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.     

Aqueous-phase secondary organic aerosol and organosulfate formation in atmospheric aerosols: a modeling study

We have examined aqueous-phase secondary organic aerosol (SOA) and organosulfate (OS) formation in atmospheric aerosols using a photochemical box model with coupled gas-phase chemistry and detailed aqueous aerosol chemistry. SOA formation in deliquesced ammonium sulfate aerosol is highest under low-NO(x) conditions, with acidic aerosol (pH = 1) and low ambient relative humidity (40%). Under these conditions, with an initial sulfate loading of 4.0 μg m(-3), 0.9 μg m(-3) SOA is predicted after 12 h. Low-NO(x) aqueous-aerosol SOA (aaSOA) and OS formation is dominated by isoprene-derived epoxydiol (IEPOX) pathways; 69% or more of aaSOA is composed of IEPOX, 2-methyltetrol, and 2-methyltetrol sulfate ester. 2-Methyltetrol sulfate ester comprises >99% of OS mass (66 ng m(-3) at 40% RH and pH 1). In urban (high-NO(x)) environments, aaSOA is primarily formed via reversible glyoxal uptake, with 0.12 μg m(-3) formed after 12 h at 80% RH, with 20 μg m(-3) initial sulfate. OS formation under all conditions studied is maximum at low pH and lower relative humidities (<60% RH), i.e., when the aerosol is more concentrated. Therefore, OS species are expected to be good tracer compounds for aqueous aerosol-phase chemistry (vs cloudwater processing).     

Identification of the mass spectral signature of organic aerosols from wood burning emissions

Throughout the winter months, the village of Roveredo, Switzerland, frequently experiences strong temperature inversions that contribute to elevated levels of particulate matter. Wood is used as fuel for 75% of the domestic heating installations in Roveredo, which makes it a suitable location to study wood burning emissions in the atmosphere in winter. An Aerodyne quadrupole aerosol mass spectrometer (Q-AMS) was used to characterize the composition of the submicrometer, non-refractory aerosol particles at this location during two field campaigns in March and December 2005. Wood burning was found to be a major source of aerosols at this location in winter. Organics dominated the composition of the aerosols from this source, contributing up to 85% of the total AMS measured mass during the afternoon and evening hours. Carbonaceous particle analysis showed that organic carbon composed up to 86% of the total carbon mass collected at evening times. Results from 14C isotope determination revealed that up to 94% of the organic mass came from non-fossil sources, which can be attributed mostlyto wood burning. The unique combination of off-line 14C isotope analysis and on-line aerosol mass spectrometry was used to identify periods during which organic mass was mainly from wood burning emissions and allowed for the identification of the AMS spectral signature of this source in the atmosphere. The identified ambient signature of wood burning was found to be very similar to the mass spectral signature obtained during the burning of chestnut wood samples in a small stove and also to the spectrum of levoglucosan. Particles from wood burning appeared to be composed of highly oxygenated organic compounds, and mass fragments 60, 73, and 137 have been suggested as marker fragments for wood burning aerosols. Mass fragment 44, which is used as a marker for oxygenated organic aerosols (OOA), contributed about 5% to the total organic signal from primary wood burning sources. The ratio of the organic mass emitted from wood burning to m/z 60 in Roveredo is 36. This ratio may be used to provide an estimate of the organic aerosol mass emitted from wood burning in other locations.     

Using proton transfer reaction mass spectrometry for online analysis of secondary organic aerosols

Proton-transfer-reaction mass spectrometry (PTR-MS) is a useful tool in ambient trace gas analysis, especially for the analysis of oxygenated volatile organic compounds (OVOC). Many OVOCs are produced during photooxidation of volatile organic compounds and contribute to both the gas phase and secondary organic aerosols (SOA). The inlet system of the PTR-MS instrument was modified to allow also for the measurement of the particulate phase of an aerosol with a high time resolution. The new inlet consists mainly of a denuder to strip off the gas phase, and a heater (120/150 degrees C) to vaporize the aerosol particles. This inlet system was tested with pinonic acid particles generated with a nebulizer and SOA particles formed during the photooxidation of 1,3,5-trimethylbenzene and alpha-pinene with NO(x) in a smog chamber. The performance of this new technique is discussed and the partitioning coefficients for the oxidation products are estimated.     

