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1.
Measurements show that 20–60% of the carbon mass present in fine atmospheric particulate matter consists of water soluble organic compounds (WSOC). However, only 5–20% of this WSOC has been identified, mainly as dicarboxylic acids. Because of their high solubility in water, multifunctional secondary compounds derived from the gas-phase oxidation of volatile organic compounds (VOC) are suspected to be key contributors to the WSOC. To test this assumption, an estimate of aqueous uptake of secondary VOC was included in a highly detailed gas-phase mechanism which treats explicitly the formation of the secondary VOC from a set of representative primary species. Simulations were conducted for 2 scenarios, representing typical rural and urban areas. It was observed that the uptake of secondary VOC can lead to WSOC mass concentrations in the range of a few C m–3, in fairly good agreement with typical WSOC mass concentrations measured. Speciation of WSOC was found to be mainly as tri- or higher multifunctional hydroxy-carbonyl species and hydroxy-hydroperoxide-carbonyl species, in urban and rural environments, respectively. However, it was also found that taking into account only the absorption of secondary VOC does not bring the carboxylic acids mass concentration in agreement with measurements. An attempt was made to explain this discrepancy by introducing chemistry occurring within deliquescent aerosols.  相似文献   

2.
Atmospheric particles contain a myriad of organiccompounds, including many multifunctional,water-soluble organic compounds. Many of thesecompounds are postulated to be secondary of origin. This work investigates the possible precursors ofseveral classes of multifunctional, water-solublesecondary organic compounds by analyzing the pathwaysleading to their formation, based on known gas-phasereactions. The analysis is termed `retrosynthetic'due to the backward direction of the analysis, fromproducts to precursors. Pathways for multi-functionalcompounds were generated combinatorially, consideringthe formation of one functional group at a time.Many multifunctional organic compounds with carboxylicacid, carbonyl, and hydroxy functional groups werefound to be first- or second-generation products ofcommon anthropogenic and biogenic volatile organiccompounds such as alkanes, alkenes, aromatics, andcyclic alkenes. The estimated yields of water-solubleorganic compounds from primary precursors ranged fromless than 1% to over 10%, based on stoichiometricconsiderations. The SOA formation index, whichcombines the concepts of yields and rates, was used tocompare the feasibility of the retrosyntheticpathways. Many of the candidate pathways involve theisomerization reaction of alkoxy radicals andoxygenated intermediate products such asmonocarboxylic acids and hydroxyaldehydes.  相似文献   

3.
A detailed procedure using non-ionic macropourous XAD-8 and XAD-4 resins is presented for the isolation and fractionation of aerosol water-soluble organic compounds (WSOC) from aerosol samples. The procedure entails adsorption of WSOC fraction onto XAD-8 and XAD-4 resins, desalting of the adsorbed organic material with ultra-pure water, elution of the retained organic matter with 40% MeOH solution and freeze-drying. Due to resin’s different properties and to certain hydrophobic/hydrophilic interactions between the resin polymers and the organic matter, two major fractions were obtained; namely the XAD-8 and the XAD-4 eluates. The XAD-8 eluate, which accounts for 55–60% of total aerosol WSOC, is represented by partially acidic compounds with significant hydrophobic moieties. The XAD-4 fraction holds few conjugated systems and a higher content of hydrophilic structures with low molecular size, and accounts for 9% of total WSOC. The isolated WSOC sub-fractions were nearly free from inorganic species, and successful recoveries of organic matter from the resins were accomplished. With this procedure the XAD-8 eluate yields a mixture representative of those WSOC that are highly conjugated compounds in atmospheric aerosols. It also allows a successful characterisation of the organic material by advanced analytical techniques without the interference of inorganic species present in the original sample of atmospheric particles.  相似文献   

