Size Distribution Of Sulfate Research Articles

Exploring the Formation of High Levels of Hydroxyl Dicarboxylic Acids at an Urban Background Site in South China

AbstractHydroxyl dicarboxylic acids (OHDCA) are ubiquitous in the atmosphere as an important constituent of secondary organic aerosol, yet the formation mechanisms remain unclear. At an urban background site on the coast of South China, we observed notable levels of OHDCA, with the highest concentration of malic acid (a typical OHDCA species) reaching 533 ng m−3. In the coastal air, the correlation between OHDCA and sulfate was better (R2 = 0.48) in the period when the relative humidity was higher and the sulfate size distribution was in a droplet mode, fitting the features of aqueous formation. In the short‐range continental air, a significant rise in OHDCA levels from morning through early afternoon (588 ng m−3) was observed under marked daytime increment of ozone that was corrected for titration loss (O3_corr, sum of ozone and nitrogen dioxide). In addition, good correlation between OHDCA and O3_corr was identified in this period, illuminating the role for gas‐phase photochemistry in regulating OHDCA formation. Therefore, the elevated OHDCA was likely attributed to aqueous photooxidation, and the dominant factors varied under different atmospheric conditions. The precursors of OHDCA could be derived from biogenic emissions, as indicated by the correlations of OHDCA with 2‐methylglyceric acid (bihourly data) and isoprene and monoterpenes (daily average data). However, anthropogenic aromatics might also be involved in OHDCA formation, especially in the short‐range continental air. The formation mechanisms probed through observational evidence will be an important reference for rectifying simulations of OHDCA and its impact on air quality and climate.

Measurement report: Vertical distribution of atmospheric particulate matter within the urban boundary layer in southern China – size-segregated chemical composition and secondary formation through cloud processing and heterogeneous reactions

Abstract. Many studies have recently been done on understanding the sources and formation mechanisms of atmospheric aerosols at ground level. However, vertical profiles and sources of size-resolved particulate matter within the urban boundary layer are still lacking. In this study, vertical distribution characteristics of size-segregated particles were investigated at three observation platforms (ground level, 118 m, and 488 m) on the 610 m high Canton Tower in Guangzhou, China. Size-segregated aerosol samples were simultaneously collected at the three levels in autumn and winter. Major aerosol components, including water-soluble ions, organic carbon, and elemental carbon, were measured. The results showed that daily average fine-particle concentrations generally decreased with height. Concentrations of sulfate and ammonium in fine particles displayed shallow vertical gradients, and nitrate concentrations increased with height in autumn, while the chemical components showed greater variations in winter than in autumn. The size distributions of sulfate and ammonium in both seasons were characterized by a dominant unimodal mode with peaks in the size range of 0.44–1.0 µm. In autumn, the nitrate size distribution was bimodal, peaking at 0.44–1.0 and 2.5–10 µm, while in winter it was unimodal, implying that the formation mechanisms for nitrate particles were different in the two seasons. Our results suggest that the majority of the sulfate and nitrate is formed from aqueous-phase reactions, and we attribute coarse-mode nitrate formation at the measurement site to the heterogeneous reactions of gaseous nitric acid on existing sea-derived coarse particles in autumn. Case studies further showed that atmospheric aqueous-phase and heterogeneous reactions could be important mechanisms for sulfate and nitrate formation, which, in combination with adverse weather conditions such as temperature inversion and calm wind, led to haze formation during autumn and winter in the Pearl River Delta (PRD) region.

Characteristics of size-resolved atmospheric inorganic and carbonaceous aerosols in urban Shanghai

