Single-particle volatility and implications for brown carbon absorption in Beijing, China.

Aerosol volatility has a substantial impact on gas-particle partitioning, aging process and hence brown carbon (BrC) absorption. Here we analyzed single-particle volatility in winter in Beijing using a thermodenuder coupled with a single particle aerosol mass spectrometer along with a suite of collocated measurements. Our results showed that elemental carbon, metals, organic nitrogen (ON) were the dominant low-volatility components. The ON-containing particles accounting for 50 % of the total low-volatility particles comprised mainly ON-organic carbon (ON-OC) particles which were associated with biomass burning and significantly enhanced during polluted periods with high relative humidity and nitrogen oxides (NOx) levels. By analyzing the relationship between single-particle volatility and BrC, we found that semi-volatile particles related to fossil fuel combustion contributed dominantly to the light absorption of BrC (~50 %). Comparatively, the low-volatility and semi-volatile particles related to biomass burning contributed 21-35 % and 10-15 %, respectively to the BrC light absorption. Our results demonstrated that single particles from different sources with different volatility showed different impacts on BrC absorption. Although low-volatility organic aerosol accounted only for ~16 % of the total ambient organics, they can contribute as much as ~30-40 % to BrC light absorption in winter in Beijing.

Chemical composition of different size ultrafine particulate matter measured by nanoparticle chemical ionization mass spectrometer.

New particle formation (NPF) is the primary source of nanoparticles and contributes a large number of concentrations of cloud condensation nuclei. In recent years, field campaigns and laboratory experiments have been conducted to promote cognition of the mechanism for NPF and its following growth processes. The chemical composition measurement of nanoparticles could help deepen understanding of the initial step of particulate matter formation. In this work, we developed a nanoparticle chemical ionization mass spectrometer to measure nanoparticles' chemical compositions during their initial growth stage. Meanwhile, a non-radioactive ion source was designed for aerosol charging and chemical ionization. Time of flight mass spectrometer coupled with integrated aerosol size selection and collection module would guarantee the picogram level detection limit and high-resolution ability to measure the matrix of ambient samples. The performance of this equipment was overall evaluated, including the transmission efficiency and collection efficiency of custom-built nano differential mobility analyzer, chemical ionization efficiency, and mass resolution of the mass spectrometer. The high sensitivity measurement of ammonium sulfate and methylammonium sulfate aerosols with diameters ranging from 10 to 25 nm could guarantee the application of this instrument in the ambient measurement.

Different characteristics of individual particles from light-duty diesel vehicle at the launching and idling state by AAC-SPAMS.

The rapid development of cities and economic prosperity greatly motivates the growth of vehicular exhaust particles, especially the diesel-exhausted particles from the large fleet of passenger and freight, which present profound implications on climate, air quality, and biological health (e.g., pulmonary, autoimmune and cardiovascular diseases). As important physiochemical properties of atmospheric aerosols, however, the mixing state and effective density of individual particles emitted from diesel-powered vehicles under different driving conditions and their environmental implications remain uncertain. Here, a single-particle aerosol mass spectrometer (SPAMS) was used to investigate the chemical composition and vacuum aerodynamic diameter (Dva), along with the aerodynamic diameter (Da) from an aerodynamic aerosol classifier (AAC), to determine the effective density of primary particles emitted from a light- duty diesel vehicle (LDDV) under the launching and idling engine states. Interestingly, the particle types and effective density appear to vary significantly with the engine status. A single particle type of Ca-rich particles, named Na-Ca-PAH, was predominant in the idling state, whose chemical components may be affected by the lubricants and incomplete combustion, contributing to a higher effective density (0.66 ± 0.21 g cm-3). In contrast, launching particles exhibited a lower effective density (0.34 ± 0.17 g cm-3) because of the substantial elemental carbon (EC). In addition, the effective density depends not only on the particle size but also on the chemical components with various abundances. EC and Ca play opposite roles in the effective density of LDDV emissions. Notably, a higher proportion of polycyclic aromatic hydrocarbons (PAHs) was observed in the idling particles, contributing to 78 ± 1.2%. Given the high contribution to these PAH-containing particles in the idling state, indispensable precautions should be taken at bus stops or waiting for pedestrians. This study provides more comprehensive insights into the initial characteristics of LDDV particles due to the launching and idling states, which is beneficial for improving the model results of source apportionment and understanding its environmental behavior regarding human health.

Individual particle investigation on the chloride depletion of inland transported sea spray aerosols during East Asian summer monsoon.