4.
In this contribution we present to our knowledge the first investigations of macromolecular, often called humic-like substances (HULIS) in cloud water samples and compare them with water-soluble extracts from atmospheric PM2.5, soils and waters to study its possible origin. Chemical analysis was done using high performance liquid chromatography (HPLC) coupled with UV and diode array detector, and HPLC coupled with ESI-MS (electrospray ionization mass spectrometer). The data have been treated by principle component analysis (PCA) and cluster analysis to state similarities and/or differences between different types of samples. Our results show that the content of organic and inorganic species is distinctly different in smaller and larger droplets suggesting varying origin. We conclude that smaller droplets are formed more from organic containing condensation nuclei (CCN) and larger droplets more from inorganic containing CCN organic compounds. Putting all experimental findings together we state that HULIS in cloud water—and consequently in particulate CCN precursors—are produced in an atmospheric polymerization process from low molecular weighted organics of different origin. Evidence is found that anthropogenic sources contribute to this pathway. Cloud drops may act as reactor in this HULIS formation process but more likely are gas-phase or gas-to-particle interactions.  相似文献   

5.
Processing of atmospheric organic matter by California radiation fogs   总被引：2，自引：0，他引：2  
Considerable effort has been put into characterizing the ionic composition of fogs and clouds over the past twenty-five years. Recently it has become evident that clouds and fogs often contain large concentrations of organic material as well. Here we report findings from a series of studies examining the organic composition of radiation fogs in central California. Organic compounds in these fogs comprise a major fraction of total solute mass, with total organic carbon sometimes reaching levels of several tens of mg/L. This organic matter is comprised of a wide variety of compounds, ranging from low molecular weight organic acids to high molecular weight compounds with molecular masses approaching several hundred to a thousand g/mole. The most abundant individual compounds are typically formic acid, acetic acid, and formaldehyde. High concentrations are also observed of some dicarboxylic acids (e.g., oxalate) and dicarbonyls (e.g., glyoxal and methylglyoxal) and of levoglucosan, an anhydrosugar characteristically emitted by biomass combustion. Many other compounds have been identified in fog water by GC/MS, including long chain n-alkanoic acids, n-alkanes, PAH, and others, although these compounds typically comprise a total of only a few percent of fog TOC. Measurements of fog scavenging of organic and elemental carbon reveal preferential scavenging of organic carbon. Tracking of individual organic compounds utilized as source type markers suggests the fogs differentially scavenge carbonaceous particles from different source types, with more active processing of wood smoke than vehicle exhaust. Observations of high deposition velocities of fog-borne organic carbon, in excess of 1 cm/s, indicate that fogs in the region represent an important mechanism for cleansing the atmosphere of pollution.  相似文献   

6.
The average composition and seasonal variations of atmospheric organic particulates with respect to n-alkanes, n-alkanoic acid, polycyclic aromatic hydrocarbon (PAHs), and nitrated polycyclic aromatic hydrocarbons (N-PAHs) were determined at the biggest municipal waste landfill in Algeria located in Oued Smar, 13 km east of downtown Algiers. Samplings were carried out from August 2002 to February 2003, and organic compounds adsorbed in air particles having an aerodynamic diameter lower than 10 μm (PM10) were characterized using gas chromatography coupled with mass spectrometric detection (GC/MSD). Total concentrations ranged from 828 to 11,068 ng per cubic meter of air for n-alkanes, from 1714 to 21,710 ng per cubic meter of air for n-alkanoic acids, from 13 to 212 ng per cubic meter of air for PAHs and from 93 to 205 pg per cubic meter of air for N-PAHs. n-Alkanoic acids accounted for 85 and 56% of the total organic composition of the aerosol measured in summer and winter, respectively, were the biggest fraction. The distribution profiles and the diagnostic ratios of some marker compounds allowed to identify the combustion and microbial activity as the major sources of particulate organic pollutants associated with direct emission. The year-time dependence of organic fraction content of aerosol in Oued Smar appeared to be related to average meteorological conditions as well as variability of rate and nature of materials wasted into the landfill.  相似文献   

