Size distributions and formation of dicarboxylic acids in atmospheric particles

The PM2.5 concentrations and the size distributions of dicarboxylic acids in Hong Kong were studied. Eleven sets of daily PM2.5 samples were obtained at a downtown sampling site during the period of 5–16 December 2000 using an R&P speciation PM2.5 sampler. About 6–12% of the total oxalic acid was found in the gas phase in some samples. A good correlation between succinate and sulfate (R²=0.88) and a moderate correlation between oxalate and sulfate (R²=0.74) were found. Sampling artifacts of oxalate, malonate and succinate were found to be negligible. A total of 18 sets of 48–96 h size distribution data on dicarboxylic acids, sulfate, nitrate and sodium at an urban site and a rural site from June 2000 to May 2001 were obtained using a Micro-Orifice Uniform Deposit Impactor. Data from both sites show similar size distribution characteristics of the dicarboxylic acids. The condensation mode of oxalate was usually observed at 0.177–0.32 μm. The location of the peak of the droplet mode of oxalate was associated with that of sulfate. When the peak of sulfate in the droplet mode appeared at 0.32–0.54 μm, the peak of oxalate sometimes appeared at 0.32–0.54 μm and sometimes shifted to 0.54–1.0 μm. When the peak of sulfate in the droplet mode appeared at 0.54–1.0 μm, the peak of oxalate sometimes appeared at 0.54–1.0 μm and sometimes shifted to 1.0–1.8 μm. Oxalate, succinate and sulfate found in the droplet mode were attributed to in-cloud formation. The slight shift of the oxalate peak from 0.32–0.54 to 0.54–1.0 μm or from 0.54–1.0 to 1.0–1.8 μm was ascribed to minor oxalate evaporation after in-cloud formation. The maximum peak of malonate sometimes appeared in the droplet mode and sometimes appeared at 3.1–6.2 μm. The formation of malonate is associated to the reactions between sea salt and malonic acid.     

Origin of low-molecular-weight dicarboxylic acids and their concentration and size distribution variation in suburban aerosol

The concentrations and size distributions of low molecular weight dicarboxylic acids in suburban particulate matter collected in early and mid-autumn 2002 and early and mid-summer 2003 in Tainan, Taiwan, were analyzed. PM_2.5 contained, on average, 449.3 ng m⁻³ oxalic acid, 53.0 ng m⁻³ malic acid, 45.5 ng m⁻³ maleic acid, 29.6 ng m⁻³ succinic acid, 20.8 ng m⁻³ malonic acid, and 11.6 ng m⁻³ tartaric acid. Bar tartaric acid, concentrations were higher during the day, indicating that these acids are photochemical products. Furthermore, the malonic acid–succinic acid ratio of 0.79 during daytime and 0.60 during nighttime demonstrates that more succinic acid is converted to malonic acid during daytime, and that aerosol dicarboxylic acids predominantly originate from photochemical oxidation during daytime. The concentration peak of oxalic acid occurred in the condensation and droplet modes (0.32–1.0 μm), as did that of sulfate. In early summer, succinic acid, malonic acid, and oxalic acid major concentration peaks occurred at 0.32–0.54 μm, indicative of the relationship created by photochemical decomposition of succinc acid into malonic acid into oxalic acid. This photochemical decomposition accelerated in mid-summer such that most concentration peaks for succinic and malonic acids also occurred at 0.32–1.0 μm. Mid-summer is also the wettest period of the four in Tainan, with 85% RH. As a result of hygroscopic reactions in mid-summer, malonic acid and oxalic acid major concentration peaks shifted from 0.32–0.54 μm or 0.54–1.0 μm to 1.0–1.8 μm, thus extending the range in which these species were found to larger particle sizes, and this shift was highly correlated with a shift in succinic acid size distribution. This latter observation offers additional evidence that succinic acid is photochemically decomposed into malonic acid and oxalic acid and that the presence of malonic and oxalic acids in the wet mid-summer atmosphere is made more obvious via hygroscopic growth. Close correlation between succinic acid and Na⁺ and succinic acid and NO₃⁻ in the coarse mode is related to sea spray.     