Size-segregated aerosol particles were collected with a 10-stage Micro-Orifice Uniform Deposit Impactor (MOUDI) at an urban site in Shanghai, China for four non-consecutive months representing four seasons from 2015 to 2016. Chemical composition, including water-soluble ions as well as organic carbon (OC), elemental carbon (EC) and secondary organic carbon (SOC) of size-resolved (0.056–18 μm) atmospheric aerosols in four seasons and in different polluted cases were studied. The size distributions of sulfate, nitrate and ammonium (SNA) and carbonaceous aerosol (OC, EC and SOC) were discussed and the potential sources of PM1.8-associated secondary species (SO42−, NO3−, SNA and SOC) in different seasons were identified by potential source contribution function (PSCF) model. Results showed that atmospheric ultrafine and fine particle pollution in Shanghai were very serious during the study period. Most of the water-soluble ions tended to be enriched in fine particles, especially being abundant in the droplet mode in polluted cases. Compared with sulfate, size distributions of nitrate and ammonium presented more significant seasonal variations and showed distinctive characteristics in polluted days. Abundant nitrate was concentrated in fine particles in cold seasons (spring and winter), whereas it was enriched in coarse mode during summer and autumn. The droplet mode sulfate with high concentration did not result in the aggravation of air pollution, while the nucleation mode sulfate may have made a great contribution to the air pollution in urban Shanghai. It was also found that the formation of air pollution in urban Shanghai had a significant link with nitrate and ammonium, especially with nitrate and ammonium in condensation mode and droplet mode, and the contribution of sulfate to the pollution formation in Shanghai would somehow be surpassed by the increasing nitrate and ammonium. OC and EC concentrations from spring to winter were found to be 11.10, 7.10, 12.30, 20.16, and 3.73, 2.84, 4.63, 7.10 μg m−3, respectively, distinctly presenting the summer minima and winter maxima in this study. The maximum OC/EC was in the droplet mode and the minimum was in the nucleation mode for both clean and polluted days. The great contribution of SOC to OC in droplet mode and the occurrence of PM pollution necessarily had an important bearing on the SOC formation in droplet mode particles. Particle acidity may play a key role in secondary organic aerosol formation and the particles with the size of 0.056–0.1 μm was the most sensitive particles to acid catalysis in SOA formation. The similar PSCF results of PM1.8-associated SOC to those of SO42−, NO3− and SNA indicated possible connections between the formation of SOC and secondary inorganic species in PM.

Chemical composition and size distribution of summertime PM<sub>2.5</sub> at a high altitude remote location in the northeast of the Qinghai–Xizang (Tibet) Plateau: insights into aerosol sources and processing in free troposphere

Abstract. Aerosol filter samples were collected at a high-elevation mountain observatory (4180 m a.s.l.) in the northeastern part of the Qinghai–Xizang (Tibet) Plateau (QXP) during summer 2012 using a low-volume sampler and a micro-orifice uniform deposit impactor (MOUDI). These samples were analyzed for water-soluble inorganic ions (WSIs), organic carbon (OC), elemental carbon (EC), water-soluble organic carbon (WSOC), and total organic nitrogen (TON) to elucidate the size-resolved chemical composition of free tropospheric aerosols in the QXP region. The average mass concentration of the sum of the analyzed species in PM2.5 (particle matter) (WSIs + OC + EC + TON) was 3.74 μg sm−3, 36% of which was sulfate, 18% OC, 17 % nitrate, 10% ammonium, 6.6% calcium, 6.4% TON, 2.6% EC, 1.5 % sodium, 0.9% chloride, 0.5% magnesium, and 0.3% potassium. The size distributions of sulfate and ammonium peaked in the accumulation mode (0.32–0.56 μm), whereas the size distributions of both nitrate and calcium peaked in the range of 1.8–3.2 μm, suggesting the formation of nitrate on mineral dust. OC, EC and TON were also predominantly found in the accumulation mode. The bulk chemical composition and the average oxidation degree of water-soluble organic matter (WSOM) were assessed using a high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS). WSOM was found to be highly oxidized in all PM2.5 samples with an average oxygen-to-carbon atomic ratio (O / C) of 1.16 and an organic mass-to-organic carbon ratio (OM / OC) of 2.75. The highly oxidized WSOM was likely related to active cloud processing during upslope air mass transport coupled with strongly oxidizing environments caused by snow/ice photochemistry. High average ratios of OC / EC (7.6) and WSOC / OC (0.79) suggested that organic aerosols were primarily made of secondary species. Secondary organic aerosol (SOA) was estimated on average accounting for 80% (62–96%) of the PM2.5, indicating that SOA is an important component of free tropospheric aerosols over the northern QXP.

