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.     

Electrostatic sampler for semivolatile aerosols: chemical artifacts

Electrostatic precipitators (ESPs) show promise as an alternative sampling method for semivolatile aerosols because they are less susceptible to adsorptive and evaporative artifacts than filter based methods. However, the corona discharge may after the chemical composition of a sampled aerosol. Chemical artifacts associated with electrostatic precipitation of semivolatile aerosols were investigated in the laboratory. ESPs and filters sampled both particles and vapors of alkanes, polycyclic aromatic hydrocarbons, and alkenes across varying concentrations. Gravimetric measurements between the two sampling methods were well correlated. Ozone generated by the ESP corona was the primary cause of alkene reactions in the gas phase. Particles collected within the corona region were vulnerable to irradiation by corona ions overtime. Particles collected outside the corona region did not react. Vapors passing through the corona reacted to a lesser extent. Vapors captured after passing through the ESP reacted with ozone that was not removed by the vapor trap. Chemical speciation of highly reactive compounds (i.e., alkenes or other compounds with relatively short half-lives outdoors) is not appropriate with ESPs. Electrostatic precipitation of these compounds is appropriate, however, when total organic carbon is of interest as the ESP does not alter the amount of mass measured gravimetrically. ESPs can make accurate measurements of more persistent semivolatile compounds, such as alkanes and PAHs.     

Gas/solid partitioning of semivolatile organic compounds (SOCs) to air filters. 3. An analysis of gas adsorption artifacts in measurements of atmospheric SOCs and organic carbon (OC). WHen using teflon membrane filters and quartz fiber filters

Adsorption of gaseous semivolatile organic compounds (SOCs) onto the filter(s) of a filter/sorbent sampler is a potential source of measurement error when determining specific SOCs as well as organic carbon (OC) levels in the atmosphere. This work examines partitioning to both Teflon membrane filters (TMFs) and quartz fiber filters (QFFs) for purposes of predicting the magnitude of the compound-dependent gas adsorption artifact as a function of various sampling parameters. The examination is based on values of Kp,face (m3 cm(-2)), the gas/filter partition coefficient expressed as [ng sorbed per cm2 of filter face]/[ng per m3 in the gas phase]. Values of Kp,face were calculated based on literature values of the gas/solid partition coefficient Kp,s [ng sorbed per m2 of filter]/[ng per m3 in gas phase] for the adsorption of various polycyclic aromatic hydrocarbons (PAHs), polychlorinated dibenzodioxins (PCDDs), and polychlorinated dibenzofurans (PCDFs) to TMFs, and for the adsorption of PAHs to QFFs. At relative humidity (RH) values below approximately 50%, the Kp,face values for PAHs are lower on TMFs than on ambient-backup QFFs. The gas adsorption artifact will therefore be lower for PAHs with TMFs than with QFFs under these conditions. In the past, corrections for the gas/filter adsorption artifact have been made by using a backup filter, and subtracting the mass amount of each compound found on the backup filter from the total (particle phase + sorbed on filter) amount found on the front filter. This procedure assumes that the ng cm(-2) amounts of each SOC sorbed on the front and backup filters are equal. That assumption will only be valid after both filters have reached equilibrium with each of the gaseous SOCs in the incoming sample air. The front filter will reach equilibrium first. The minimum air sample volume Vmin,f+b required to reach gas/filter sorption equilibrium with a pair of filters is 2Kp,face Afilter where Afilter (cm2) is the per-filter face area. Kp,face values, and therefore Vmin,f+b values, depend on the compound, relative humidity (RH), temperature, and filter type. Compound-dependent Vmin,f+b values are presented for PAHs and PCDD/Fs on both TMFs and QFFs. Compound-dependent equations which give the magnitude of the filter adsorption artifact are presented for a range of different sampling arrangements and circumstances. The equations are not intended for use in actually correcting field data because of uncertainties in actual field values of relevant parameters such as the compound-dependent Kp,face and gas/particle Kp values, and because of the fact that the equations assume ideal step-function chromatographic movement of gas-phase compounds through the adsorbing filter. Rather, the main utility of the equations is as guidance tools in designing field sampling efforts that utilize filter/sorbent samplers and in evaluating prior work. The results indicate that some backup-filter-based corrections described in the literature were carried out using sample volumes that were too small to allow proper correction for the gas adsorption artifactfor some specific SOCs of interest. Similar conclusions are reached regarding artifacts associated with the measurement of gaseous and particulate OC.     

