Organic Compounds In Atmospheric Aerosols Research Articles

Molecular characteristics and stable carbon isotope compositions of dicarboxylic acids and related compounds in wintertime aerosols of Northwest China

Dicarboxylic acids are one of the important water-soluble organic compounds in atmospheric aerosols, causing adverse effects to both climate and human health. More attention has therefore been paid to organic acids in aerosols. In this study, the molecular distribution and diurnal variations of wintertime dicarboxylic acids in a rural site of Guanzhong Plain, Northwest China, were explored. Oxalic acid (C2, day: 438.9 ± 346.8 ng m−3, night: 398.8 ± 392.3 ng m−3) is the most abundant compound followed by methylglyoxal (mGly, day: 207.8 ± 281.1 ng m−3, night: 222.9 ± 231.0 ng m−3) and azelaic (C9, day: 212.8 ± 269.1 ng m−3, night: 211.4 ± 136.7 ng m−3) acid. The ratios of C9/C6 and C9/Ph indicating that atmospheric dicarboxylic acids in winter in the region mainly come from biomass burning. Furthermore, secondary inorganic ions (NO3−, SO42−, and NH4+), relative humidity, liquid water content, and in-situ pH of aerosols are highly linearly correlated with C2, suggesting that liquid phase oxidation is an important pathway for the formation of dicarboxylic acids. The δ13C analysis of C2 suggested that lighter carbon isotope compositions tend to be oxidized to form aqueous-phase secondary organic aerosols (aqSOA), leading to the decay of 13C in aqSOA products rather than aerosol aging. This study provides a theoretical basis for the mechanism of formation of dicarboxylic acid.

Enhanced Nitrite Production from the Aqueous Photolysis of Nitrate in the Presence of Vanillic Acid and Implications for the Roles of Light-Absorbing Organics.

A prominent source of hydroxyl radicals (•OH), nitrous acid (HONO) plays a key role in tropospheric chemistry. Apart from direct emission, HONO (or its conjugate base nitrite, NO2-) can be formed secondarily in the atmosphere. Yet, how secondary HONO forms requires elucidation, especially for heterogeneous processes involving numerous organic compounds in atmospheric aerosols. We investigated nitrite production from aqueous photolysis of nitrate for a range of conditions (pH, organic compound, nitrate concentration, and cation). Upon adding small oxygenates such as ethanol, n-butanol, or formate as •OH scavengers, the average intrinsic quantum yield of nitrite [Φ(NO2-)] was 0.75 ± 0.15%. With near-UV-light-absorbing vanillic acid (VA), however, the effective Φ(NO2-) was strongly pH-dependent, reaching 8.0 ± 2.1% at a pH of 8 and 1.5 ± 0.39% at a more atmospherically relevant pH of 5. Our results suggest that brown carbon (BrC) may greatly enhance the nitrite production from the aqueous nitrate photolysis through photosensitizing reactions, where the triplet excited state of BrC may generate solvated electrons, which reduce nitrate to NO2 for further conversion to nitrite. This photosensitization process by BrC chromophores during nitrate photolysis under mildly acidic conditions may partly explain the missing HONO in urban environments.

Changes in Light Absorptivity of Molecular Weight Separated Brown Carbon Due to Photolytic Aging.

Brown carbon (BrC) consists of those organic compounds in atmospheric aerosols that absorb solar radiation and may play an important role in planetary radiative forcing and climate. However, little is known about the production and loss mechanisms of BrC in the atmosphere. Here, we study how the light absorptivity of BrC from wood smoke and secondary BrC generated from the reaction of ammonium sulfate with methylglyoxal changes under photolytic aging by UVA radiation in the aqueous phase. Owing to its chemical complexity, BrC is separated by molecular weight using size exclusion chromatography, and the response of each molecular weight fraction to aging is studied. Photolytic aging induced significant changes in the light absorptivity of BrC for all molecular weight fractions; secondary BrC was rapidly photoblenched, whereas for wood smoke BrC, both photoenhancement and photobleaching were observed. Initially, large biomass burning BrC molecules were rapidly photoenhanced, followed by slow photolysis. As a result, large BrC molecules dominated the total light absorption of aged biomass burning BrC. These experimental results further support earlier observations that large molecular weight BrC compounds from biomass burning can be relatively long-lived components in atmospheric aerosols, thus more likely to have larger impacts on aerosol radiative forcing and could serve as biomass burning tracers.