One-year observations of size distribution characteristics of major aerosol constituents at a coastal receptor site in Hong Kong – Part 1: Inorganic ions and oxalate

Abstract. Size distribution data of major aerosol constituents are essential in source apportioning of visibility degradation, testing and verification of air quality models incorporating aerosols. We report here 1-year observations of mass size distributions of major inorganic ions (sulfate, nitrate, chloride, ammonium, sodium, potassium, magnesium and calcium) and oxalate at a coastal suburban receptor site in Hong Kong, China. A total of 43 sets of size-segregated samples in the size range of 0.056–18 μm were collected from March 2011 to February 2012. The size distributions of sulfate, ammonium, potassium and oxalate were characterized by a dominant droplet mode with a mass mean aerodynamic diameter (MMAD) in the range of ~ 0.7–0.9 μm. Oxalate had a slightly larger MMAD than sulfate on days with temperatures above 22 °C as a result of the process of volatilization and repartitioning. Nitrate was mostly dominated by the coarse mode but enhanced presence in fine mode was detected on winter days with lower temperature and lower concentrations of sea salt and soil particles. This data set reveals an inversely proportional relationship between the fraction of nitrate in the fine mode and product of the sum of sodium and calcium in equivalent concentrations and the dissociation constant of ammonium nitrate (i.e., (1/([Na+] + 2[Ca2+]) × (1/Ke')) when Pn_fine is significant (> 10%). The seasonal variation observed for sea salt aerosol abundance, with lower values in summer and winter, is possibly linked with the lower marine salinities in these two seasons. Positive matrix factorization was applied to estimate the relative contributions of local formation and transport to the observed ambient sulfate level through the use of the combined data sets of size-segregated sulfate and select gaseous air pollutants. On average, the regional/super-regional transport of air pollutants was the dominant source at this receptor site, especially on high-sulfate days while local formation processes contributed approximately 30% of the total sulfate. This work provides field-measurement-based evidence important for understanding both local photochemistry and regional/super-regional transport in order to properly simulate sulfate aerosols in air quality models.

Fractionation of sulfur isotopes during heterogeneous oxidation of SO<sub>2</sub> on sea salt aerosol: a new tool to investigate non-sea salt sulfate production in the marine boundary layer

Abstract. The oxidation of SO2 to sulfate on sea salt aerosols in the marine environment is highly important because of its effect on the size distribution of sulfate and the potential for new particle nucleation from H2SO4 (g). However, models of the sulfur cycle are not currently able to account for the complex relationship between particle size, alkalinity, oxidation pathway and rate – which is critical as SO2 oxidation by O3 and Cl catalysis are limited by aerosol alkalinity, whereas oxidation by hypohalous acids and transition metal ions can continue at low pH once alkalinity is titrated. We have measured 34S/32S fractionation factors for SO2 oxidation in sea salt, pure water and NaOCl aerosol, as well as the pH dependency of fractionation. Oxidation of SO2 by NaOCl aerosol was extremely efficient, with a reactive uptake coefficient of ≈0.5, and produced sulfate that was enriched in 32S with αOCl = 0.9882±0.0036 at 19 °C. Oxidation on sea salt aerosol was much less efficient than on NaOCl aerosol, suggesting alkalinity was already exhausted on the short timescale of the experiments. Measurements at pH = 2.1 and 7.2 were used to calculate fractionation factors for each step from SO2(g) → multiple steps → SOOCl2−. Oxidation on sea salt aerosol resulted in a lower fractionation factor than expected for oxidation of SO32− by O3 (αseasalt = 1.0124±0.0017 at 19 °C). Comparison of the lower fractionation during oxidation on sea salt aerosol to the fractionation factor for high pH oxidation shows HOCl contributed 29% of S(IV) oxidation on sea salt in the short experimental timescale, highlighting the potential importance of hypohalous acids in the marine environment. The sulfur isotope fractionation factors measured in this study allow differentiation between the alkalinity-limited pathways – oxidation by O3 and by Cl catalysis (α34 = 1.0163±0.0018 at 19 °C in pure water or 1.0199±0.0024 at pH = 7.2) – which favour the heavy isotope, and the alkalinity non-limited pathways – oxidation by transition metal catalysis (α34 = 0.9905±0.0031 at 19 °C, Harris et al., 2012a) and by hypohalites (α34 = 0.9882±0.0036 at 19 °C) – which favour the light isotope. In combination with field measurements of the oxygen and sulfur isotopic composition of SO2 and sulfate, the fractionation factors presented in this paper may be capable of constraining the relative importance of different oxidation pathways in the marine boundary layer.