Effects of dilution on fine particle mass and partitioning of semivolatile organics in diesel exhaust and wood smoke

Experiments were conducted to examine the effects of dilution on fine particle mass emissions from a diesel engine and wood stove. Filter measurements were made simultaneously using three dilution sampling systems operating at dilution ratios ranging from 20:1 to 510:1. Denuders and backup filters were used to quantify organic sampling artifacts. For the diesel engine operating at low load and wood combustion, large decreases in fine particle mass emissions were observed with increases in dilution. For example, the PM2.5 mass emission rate from a diesel engine operating at low load decreased by 50% when the dilution ratio was increased from 20:1 to 350:1. Measurements of organic and elemental carbon indicate that the changes in fine particle mass with dilution are caused by changes in partitioning of semivolatile organic compounds. At low levels of dilution semivolatile species largely occur in the particle phase, but increasing dilution reduces the concentration of semivolatile species, shifting this material to the gas phase in order to maintain phase equilibrium. Emissions of elemental carbon do not vary with dilution. Organic sampling artifacts are shown to vary with dilution because of the combination of changes in partitioning coupled with adsorption of gas-phase organics by quartz filters. The fine particle mass emissions from the diesel engine operating at medium load did not vary with dilution because of the lower emissions of semivolatile material and higher emissions of elemental carbon. To measure partitioning of semivolatile materials under atmospheric conditions, partitioning theory indicates that dilution samplers need to be operated such that the diluted exhaust achieves atmospheric levels of dilution. Too little dilution can potentially overestimate the fine particle mass emissions, and too much dilution (with clean air) can underestimate them.     

Phase and size distribution of polycyclic aromatic hydrocarbons in diesel and gasoline vehicle emissions

Emission measurements were obtained for a variety of military vehicles at Hill Air Force Base (Ogden, UT) in November 2000 as part of a Strategic Environmental Research and Development Program. Aircraft ground support equipment vehicles using gasoline, diesel, and JP8 fuels were tested using chassis dynamometers under predetermined load. The exhaust from the tested vehicle was passed to a dilution tunnel where it was diluted 30-40 times and collected using Micro-Orifice Uniform Deposit Impactor (MOUDI) fitted with aluminum substrates, an XAD-coated annular denuder, and a filter followed by a solid adsorbent. All MOUDI substrates were analyzed for mass and for organic and elemental (EC) carbon by the thermal/optical reflectance method and for polycyclic aromatic hydrocarbons (PAHs) by GC/MS. Black carbon was measured with a photoacoustic instrument. The denuder and filter/solid adsorbent samples were analyzed for semivolatile PAH. Overall, there is more mass and higher EC contribution when the vehicle is run under higher load in comparison with the low load. However, older vehicles generally show more mass and EC emissions than newer vehicles, and there is a shift toward smaller particle sizes for the low load, which is most pronounced for newer vehicles. The particle-associated semivolatile PAHs and nonvolatile four-through six-ring PAHs are present predominantly on the submicron particles collected on MOUDI stages 0.1-0.18, 0.18-0.32, and 0.32-0.56 microm. For the low-load runs, the distribution of PAHs seems to be shifted toward smaller size particles. The gas-particle phase distribution of semivolatile PAHs depends also on the engine loading. For idle, not only are the more volatile two- and three-ring PAHs, from naphthalene to dimethylphenanthrenes, retained on the denuder portion, but also less volatile four-ring PAHs, such as fluoranthene and pyrene, are retained by the denuder at the 80-90% range, which implies that they are present predominantly in the gas phase. In contrast, for engines under high loads, a much larger portion of three- and four-ring PAHs are partitioned to the particle phase.     

Hydrocarbon condensation in heavy-duty diesel exhaust

The semivolatile mass fraction of diesel exhaust particles was studied using size-resolved on-line techniques (DMA-ELPI; TDMA-ELPI). The average density of the semivolatile liquid on the particles was measured to be approximately 0.8 g/cm3. The measured size resolved values of mass transfer imply that condensation, or diffusion-limited mass transfer, plays a major role in driving the volatile matter to the diesel exhaust particles. The measured mass change values correspond to highly size dependent mass fractions for the semivolatile component, ranging from approximately 20-80%. Integrated over particle size distribution, the volatile mass fractions were 25 and 45% for the two load points studied. Calculation, based on the measured particle properties, indicates that only 10% volatile mass fraction could be explained by monolayer adsorption. The size resolved changes in particle effective density, fractal dimension, volatile mass fractions and mass are all in agreement with theoretical considerations of condensation.     

