Water uptake characteristics of individual atmospheric particles having coatings

We used an environmental transmission electron microscope to observe deliquescence and hygroscopic growth of atmospheric particles with hygroscopic coatings over the range 0–100% relative humidity (RH). The particles were collected from polluted and clean environments. Types included a sulfate-coated NaCl/silicate aggregate particle, a sulfate-coated sea-salt particle, and a Mg-rich, chloride-coated sea-salt particle. They all exhibited initial water uptake between 50% and 60% RH, although the first major morphological changes occurred at 70% RH. A deliquescence sphere, adjacent to the core particle, formed between 70% and 76% RH when deliquescence occurred or when the liquid phase was able to break out of the solid exterior coating. The deliquescence sphere grew to engulf the particle with increasing RH. Some particles developed a splatter zone associated with a particle coating. Efflorescence occurred over the range 49–44% RH. Our results indicate that some coated particles undergo a multi-step deliquescence process and that composition of the different phases within the coating affects deliquescence and hygroscopic growth below 76% RH. Above 76% RH, the dominant hygroscopic growth was due to water uptake by NaCl. Efflorescence of these particles also was strongly linked to NaCl, although the presence of other phases inhibited formation of a single NaCl crystal. Our results show that the observed coatings can both enhance particle solubility and lower the effective deliquescence RH of the particle. Thus, these coatings cause important phase and size changes for aerosol particles that could feed back into many other chemical and physical processes that contribute to radiative forcing within the atmosphere.     

Roadside aerosol study using hygroscopic,organic and volatility TDMAs: Characterization and mixing state

Traffic-related aerosol particles are ubiquitous in the urban atmosphere. As they are produced at ground level, they can also cause adverse health effects to urban dwellers. However, knowledge of the formation, transformation and chemically resolved size distribution of urban ultrafine particles is incomplete. Thus, more of these measurements are needed for better assessment of ambient air quality and its potential health effects. The particle number concentration, aerosol black carbon (BC) concentration and size distribution of traffic-related aerosols were measured near two major roads in Kuopio, Finland, from 16 June to 5 July, 2004. Furthermore, the properties of roadside aerosol particles were examined with the Tandem Differential Mobility Analyzer technique (TDMA). A suite of TDMA instruments relying on water (hygroscopic TDMA) and ethanol (organic TDMA) condensation as well as heating (volatility TDMA) were deployed to study the composition of the nucleation and Aitken mode particles (D_p = 10–50 nm) formed from vehicle exhaust. The results show that a simple three-component model was able to reproduce characteristic insoluble, organic and water-soluble volume fractions. Insoluble constituents were dominant in the Aitken mode particles, whereas organic compounds dominated the nucleation mode sizes. On average, only a small volume fraction was water-soluble, but a clear external mixing was observed particularly when enough time was allowed after the tail pipe emissions. The contribution of the insoluble material was seen to increase as a function of particle size, being typically less than 10% at 10 nm and between 20 and 50% at 50 nm, in contrast to the organic fraction, which decreased from about 80% at nucleation mode size range to 50–60% at 50 nm.     

Soot particles and their impacts on the mass cycle in the Tibetan atmosphere

Atmospheric aerosol particles in urban and mountain areas around Lhasa city (29.65°N, 91.13°E) in the Tibetan Plateau were collected in the summers of 1998 and 1999. The particles were analyzed with electron microscopes and an energy dispersive X-ray spectrometer. Individual particle morphology, elemental composition and mixture of sulfate and nitrate were investigated. In the urban area, soot particles emitted from vegetation burning were dominant. These particles were characterized by chain or aggregate morphologies, and an elemental composition of potassium and sulfur. Such particles were frequently detected in mountain areas out of the city, where they formed droplets acting as condensation nuclei. Quantitative estimation indicated that sulfur was accumulated onto the soot particles during their dispersion from the urban area to mountain areas. Sulfate and nitrate detections indicated that soot particles collected in the urban area did not contain nitrate and BaCl₂-reactive sulfate, which revealed that the combination of sulfur and potassium in the particles was not K₂SO₄. In contrast, the particles dispersed to mountain areas contained BaCl₂-reactive sulfate and some contained nitrate, suggesting that soot particles emitted from the urban area could increase the buffering capacity of aerosol particles and enhance the formation of particulate sulfate through heterogeneous conversion in the Tibetan atmosphere.     