Influence of mineral dust mixing-state and reaction probabilities on size-resolved sulfate formation in Northeast Asia

Significant differences were found between two particulate sulfate size-distributions measured using a MOUDI impactor at Gosan, Jeju Island, Korea, and simulated via the Lagrangian photochemical model under a condition of aerosol internal mixing between mineral dust and urban pollution particles. It was suspected that these differences might have resulted from: (1) the assumption of aerosol internal mixing and (2) the uses of identical reaction probabilities (γ) of the gaseous sulfate precursors (SO2 and H2SO4) onto both urban pollution particles and mineral dust in the Lagrangian photochemical model simulations. In this study; therefore, some cases of aerosol external mixing between urban-derived pollution aerosols and mineral dust were investigated, with different magnitudes of γ for the gas-phase sulfate precursors onto the two different condensing media. The model simulations under the external mixing condition, with different magnitudes of the reaction probabilities (γi,urban and γi,dust) onto urban pollution particles and mineral dust, successfully reproduced the size-dependent particulate sulfate formation measured at the Gosan station. Further attempts were made to approximate the magnitudes of γSO2,urban and γH2SO4,dust under external mixing state conditions with the fixed γSO2,dust and γH2SO2,urban values of 10−4 and 1.0. The best-estimates of γSO2,urban and γH2SO4,dust found in this study were in the orders of 10−4–10−5 and 10−2–10−3, respectively.

Size-resolved aerosol chemistry on Whistler Mountain, Canada with a high-resolution aerosol mass spectrometer during INTEX-B

Abstract. An Aerodyne High Resolution Time-of-Flight Aerosol Mass Spectrometer (HR-ToF-AMS) was deployed at the peak of Whistler Mountain (2182 m above sea level), British Columbia, from 19 April to 16 May 2006, as part of the Intercontinental Chemical Transport Experiment Phase B (INTEX-B) campaign. The mass concentrations and size distributions of non-refractory submicron particle (NR-PM1) species (i.e., sulfate, nitrate, ammonium, chloride, and organics) were measured in situ at 10-min time resolution. The HR-ToF-AMS results agreed well with collocated measurements. The average concentration of non-refractory submicron particulate matter (NR-PM1; 1.9 μg m−3) is similar to those observed at other remote, high elevation sites in North America. Episodes of enhanced aerosol loadings were observed, due to influences of regional and trans-Pacific transport of air pollution. Organics and sulfate were the dominant species, on average accounting for 55% and 30%, respectively, of the NR-PM1 mass. The average size distributions of sulfate and ammonium both showed an accumulation mode peaking at ~500 nm in vacuum aerodynamic diameter (Dva) while those of organic aerosol (OA) and nitrate peaked at ~300 nm. The size differences suggested that sulfate and OA were mostly present in external mixtures from different source origins. We also quantitatively determined the elemental composition of OA using the high resolution mass spectra. Overall, OA at Whistler Peak was highly oxygenated, with an average organic-mass-to-organic-carbon ratio (OM/OC) of 2.28±0.23 and an atomic ratio of oxygen-to-carbon (O/C) of 0.83±0.17. The nominal formula for OA was C1H1.66N0.03O0.83 for the entire study. Two significant trans-Pacific dust events originated from Asia were observed at Whistler Peak during this study. While both events were characterized with significant enhancements of coarse mode particles and mineral contents, the composition and characteristics of NR-PM1 were significantly different between them. One trans-Pacific event occurred on 15 May 2006, during which ammonium sulfate contributed >90% of the total NR-PM1 mass. This event was followed by a high OA episode likely associated with regional emissions. In total, three enhanced regional OA events, each of which lasted 2–3 days, were observed during this study. In contrast to the two dust events, the regional OA events were generally characterized with higher OA/sulfate ratio, less oxidized OA, and lower OM/OC ratio.

Formation of submicron sulfate and organic aerosols in the outflow from the urban region of the Pearl River Delta in China

Size-resolved chemical compositions of non-refractory submicron aerosols were measured using a quadrupole Aerodyne aerosol mass spectrometer at a rural site near Guangzhou in the Pearl River Delta (PRD) of China in the summer of 2006. Two cases characterized as the outflows from the PRD urban region with plumes of high SO 2 concentration were investigated. The evolution of sulfate size distributions was observed on a timescale of several hours. Namely mass concentrations of sulfate in the condensation mode (with vacuum aerodynamic diameters ( D va ) < 300 nm) increased at a rate of about 0.17–0.37 ppbv h −1 during the daytime. This finding was consistent with the sulfuric acid production rates of about 0.17–0.3 ppbv h −1, as calculated from the observed gas-phase concentrations of OH (∼3.3 × 10 6–1.7 × 10 7 cm −3) and SO 2 (∼3–21.2 ppbv). This implies that the growth of sulfate in the condensation mode was mainly due to gas-phase oxidation of SO 2. The observed rapid increase was caused mainly by the concurrent high concentrations of OH and SO 2 in the air mass. The evolution of the mass size distributions of m/ z 44, a tracer for oxygenated organic aerosol (OOA), was very similar to that of sulfate. The mass loadings of m/ z 44 were strongly correlated with those of sulfate ( r 2 = 0.99) in the condensation mode, indicating that OOA might also be formed by the gas-phase oxidation of volatile organic compound (VOC) precursors. It is likely that sulfate and OOA were internally mixed throughout the whole size range in the air mass.