Identification of dicarboxylic acids and aldehydes of PM10 and PM2.5 aerosols in Nanjing,China

In this study aerosol samples of PM10 and PM2.5 collected from 18 February 2001 to 1 May 2001 in Nanjing, China were analyzed for their water-soluble organic compounds. A series of homologous dicarboxylic acids (C_2–10) and two kinds of aldehydes (methylglyoxal and 2-oxo-malonaldehyde) were detected by GC and GC/MS. Among the identified compounds, the concentration of oxalic acid was the highest at all the five sites, which ranged from 178 to 1423 ng/m³. The second highest concentration of dicarboxylic acids were malonic and succinic acids, which ranged from 26.9 to 243 ng/m³. Higher level of azelaic acid was also observed, of which the maximum was 301 ng/m³. As the highest fraction of dicarboxylic acids, oxalic acid comprised from 28% to 86% of total dicarboxylic acids in PM10 and from 41% to 65% of total dicarboxylic acids in PM2.5. The dicarboxylic acids (C₂, C₃, C₄) together accounted for 38–95% of total dicarboxylic acids in PM10 and 59–87% of dicarboxylic acids in PM2.5. In this study, the total dicarboxylic acids accounted for 2.8–7.9% of total organic carbon (TOC) of water-soluble matters for PM10 and 3.4–11.8% of TOC for PM2.5. All dicarboxylic acids detected in this study together accounted for about 1% of particle mass. The concentration of azelaic acid was higher at one site than others, which may be resulted from higher level of volatile fat used for cooking. The amounts of dicarboxyic acids (C_2,3,4,9) and 2-oxo-malonaldehyde of PM2.5 were higher in winter and lower in spring. Compared with other major metropolitans in the world, the level of oxalic acid concentration of Nanjing is much higher, which may be contributed to higher level of particle loadings, especially for fine particles.     

Sulphate aerosol size distributions at Mumbai,India, during the INDOEX-FFP (1998)

Sulphate size distributions were measured at the coastal station of Mumbai (formerly Bombay) through 1998, during the Indian ocean experiment (INDOEX) first field phase (FFP), to fill current gaps in size-resolved aerosol chemical composition data. The paper examines meteorological, seasonal and source-contribution effects on sulphate aerosol and discusses potential effects of sulphate on regional climate. Sulphate size-distributions were largely trimodal with a condensation mode (mass median aerodynamic diameter or MMAD 0.6 μm), a droplet mode (MMAD 1.9–2.4 μm) and a coarse mode (MMAD 5 μm). Condensation mode sulphate mass-fractions were highest in winter, consistent with the high meteorological potential for gas-to-particle conversion along with low relative humidity (RH). The droplet mode concentrations and MMADs were larger in the pre-monsoon and winter than in monsoon, implying sulphate predominance in larger sized particles within this mode. In these seasons the high RH, and consequently greater aerosol water in the droplet mode, would favour aerosol-phase partitioning and reactions of SO₂. Coarse mode sulphate concentrations were lowest in the monsoon, when continental contribution to sulphate was low and washout was efficient. In winter and pre-monsoon, coarse mode sulphate concentrations were somewhat higher, likely from SO₂ gas-to-particle conversion. Low daytime sulphate concentrations with a large coarse fraction, along with largely onshore winds, indicated marine aerosol predominance. High nighttime sulphate concentrations and a coincident large fine fraction indicated contributions from anthropogenic/industrial sources or from gas-to-particle conversion. Monthly mean sulphate concentrations increased with increasing SO₂ concentrations, RH and easterly wind direction, indicating the importance of gas-to-particle conversion and industrial sources located to the east. Atmospheric chemistry effects on sulphate size distributions in Mumbai, indicated by this data, must be further examined.     