Spectroscopic study of organic coatings on fine particles,exposed to ozone and simulated sunlight

This work intends to quantify the variation in optical properties of aerosol by in-situ spectroscopic monitoring the ozonolysis of a mixture of typical biomass burning compounds. The reaction occurs on silica and glass particles in the presence of simulated sunlight.Fused silica particles (Aerosil) were coated with a thin film of a 1:1 mixure of 4-phenoxyphenol with 4-carboxyphenone as a photosensitizer. UV–VIS spectra of dichloromethane extracts from the particles recorded before and after treatment, show development of a new band after prolonged ozone and light exposure.Changes in optical properties are reported, and variations of spectroscopic features are discussed. We show that the ozone-induced heterogeneous photochemical reaction does produce species absorbing light in the solar spectral range. Further, we demonstrate that the heterogeneous photosensitized reactions at 200 ppb ozone (strongly ozone polluted regions) for a time period of 7 h aging process, can increase light absorption of atmospheric aerosols in the tropospheric actinic window (>290 nm) by 0.4 absorption units ng-C^?1 O₃ ppm^?1 in the region 290–358 nm and by 1.0 absorption units ng-C^?1 O₃ ppm^?1 in the region 360–448 nm.Chemical changes of such surface films were identified by diffuse reflectance infrared Fourier transform spectroscopy of coated glass spheres, and we suggest formation of humic-like substances comparable to those reported in continental aerosol.     

空气和土壤中酞酸酯的污染及其相关性分析

对天津市11个采样点的空气颗粒物和土壤样品进行采样调查,采用气相色谱/质谱联用仪分析样品中15种酞酸酯类化合物(PAEs)的含量。结果表明,11个采样点空气颗粒物样品中总酞酸酯类化合物(TPAEs)以体积计质量浓度为90.87～1355.70ng/m3,以质量计质量浓度为783.84～8712.37mg/kg;土壤中TPAEs质量浓度为0.53～2.53mg/kg。邻苯二甲酸二丁酯(DBP)与邻苯二甲酸二(2-乙基己基)酯(DEHP)是空气颗粒物和土壤样品中的主要污染物。土壤与空气颗粒物中TPAEs和DBP存在相关关系,Pearson相关系数分别为0.825和0.864(双尾检验,显著性水平0.01),且空气颗粒物中各种PAEs浓度为土壤PAEs浓度的数百至数万倍,说明空气沉降可能是土壤PAEs污染的主要原因之一。     

The inportance of organic and elemental carbon in the fine atmospheric aerosol particles

During a field campaign the chemical character of fine (d<2.5 μm) aerosol particles was studied at K-puszta, Hungary within the framework of a project of the European Union. The organic and elemental carbon fraction, as well as the concentration of major inorganic constituents with respect to the total fine aerosol mass are presented in this paper. It was found that organic compounds constituted a significant fraction of the total fine aerosol mass, their contribution is comparable to or larger than that of the major water soluble ions. The diurnal variation of aerosol composition was also studied. It can be concluded that the relative abundance of the major constituents is practically the same during the day and at night. The samples were also classified and studied according to the air mass history. It is stated that the aerosol can be separated into two populations with different regression lines between organic and elemental carbon.     

Assessment of the aerosol water content in urban atmospheric particles by the hygroscopic growth measurements in Sapporo,Japan

Aerosol water content (AWC) of urban atmospheric particles was investigated based on the hygroscopic growth measurements for 100 and 200 nm particles using a hygroscopicity tandem differential mobility analyzer in Sapporo, Japan in July 2006. In most of the humidogram measurements, presence of less and more hygroscopic mode was evident from the different dependence on relative humidity (RH). The volume of liquid water normalized by that of dry particle (V_w(RH)/V_dry) was estimated from the HTDMA data for 100 and 200 nm particles. The RH dependence of V_w(RH)/V_dry was well represented by a fitted curve with a hygroscopicity parameter κ_eff. The κ_eff values for 200 nm particles were in general higher than those for 100 nm particles, indicating a higher hygroscopicity of 200 nm particles. Based on the κ_eff values, the volume mixing ratios of water-soluble inorganic compounds (ammonium sulfate equivalent) were estimated to be on average 31% and 45% for 100 and 200 nm particles, respectively. The diurnal variation of κ_eff, with relatively higher values in the noontime and nighttime and lower values in the morning and evening hours, was observed for both particle sizes. The V_w(RH)/V_dry values under ambient RH conditions were estimated from κ_eff to range from 0.05 to 2.32 and 0.06 to 2.43 for 100 nm and 200 nm particles, respectively. The degree of correlation between κ_eff and V_w(RH)/V_dry at ambient RH suggests a significant contribution of the variation of κ_eff to atmospheric AWC in Sapporo.     