Towards the isolation and estimation of elemental carbon in atmospheric aerosols using supercritical fluid extraction and thermo-optical analysis

Air-starved combustion of biomass and fossil fuels releases aerosols, including airborne carbonaceous particles, causing negative climatic and health effects. Radiocarbon analysis of the elemental carbon (EC) fraction can help apportion sources of its emission, which is greatly constrained by the challenges in isolation of EC from organic compounds in atmospheric aerosols. The isolation of EC using thermo-optical analysis is however biased by the presence of interfering compounds that undergo pyrolysis during the analysis. EC is considered insoluble in all acidic, basic, and organic solvents. Based on the property of insolubility, a sample preparation method using supercritical CO2 and methanol as co-solvent was developed to remove interfering organic compounds. The efficiency of the method was studied by varying the density of supercritical carbon dioxide by means of temperature and pressure and by varying the methanol content. Supercritical CO2 with 10% methanol by volume at a temperature of 60 °C, a pressure of 350 bar and 20 min static mode extraction were found to be the most suitable conditions for the removal of 59 ± 3% organic carbon, including compounds responsible for pyrolysis with 78 ± 16% EC recovery. The results indicate that the method has potential for the estimation and isolation of EC from OC for subsequent analysis methods and source apportionment studies.

Size-resolved characterisation of organic compounds in atmospheric aerosols collected at Welgegund, South Africa

The organic fraction of atmospheric aerosols is 20 to 90 % of which only a small percentage has been chemically characterised. Two-dimensional gas chromatography with a time-of-flight mass spectrometer (GCxGC-TOFMS) is a powerful instrument used to chemically characterise organic compounds. Size-resolved characterisation and semi-quantification of ambient organic aerosol compounds were performed with a GCxGC-TOFMS for the first time in South Africa. Twenty-four-hour samples were collected for 1 year for three different size ranges. A combined total of 1056 different organic compounds could be tentatively characterised. The largest number of organic compounds tentatively identified was PM2.5–1 (particles in the size range 1–2.5 μm), while this size fraction also had the highest total number of normalised response factors (∑NRF). On average, 52, 26, 6, 13 and 3 % of species tentatively identified were oxygenated species, hydrocarbons, halogenated compounds, N-containing compounds and S-containing compounds, respectively. Oxygenated compounds were the most abundant species. Alkane and mono-aromatic species were the largest number of hydrocarbons tentatively identified with the highest ∑NRFs. The largest number of oxygenated species tentatively characterised were carboxylic acids and esters, while ether compounds had the highest ∑NRFs. Most of the halogenated compounds tentatively identified were chlorinated species with the highest ∑NRFs in two size fractions. Iodate species had a significantly higher ∑NRF in the PM2.5–1 size fraction. The largest number of N-containing species tentatively characterised with the highest ∑NRFs were amines. A small number of S-containing compounds with low ∑NRFs were tentatively identified. The major sources of organic compounds measured at Welgegund were considered to be biomass burning and air masses moving over the anthropogenically impacted source regions.

Comparison of abundances, compositions and sources of elements, inorganic ions and organic compounds in atmospheric aerosols from Xi'an and New Delhi, two megacities in China and India

Wintertime TSP samples collected in the two megacities of Xi'an, China and New Delhi, India were analyzed for elements, inorganic ions, carbonaceous species and organic compounds to investigate the differences in chemical compositions and sources of organic aerosols. The current work is the first time comparing the composition of urban organic aerosols from China and India and discussing their sources in a single study. Our results showed that the concentrations of Ca, Fe, Ti, inorganic ions, EC, PAHs and hopanes in Xi'an are 1.3–2.9 times of those in New Delhi, which is ascribed to the higher emissions of dust and coal burning in Xi'an. In contrast, Cl−, levoglucosan, n-alkanes, fatty alcohols, fatty acids, phthalates and bisphenol A are 0.4–3.0 times higher in New Delhi than in Xi'an, which is attributed to strong emissions from biomass burning and solid waste incineration. PAHs are carcinogenic while phthalates and bisphenol A are endocrine disrupting. Thus, the significant difference in chemical compositions of the above TSP samples may suggest that residents in Xi'an and New Delhi are exposed to environmental hazards that pose different health risks.Lower mass ratios of octadecenoic acid/octadecanoic acid (C18:1/C18:0) and benzo(a)pyrene/benzo(e)pyrene (BaP/BeP) demonstrate that aerosol particles in New Delhi are photochemically more aged. Mass closure reconstructions of the wintertime TSP indicate that crustal material is the most abundant component of ambient particles in Xi'an and New Delhi, accounting for 52% and 48% of the particle masses, respectively, followed by organic matter (24% and 23% in Xi'an and New Delhi, respectively) and secondary inorganic ions (sulfate, nitrate plus ammonium, 16% and 12% in Xi'an and New Delhi, respectively).