Single particle mass spectrometry of oxalic acid in ambient aerosols in Shanghai: Mixing state and formation mechanism

Oxalic acid in individual aerosol particles was measured using single particle aerosol time-of-flight mass spectrometry (ATOFMS) in the summer of 2007 in Shanghai, China. Oxalate was found in 3.4% of total particles with diameters in the range of 0.2 – 2.0 μm. Size, chemical composition and hourly temporal counts of single particles that contained oxalic acid were measured. The predominant types of oxalate-containing particles were characterized to distinguish the primary and secondary sources of oxalic acid. Biomass burning was revealed as a major primary source of oxalic acid which contributed more than 20% of the oxalate-containing particles. Evidences for two different formation pathways of oxalic acid were observed in our experiment. The number fraction of oxalate-containing particles correlated with that of sulfate particles and the changes of air parcel backward trajectories, suggesting that in-cloud processing played important roles in oxalic acid formation. The diurnal patterns of dust and sea salt particle counts fitted well with the ambient relative humidity variation, suggesting that heterogeneous reactions occurring in hydrated/deliquesced aerosols also contributed to the production of oxalic acid.     

Chemical fingerprint and source apportionment of PM 2.5 in highly polluted events of southern Taiwan

To investigate the spatial distribution and diurnal variation of the chemical composition of PM2.5 pollution in an industrial city of southern Taiwan, 12-h PM2.5 was diurnally continuously collected simultaneously at the Kaoping Air Quality Zone (KAQZ) during one highly PM2.5-polluted episode. Water-soluble ions, metallic elements, carbonaceous contents, dicarboxylic acids, and anhydrosugars were analyzed to characterize the chemical fingerprint of PM2.5. Backward trajectory simulation and chemical mass balance (CMB) receptor modeling were applied to identify the potential sources of PM2.5 and their contributions. It showed that Chaozhou (rural area) accompanying the highest SORs and NORs suffered from the most severe PM2.5 pollution during the episode. Sulfate (SO42−) was probably formed by the atmospheric chemical reaction in the daytime, while NO3− processed at nighttime at the KAQZ. A homogeneous formation of NO3− occurred at Chaozhou. The concentrations of Zn, Pb, Fe, Cu, V, and Al, mainly emitted from anthropogenic sources, increased significantly at the KAQZ. The highest OC, SOC/OC, and DA/OCs at Daliao (industrial area) were attributed to the transformation of primary VOCs to secondary OC via photo-oxidation during the episode. Oxalic acid was mainly produced through photochemical reactions since a high correlation between oxalic acid and Ca2+ was observed at Nanzi (urban area) and Daliao during the episode. During the episode, PM2.5 mostly originated from local primary or secondary aerosol than long-range overseas transport. The dominant source was anthropogenic emissions, accounting for 67.1% and 70.4% of PM2.5 at Nanzi and Daliao, respectively. At Chaozhou, the contribution of anthropogenic emissions was the lowest (42.4%), but secondary aerosols had the highest contribution of 38.3% of PM2.5 among the three areas during the episode.     

The influence of tropical cyclone Melor on PM10 concentrations during an aerosol episode over the Pearl River Delta region of China: Numerical modeling versus observational analysis

In this article, numerical simulations and observational analyses have been made for the aerosol episode that occurred over the Pearl River Delta (PRD) region in China during 1–3 November 2003. An air quality modeling system that consisted of the mesoscale model MM5, chemical transport model MODELS-3/CMAQ, and air pollutant emission model SMOKE, was employed. Studies have shown that this particulate matter (PM) pollution episode was apparently associated with the activity of tropical cyclone (TC) Melor. Model simulations revealed that Melor spawned this PM episode through dynamic and thermodynamic processes. The strong compensating subsidence induced by Melor's peripheral circulations created favorable meteorological conditions that enhanced local aerosol pollution. This strong downward motion produced significant adiabatic warming (2–4 °C daily) and dramatic drying in the low-level troposphere over the PRD. As a result, the PRD region was blanketed with a dry and warm air layer that strengthened the static stability of the lower troposphere. The descending motion also tended to dramatically lower the heights of the planetary boundary layer (PBL) through its dynamic effect. The fair weather created by this synoptic pattern further intensified the nocturnal temperature inversions through enhanced radiative cooling. All of these factors promoted a stagnant local atmosphere with very light winds near the surface. The horizontal and vertical dispersions of locally emitted aerosol particles were largely suppressed, leading to the accumulation of large amounts of PMs near local emission sources in the PRD region. As Melor drew near, changes in surface winds strengthened the horizontal transport of aerosol particles from inland sources to the area of Hong Kong downstream. This horizontal advection greatly contributed to the high PM₁₀ (particulate matters less than 10 μm in diameters) concentrations in Hong Kong.     

