Size distributions of nano/micron dicarboxylic acids and inorganic ions in suburban PM episode and non-episodic aerosol

The distribution of nano/micron dicarboxylic acids and inorganic ions in size-segregated suburban aerosol of southern Taiwan was studied for a PM episode and a non-episodic pollution period, revealing for the first time the distribution of these nanoscale particles in suburban aerosols. Inorganic species, especially nitrate, were present in higher concentrations during the PM episode. A combination of gas-to-nuclei conversion of nitrate particles and accumulation of secondary photochemical products originating from traffic-related emissions was likely a crucial cause of the PM episode. Sulfate, ammonium, and oxalic acid were the dominant anion, cation, and dicarboxylic acid, respectively, accounting for a minimum of 49% of the total anion, cation or dicarboxylic acid mass. Peak concentrations of these species occurred at 0.54 μm in the droplet mode during both non-episodic and PM episode periods, indicating an association with cloud-processed particles. On average, sulfate concentration was 16–17 times that of oxalic acid. Oxalic acid was nevertheless the most abundant dicarboxylic acid during both periods, followed by succinic, malonic, maleic, malic and tartaric acid. The mass median aerodynamic diameter (MMAD) of oxalic acid was 0.77 μm with a bi-modal presence at 0.54 μm and 18 nm during non-episodic pollution and an MMAD of 0.67 μm with mono-modal presence at 0.54 μm in PM episode aerosol. The concomitant formation of malonic acid and oxalic acid was attributed to in-cloud processes. During the PM episode in the 5–100 nm nanoscale range, an oxalic acid/sulfate mass ratio of 40.2–82.3% suggested a stronger formation potential for oxalic acid than for sulfate in the nuclei mode. For total cations (TC), total inorganic anions (TIA) and total dicarboxylic acids (TDA), major contributing particles were in the droplet mode, with least in the nuclei mode. The ratio of TDA to TIA in the nuclei mode increased greatly from 8.40% during the non-episodic pollution period to 28.08% during the PM episode, favoring dicarboxylic acid formation in the nuclei mode. The evidence suggests stronger formation strength and contribution potential exists for dicarboxylic acids than for inorganic salts in nanoscale particles, especially in PM episode aerosol.     

Ion balances of size-resolved tropospheric aerosol samples: implications for the acidity and atmospheric processing of aerosols

A large set of size-resolved aerosol samples was inspected with regard to their ion balance to shed light on how the aerosol acidity changes with particle size in the lower troposphere and what implications this might have for the atmospheric processing of aerosols. Quite different behaviour between the remote and more polluted environments could be observed. At the remote sites, practically the whole accumulation mode had cation-to-anion ratios clearly below unity, indicating that these particles were quite acidic. The supermicron size range was considerably less acidic and may in some cases have been close to neutral or even alkaline. An interesting feature common to the remote sites was a clear jump in the cation-to-anion ratio when going from the accumulation to the Aitken mode. The most likely reason for this was cloud processing which, via in-cloud sulphate production, makes the smallest accumulation-mode particles more acidic than the non-activated Aitken-mode particles. A direct consequence of the less acidic nature of the Aitken mode is that it can take up semi-volatile, water-soluble gases much easier than the accumulation mode. This feature may have significant implications for atmospheric cloud condensation nuclei production in remote environments. In rural and urban locations, the cation-to-anion ratio was close to unity over most of the accumulation mode, but increased significantly when going to either larger or smaller particle sizes. The high cation-to-anion ratios in the supermicron size range were ascribed to carbonate associated with mineral dust. The ubiquitous presence of carbonate in these particles indicates that they were neutral or alkaline, making them good sites for heterogeneous reactions involving acidic trace gases. The high cation-to-anion ratios in the Aitken mode suggest that these particles contained some water-soluble anions not detected by our chemical analysis. This is worth keeping in mind when investigating the hygroscopic properties or potential health effects of ultrafine particles in polluted environments.     

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.     