7.
The presence of amino acids in atmospheric precipitation and aerosols has been noted for many years, yet relatively little is known about these or other nitrogen containing organic compounds in the atmosphere. Marine and continental rainwater analyses indicate that atmospheric aerosols, and subsequently atmospheric precipitation, may contain substantial levels of free and combined amino acids. The most likely source of amino N in the remote marine atmosphere appears to be the injection of proteinaceous material through the action of bursting bubbles at the sea-air interface or the long range transport from terrestrial sources. The capacity of these substrates to undergo photooxidation and photodegradation in the atmosphere to simpler species, such as ammonium ions, carboxylic acids, and for the S containing amino acids, oxidized forms of sulfur, has received little attention from atmospheric chemists. The photochemistry of covalently bound amino groups, particularly as found in peptides and amino acids, is discussed here with the purpose of summarizing what is known of their occurrence and their possible importance to atmospheric chemistry.  相似文献   

8.
Total suspended particles (TSP), collected during June 2002 to July 2003 in Guangzhou, a typical economically developed city in South China, were analyzed for the organic compound compositions using gas chromatography–mass spectrometry (GC/MS). Over 140 organic compounds were detected in the aerosols and grouped into different classes including n-alkanes, hopanoids, polycyclic aromatic hydrocarbons, alkanols, fatty acids, dicarboxylic acids excluding oxalic acid, polyols/polyacids, lignin products, phytosterols, phthalates and water-soluble sugars. The total amounts of the identified organic compounds including unresolved complex mixture (UCM) ranged from 3112 ng/m3 in spring to 5116 ng/m3 in winter, comprising on seasonal average 2.8% of TSP. Primary organic compounds peaked in winter although there are no heating systems burning fuels in Guangzhou. The highest saccharide levels occurred in fall due to agricultural activities. This study demonstrated that utilization of fossil fuels, biomass burning, soil resuspension and plastic/refuse burning are the major contributors to the identified organic compounds in the urban atmosphere of South China.  相似文献   

9.
《Atmospheric Research》2008,87(3-4):249-260
The average composition and seasonal variations of atmospheric organic particulates with respect to n-alkanes, n-alkanoic acid, polycyclic aromatic hydrocarbon (PAHs), and nitrated polycyclic aromatic hydrocarbons (N-PAHs) were determined at the biggest municipal waste landfill in Algeria located in Oued Smar, 13 km east of downtown Algiers. Samplings were carried out from August 2002 to February 2003, and organic compounds adsorbed in air particles having an aerodynamic diameter lower than 10 μm (PM10) were characterized using gas chromatography coupled with mass spectrometric detection (GC/MSD). Total concentrations ranged from 828 to 11,068 ng per cubic meter of air for n-alkanes, from 1714 to 21,710 ng per cubic meter of air for n-alkanoic acids, from 13 to 212 ng per cubic meter of air for PAHs and from 93 to 205 pg per cubic meter of air for N-PAHs. n-Alkanoic acids accounted for 85 and 56% of the total organic composition of the aerosol measured in summer and winter, respectively, were the biggest fraction. The distribution profiles and the diagnostic ratios of some marker compounds allowed to identify the combustion and microbial activity as the major sources of particulate organic pollutants associated with direct emission. The year-time dependence of organic fraction content of aerosol in Oued Smar appeared to be related to average meteorological conditions as well as variability of rate and nature of materials wasted into the landfill.  相似文献   