Size-segregated chemistry of particulate dicarboxylic acids in the Arctic atmosphere

Gas–particle interactions of low-molecular-weight dicarboxylic acids were studied at a coastal Arctic site during the summer. Size segregated measurements with a Berner low-pressure impactor displayed up to four modes for ionic compounds: an Aitken mode, an accumulation mode, and two supermicron modes. The lower supermicron mode was ascribed to sea-salt, whereas the upper mode consisted mostly of species associated with continental particles. All four modes could be identified for oxalic acid, with the lower supermicron mode being the dominant. Malonic acid displayed a supermicron mode but was not found in the submicron size range. Succinic acid had an accumulation mode and, in a few samples, a supermicron mode. Glutaric acid displayed sometimes and accumulation mode, sometimes a supermicron mode, and occasionally both. The most probable formation pathway for submicron oxalic and glutaric acid was condensation from the gas phase, even though production in cloud droplets cannot be ruled out either. A slightly different formation pathway may have been important for submicron succinic acid production. Supermicron oxalic acid was probably formed by condensation from the gas-phase, by heterogeneous reactions occurring on the surface of pre-existing sea-salt and continental particles, or in cloud droplets. A larger mass median diameter for supermicron malonic and glutaric acid might be indicative of liquid-phase production in aqueous sea-salt particles. Evidence on possibly substantial sampling artifacts related to measuring dicarboxylic acids using filters were also obtained.     

Effects of soil dust episodes and mixed fuel sources on source apportionment of PM10 particles in Kuopio,Finland

A receptor modeling study was carried out in Kuopio, Finland, between January and April 1994. Near the center of town, the daily mean concentrations were measured for PM10, sulphur dioxide, carbon monoxide and Black Smoke. Elemental concentrations of PM10 samples for 38 days were analyzed by ICP-MS. The main sources and their contributions to the measured concentrations of PM10 particles were solved by receptor modeling using a factor analysis-multiple linear regression (FA-MLR) model. Because a dust episode was very strong during two sampling days, the FA analysis was strongly influenced by this episode and did not give main factors. The factor analysis, when the two episode days were omitted, gave credible factors related to the sources in the study area. The four major sources and their estimated contributions to the average PM10 concentration of 27.2 μg m^-3 were: soil and street dust 46–48%, heavy fuel oil burning 12–18%, traffic exhaust 10–14%, wood burning ca. 11% and unidentified sources 15–25%. However, during spring dust episode days, with maximum PM10 concentration of 150 μg m^-3, the main source of PM10 was soil.     

Aerosol mass-size distributions at a tropical coastal environment: response to mesoscale and synoptic processes