Determination of malic acid and other C4 dicarboxylic acids in atmospheric aerosol samples

An ion chromatographic method was developed which is able to separate five unsubstituted and hydroxy C4 dicarboxylic acids, succinic, malic, tartaric, maleic and fumaric acid, besides the other unsubstituted C2-C5 dicarboxylic acids, oxalic, malonic and glutaric acids, as well as inorganic ions in samples extracted from atmospheric particulate matter. By the application of this method it was found for both rural and urban sites and for various types of air masses that in the summer-time malic acid is the most prominent C4 diacid (64 ng m(-3) by average), exceeding succinic acid concentration (28 ng m(-3) by average) considerably. In winter-time considerably less, a factor of 4-15, C4 acids occurred and succinic acid was more concentrated than malic acid. Tartaric, fumaric and maleic acids were less concentrated (5.1, 5.0 and 4.5 ng m(-3) by average, respectively). Tartaric acid was observed for the first time in ambient air. The results indicate that in particular anthropogenic sources are important for the precursors of succinic, maleic and fumaric acids. Biogenic sources seem to influence the occurrence of malic acid significantly.     

Formation of particulate sulfur species (sulfate and methanesulfonate) during summer over the Eastern Mediterranean: A modelling approach

To improve our understanding of the mechanisms of particulate sulfur formation (non sea-salt sulfate, nss-SO₄²⁻) and methanesulfonate (MS_x used here to represent the sum of gaseous methanesulfonic acid, MSA, and particulate methanesulfonate, MS⁻) in the eastern Mediterranean and to evaluate the relative contribution of biogenic and anthropogenic sources to the S budget, a chemical box model coupled offline with an aerosol–cloud model has been used.Based on the measurements of gaseous dimethyl sulfide (DMS) and methanesulfonic acid (MSA) and the MSA sticking coefficient determined during the Mediterranean Intensive Oxidant Study (MINOS) experiment, the yield of gaseous MSA from the OH-initiated oxidation of DMS was calculated to be about 0.3%. Consequently, MSA production from gas-phase oxidation of DMS is too small to explain the observed levels of MS⁻. On the other hand, heterogeneous reactions of dimethyl sulfoxide (DMSO) and its gas-phase oxidation product methanesulfinic acid (MSIA) can account for most of the observed MS⁻ levels. The modelling results indicate that about 80% of the production of MS⁻ can be attributed to heterogeneous reactions.Observed submicron nss-SO₄²⁻ levels can be fully explained by homogeneous (photochemical) gas-phase oxidation of sulfur dioxide (SO₂) to sulfuric acid (H₂SO₄), which is subsequently scavenged by (mainly submicron) aerosol particles. The predominant oxidant during daytime is hydroxyl radical (OH) showing very high peak levels in the area during summer mostly under cloudless conditions. Therefore, during summer in the east Mediterranean, heterogeneous sulfate production appears to be negligible. This result is of particular interest for sulfur abatement strategy. On the other hand only about 10% of the supermicron nss-SO₄²⁻ can be explained by condensation of gas-phase H₂SO₄, the rest must be formed via heterogeneous pathways.Marine biogenic sulfur emissions contribute up to 20% to the total oxidized sulfur production (SO₂ and H₂SO₄) in good agreement with earlier estimates for the area.     

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.     

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.     

Mineral dust is a sink for chlorine in the marine boundary layer

Dust particles affect the budgets of important traces gases by providing a surface on which heterogeneous reactions can occur. The uptake of soluble species on dust alters the physical, chemical, and optical properties and the overall ability of dust to act as cloud condensation and ice nuclei. It is commonly assumed that all measured chloride in particulate filter samples is associated with sea-salt particles and any chloride in dust occurs as the result of internal mixtures of sea-salt and dust particles, formed by cloud processing. Here we show high temporal resolution data demonstrating the direct uptake of chlorine by dust via heterogeneous reaction with HCl(g). This reaction added significant amounts of chlorine to the dust particles during a major dust storm, representing 4–9% of the individual dust particle mass. Up to 65±4% of the dust particles contained chlorine due to this heterogeneous reaction during the dust front. Ignoring this process leads to an overestimation of sea-salt concentrations from bulk measurements, and an underestimation of the degree of sea-salt aging. The uptake of chloride will change the pH and hygroscopic properties of the dust and thus can influence the budgets of other reactive gases. Including this heterogeneous process in atmospheric measurements and chemical transport models will improve our ability to predict the atmosphere's composition and radiation budget with greater accuracy.     