Inland transported sea spray aerosol (SSA) particles along with multiphase reactions are essential to drive the regional circulation of nitrogen, sulfur and halogen species in the atmosphere. Specially, the physicochemical properties of SSA will be significantly affected by the displacement reaction of chloride. However, the role of organic species and the mixing state on the chloride depletion of SSA during long-range inland transport remains unclear. Hence, a single particle aerosol mass spectrometer (SPAMS) was employed to investigate the particle size and chemical composition of individual SSA particles over inland southern China during the East Asian summer monsoon. Based on the variation of chemical composition, SSA particles were clustered into SSA-Aged, SSA-Bio and SSA-Ca. SSA-Aged was regarded as the aged Na-rich SSA particles. In comparison to the SSA-Aged, SSA-Bio involved some extra organic species associated with biological origin (i.e., organic nitrogen and phosphate). Each type occupies for approximately 50% of total detected SSA particles. Besides, SSA-Ca may relate to organic shell of Na-rich SSA particles, which is negligible (~3%). Tight correlation between Na and diverse organic acids was exhibited for the SSA-Aged (r2 = 0.52, p < 0.01) and SSA-Bio (r2 = 0.61, p < 0.01), reflecting the impact of organic acids to the chloride displacement during inland transport SSA particles. The chloride depletion occupied by organic acids is estimated to be up to 34%. It is noted that distinctly different degree of chloride depletion was observed between SSA-Aged and SSA-Bio. It is more likely to be attributed to the associated organic coatings for the SSA-Bio particles, which inhibits the displacement reactions between acids and chloride. As revealed from the mixing state of SSA-Bio, defined hourly mean peak area ratio of Cl / Na increases with the increasing phosphate and organic nitrogen. This finding provides additional basis for the improvement of modeling simulations in chlorine circulation and a comprehensive understanding of the effects of organics on chloride depletion of SSA particles.

Study of gas-phase reactions of NO2+ with aromatic compounds using proton transfer reaction time-of-flight mass spectrometry.

The study of ion chemistry involving the NO2+ is currently the focus of considerable fundamental interest and is relevant in diverse fields ranging from mechanistic organic chemistry to atmospheric chemistry. A very intense source of NO2+ was generated by injecting the products from the dielectric barrier discharge of a nitrogen and oxygen mixture upstream into the drift tube of a proton transfer reaction time-of-flight mass spectrometry (PTR-TOF-MS) apparatus with H3 O+ as the reagent ion. The NO2+ intensity is controllable and related to the dielectric barrier discharge operation conditions and ratio of oxygen to nitrogen. The purity of NO2+ can reach more than 99% after optimization. Using NO2+ as the chemical reagent ion, the gas-phase reactions of NO2+ with 11 aromatic compounds were studied by PTR-TOF-MS. The reaction rate coefficients for these reactions were measured, and the product ions and their formation mechanisms were analyzed. All the samples reacted with NO2+ rapidly with reaction rate coefficients being close to the corresponding capture ones. In addition to electron transfer producing [M]+ , oxygen ion transfer forming [MO]+ , and 3-body association forming [M·NO2 ]+ , a new product ion [M-C]+ was also formed owing to the loss of C═O from [MO]+ .This work not only developed a new chemical reagent ion NO2+ based on PTR-MS but also provided significant interesting fundamental data on reactions involving aromatic compounds, which will probably broaden the applications of PTR-MS to measure these compounds in the atmosphere in real time.

Quantification and risk assessment of organic products resulting from non-thermal plasma removal of toluene in nitrogen.

RATIONALE: Non-thermal plasma (NTP) has proven to be an effective approach for the removal of volatile organic compounds (VOCs). However, harmful organic by-products, produced during NTP-mediated removal of VOCs, hinder practical applications of this technology. It is necessary to characterize the organic by-products to assess their health risks. METHODS: A method is proposed for analyzing and evaluating organic by-products for NTP-mediated removal of VOCs in this work. NTP generated by a coaxial dielectric barrier discharge (DBD) reactor was used for the removal of a model VOC, toluene, in nitrogen. Organic products were characterized using a real-time proton transfer reaction time-of-flight mass spectrometry (PTR-TOF-MS) apparatus. RESULTS: The PTR-TOF-MS apparatus has been shown to be effective for real-time high-sensitivity detection of trace VOCs. The main observed organic compounds, with concentrations on the order of ppb/ppm, were hydrogen cyanide, acetonitrile, propanenitrile, benzene, benzonitrile, and benzyl nitrile, etc. CONCLUSIONS: A health-related index (HRI) was introduced to assess the health risks associated with these organic products. The HRI was not correlated with the removal efficiency (η), with higher η possibly yielding higher HRI, associated with higher health risks. Specific input energy (SIE) was a key factor affecting the formation of the observed organic products and their HRI values. We conclude that in practical applications, SIE, HRI, and η must be balanced.