Highly time- and size-resolved characterization of submicron aerosol particles in Beijing using an Aerodyne Aerosol Mass Spectrometer

Atmospheric aerosols are a major pollutant in Beijing—a megacity in China. To achieve a better understanding of the characteristics, sources and processes of aerosols in Beijing, an Aerodyne Aerosol Mass Spectrometer (AMS) was deployed at an urban site in July 2006 to obtain size-resolved chemical composition of non-refractory submicron particles (NR-PM 1) at 5 min resolution. During this study, NR-PM 1 was on average composed of 25% sulfate, 22% nitrate, 16% ammonium, 1.4% chloride and 35% of organic aerosol (OA) species. The average size distributions of sulfate, nitrate and ammonium were very similar and characterized by a prominent accumulation mode peaking at D va ≈ 600 nm. The average size distribution of OA was significantly broader due to the presence of an ultrafine mode. Multivariate analysis of the AMS organic spectra with Positive Matrix Factorization (PMF) identified a hydrocarbon-like OA (HOA) and two oxygenated OA (OOA) components. The HOA component likely corresponded to primary OA material associated with combustion-related emissions. The two OOA components, which likely corresponded to more oxidized (OOA I) and less oxidized (OOA II) secondary OA materials, accounted for 45 ± 16% and 16 ± 7.2%, respectively, of the observed OA mass. OOA I correlated well with sulfate while OOA II correlated well with nitrate. The particle loading, composition and size distributions observed during this campaign were highly variable. Backtrajectory analysis indicates that this variability correlated with the varying impacts of regional and local sources and processes.

The effect of organic compounds on the growth rate of cloud droplets in marine and forest settings

Abstract. Organic matter represents an important fraction of the fine particle aerosol, yet our knowledge of the roles of organics in the activation of aerosol particles into cloud droplets is poor. A cloud condensation nucleus (CCN) counter is used to examine the relative growth rates of cloud droplets for case studies from field measurements on the North Pacific Ocean and in a coniferous forest. A model of the condensational growth of water droplets, on particles dissolving according to their solubility in water, is used to simulate the initial scattering of the droplets as they grow in the CCN counter. Simulations of the growth rates of fine particles sampled in the marine boundary layer of the North Pacific Ocean shows no evidence of natural marine organic material contributing to the CCN water uptake but there is an indication of an influence from organics from diesel ship emissions on the size distribution of sulphate and the ability of these particles to act as CCN. Simulations of the observations of water uptake on biogenic organic aerosol particles sampled in a coniferous forest indicate an impact of the organic on the water uptake rates, but one that is still smaller than that of pure sulphate. The existence of organics becomes important in determining the water uptake as the organic mass increases relative to sulphate. The values of the organic component of the hygroscopicity parameter κ that describes the CCN activity were found to be negligible for the marine particles and 0.02–0.05 for the forest particles.

Cloud processing of nitrate

The role of clouds in the transport and transformation of tropospheric pollutants was investigated through airborne measurements made out of Cleveland, Ohio, from 21 July to 18 August 2004, as part of the International Consortium for Atmospheric Research on Transport and Transformation 2004 program. Observations of gas‐phase nitrate, size‐resolved particulate nitrate, cloud water nitrate, and size‐distributed cloud residual nitrate are used to examine changes in the partitioning of nitrate from precloud to postcloud as a function of particle size. The [NO3−]/[SO42−] ratio was highest in the bulk cloud water and higher in the cloud droplet residuals compared with the below‐cloud aerosols. Most of the nitrate entered the cloud water as HNO3, and in 30% of 43 size distributions examined, the nitrate in the cloud droplets was found in residual particle sizes smaller than those of sulfate. Simulations from a trace gas‐aerosol‐cloud parcel model show that this size difference results from differences in the processes by which nitrate and sulfate enter cloud water. The transfer of HNO3 to cloud droplets is governed primarily by gas‐phase mass transfer to the droplets, leading to greater accumulation in the smaller, more numerous droplets with higher total surface area. In contrast, much of the sulfate in the cloud water is the result of nucleation scavenging, which distributes the sulfate mass toward slightly larger sizes. The extent of separation between nitrate and sulfate is dependent on the cloud base sulfate size distribution and the factors that govern both HNO3 and SO2 uptake, with subsequent S(IV) oxidation.