Low molecular weight dicarboxylic acids in PM10 in a city with intensive solid fuel burning

In this work, PM(10) samples were collected in a winter and a summer in Christchurch, a New Zealand city having intensive wood and coal burning and a serious air pollution problem in winter. Oxalic, malonic, succinic, maleic, glutaric and adipic acids in the samples were analysed using ion chromatography. It was suggested that solid fuel burning had large influence on the occurrence of these low molecular weight dicarboxylic acids resulting in significantly higher wintertime concentrations of maleic acid, oxalic acid and glutaric or adipic acid. The most pronounced feature observed was that maleic acid was the second most abundant species of the detected DCAs in the winter (with a mean of 74 ngm(-3) and the highest concentration ever reported of 231 ngm(-3)). In contrast, malonic acid experienced a low abundance in both seasons. The observed seasonal patterns and molecular distribution were inconsistent with those in most other urban areas. On an average, the total detected dicarboxylic acids accounted for about 0.5% of PM(10) mass with a maximum of 1.4% in the winter. The relative importance of different sources to individual dicarboxylic acids varied with seasons and is discussed in detail.     

Organic acids in continental background aerosols

With a newly developed method aerosol samples from three distinctly different continental sites were analyzed: an urban site (Vienna), a savanna site in South Africa (Nylsvley Nature Reserve, NNR) and a free tropospheric continental background site (Sonnblick Observatory, SBO). In all samples a range of monocarboxylic acids (MCAs) and dicarboxylic acids (DCAs) has been identified and quantified. The three most abundant MCAs in Vienna were the C18, C16 and C14 acids with concentrations of 66, 45 and 36 ng m^-3, respectively. At the mid tropospheric background site (SBO) the three most abundant MCAs were the C18, C16 and C12 acid. For the DCAs at all three sites oxalic, malonic and succinic acid were the dominant compounds. For some individual compounds an information about the sources could be obtained. For example the determined unsaturated MCAs in South Africa appear to result from biogenic sources whereas in Vienna those acids are considered to be derived from combustion processes. Oxalic and glyoxalic acid appear to have a free tropospheric air chemical source. The relative high amounts at SBO in comparison to Vienna can only be explained by secondary formation of oxalic acid in the atmosphere.     

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.     

Halogen production from aqueous tropospheric particles

Box model studies have been performed to study the role of aqueous phase chemistry with regard to halogen activation for marine and urban clouds and the marine aerosol as well. Different chemical pathways leading to halogen activation in diluted cloud droplets and highly concentrated sea salt aerosol particles are investigated. The concentration of halides in cloud droplets is significantly smaller than in sea-salt particles, and hence different reaction sequences control the overall chemical conversions. In diluted droplets radical chemistry involving OH, NO(3), Cl/Cl(2)(-)/ClOH(-), and Br/Br(2)(-)/BrOH(-) gains in importance and pH independent pathways lead to the release of halogens from the particle phase whereas the chemistry in aerosol particles with high electrolyte concentrations is controlled by non-radical reactions at high ionic strengths and relatively low pH values.For the simulation of halogen activation in tropospheric clouds and aqueous aerosol particles in different environments a halogen module was developed including both gas and aqueous phase processes of halogen containing species. This module is coupled to a base mechanism consisting of RACM (Regional Atmospheric Chemistry Mechanism) and the Chemical Aqueous Phase Radical Mechanism CAPRAM 2.4 (MODAC-mechanism). Phase exchange is described by the resistance model by Chemistry of Multiphase Atmospheric Systems, NATO ASI Series, 1986.It can be shown that under cloud conditions the bromine atom is mainly produced by OH initiated reactions, i.e. its concentration maximum is reached at noon. In contrast, the concentration level of chlorine atoms is linked to NO(3) radical chemistry leading to a smaller amplitude between day and night time concentrations.The contribution of radical processes to halogen atom formation in the particle phase is evident, e.g. by halogen atoms which undergo direct phase transfer. Furthermore, the application of the multiphase model for initial concentrations for sea-salt aerosols shows that the particle phase can act as a main source of halogen containing molecules (Cl(2), BrCl, Br(2)) which are photolysed in the gas phase to yield halogen atoms (about 70% of all Cl sources and more than 99% for Br).     

