted by the diesel engine decreased with increasing revolution per minute and rated torque in case of all the fuel types. The mixing ratio of the fuels did not linearly affect the total emission but had a minimum at 75% biodiesel content. We also studied the thermal evolution of the emitted particulates using a specially designed thermodenuder (TD) heated at specific temperatures (50 °C, 120 °C, and 250 °C). The first transition, when the temperature was increased from 50 °C to 120 °C resulted in lower number concentrations with small relative shifts of the peak position. However, in case of the second transition, when the temperature reached 250 °C the individual volatile particulates adsorbed onto the surface of soot particles were completely or partly vaporised resulting in lower total number concentrations with a substantial shift in peak position.

Light absorption and morphological properties of soot-containing aerosols observed at an East Asian outflow site, Noto Peninsula, Japan

Abstract. The coating of black carbon (BC) with inorganic salts and organic compounds can enhance the magnitude of light absorption by BC. To elucidate the enhancement of light absorption of aged BC particles and its relation to the mixing state and morphology of individual particles, we conducted observations of particles at an Asian outflow site in Noto Peninsula, Japan, in the spring of 2013. Absorption and scattering coefficients at 405, 532, and 781 nm and mass concentrations/mixing states of refractory BC in PM2.5 were measured using a three-wavelength photoacoustic soot spectrometer and a single-particle soot photometer (SP2), respectively, after passage through a thermodenuder (TD) maintained at 300 or 400 °C or a bypass line maintained at room temperature (25 °C). The average enhancement factor of BC light absorption due to coating was estimated by comparing absorption coefficients at 781 nm for particles that with and without passing through the TD at 300 °C and was found to be 1.22. The largest enhancements (&gt; 1.30) were observed under high absorption coefficient periods when the air mass was long-range transported from urban areas in China. Aerosol samples were also analyzed using a transmission electron microscope (TEM) equipped with an energy dispersive X-ray analyzer. The morphological features and mixing states of soot-containing particles of four samples collected during the high absorption events were analyzed by comparing microphotographs before and after the evaporation of beam-sensitive materials by irradiation with a high-density electron beam. The majority of the soot in all samples was found as mixed particles with sulfate-containing spherules or as clusters of such spherules. For samples showing high enhancement (&gt; 1.30) of BC light absorption, the TEM showed that the internally mixed soot-containing particles tended to have a more spherical shape and to be thickly coated. The SP2 measurements also suggested that the proportion of thickly coated soot was greater. Thus, the observed enhancement of BC light absorption was found to differ according to the mixing states and morphology of soot-containing particles. The enhancement of BC light absorption in our in situ measurements and its relation with individual features of soot-containing particles will be useful to evaluate direct radiative forcing in the downwind areas of large emission sources of BC.