Regular measurements of total mass concentration and mass-size distribution of near-surface aerosols, made using a ten-channel Quartz Crystal Microbalance (qcm) Impactor for the period October 1998–December 1999 at the tropical coastal station Trivandrum (8.5°N, 77°E), are used to study the response of aerosol characteristics to regional mesoscale and synoptic processes. Results reveal that aerosol mass concentrations are generally higher under land breeze conditions. The sea breeze generally has a cleansing effect, depleting the aerosol loading. The continental air (LB regime) is richer in accumulation mode (submicron) aerosols than the marine air. On a synoptic scale, aerosol mass concentration in the submicron mode decreased from an average high value of ∼86 μg m⁻³ during the dry months (January–March) to ∼11 μg m⁻³ during the monsoon season (June–September). On the contrary mass concentration in the supermicron mode increased from a low value of ∼15 μg m⁻³ during the dry months to reach a comparatively high value of ∼35 μg m⁻³ during April, May. Correspondingly, the effective radius (R_eff) increased from a low value of 0.15–0.17 μm to ∼0.3 μm indicating a seasonal change in the size distribution. The mass-size distribution shows mainly three modes, a fine mode (∼0.1 μm); a large mode (∼0.5 μm) and a coarse mode (∼3 μm). The fine mode dominates in winter. In summer the large mode becomes more conspicuous and the coarse mode builds up. The fine mode is highly reduced in monsoon and the large and coarse modes continue to remain high (replenished) so that their relative dominance increases. The size distribution tends to revert to the winter pattern in the post-monsoon season. Accumulation (submicron) aerosols account for ∼98% of the total surface area and ∼70% of the total volume of aerosols during winter. During monsoon, even though they still account for ∼90% of the area, their contribution to the volume is reduced to ∼50%; the coarse aerosols account for the rest.     

Deposition rates on smooth surfaces and coagulation of aerosol particles inside a test chamber

Because aerosol particle deposition is an important factor in indoor air quality, many empirical and theoretical studies have attempted to understand the process. In this study, we estimated the deposition rate of aerosol particles on smooth aluminum surfaces inside a test chamber. We investigated the influence of turbulent intensity due to ventilation and fan operation. We also investigated two important processes in particle deposition: turbophoresis, which is significant for micron particles, and coagulation, which is relevant to ultrafine particles (UFP diameter <0.1 μm) at high particle concentrations. Our analysis included semi-empirical estimates of the deposition rates that were compared to available deposition models and verified with simulations of an aerosol dynamics model. In agreement with previous studies, this study found that induced turbulent intensity greatly enhanced deposition rates of fine particles (FP diameter <1 μm). The deposition rate of FP was proportional to the ventilation rate, and it increased monotonically with fan speed. With our setup, turbophoresis was very important for coarse particles larger than 5 μm. The coagulation of aerosol particles was insignificant when the particle concentration was less than 10⁴ cm^?3 during fan operation. The model simulation results verified that the aerosol dynamics module incorporated in our Multi-Compartment and Size-Resolved Indoor Aerosol Model (MC-SIAM) was valid. The behavior of aerosol particles inside our chamber was similar to that found in real-life conditions with the same ventilation rates (0.018–0.39 h^?1) and similar air mixing modes. Therefore, our findings provide insight into indoor particle behavior.     

Observations and modelling of aerosol growth in marine stratocumulus—case study

Airborne measurements of the growth of the marine accumulation mode after multiple cycles through stratocumulus cloud are presented. The nss-sulphate cloud residual mode was log-normal in spectral shape and it’s mode radius was observed to progressively increase in size from 0.78 to 0.94 μm over 155 min of air parcel evolution through the cloudy marine boundary layer. The primary reason for this observed growth was thought to result from aqueous phase oxidation of SO₂ to aerosol sulphate in activated cloud drops. An aqueous phase aerosol–cloud-chemistry model was used to simulate this case study of aerosol growth and was able to closely reproduce the observed growth. The model simulations illustrate that aqueous phase oxidation of SO₂ in cloud droplets was able to provide enough additional sulphate mass to increase the size of activated aerosol. During a typical cloud cycle simulation, ≈4.6 nmoles kg^-1_air (0.44 μg m^-3) of sulphate mass was produced with ≈70% of sulphate production occurring in cloud droplets activated upon sea-salt nuclei and ≈30% occurring upon nss-sulphate nuclei, even though sea-salt nuclei contributed less than 15% to the activated droplet population. The high fraction of nss-sulphate mass internally mixed with sea-salt aerosol suggests that aqueous phase oxidation of SO₂ in cloud droplets activated upon sea-salt nuclei is the dominant nss-sulphate formation mechanism and that sea-salt aerosol provides the primary chemical sink for SO₂ in the cloudy marine boundary layer.     