10.
The influence of surface tension on the formation of secondary organic aerosol (SOA) is investigated in this study using a size-dependent absorptive partitioning model. A theoretical framework is offered to estimate the surface tension of multi-component aerosols consisting of organic compounds and water. The size-dependent influence of surface tension on the absorptive partitioning of semi-volatile organic compounds is examined via numerical simulations of systems of representative pre-existing aerosol (PA) components and semi-volatile organic compounds that have been observed to constitute SOA. Results indicate that if nonpolar organic species constitute a significant fraction of the PA, the Kelvin effect on SOA formation may be negligible. However, if PA is dominated by polar organic compounds, the Kelvin effect on SOA formation is significant when the PA initial diameter is smaller than approximately 200 nm. If the PA is an aqueous aerosol, the Kelvin effect on SOA formation is most important. A simplified computational scheme for estimation of the Kelvin effect is developed in this study and feasibly could be coupled into three-dimensional air quality models that simulate SOA formation. Available observations also suggest that future modeling and analysis of SOA formation may need to consider the Kelvin effect. Concrete testing of the purely theoretical model presented here requires carefully designed observations that examine the phase distribution of secondary organic compounds between the gas phase and aerosol particles small enough to be affected by surface tension.  相似文献   

11.
During the ACE-Asia field campaign, 41 aerosol filter samples were obtained by airborne sampling over the ocean to the north, south and west of Japan, generally under conditions of outflow from the Asian continent. These samples were analyzed for their water-soluble chemical components, particularly organic species. Suites of inorganic anions, carbohydrates, organic acids and metallic elements were identified and quantified (21 distinct species). Simultaneously, measurements were made of the aerosol hygroscopicity and light scattering. A factor analysis performed on the compositional data identified several sources for the aerosols sampled during the field campaign. Regression of the light-scattering data onto tracers for each of these factors suggests that the aerosol light scattering could be largely attributed to three of these factors: anthropogenic emissions, biomass burning, and soil dust. Similarly, the aerosol hygroscopicity was largely consistent with an empirical mixing model based on past measurements of the hygroscopicity of these individual aerosol types. Limited size-resolved , aerosol composition measurements were also obtained and suggested different sources for various chemical species.  相似文献   

12.
In a standard reference air dust (NIST 1648 – urban particulate matter) as well as in airborne particulate matter collected in German urban and rural areas (Dortmund, Sauerland) 10% and more of the organic carbon can be attributed to macromolecular substances like humic and fulvic acids (HA, FA). Indirect evidence for the presence of humin was also obtained. HA and FA extracted from NIST 1648 and other urban and rural atmospheric particles using 0.1 m NaOH and isolated by ion-exchangers were characterized by their molecular-size distribution applying multistage ultrafiltration, their carbon content and their UV/VIS, Fourier-transformed infrared (FTIR) and nuclear magnetic resonance (1H-NMR) spectra. Summarizing, the structural studies exhibit that these humic-like substances (HULIS) contained in air dust samples are small in their molecular size and rich in aliphatic and carbohydrate substructures compared to HA and FA from soils and aquatic systems.  相似文献   

13.
Water-soluble dicarboxylic acids (DCAs), ketoacids, and α-dicarbonyls in the marine aerosol samples collected over the Southern Ocean and western Pacific Ocean were determined. Oxalic acid was the most abundant species, followed by malonic acid and then succinic acid. It is suggested that aerosol concentrations of the organics over the Southern Ocean in this work represent their global background levels. Over the Southern Ocean, total concentrations of DCAs ranged from 2.9 to 7.2 ng m−3 (average: 4.5 ng m−3), ketoacids from 0.14 to 0.40 ng m−3 (av.: 0.28 ng m−3), and dicarbonyls from 0.06 to 0.29 ng m−3 (av.: 0.11 ng m−3). Over the western Pacific, total concentrations of DCAs ranged from 1.7 to 170 ng m−3 (av.: 60 ng m−3), ketoacids from 0.08 to 5.3 ng m−3 (av.: 1.8 ng m−3), and dicarbonyls from 0.03 to 4.6 ng m−3 (av.: 0.95 ng m−3). DCAs over the western Pacific have constituted a large fraction of organic aerosols with a mean DCAs-C/TC (total carbon) of 7.0% (range: 0.59–14%). Such a high value was in contrast to the low DCAs-C/TC (av.: 1.8%; range: 0.89–4.0%) for the Southern Ocean aerosols. Based on the relative abundances and latitudinal distributions of these organics, we propose that long-range atmospheric transport is more important over the western Pacific Ocean, in contrast, in situ photochemical production is more significant over the Southern Ocean although absolute concentrations of the organics are much lower.  相似文献   