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 μm 3 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 μm 3 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 μm 3 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 SO 2, is present, SO 2-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 6×10 6 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.

Analysis of Sulfur in Deposited Aerosols by Thermal Decomposition and Sulfur Dioxide Analyzer

A thermal decomposition method that measures aerosol sulfur at the nanogram level directly from the collection substrate is described. A thermal decomposition apparatus was designed. A stainless steel strip was used as the aerosol collection substrate. A 0.1 mol/L MnCl2 solution was added as the thermal decomposition catalyst. Currents were passed through the strip where aerosol particles had been deposited. In this way, the strip was heated at 780 +/- 10 degrees C, and particulate sulfur was evaporated. A sulfur dioxide analyzer (SDA) with flame photometric detector (FPD) was used to detect gaseous sulfur. High sulfur recoveries from (NH4)2SO4 and other inorganic sulfates, such as NH4HSO4, K2SO4, MgSO4, and CaSO4, were obtained. From the sulfur blank and the calibration, a lower limited detection of 0.2 ng of sulfur and the determination range of 3.3-167 ng of sulfur were estimated. The method is effective for measuring the sulfate size distributions of urban aerosols in a small sample air volume of 50-60 L. The method is applicable to measuring the sulfur in aqueous extracts of size-segregated urban aerosols collected by impactor and comparing the results with the sulfate data measured by ion chromatography.

Indoor-outdoor relationship of suspended particulate matter and its chemical composition at different sizes

The indoor-outdoor concentration relationship of particulate matter PM9.0 (aerodynamic diameter 9 µm or smaller) and its chemical composition (sulfate, nitrate, chloride and ammonium) has been studied. Samples were collected using four identical Anderson impactors, each one collecting nine size ranges by eight impactor stages (9, 5.8, 4.7, 3.3, 2.1, 1.1, 0.65 and 0.43 µm) plus a back-up filter representing particles finer than 0.45 µm. Concentrations of sulfate, nitrate and chloride were determined by ion chromatography, and an ammonium-selective ion electrode plus a Corning pH ion meter were used to determine ammonium ion. The results revealed that sulfate was the predominant component and chloride the least abundant. The size distribution of sulfate, nitrate and ammonium very strongly peaked near 0.65 µm and with very little at the larger sizes. The chloride concentration was depleted in the fine particles and enhanced in the relatively coarser particles, with the peak at 3.3 µm. All these concentrations had a significant linear relationship with mass concentrations in outdoor samples. In indoor samples, the same relation was observed only for sulfate and ammonium, which were also significantly correlated with each other. Furthermore, indoor sulfate, chloride and ammonium concentrations were higher towards the finest particle sizes, indicating a higher potential inhalation health hazard. The study also confirmed that indoor air quality depends on outdoor atmospheric pollution level, indoor activities and virtually on the particle size. Finally, the study would assist in selecting the type of collector required to reduce the level of particulates to an acceptable level for indoor ambient air.

Scavenging Efficiency of ‘Aerosol Carbon’ and Sulfate in Supercooled Clouds at Mt. Sonnblick (3106 m a.s.l., Austria)

Cloud water and interstitial aerosol samples collected at Mt. Sonnblick (SBO) were analyzed for sulfate and ‘aerosol carbon’ to calculate in-cloud scavenging efficiencies. Scavenging efficiencies for sulfate (eSO) ranged from 0.52 to 0.99 with an average of 0.80. ‘Aerosol carbon’ was scavenged less efficiently with an average value (eAC) of 0.45 and minimum and maximum values of 0.14 and 0.81, respectively. Both eSO and eAC showed a marked, but slightly different, dependence on the liquid water content (LWC) of the cloud. At low LWC, eSO increased with rising LWC until it reached a relatively constant value of 0.83 above an LWC of ≈ 0.3 g/m3. In the case of ‘aerosol carbon’, we obtained a more gradual increase of eAC up to an LWC of ≈ 0.5 g/m3. At higher LWCs, e_ remained relatively constant at 0.60. As the differences between eSO and eA varied across the LWC range observed at SBO, we assume that part of the ‘aerosol carbon’ was incorporated into the cloud droplets independently from sulfate. This hypothesis is supported by size classified aerosol measurements. The differences in the size distributions of sulfate and total carbon point to a partially external mixture. Thus, the different chemical nature and the differences in the size and mixing state of the aerosol particles are the most likely candidates for the differences in the scavenging behavior.