Carbonaceous aerosol in jet engine exhaust: emission characteristics and implications for heterogeneous chemical reactions

Characteristic parameters of black carbon aerosol (BC) emitted from jet engine were measured during ground tests and in-flight behind the same aircraft. Size distribution features were a primary BC mode at a modal diameter D≈0.045 μm, and a BC agglomeration mode at D<0.2 μm. The total BC number concentration at the engine exit was 2.9×10⁷ cm^-3 with good agreement between model results and in-flight measured number concentrations of non-volatile particles with D⩾0.014 μm. A comparison between total number concentration of BC particles and the non-volatile fraction of the total aerosol at the exit plane suggests that the non-volatile fraction of jet engine exhaust aerosol consists almost completely of BC. In-flight BC mass emission indices ranged from 0.11 to 0.15 g BC (kg fuel)^-1. The measured in-flight particle emission value was 1.75±0.15×10¹⁵ kg^-1 with corresponding ground test values of 1.0–8.7×10¹⁴ kg^-1. Both size distribution properties and mass emission indices can be scaled from ground test to in-flight conditions. Implications for atmospheric BC loading, BC and cirrus interaction and the potential of BC for perturbation of atmospheric chemistry are briefly outlined.     

Composition and mixing state of the urban background aerosol in the Rhein-Main area (Germany)

Size-resolved aerosol particle samples in the size range 0.1–10 μm aerodynamic diameter were collected in the years 2003 and 2004 at an urban background station in Mainz, Germany. Size, morphology, chemical composition and mixing state of more than 5400 individual particles of 7 selected sampling days were analyzed in detail by scanning electron microscopy and energy-dispersive X-ray microanalysis. In addition, transmission electron microscopy, aerosol mass spectrometry and atomic force microscopy were applied to obtain detailed information about the mixing state of the particles. The fine particle fraction (diameter<1 μm) is always dominated by complex secondary aerosol particles (⩾90% by number) independent from air mass origin. These particles are complex internal mixtures of ammonium and sodium sulfates, nitrates, and organic material. Between 20% and 40% of the complex secondary aerosol particles contain soot inclusions. The composition of the coarse particle fraction (>1 μm diameter) is strongly dependant on air mass history with variable abundances of complex secondary aerosol particles, aged sea salt, silicates, silicate mixtures, calcium sulfates, calcium sulfate/carbonate mixtures, calcium nitrate/carbonate mixtures, biological particles, and external soot.The dominance of complex secondary aerosol particles shows that reduction of the precursor gases is a major goal for successful reduction strategies for PM₁₀.     

Performance evaluation of six different aerosol samplers in a particulate matter generation chamber

The present study was carried out with the aim of evaluating the performance of six different aerosol samplers in terms of mass concentration, particle size distribution, and mass fraction for the international size-sampling conventions. The international size-sampling criteria were defined as inhalable, thoracic, and respirable mass fractions with 50% cutoff at an aerodynamic equivalent diameter of 100 μm, 10 μm, and 4 μm, respectively. Two Andersen, four total suspended particulate (TSP), two RespiCon, four PM₁₀, two DustTrak, and two SidePak samplers were selected and tested to quantitatively estimate human exposure in a carefully controlled particulate matter (PM) test chamber. The overall results indicate that (1) Andersen samplers underestimate total suspended PM and overestimate thoracic and respirable PM due to particle bounce and carryover between stages, (2) TSP samplers provide total suspended PM as reference samplers, (3) TSP samplers quantified by a coulter counter multisizer provide no information below an equivalent spherical diameter of 2 μm and therefore underestimate respirable PM, (4) RespiCon samplers are free from particle bounce as inhalable samplers but underestimate total suspended PM, (5) PM₁₀ samplers overestimate thoracic PM, and (6) DustTrak and SidePak samplers provide relative PM concentrations instead of absolute PM concentrations.     