14.
Partitioning of semivolatile organic compounds between gas, organic aerosol, and aqueous aerosol phases has been described in atmospheric models using Raoult’s Law and/or Henry’s Law, with activity coefficients accounting for nonideal behavior in the aerosol solutions. Raoult’s Law and Henry’s Law are thermodynamically consistent with each other as long as the parameters defining their different reference states are accurately known. Unfortunately, saturation vapor pressures, Henry’s law constants, and activity coefficients for organic aerosol compounds must typically be estimated. As a result, thermodynamic inconsistencies can arise when using Raoult’s and Henry’s Law approaches together due to errors in estimation methods. A test of predicted partitioning parameters for representative semivolatile organics suggests overall errors of at least an order of magnitude. Box model simulations with a simplified partitioning scenario demonstrate that these estimation errors can significantly alter partitioning for many compounds and, more importantly, that thermodynamic inconsistencies will lead to even greater errors than those due solely to uncertain parameters. To avoid these errors, a common reference state should be used to define equilibrium among all phases, improved estimation methods and measurements should continue to be pursued, and alternative reference states that better represent typical organic aerosol mixtures should be explored.  相似文献   

15.
The solvent-extractable organic compounds of atmospheric PM10 samples, collected over two years beginning in 2003 at urban and suburban sites of Beijing, were characterized using gas chromatography–mass spectrometry (GC–MS). The elemental carbon (EC) contents were determined and ranged from 4.3 to 42 μg m− 3. Organic compounds in total extracts were identified and included unresolved complex mixture (UCM) and series of n-alkanes, n-alkanols, n-alkanoic acids, polycyclic aromatic hydrocarbons (PAHs); saccharides, alkanedioic acids, steroids, and other biomarkers and source tracers. The seasonal variations of their relative abundances are discussed. The abundance order for the major molecular classes in the particulate organic matter (POM) was the following: UCM > saccharides > n-alkanoic acids >n-alkanes > n-alkanols > PAHs > hydroxy-PAHs > other biomarker tracers. Based on the genetic significance of the molecular tracers, the dominant sources of POM are proposed for the two sampling sites. The emissions from fossil fuel use (both coal and petroleum products), biomass combustion, other pyrolysis sources, higher plant wax, and secondary products contribute > 98.0% of the POM mass. The fossil fuel use (average = 65% of POM) is the largest contributor and derives mainly from vehicular traffic.  相似文献   

16.
The atmospheric processing by ozone of peptide-containing mixed particles was investigated as proxies for biogenic and sea spray primary organic aerosol. Reactions were performed in a flow reactor and particle composition was monitored by photoelectron resonance capture ionization aerosol mass spectrometry. Mixed particles containing dipeptides in a saturated organic matrix of stearic and palmitic acids showed no reaction under ozonolysis at exposure levels of 2.5 × 10−4 atm s O3. However reactions of mixed particles of a dipeptide (Leu-Leu) in an unsaturated matrix (oleic acid) under the same conditions resulted in a rapid loss of the peptide ion signal, as well as the carrier matrix, and appearance of a number of ion signals corresponding to secondary products. High molecular weight imides and amides have been identified corresponding to possible reactions of ozonolysis products and reactive intermediates (i.e. aldehydes, stabilized Criegee intermediates). Additionally, tautomerisation of the imides to enamines in the particle phase is postulated, with ozonolysis of the enamine followed by regioselective decomposition of the primary ozonide to form an amide whereby the peptide incorporates an aldehydic group at the N-terminus. The same general reactivity pattern was observed for mixed particles of diglycine and oleic acid. This behavior was not observed in solution phase experiments, where the tautomerisation favors the more stable imine form, indicating that particulate phase reactions of this nature may be dependent on the specific particle physical properties. The implications of this chemistry with respect the atmospheric aging of cell-derived organic aerosol are discussed.  相似文献   