Quantitative analysis of volatile organic compounds (VOCs) in atmospheric particles

There are a number of difficulties associated with the quantitative analysis of volatile organic compounds (VOCs) in atmospheric particles. Therefore, majority of the previous studies on VOCs associated with particles have been qualitative. Air samples were collected in Izmir, Turkey to determine ambient particle and gas phase concentrations of several aromatic, oxygenated and halogenated VOCs. Samples were quantitatively analyzed using thermal desorption–gas chromatography/mass spectrometry. Gas-phase concentrations ranged between 0.02 (bromoform) and 4.65 μg m⁻³ (toluene) and were similar to those previously measured at the same site. Particle-phase concentrations ranged from 1 (1,3-dichlorobenzene) to 933 pg m⁻³ (butanol). VOCs were mostly found in gas-phase (99.9±0.25%). However, the particulate VOCs had comparable concentrations to those reported previously for semivolatile organic compounds. The distribution of particle-phase VOCs between fine (d_p<2.5 μm) and coarse (2.5 μm<d_p<10 μm) fractions was also investigated. It was found that VOCs were mostly associated with fine particles.     

Characterization of carbon fractions for atmospheric fine particles and nanoparticles in a highway tunnel

Fine particles (PM_2.5) and nanoparticles (PM_0.1) were sampled using Dichotomous sampler and MOUDI, respectively, in Xueshan Tunnel, Taiwan. Eight carbon fractions were analyzed using IMPROVE thermal-optical reflectance (TOR) method. The concentrations of different temperature carbon fractions (OC1–OC4, EC1–EC3) in both PM_2.5 and PM_0.1 were measured and the correlations between OC and EC were discussed. Results showed that the ratios of OC/EC were 1.26 and 0.67 for PM_2.5 and PM_0.1, respectively. The concentration of EC1 was found to be more abundant than other elemental carbon fractions in PM_2.5, while the most abundant EC fraction in PM_0.1 was found to be EC2. The variation of contributions for elemental carbon fractions was different among PM_2.5 and PM_0.1 samples, which was partly owing to the metal catalysts for soot oxidation. The correlations between char-EC and soot-EC showed that char-EC dominated EC in PM_2.5 while soot-EC dominated EC in PM_0.1. Using eight individual carbon fractions, the gasoline and diesel source profiles of PM_0.1 and PM_2.5 were extracted and analyzed with the positive matrix factorization (PMF) method.     

Water-soluble organic nitrogen (WSON) in size-segregated atmospheric particles over the Eastern Mediterranean

Atmospheric water-soluble organic nitrogen (WSON) was determined on size-segregated aerosol particles collected during a two years period (2005–2006) in a remote marine location in the Eastern Mediterranean (Finokalia, Crete island). Average concentration of WSON was 5.5 ± 3.9 nmol m^?3 and 11.6 ± 14.0 nmol m^?3 for coarse (PM_1.3-10) and fine (PM_1.3) mode respectively, corresponding to 13% of Total Dissolved Nitrogen (TDN) in both modes. Air masses origin and correlation with tracers of natural and anthropogenic sources indicate that combustion process (biomass burning and fossil fuel) and African dust play an important role in regulating levels of WSON in both coarse and fine aerosol fractions. Chemical speciation of organic nitrogen pool was attempted by analyzing 47 fine aerosol samples (PM₁) for 17 free amino acids (N-FAA), dimethylamine (DMA) and trimethylamine (TMA). The average concentration of N-FAA was 0.5 ± 0.5 nmol m^?3, while the average concentration of DMA was 0.2 ± 0.8 nmol m^?3, TMA was below detection limit. The percentage contribution of N-FAA and DMA to WSON was 2.1 ± 2.3% and 0.9 ± 3.4%, respectively.     

Light absorption by water-soluble organic carbon in atmospheric fine particles in the central Tibetan Plateau

Environmental Science and Pollution Research - Brown carbon (BrC) has recently received much attention because of its light absorption features. The chemical compositions, optical properties, and...     