Effect of biomass burning and regional background aerosols on CCN activity derived from airborne in-situ measurements

Airborne in-situ measurements were analyzed to investigate the effects of biomass burning and regional background aerosols on cloud condensation nuclei (CCN) activity in the Pacific Dust Experiment (PACDEX) during April and May 2007. Airmass trajectories with both horizontal and vertical motions were provided to identify the aerosol sources. In the biomass burning cases, the elevated aerosol layers were clearly observed at dry conditions because of the convection of airmass in the source region. The relative aging of aerosols was supported by the ratios of BC to particles with size ranging from 0.1 to 1.0 μm (N_0.1–1.0) and BC to carbon monoxide. Compared to aerosols in the precedent plume of biomass burning, aged particles in the latter plume were more activated to CCN at 0.4% (CCN_0.4%) than 0.1% supersaturation (CCN_0.1%) due to aerosols chemical modification during the aging process. On the other hand, significant difference of CCN_0.4% and CCN_0.1% at regional background aerosols over the Pacific Ocean was due to the activated particles below 1 μm in diameter. Although higher concentrations of aged particles were observed over the eastern Pacific Ocean, activated aerosols to cloud droplet was comparatively similar in the western Pacific Ocean because of the similar concentrations of N_0.1–1.0 in both cases.     

Distribution characteristics of polycyclic aromatic hydrocarbons with particle size in urban aerosols at the roadside in Ho Chi Minh City,Vietnam

The purpose of this study was to characterize size distributions of atmospheric polycyclic aromatic hydrocarbons (PAHs) with 4–6 rings at the roadside in Ho Chi Minh City, Vietnam. Ten PAHs (fluoranthene, pyrene, triphenylene, benzo[a]anthracene, chrysene, benzo[b]fluoranthene, benzo[k]fluoranthene, benzo[a]pyrene, benzo[ghi]perylene and indeno[1,2,3-cd]pyrene) in atmospheric particulate matters (PM) at the roadside were measured in the dry and rainy seasons in 2005 at Ho Chi Minh City, using a low-pressure cascade impactor. The PM were separated into nine fractions by their aerodynamic diameter, i.e. >9.0, 9.0–5.8, 5.8–4.7, 4.7–3.3, 3.3–2.1, 2.1–1.1, 1.1–0.7, 0.7–0.4 and <0.4 μm (a final filter). PAHs were analyzed by high-performance liquid chromatography with fluorescence detection. Total PAHs measured were higher in the rainy season than in the dry season. The mass of coarse particles occupied a higher fraction than that of fine particles in both seasons. Total PAHs were mainly concentrated in particles with aerodynamic diameter smaller than 0.4 μm. The particle size distributions of PAHs investigated were bi-modal with a peak in fine particle mode (<2.1 μm) and another peak in coarse particle mode (>2.1 μm). Generally, 5,6-ring PAHs associated mainly with fine particles and 4-ring PAHs spread out in both fine and coarse particles.     

SOA from methylglyoxal in clouds and wet aerosols: Measurement and prediction of key products

Aqueous OH radical oxidation of methylglyoxal in clouds and wet aerosols is a potentially important global and regional source of secondary organic aerosol (SOA). We quantify organic acid products of the aqueous reaction of methylglyoxal (30–3000 μM) and OH radical (approx. 4 × 10^?12 M), model their formation in the reaction vessel and investigate how the starting concentrations of precursors and the presence of acidic sulfate (0–840 μM) affect product formation. Predicted products were observed. The predicted temporal evolution of oxalic acid, pyruvic acid and total organic carbon matched observations at cloud relevant concentrations (30 μM), validating this methylglyoxal cloud chemistry, which is currently being implemented in some atmospheric models of SOA formation. The addition of sulfuric acid at cloud relevant concentrations had little effect on oxalic acid yields. At higher concentrations (3000 μM), predictions deviate from observations. Larger carboxylic acids (≥C₄) and other high molecular weight products become increasingly important as concentration increases, suggesting that small carboxylic acids are the major products in clouds while larger carboxylic acids and oligomers are important products in wet aerosols.     