Sampling atmospheric carbonaceous aerosols using an integrated organic gas and particle sampler

Measurement of particle-bound organic carbon (OC) may be complicated by sampling artifacts such as adsorption of gas-phase species onto particles or filters or evaporation of semivolatile compounds off the particles. A denuder-based integrated organic gas and particle sampler (IOGAPS), specifically designed to minimize sampling artifacts, has been developed to sample atmospheric carbonaceous aerosols. IOGAPS is designed to first remove gas-phase chemicals via sorption to the XAD-coated denuder, and subsequently particles are trapped on a quartz filter. A backup sorbent system consisting of sorbent- (XAD-4 resin) impregnated filters (SIFs) was used to capture the semivolatile OC that evaporates from the particles accumulated on the upstream quartz filter. A traditional filter pack (FP) air sampler, which uses a single quartz filter to collect the particles, was employed for comparison in this study. Elemental and organic carbon were determined from filter punches by a thermal optical transmittance aerosol carbon analyzer. Field measurements show that there was no significant difference between the elemental carbon concentrations determined by the FP and IOGAPS, indicating that particle loss during the transit through the denuder tube was negligible. Compared with the OC determined by FP (3.9-12.6 microg of C/m3), the lower OC observed on the quartz filter in the IOGAPS (2.2-6.0 microg of C/m3) was expected because of the removal of gas-phase organics by the denuder. Higher semivolatile organic carbon (SVOC) on the backup SIFs during the night (1.24-8.43 microg of C/m3) suggests that more SVOC, emitted from primary sources or formed as secondary organic compounds, partitions onto the particles during the night because of the decreased ambient temperature. These data illustrate the utility of an IOGAPS system to more accurately determine the particle-bound OC in comparison to FP-based systems.     

Contribution of biomass burning to atmospheric polycyclic aromatic hydrocarbons at three European background sites

Radiocarbon analysis of atmospheric polycyclic aromatic hydrocarbons (PAHs) from three background areas in Sweden, Croatia, and Greece was performed to apportion their origin between fossil and biomass combustion. Diagnostic ratios of PAHs implied that wood and coal combustion was relatively more important in the northern European site, while combustion of fossil fuels was the dominant source of PAHs to the two central-southern European background sites. The radiocarbon content (delta14C) of atmospheric PAHs in Sweden ranged between -388 per thousand and -381 per thousand, while more depleted values were observed for Greece (-914 per thousand) and Croatia (-888 per thousand). Using a 14C isotopic mass balance model it was calculated that biomass burning contributes nearly 10% of the total PAH burden in the studied southern European atmosphere with fossil fuel combustion making up the 90% balance. In contrast, biomass burning contributes about 50% of total PAHs in the atmosphere at the Swedish site. Our results suggest that the relative contributions of biomass burning and fossil fuels to atmospheric PAHs may differ considerably between countries, and therefore, different national control strategies might be needed if a further reduction of these pollutants is to be achieved on a continental-global scale.     

NMR determination of total carbonyls and carboxyls: a tool for tracing the evolution of atmospheric oxidized organic aerosols

Nuclear magnetic resonance (NMR) spectroscopy is used to investigate the chemical composition of organic aerosol in terms of functional group distribution with a special focus on secondary organic aerosol (SOA) formation. The knowledge of the functional group composition is a benchmark for understanding how SOA components partition into the particulate phase and undergo chemical transformation. The paper presents a new chemical derivatization procedure coupled to proton NMR (1H NMR) analysis for the specific determination of total carbonylic groups in atmospheric aerosol samples, which couples with the procedure for determination of total carboxylic acid groups described in a previous work. A first deployment of the combined techniques for the analysis of PM10 samples collected in the Po Valley in the warm season shows that the concentration in the particulate phase of total carbonyls varies and covaries with respect to those of carboxylic acids and of less-oxidized functional groups. The proposed methodology provides the breakdown of the oxygenated fraction of the organic aerosol into major functional groups through well-established chemical methods and can be used to benchmark the more sensitive and widely used aerosol mass spectrometric techniques.     