Gas-to-particle conversion in the atmosphere: I. Evidence from empirical atmospheric aerosols

Condensable vapours such as sulphuric acid form aerosol in the atmosphere by the competing mechanisms of condensation on existing aerosol and the nucleation of new aerosol. Observational and theoretical evidence for the relative magnitudes of the competing processes is reviewed, and a number of general conclusions are made. Condensation is sensitive to the sticking probability of sulphuric acid molecules on aerosol particles, but there is now good evidence that it should be close to unity. In this case, equilibration timescales between acid vapour and the aerosol in most of the atmosphere are of the order of minutes or less, so that the acid concentration on such timescales given simply by the production rate times the equilibration time. When the acid concentration exceeds a threshold, nucleation will occur. The atmospheric aerosol therefore follows a history of initial formation in a nucleation burst followed by growth and coagulation with final removal by precipitation. This leads to the inverse correlation between aerosol number concentration and mass concentration found by Clarke (1992. Journal of Atmospheric Chemistry 14, 479–488) in the free troposphere. Binary homogeneous nucleation of sulphuric acid/water droplets, for which various simplified rates are compared, may dominate in such regions, but other mechanisms are possible elsewhere. A detailed analysis is performed of the number concentrations, removal rates, and masses of the components of the different types of global aerosols proposed empirically by Jaenicke (1993. Tropospheric Aerosols, Aerosol-Cloud-Climate Interaction. Academic Press, New York). There is a striking correlation between number concentrations in the nucleation and accumulation modes; and the giant aerosol mode, which if it is present dominates the mass, has little effect on the gas-to-particle conversion process. The mass of the atmospheric aerosol is therefore uncorrelated with the magnitude of molecular aerosol removal by condensation.     

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.     

粉煤燃烧过程中细粒子形成机理的研究

煤是一种有机沉淀岩 ,主要包括有机碳化合物和无机矿物。在燃烧的高温条件下 ,煤中的矿物质首先经历热分解和气化 ,当烟气冷却时 ,它们经过冷凝成核、凝结和团聚等作用 ,形成大量细粒子。这些细粒子的排放会对大气环境和人类健康造成严重的影响。研究燃烧过程中细粒子的形成机理将为其污染防治提供理论基础和科学依据。本文系统地综述了煤燃烧过程中矿物质和痕量元素的气化、冷凝成核、表面凝结、团聚的机理、模拟和预测方法以及细粒子形成机理的研究进展。     

Light scattering from sea-salt aerosols at Interagency Monitoring of Protected Visual Environments (IMPROVE) sites