The physical characteristics of sulfur aerosols

A review of the physical characteristics of sulfur-containing aerosols, with respect to size distribution of the physical distributions, sulfur distributions, distribution modal characteristics, nuclei formation rates, aerosol growth characteristics, and in situ measurement, has been made.Physical size distributions can be characterized well by a trimodal model consisting of three additive lognormal distributions.When atmospheric physical aerosol size distributions are characterized by the trimodal model, the following typical modal parameters are observed:1. Nuclei mode – geometric mean size by volume, DGV_n, from 0.015 to 0.04 μm. σ_gn=1.6, nucler mode volumes from 0.0005 over the remote oceans to 9 μm³ cm⁻³ on an urban freeway.2. Accumulation mode – geometric mean size by volume, DGV_a, from 0.15 to 0.5 μm, σ_ga=1.6–2.2 and mode volume concentrations from 1 for very clean marine or continental backgrounds to as high as 300 μm³ cm⁻³ under very polluted conditions in urban areas.3. Coarse particle mode – geometric mean size by volume, DGV_c, from 5 to 30 μm, σ_gn=2–3, and mode volume concentrations from 2 to 1000 μm³ cm⁻³.It has also been concluded that the fine particles (D_p<2 μm) are essentially independent in formation, transformation and removal from the coarse particles (D_p>2 μm).Modal characterization of impactor-measured sulfate size distributions from the literature shows that the sulfate is nearly all in the accumulation mode and has the same size distribution as the physical accumulation mode distribution.Average sulfate aerodynamic geometric mean dia. was found to be 0.48±0.1 μm (0.37±0.1 μm vol. dia.) and σ_g=2.00±0.29. Concentrations range from a low of about 0.04 μg m⁻³ over the remote oceans to over 8 μg m⁻³ under polluted conditions over the continents.Review of the data on nucleation in smog chambers and in the atmosphere suggests that when SO₂, is present, SO₂-to-aerosol conversion dominates the Aitken nuclei count and, indirectly, through coagulation and condensation, the accumulation mode size and concentration. There are indications that nucleation is ubiquitous in the atmosphere, ranging from values as low as 2 cm⁻³ h⁻¹ over the clean remote oceans to a high of 6×10⁶ cm⁻³ h⁻¹ in a power plant plume under sunny conditions.There is considerable theoretical and experimental evidence that even if most of the mass for the condensational growth of the accumulation mode comes from hydrocarbon conversion, sulfur conversion provides most of the nuclei.     

Chemical composition of PM10 and PM2.5 collected at ground level and 100 meters during a strong winter-time pollution episode in Xi'an, China

An intensive sampling of aerosol particles from ground level and 100 m was conducted during a strong pollution episode during the winter in Xi'an, China. Concentrations of water-soluble inorganic ions, carbonaceous compounds, and trace elements were determined to compare the composition of particulate matter (PM) at the two heights. PM mass concentrations were high at both stations: PM10 (PM with aerodynamic diameter < or =10 microm) exceeded the China National Air Quality Standard Class II value on three occasions, and PM2.5 (PM with aerodynamic diameter < or =2.5 microm) exceeded the daily U.S. National Ambient Air Quality Standard more than 10 times. The PM10 organic carbon (OC) and elemental carbon (EC) were slightly lower at the ground than at 100 m, both in terms of concentration and percentage of total mass, but OC and EC in PM2.5 exhibited the opposite pattern. Major ionic species, such as sulfate and nitrate, showed vertical variations similar to the carbonaceous aerosols. High sulfate concentrations indicated that coal combustion dominated the PM mass both at the ground and 100 m. Correlations between K+ and OC and EC at 100 m imply a strong influence from suburban biomass burning, whereas coal combustion and motor vehicle exhaust had a greater influence on the ground PM. Stable atmospheric conditions apparently led to the accumulation of PM, especially at 100 m, and these conditions contributed to the similarities in PM at the two elevations. Low coefficient of divergence (CD) values reflect the similarities in the composition of the aerosol between sites, but higher CDs for fine particles compared with coarse ones were consistent with the differences in emission sources between the ground and 100 m.