Research Watch: Secondary organic aerosols

Air Quality.     

Primary sources and secondary formation of organic aerosols in beijing, china

Ambient aerosol samples were collected at an urban site and an upwind rural site of Beijing during the CAREBEIJING-2008 (Campaigns of Air quality REsearch in BEIJING and surrounding region) summer field campaign. Contributions of primary particles and secondary organic aerosols (SOA) were estimated by chemical mass balance (CMB) modeling and tracer-yield method. The apportioned primary and secondary sources explain 73.8% ± 9.7% and 79.6% ± 10.1% of the measured OC at the urban and rural sites, respectively. Secondary organic carbon (SOC) contributes to 32.5 ± 15.9% of the organic carbon (OC) at the urban site, with 17.4 ± 7.6% from toluene, 9.7 ± 5.4% from isoprene, 5.1 ± 2.0% from α-pinene, and 2.3 ± 1.7% from β-caryophyllene. At the rural site, the secondary sources are responsible for 38.4 ± 14.4% of the OC, with the contributions of 17.3 ± 6.9%, 13.9 ± 9.1%, 5.6 ± 1.9%, and 1.7 ± 1.0% from toluene, isoprene, α-pinene, and β-caryophyllene, respectively. Compared with other regions in the world, SOA in Beijing is less aged, but the concentrations are much higher; between the sites, SOA is more aged and affected by regional transport at the urban site. The high SOA loading in Beijing is probably attributed to the high regional SOC background (～2 μg m(-3)). The toluene SOC concentration is high and comparable at the two sites, implying that some anthropogenic components, at least toluene SOA, are widespread in Beijing and represents a major factor in affecting the regional air quality. The aerosol gaseous precursor concentrations and temperature correlate well with SOA, both affecting SOA formation. The significant SOA enhancement with increasing water uptake and acidification indicates that the aqueous-phase reactions are largely responsible SOA formation in Beijing.     

Uncertainties in modeling secondary organic aerosols: three-dimensional modeling studies in Nashville/western Tennessee

The formation of secondary organic aerosols (SOA) is simulated for the Nashville/western Tennessee domain using three recent SOA modules incorporated into the three-dimensional air quality model, CMAQ. The Odum/Griffin et al. and CMU/STI modules represent SOA absorptive partitioning into a mixture of primary and secondary particulate organic compounds (OC), with some differences in the formulation of the absorption process and the selection of SOA species and their precursors. Empirical representations based on measured laboratory SOA yields are used for condensable organic products in both these modules. The AEC module simulates SOA absorption into organic and aqueous particulate phases, and a representation based on an explicit gas-phase mechanism is used in the AEC module. Predicted SOA concentrations can vary by a factor of 10 or more. In general, the gas-phase mechanistic approach predicts a higher yield of SOA than those based on laboratory yields. There exist some differences in the two empirical modules despite their similar basis on experimental data. All three modules predict a dominance of SOA of biogenic origin as compared to SOA of anthropogenic origin. The causes for differences among the three SOA modules include the representation of terpenes, the mechanistic versus empirical representation of SOA-forming reactions, the identities of SOA, and the parameters used in the gas/particle partitioning calculations. Two sensitivity studies show that formation of water-soluble SOA and temperature dependence may be areas of key uncertainties affecting current models.     