17.
Ambient concentrations of isoprene and several of its atmospheric oxidation productsmethacrolein, methylvinyl ketone, formaldehyde, formic acid, acetic acid, and pyruvic acid-were measured in a central Pennsylvania deciduous forest during the summer of 1988. Isoprene concentrations ranged from near zero at night to levels in excess of 30 ppbv during daylight hours. During fair weather periods, midday isoprene levels normally fell in the 5–10 ppbv range. Methacrolein and methylvinyl ketone levels ranged from less than 0.5 ppbv to greater than 3 ppbv with average midday concentrations in the 1 to 2 ppbv range. The diurnal behavior of formaldehyde paralleled that of isoprene with ambient concentrations lowest (1 ppbv) in the predawn hours and highest (>9.0 ppbv) during the afternoon. The organic acids peaked during the midday period with average ambient concentration of 2.5, 2.0, and 0.05 ppbv for formic, acetic, and pyruvic acid, respectively. These data indicate that oxygenated organics comprise a large fraction of the total volatile organic carbon containing species present in rural, forested regions of the eastern United States. Consequently, these compounds need to be included in photochemical models that attempt to simulate oxidant behavior and/or atmospheric acidity in these forested regions.  相似文献   

18.
In this study the chemical nature of the bulk of water soluble organic compounds in fine atmospheric aerosol collected during summer 1998 at the Jungfraujoch, Switzerland (3580 m asl) is characterised. The mass concentration of water soluble organic substances was similar to those of major inorganic ions, and the water soluble organic matter was found to be composed of two main fractions: (i) highly polyconjugated, acidic compounds with a varying degree of hydrophobicity and (ii) slightly polyconjugated, neutral and very hydrophilic compounds. The contribution of both fractions to the total water soluble organic carbon was about 50%. Separation into individual components was impossible either by HPLC or capillary electrophoresis which indicates the presence of a high number of chemically similar but not identical species. Results obtained by ultrafiltration and HPLC-MS have shown that the molecular weights are of the order of several hundreds. Most of the protonation constants for the acidic compounds determined by capillary electrophoresis were in the range 104–107.  相似文献   

19.
随着工业、交通运输业迅猛发展及人口的剧增,广州、香港和澳门的大气环境质量越来越引起人们的关注。对该地区挥发性有机污染物（ＶＯＣｓ）和气溶胶中半挥发及不易挥发的有机污染物进行的初步研究表明,大气环境中有机污染物主要是苯系物的ＶＯＣｓ、多环芳烃（ＰＡＨｓ）和正构烷烃类。一些分子标志物,如β－胡萝卜烷、正构烷烃及荧蒽／芘、间四联苯／荧蒽、不同环数多环芳烃分布等参数,是比较有效的有机污染源判别指标  相似文献   

20.
Abstract This paper describes the effect of the presence of water-soluble organic compounds (WSOC) in aerosol particles on the aerosol critical supersaturation as defined by the Köhler theory and on cloud condensation nuclei (CCN) number concentration. Taking into account both the soluble mass increase and the surface tension depression due to WSOC, we calculated a substantial decrease of the aerosol critical supersaturation, which results in a large increase in CCN number concentration. CCN supersaturation spectra were computed for three different aerosol types: marine, rural and urban. The increase of CCN number concentration in the presence of WSOC (with respect to the case when only the inorganic aerosol compounds are considered) varies with aerosol type, with an increase up to 13% in the marine case, up to 97% in the rural case, and up to 110% in the urban case, for the supersaturation range typical of atmospheric conditions.  相似文献   

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