Characterization of organic compounds in aerosol particles from a coniferous forest by GC-MS

Atmospheric aerosol particles were collected in a Finnish Scots pine forest as part of a European Union project. Sampling was done in March-April 2003 with a high-volume sampler. Dynamic ultrasonic-assisted solvent extraction and gas chromatography-mass spectrometry (GC-MS) were applied to the analysis of aerosol samples for analytes such as n-alkanes, polycyclic aromatic hydrocarbons (PAH), oxidized polycyclic aromatic hydrocarbons (oxy-PAHs), sesquiterpenes (SQT) and oxidized sesquiterpenes (oxy-SQT). The highest concentrations were found for the n-alkanes, which were present in a wide range (C11-C32) indicating both biogenic and anthropogenic sources. PAH compounds were found in every sample while oxy-PAH compounds were present in low concentrations in a few samples. A few oxidized monoterpenes, most notably (-)-verbenone and pinonaldehyde, were found in several samples in concentrations clearly exceeding the PAH concentrations. The effect of temperature could be seen in most samples, where the concentrations of n-alkanes declined with decreasing temperatures. Particle formation events were accompanied by higher concentrations of heavy n-alkanes, verbenone and pinonaldehyde.     

Seasonal characteristics of water-soluble organic carbon in atmospheric particles in the inland Kanto plain,Japan

An investigation of water-soluble organic carbon (WSOC) in atmospheric particles was conducted as an index of the formation of secondary organic aerosol (SOA) from April 2005 to March 2006 at Maebashi and Akagi located in the inland Kanto plain in Japan. Fine (<2.1 μm) and coarse (2.1–11 μm) particles were collected by using an Andersen low-volume air sampler, and WSOC, organic carbon (OC), elemental carbon (EC), and ionic components were measured. The mean mass concentrations of the fine particles were 22.2 and 10.5 μg m^?3 at Maebashi and Akagi, respectively. The WSOC in fine particles accounted for a large proportion (83%) of total WSOC. The concentration of fine WSOC ranged from 1.2 to 3.5 μg-C m^?3 at Maebashi, rising from summer to fall. At Akagi, it rose from spring to summer, associated with the southerly wind from urban areas. The WSOC/OC ratio increased in summer at both sites, but the ratio at Akagi was higher, which we attributed to differences in primary emissions and secondary formation between the sites. The fine WSOC concentration was significantly positively correlated with concentrations of SO₄^2?, EC, and K⁺, and we inferred that WSOC was produced by photochemical reaction and caused by the combustion of both fuel and biomass. We estimated that SOA accounted for 11–30% of the fine particle mass concentration in this study, suggesting that SOA is a significant year-round component in fine particles.     

Sources of atmospheric particles over Australia

Total particle concentrations have been measured from ground level to about 6000 m over more than 100,000 km of flight path in the Australian region during seven separate excursions spread over three years. Median concentrations in maritime air masses below the lowest temperature inversion averaged about 220 cm⁻³ except in the vicinity of extensive coral reefs where the median concentration was 1590 cm⁻³ Average median concentrations were 160 cm⁻³ above temperature inversions in maritime air masses and 220 cm ⁻³ above temperature inversions in continental air masses. Median concentrations in the well-mixed lower layer of continental air masses averaged only 680 cm⁻³, far lower than that found by most other observers in tropical or temperate lands.Particle production by one of the smaller metropolitan areas at 4.10¹⁹ s⁻¹ was shown to exceed the estimates from all natural sources, indicating that particles resulting from human activities may often dominate the continental aerosol over much of Australia.     

Classification of multiple types of organic carbon composition in atmospheric particles by scanning transmission X-ray microscopy analysis

A scanning transmission X-ray microscope at the Lawrence Berkeley National Laboratory is used to measure organic functional group abundance and morphology of atmospheric aerosols. We present a summary of spectra, sizes, and shapes observed in 595 particles that were collected and analyzed between 2000 and 2006. These particles ranged between 0.1 and 12 μm and represent aerosols found in a large range of geographical areas, altitudes, and times. They include samples from seven different field campaigns: PELTI, ACE-ASIA, DYCOMS II, Princeton, MILAGRO (urban), MILAGRO (C-130), and INTEX-B. At least 14 different classes of organic particles show different types of spectroscopic signatures. Different particle types are found within the same region while the same particle types are also found in different geographical domains. Particles chemically resembling black carbon, humic-like aerosols, pine ultisol, and secondary or processed aerosol have been identified from functional group abundance and comparison of spectra with those published in the literature.     

基因工程的潜在影响及其对有机食品产业的冲击

基因工程的研究发展非常迅速，使其在农业和食品加工领域的应用成为不可避免，但其安全性问题在世界范围内引起了非常广泛的争议。从基因工程内涵和有机农业的要求及目标出发，讨论了基因工程的潜在影响及其对发展有机食品产业的冲击。认为有机农业运动面临的紧迫问题是尽快协调所有的行动方案来保证有机食品永远不涉及基因工程生物体。有机农业正面临基因工程的挑战，其发展的潜力是建立一个完全独立的有机食品市场。