Apportionment of primary and secondary organic aerosols in southern California during the 2005 study of organic aerosols in riverside (SOAR-1)

Ambient sampling was conducted in Riverside, California during the 2005 Study of Organic Aerosols in Riverside to characterize the composition and sources of organic aerosol using a variety of state-of-the-art instrumentation and source apportionmenttechniques. The secondary organic aerosol (SOA) mass is estimated by elemental carbon and carbon monoxide tracer methods, water soluble organic carbon content, chemical mass balance of organic molecular markers, and positive matrix factorization of high-resolution aerosol mass spectrometer data. Estimates obtained from each ofthese methods indicate that the organic fraction in ambient aerosol is overwhelmingly secondary in nature during a period of several weeks with moderate ozone concentrations and that SOA is the single largest component of PM1 aerosol in Riverside. Average SOA/OA contributions of 70-90% were observed during midday periods, whereas minimum SOA contributions of approximately 45% were observed during peak morning traffic periods. These results are contraryto previous estimates of SOAthroughout the Los Angeles Basin which reported that, other than during severe photochemical smog episodes, SOA was lower than primary OA. Possible reasons for these differences are discussed.     

Fractionation of stable isotope-labeled organic pollutants as a potential tracer of atmospheric transport processes

To test the potential for using stable isotope fractionation to examine the atmospheric transport of semivolatile organic compounds (SOCs), we conducted simplified distillation experiments in the laboratory and a tracer-release experiment using mixtures of stable isotope-labeled (D and 13C) and unlabeled SOCs. Perdeuterated phenanthrene and alpha-hexachlorocyclohexane were transported more slowly via air-water gas exchange in our laboratory experiments, resulting in significant isotope fractionation of perdeuterated/unlabeled compound mixtures. In contrast, isotope fractionation of 13C6-labeled SOCs was much lower. A field tracer-release study was then conducted by spiking a seawater retention pond with a mixture of D10-labeled, 13C2-labeled, and unlabeled phenanthrene and examining isotope fractionation of the mixture after air-water gas exchange. No preferential fractionation of D10-vs 13C2-labeled phenanthrene was observed in the pond water; however, greater fractionation of D10-vs 13C2-labeled phenanthrene was observed in air samples collected within a 1-100 m radius of the pond. Thus, stable isotope tracers may provide a means of examining the atmospheric transport and air-earth exchange rates of POPs in an environmental realistic setting.     

Characterization of water-soluble organic carbon in urban atmospheric aerosols using solid-state 13C NMR spectroscopy

Solid-state 13C nuclear magnetic resonance (NMR) spectroscopy has been used to investigate the distribution of carbon functional groups in urban Atlanta aerosol fine (PM2.5) particles. Carbonaceous aerosol particles comprise a significant fraction of the ambient particle mass and are environmentally significant as they may influence radiative and cloud-nucleating properties and can also produce adverse health effects upon inhalation. The water-soluble organic carbon (WSOC) fraction was extracted from multiple 24 h integrated high-volume quartz filter samples and further separated into recovered hydrophobic and hydrophilic fractions using an approach similar to that used to extract humic and fulvic acids from aqueous samples. Solid-state 13C NMR results indicate that WSOC in urban atmospheric aerosol particles is mostly aliphatic in nature (approximately 95% by C mass) with major contributions from alkyl and oxygenated alkyls (approximately 80%), carboxylic acid (approximately 10%), and aromatic functional groups (approximately 4%). The aromatic C is associated with the recovered hydrophobic fraction of WSOC. These spectra have been compared to the 13C NMR results obtained from Suwannee River humic acid and a fractionated biomass burning sample. WSOC, and more importantly, its recovered hydrophobic fraction, is found to be only qualitatively similar to aqueous humic material. The biomass burning sample is significantly different from urban Atlanta WSOC and is composed of substantial amounts of sugar derivatives and phenolic compounds, as expected. The NMR results demonstrate the potential of this technique to investigate aerosol WSOC composition and to study its variations with changes in parameters such aerosol sources.     