Reactions of semivolatile organics and their effects on secondary organic aerosol formation

Secondary organic aerosol (SOA) constitutes a significant fraction of total atmospheric particulate loading, but there is evidence that SOA yields based on laboratory studies may underestimate atmospheric SOA. Here we present chamber data on SOA growth from the photooxidation of aromatic hydrocarbons, finding that SOA yields are systematically lower when inorganic seed particles are not initially present. This indicates that concentrations of semivolatile oxidation products are influenced by processes beyond gas-particle partitioning, such as chemical reactions and/or loss to chamber walls. Predictions of a kinetic model in which semivolatile compounds may undergo reactions in both the gas and particle phases in addition to partitioning are qualitatively consistent with the observed seed effect, as well as with a number of other recently observed features of SOA formation chemistry. The behavior arises from a kinetic competition between uptake to the particle phase and reactive loss of the semivolatile product. It is shown that when hydrocarbons react in the absence of preexisting organic aerosol, such loss processes may lead to measured SOA yields lower than would occur under atmospheric conditions. These results underscore the need to conduct studies of SOA formation in the presence of atmospherically relevant aerosol loadings.     

Development and evaluation of a personal particulate organic and mass sampler

Accurate measurement of personal exposure to particulate matter and its constituents requires samplers that are accurate, compact, lightweight, inexpensive, and convenient to use. The personal particulate organic and mass sampler (PPOMS) has been developed to meet these criteria. The PPOMS uses activated carbon-impregnated foam as a combined 2.5-microm size-selective inlet and denuder for assessment of fine particle mass and organic carbon. Proof of the PPOMS concept has been established by comparing mass and organic carbon in particles collected with collocated samplers in Seattle, at a central outdoor site, and in residences. Daily particulate mass concentrations averaged 10.0 +/- 5.2, 12.0 +/- 5.3, and 11.2 +/- 5.1 microg m(-3) for the Federal Reference Method, the Harvard Personal Exposure Monitor, and the PPOMS, respectively, for 10 24-h sampling periods. During a series of PM2.5 indoor organic carbon (OC) measurements from single quartz filters, the apparent indoor OC averaged 7.7 +/- 0.8 microg of C m(-3), which was close to the indoor PM2.5 mass from collocated Teflon filters (7.3 +/- 2.3 microg of C m(-3)), indicating the presence of a large positive OC artifact. In collocated measurements, the PPOMS eliminated this artifact just as well as the integrated gas and particle sampler that incorporated a macroreticular polystyrene-divinylbenzene (XAD-4) resin-coated denuder, yielding OC concentrations of 2.5 +/- 0.4 and 2.4 +/- 1.0 microg of C m(-3), respectively. Thermal analysis for OC indicated that the indoor positive artifact was due to adsorption of gas-phase semivolatile organic compounds (SVOC). This study shows that the PPOMS design provides a 2.5-microm size-selective inlet that also prevents the adsorption of gas-phase SVOC onto quartz filters, thus eliminating the filter positive artifact The PPOMS meets a significant current challenge for indoor and personal sampling of particulate organic carbon. The PPOMS design can also simplify accurate ambient sampling for PM2.5.     

Improved characterization of gas-particle partitioning for per- and polyfluoroalkyl substances in the atmosphere using annular diffusion denuder samplers

Gas-phase perfluoroalkyl carboxylic acids (PFCAs) sorb strongly on filter material (i.e., GFF, QFF) used in conventional high volume air samplers, which results in an overestimation of the particle-phase concentration. In this study, we investigated an improved technique for measuring the gas-particle partitioning of per- and polyfluoroalkyl substances (PFASs) using an annular diffusion denuder sampler. Samples were analyzed for 7 PFAS classes [i.e., PFCAs, perfluoroalkane sulfonic acids (PFSAs), fluorotelomer alcohols (FTOHs), fluorotelomer methacrylates (FTMACs), fluorotelomer acrylates (FTACs), perfluorooctane sulfonamides (FOSAs), and perfluorooctane sulfonamidoethanols (FOSEs)]. The measured particulate associated fraction (Φ') using the diffusion denuder sampler generally followed the trend FTACs (0%) < FTOHs (~8%) < FOSAs (~21%) < PFSAs (~29%) < FOSEs (~66%), whereas the Φ' of the C(8)-C(18) PFCAs increased with carbon chain length, and ranged from 6% to 100%. The ionizability of some PFASs, when associated with particles, is an important consideration when calculating the gas-particle partitioning coefficient as both ionic and neutral forms can be present in the particles. Here we differentiate between a gas-particle partitioning coefficient for neutral species, K(p), and one that accounts for both ionic and neutral species of a compound, K(p)'. The measured K(p)' for PFSAs and PFCAs was 4-5 log units higher compared to the interpolated K(p) for the neutral form only. The measured K(p)' can be corrected (to apply to the neutral form only) with knowledge of the pK(a) of the chemical and the pH of the condensed medium ("wet" particle or aqueous aerosol). The denuder-based sampling of PFASs has yielded a robust data set that demonstrates the importance of atmospheric pH and chemical pK(a) values in determining gas-particle partitioning of PFASs.     