Thermal Desorption Comprehensive Two-Dimensional Gas Chromatography: An Improved Instrument for In-Situ Speciated Measurements of Organic Aerosols

The organic fraction is a major constituent of fine atmospheric particulate matter, though its chemical composition is complex and not well understood. This complexity presents an extreme analytical challenge and is well suited to analysis by comprehensive two-dimensional gas chromatography (GC × GC). This has recently been coupled to a thermal desorption aerosol gas (TAG) chromatograph instrument to provide improved in-situ, hourly measurement of speciated organic compounds in atmospheric aerosols (2D-TAG). The original 2D-TAG instrument utilized a flame ionization detector, dual-stage modulator, and a second-dimension column that proved to be thermally unstable under optimal analysis conditions, which limited compound identification, instrument robustness, and time resolution. In this paper, we address these shortcomings by demonstrating the successful integration of a time-of-flight mass spectrometer (TOFMS), development of a simplified hybrid thermo-pneumatic modulator, and incorporation of a more thermally stable secondary column. These improvements resulted in an instrument capable of providing detailed speciated information of organic tracer compounds in atmospheric aerosols in near real time.

Measurement of Aerosol Organic Compounds Using a Novel Collection/Thermal-Desorption PTR-ITMS Instrument

We report the development and characterization of a proton-transfer-reaction ion trap mass spectrometer for the speciated measurement of organic compounds in atmospheric aerosols and show results from its first field deployment. The instrument uses an aerosol collection inlet to accumulate aerosol mass followed by rapid thermal desorption to volatilize the organic compounds for in situ analysis. We have performed laboratory studies to characterize instrument performance and the instrument was deployed aboard a NOAA research vessel during the Texas Air Quality Study 2006/Gulf of Mexico Atmospheric Composition and Climate Study (TexAQS 2006/GoMACCS) in August–September 2006. The laboratory-determined detection limit for glutaric acid in mixed glutaric acid/NH 4 HSO 4 test aerosols was 0.22 ng collected mass, which corresponds to an estimated detection limit of 12 ng m−3 for a 10 min sample based on the instrument sample flow rate of 1.8 L min−1. During TexAQS 2006/GoMACCS, signals well above the detection limit were observed at a number of mass to charge ratios, mostly occurring during an extended period of active pollution photochemistry, but also including detection of possible primary emissions of aerosol-phase pyridine.

Quantification of Hourly Speciated Organic Compounds in Atmospheric Aerosols, Measured by an In-Situ Thermal Desorption Aerosol Gas Chromatograph (TAG)

The Thermal desorption Aerosol Gas chromatograph (TAG) is a recently developed instrument for the in-situ, hourly measurement of speciated organic compounds in atmospheric aerosols. This paper presents a method for the in-field calibration of this instrument, with the objective of providing quantitative concentrations for a large suite of low polarity organic compounds. A new collection and thermal desorption cell was developed that incorporates an injection port for in-situ calibrations with liquid standard mixtures. Two classes of injection standards, instrument tracking and auxiliary, provide the means to calibrate the instrument in the field for a wide range of compounds. A routinely injected tracking standard suite of compounds generates a time-dependent correction of detector drift through the course of a measurement study that accounts for the bulk of the change in response of the TAG instrument. Injection response data for the tracking standard is also used to measure instrument precision and limits of quantitation. Auxiliary standards extend the range of compounds calibrated through use of relative response factors. The accuracy of this in-situ calibration approach is assessed through comparisons of TAG analyzed reference filter punches to published NIST assay values. A subset of compound classes, alkanes and PAHs, are used to illustrate the method and provide a means of reducing an 11-day period of data collected in Riverside, CA during the fall of 2005.

Comprehensive two-dimensional gas chromatography coupled to time-of-flight mass spectrometry in the identification of organic compounds in atmospheric aerosols from coniferous forest

Comprehensive two-dimensional gas chromatography coupled to time-of-flight mass spectrometry (GC × GC–TOF–MS) was applied in the identification of organic compounds in atmospheric aerosols from coniferous forest. The samples were collected at Hyytiälä, Finland, as part of the QUEST campaign, in Spring 2003. Manual and automated search procedures were compared in the identification. An automated procedure is preferable when a large number of data files need to be processed; but manual search was more accurate with the present samples, where the number of compounds was large and most of the compounds of interest were present at trace level. Altogether, about 50 compounds were identified on the basis of mass spectra and linear retention indices. The identified compounds included oxidised monoterpenes, acyclic alkanes, alkenes, ketones and aldehydes, as well as a few alcohols, acids, and aromatic compounds.