A method is described to estimate light scattering (Bsp) by sea-salt aerosols at coastal locations in the Interagency Monitoring of Protected Visual Environments (IMPROVE) network. Dry mass scattering efficiencies for fine and coarse sea-salt particles were based on previously measured dry sea-salt size distributions. Enhancement of sea-salt particle scattering by hygroscopic growth was based on NaCl water activity data. Sea-salt aerosol mass at the IMPROVE site in the Virgin Islands (VIIS) was estimated from strontium (Sr) concentrations in IMPROVE aerosol samples. Estimated Bsp, including contributions from sea-salt mass based on Sr, agreed well with measured Bsp at the VIIS IMPROVE site. On average, sea salt accounted for 52% of estimated Bsp at this site. Sea-salt aerosol mass cannot be reliably estimated from Sr unless its crustal enrichment factor exceeds 10. Sodium (Na) concentrations are not accurately determined by X-ray fluorescence analysis in IMPROVE samples. It is recommended that Na be measured in the fine and coarse modes by a more appropriate method, such as atomic absorption spectroscopy or ion chromatography, to account for scattering by sea-salt particles at IMPROVE sites where such contributions may be significant.     

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.     

Changes of organic acid exudation and rhizosphere pH in rice plants under chromium stress.

The effect of chromium (Cr) stress on the changes of rhizosphere pH, organic acid exudation, and Cr accumulation in plants was studied using two rice genotypes differing in grain Cr accumulation. The results showed that rhizosphere pH increased with increasing level of Cr in the culture solution and with an extended time of Cr exposure. Among the six organic acids examined in this experiment, oxalic and malic acid contents were relatively higher, and had a significant positive correlation with the rhizosphere pH, indicating that they play an important role in changing rhizosphere pH. The Cr content in roots was significantly higher than that in stems and leaves. Cr accumulation in plants was significantly and positively correlated with rhizosphere pH, and the exudation of oxalic, malic and citric acids, suggesting that an increase in rhizosphere pH, and exudation of oxalic, malic and citric acid enhances Cr accumulation in rice plants.     

Air parcel model simulations of a convective cloud: Bacteria acting as immersion ice nuclei

The effects of bacteria acting as immersion ice nuclei were investigated in numerical sensitivity studies and compared to the efforts of other ice nuclei such as mineral dust and soot particles. An adiabatic air parcel model was employed simulating convective situations with different initial aerosol particle distributions. The maximum fractions of active ice nuclei were based on field measurements of the proportioning of atmospheric aerosol particle types in continental and marine air masses. Recent field measurements of bacteria concentrations in cloud water and in snow samples were used. From the concentrations in bulk samples the concentration in mean sized cloud droplets was estimated. Immersion freezing was described based on laboratory measurements to constrain the freezing fraction versus temperature. The results indicated that the effects of diminutive amounts of bacteria on ice formation in convective clouds, while being significantly less than the effects of mineral dust particles, might be comparable to the expected effects of soot particles acting as ice nuclei. It can be predicted that bacterial ice nuclei would have to be enriched by at least 10⁴ times reported concentrations in cloud water in order to equate to the impact of mineral dust ice nuclei present in 20–25% of all cloud droplets.     

Light Scattering from Sea-Salt Aerosols at Interagency Monitoring of Protected Visual Environments (IMPROVE) Sites

Abstract

A method is described to estimate light scattering (Bsp) by sea-salt aerosols at coastal locations in the Interagency Monitoring of Protected Visual Environments (IMPROVE) network. Dry mass scattering efficiencies for fine and coarse sea-salt particles were based on previously measured dry sea-salt size distributions. Enhancement of sea-salt particle scattering by hygroscopic growth was based on NaCl water activity data. Sea-salt aerosol mass at the IMPROVE site in the Virgin Islands (VIIS) was estimated from strontium (Sr) concentrations in IMPROVE aerosol samples. Estimated Bsp, including contributions from sea-salt mass based on Sr, agreed well with measured Bsp at the VIIS IMPROVE site. On average, sea salt accounted for 52% of estimated Bsp at this site. Sea-salt aerosol mass cannot be reliably estimated from Sr unless its crustal enrichment factor exceeds 10. Sodium (Na) concentrations are not accurately determined by X-ray fluorescence analysis in IMPROVE samples. It is recommended that Na be measured in the fine and coarse modes by a more appropriate method, such as atomic absorption spectroscopy or ion chromatography, to account for scattering by sea-salt particles at IMPROVE sites where such contributions may be significant.