Aerosols in a Mediterranean Forest: Sulfates, Particle Size Distribution, and Growth Rates

ABSTRACT Particle size distribution measurements in 16 nonlinear intervals covering the 0.1–7.5 μm range and concurrent sulfate concentrations were continuously recorded in September 1996 over the period of two weeks in a Mediterranean forest. Sulfate size distribution was derived from a linear correlation fit between the concentrations and the number of particles recorded at each particle size interval. The results revealed two modal diameters for sulfates, with typical diameters at 0.3 and 0.675 μm. These results were associated with two different dominant chemical mechanisms governing sulfate formation. In order to describe the dominant chemical mechanism, the growth law approach was applied. Growth rates were determined using the parameter estimates of the fitted particle size distribution function. By matching these data with sulfate concentrations, the dominant chemical reactions were identified. The results have shown that sulfate formation is governed by both homogeneous and heterogeneous reactions and that the latter process was dominant. Condensation reactions prevailed in the early morning and late afternoon, and volume reactions at night, particularly in high-moisture conditions. From the observational data, the gas-to-particle conversion rate for sulfur dioxide (SO2) at nighttime was also derived, yielding a 2.18%/hr-1.

Heterogeneous sulfate production in the remote marine environment: Cloud processing and sea‐salt particle contributions

Heterogeneous sulfate production in the remote marine boundary layer is studied by combining measurements collected during the first Southern Hemisphere marine Aerosol Characterization Experiment (ACE 1) with two numerical models: one simulating heterogeneous sulfate production in sea‐salt aerosol water (SSAW) and the other simulating cloud processing. The models calculate oxidation of SO2 by O3 and H2O2 via aqueous‐phase reactions both in SSAW and in cloud droplets. Model calculations indicate that as much as 50–75% of the observed non‐sea‐salt (NSS) sulfate in particles in the ambient diameter size range of 0.9–16 μm during the ACE 1 measurement period is due to production in SSAW, with cloud processing producing the remainder. The initial alkalinity of the wind‐generated sea‐salt aerosols can strongly influence sulfate production. Changing the effective alkalinity of SSAW from a value typical of seawater to a value based on the measurements taken at Cape Grim results in a better match to the observed NSS sulfate size distribution with up to 75% of the predicted supermicrometer NSS sulfate being due to heterogeneous conversion in SSAW. The average rates of removal of sulfate due to dry and wet deposition for the 0.4–16 μm size range are 38 and 14 ng m−3 d−1 respectively.

Computer simulation of the transport, formation and dynamics of atmospheric sulfate particles

The present paper investigates the transport, formation and dynamics of atmospheric sulfate particles under different meteorological conditions from point sources. Emissions of SO2 from one and multiple local point sources were modeled. The advection and diffusion of gaseous and particulate matter are described by the atmospheric diffusion equation which is solved numerically using a new developed 3-dimensional model. The evolution of the aerosol size distribution with time was described using the aerosol general dynamic equation. Under fog conditions aqueous phase oxidation is the primary mechanism for sulfate formation. The condensation mechanism from the vapor to liquid phase is the dominant process for sulfate production at moderate relative humidities. The observed mass size distribution of sulfate suggests that the major contribution in the mass size distribution during continental conditions is from long range transport.

Competition between Sea Salt and Sulfate Particles as Cloud Condensation Nuclei

Abstract The influence of sea salt on the cloud droplet activation of sulfate particles is investigated using a size-resolving model of the aerosol activation process. The authors found that the total number concentration of activated cloud droplets increases with increasing sea salt concentration if the sulfate number concentrations are relatively low and updrafts are strong, but it decreases with higher sea salt if sulfate number concentrations are high and cloud updrafts are weak. The increase is due to the activation of accumulation mode sea salt particles, while the decrease is due to the reduction in maximum cloud supersaturation due to competition with coarse mode sea salt particles. These conclusions are insensitive to the sulfate size distribution and surface wind speed.