Multiphase chemical kinetics of NO3 radicals reacting with organic aerosol components from biomass burning

Multiphase reactions with nitrate radicals are among the most important chemical aging processes of organic aerosol particles in the atmosphere especially at nighttime. Reactive uptake of NO(3) by organic compounds has been observed in a number of studies, but the pathways of mass transport and chemical reaction remained unclear. Here we apply kinetic flux models to experimental NO(3) exposure studies. The model accounts for gas phase diffusion within a cylindrical flow tube, reversible adsorption of NO(3), surface-bulk exchange, bulk diffusion, and chemical reactions from the gas-condensed phase interface to the bulk. We resolve the relative contributions of surface and bulk reactions to the uptake of NO(3) by levoglucosan and abietic acid, which serve as surrogates and molecular markers of biomass burning aerosol (BBA). Applying the kinetic flux model, we provide the first estimate of the diffusion coefficient of NO(3) in amorphous solid organic matrices (10(-8)-10(-7) cm(2) s(-1)) and show that molecular markers are well-conserved in the bulk of solid BBA particles but undergo rapid degradation upon deliquescence/liquefaction at high relative humidity, indicating that the observed concentrations and subsequent apportionment of the biomass burning source could be significantly underestimated.     

A model evaluation of the NO titration technique to remove atmospheric oxidants for the determination of atmospheric organic compounds

Chemical artifact is a problem in the sampling of atmospheric organic species for a relatively long sampling period. In this study, we evaluated a technique for the removal of atmospheric oxidants with added NO during gas and aerosol sampling by theoretical approach using a Regional Atmospheric Chemistry Mechanism (RACM) model. The elimination of O3 in the sample air is regulated predominantly by the reaction of NO and O3 in all simulated cases. We found that, without any oxidant scavenger, OH and NO3 concentrations in the sampler can be kept high even when wall loss processes of radicals are taken into account The relatively high concentration of OH is mainly due to the production of HO(x) in the sample air via the decomposition of HO2NO2 and O3-olefin reactions, whereas NO3 is produced by the decomposition of N2O5. Addition of NO with appropriate concentrations was found to effectively reduce both OH and NO3 concentrations in the sampling devices. This study demonstrates that scavenging of OH and NO3 as well as O3 is important for the study of chemical speciation of organic compounds and that NO addition is a useful technique to eliminate these oxidants.     

Wintertime organic aerosols in Christchurch and Auckland, New Zealand: contributions of residential wood and coal burning and petroleum utilization

Wintertime PM10 samples from two New Zealand cities (Christchurch and Auckland) have been characterized using gas chromatography - mass spectrometry for biomass burning tracers, hopanes, n-alkanes, fatty acids, n-alkanols and sugars. The aerosol samples of Christchurch, which were heavily influenced by residential wood and coal burning, showed substantially higher ambient concentrations for most of the organic compounds than those of Auckland, where major sources of aerosols were vehicular emissions and sea-salt. Mass ratios between the biomass burning tracers studied were found to be significantly different (e.g., beta-sitosterol to nssK+ ratios were more than three times higher in Christchurch than in Auckland), although levoglucosan to nssK+ ratios were similar at the both sites. We also estimated, for the first time using stereochemical configurations of hopanes, that 60% of fossil fuel emissions came from petroleum utilization with the remaining 40% being from coal burning in Christchurch. In contrast, contribution of coal burning was negligible in Auckland. Moreover, contributions of most biomass burning tracers to organic carbon (OC) were significantly higher in Christchurch than in Auckland. On the other hand, saccharides (excluding levoglucosan) and hopanes accounted for larger fractions of OC in Auckland. This study demonstrates that intensive wood and coal burning can significantly affect organic aerosol composition in an urban environment.     

Alkyl amides and nitriles as novel tracers for biomass burning

The occurrence of n-alkanoic acids, amides, and nitriles in samples of aerosol particulate matter from Kuala Lumpur and Santiago suggests that emissions from cooking and biomass burning are the primary sources of these organic markers in the atmosphere. It is proposed that fatty acids react with ammonia during biomass burning or combustion to produce amides and nitriles, which can be applied as useful biomarker tracers. To test this hypothesis, nonadecanoic acid and hexadecanamide were used as reactants in hydrous pyrolysis experiments. These experiments produced amides and nitriles and indicated that ammonia is an essential agent in their formation. Thus amides and nitriles are of utility as indicators for input from combustion and biomass burning in the ambient atmosphere.