An In-Situ Instrument for Speciated Organic Composition of Atmospheric Aerosols:Thermal DesorptionAerosolGC/MS-FID (TAG)

We introduce a new in-situ instrument, Thermal desorption Aerosol GC/MS-FID (TAG), capable of hourly measurements of speciated organic compounds in atmospheric aerosols. Aerosol samples are collected into a thermal desorption cell by means of humidification and inertial impaction. The sample is thermally desorbed and transferred with helium carrier gas into a gas chromatography (GC) column, with subsequent detection by both quadrupole mass spectrometer (MS) and a flame ionization detector (FID). The collection and analysis steps are automated, yielding around the clock speciation. This approach builds on the extensive body of knowledge available for quantification and source apportionment of organic aerosols from past research using filter-based GC/MS analyses, but it is the first instrument to achieve in-situ time resolved measurements for an essentially unlimited number of samples, making it possible to analyze changes in organic aerosol speciation over timescales ranging from hours to seasons.

Secondary organic compounds in atmospheric aerosols: speciation and formation mechanisms

Taking into account their atmospheric characteristics, generally under photochemical conditions, forested areas of Mediterranean countries constitute an appropriate environment to investigate the secondary organic aerosols. The objective of this study was to study in situ the aerosol composition, particularly in the photo-oxidation products of biogenic volatile organic compounds, taking into consideration anthropogenic inputs, and to explain how these compounds appear in the aerosols. Atmospheric particulate matter was collected at two sites: an Abies boressi forest in central Greece and at Giesta, a coastal-rural site in the centre of Portugal. The collected aerosol was extracted with solvents and characterised by gas chromatography and mass spectrometry. The detected secondary organics include alkene derivatives, oxo-, di- and monocarboxylic acids, oxy-aromatics, aza and thia arenes, and many terpene photo-oxidation products. This in situ experiment allowed confirming the presence of secondary constituents, which have been studied almost exclusively under simulated laboratory conditions. Some reaction pathways leading to the formation of compounds in the particulate phase from precursors are presented.

Hygroscopicity of Water-Soluble Organic Compounds in Atmospheric Aerosols: Amino Acids and Biomass Burning Derived Organic Species

Amino acids and organic species derived from biomass burning can potentially affect the hygroscopicity and cloud condensation activities of aerosols. The hygroscopicity of seven amino acids (glycine, alanine, serine, glutamine, threonine, arginine, and asparagine) and three organic species most commonly detected in biomass burning aerosols (levoglucosan, mannosan, and galactosan) were measured using an electrodynamic balance. Crystallization was observed in the glycine, alanine, serine, glutamine, and threonine particles upon evaporation of water, while no phase transition was observed in the arginine and asparagine particles even at 5% relative humidity (RH). Water activity data from these aqueous amino acid particles, except arginine and asparagine, was used to revise the interaction parameters in UNIQUAC functional group activity coefficients to give predictions to within 15% of the measurements. Levoglucosan, mannosan, and galactosan particles did not crystallize nor did they deliquesce. They existed as highly concentrated liquid droplets at low RH, suggesting that biomass burning aerosols retain water at low RH. In addition, these particles follow a very similar pattern in hygroscopic growth. A generalized growth law (Gf = (1 - RH/100)-0.095) is proposed for levoglucosan, mannosan, and galactosan particles.

Water uptake by particles containing humic materials and mixtures of humic materials with ammonium sulfate

Recent field studies show that a large fraction of the previously uncategorized organic compounds in atmospheric aerosols are polycarboxylic acids resembling the humic materials (HMs) in soil. The presence of these compounds may alter the water uptake and deliquescence characteristics of particles. We have measured the water uptake by pure HM and by mixed HM/ammonium sulfate particles as a function of relative humidity (RH). We find that the water uptake behavior varies with the type, source, and isolation method of the HM. Two of the three pure humic acids (HAs) and the fulvic acid (FA) studied here exhibited very little water uptake up to ∼90% RH, while the fourth material, HA from the Fluka chemical company, deliquesced at 70% RH and showed continuous water uptake to ∼90% RH. For comparison, water uptake by polyacrylic acids of two chain lengths and by phthalic acid were also measured. These species also took up small amounts of water over the range of RHs studied. Particle size and chain length had very little effect on water uptake. The mixed organic/ammonium sulfate particles took up a reduced amount of water relative to pure ammonium sulfate, with the exception of the Fluka HA. We modeled the water uptake of mixed particles assuming that ammonium sulfate and HM took up water independently, and results are consistent with the measured water uptake by mixed particles.