Modeling semivolatile organic aerosol mass emissions from combustion systems

Experimental measurements of gas-particle partitioning and organic aerosol mass in diluted diesel and wood combustion exhaust are interpreted using a two-component absorptive-partitioning model. The model parameters are determined by fitting the experimental data. The changes in partitioning with dilution of both wood smoke and diesel exhaust can be described by two lumped compounds in roughly equal abundance with effective saturation concentrations of approximately 1600 microg m(-3) and approximately 20 microg m(-3). The model is used to investigate gas-particle partitioning of emissions across a wide range of atmospheric conditions. Under the highly dilute conditions found in the atmosphere, the partitioning of the emissions is strongly influenced by the ambient temperature and the background organic aerosol concentration. The model predicts large changes in primary organic aerosol mass with varying atmospheric conditions, indicating that it is not possible to specify a single value for the organic aerosol emissions. Since atmospheric conditions vary in both space and time, air quality models need to treat primary organic aerosol emissions as semivolatile. Dilution samplers provide useful information about organic aerosol emissions; however, the measurements can be biased relative to atmospheric conditions and constraining predictions of absorptive-partitioning models requires emissions data across the entire range of atmospherically relevant concentrations.     

Laboratory measurements of thermodynamics of adsorption of small aromatic gases to n-hexane soot surfaces

The adsorption isotherms of a series of aromatic hydrocarbons on n-hexane soot were measured as a function of temperature and partial pressure in a coated-wall flow tube coupled to an electron-impact mass spectrometer. The specific surface area was determined for each of the samples by measuring the BET isotherm of Kr at 77 K. The gas-to-surface uptakes were fully reversible with the extent of adsorption increasing with decreasing temperature and increasing partial pressures. At low partial pressures, the isotherms were well modeled by the Langmuir isotherm for all experimental conditions, and the adsorption was found to saturate at one monolayer of coverage at approximately 2 x 10(14) molecule cm(-2). For the less volatile species, evidence for multilayer adsorption was observed and the BET isotherm was used instead. The experimental enthalpies of adsorption were consistently higher than the enthalpies of vaporization for all compounds. A linear free-energy relationship was developed between the Langmuir equilibrium constant for adsorption and the compound's (sub-cooled) liquid vapor pressure, providing validation for the use of such relationships in assessing gas-particle partitioning of aromatic hydrocarbons to soot aerosols in the environment. The experimental results were compared to the Junge-Pankow gas-to-aerosol partitioning model.     

Size-dependent volatility of diesel nanoparticles: chassis dynamometer experiments

We analyzed the size-dependent volatility of nanoparticles in a diameter range of 30-70 nm in diesel exhaust emissions. The test system included a medium-duty diesel truck on a chassis dynamometer, a single-stage dilution tunnel, a tandem differential mobility analyzer (TDMA) equipped with an electric furnace, and a condensation particle counter. The size shifts of monodispersed diesel nanoparticles under changing furnace temperatures were measured by TDMA in the gas phase. Together with the reduction of average particle size and volume, we observed the development of bimodal size distributions resulting from the separation between semivolatile and nonvolatile species as the furnace temperature was increased. While 91-98% of the particles were found to be semivolatile species by total volume during the idling engine condition, only 6-9% were semivolatile during the one-half engine load condition. We also found that smaller particles contained a larger fraction of semivolatile species.     

Inhalation exposure to haloacetic acids and haloketones during showering

Inhalation exposure to haloacetic acids (HAAs) and haloketones (HKs) in contaminated drinking water occurs during showering. The size distribution of the aerosols generated by a shower was determined using an eight size-range particle counter, which measured particles from 0.1 to >2 microm. An exponential increase in aerosol numbers was observed while the shower water was on, while the aerosol numbers declined exponentially once the water was turned off. The half-lives of the shower aerosols were longer than 5 min after the shower water was turned off. Although the majority of the shower-generated aerosols were smaller than 0.3 microm, these aerosols only contributed approximately 2% to the measured total aerosol mass. The total shower-generated particulate HAA and HK concentrations collected on an open face filter were approximately 6.3 and 0.13 microg/m3, respectively, for shower water HAA and HK concentrations of 250 and 25 microg/L, respectively. The vapor-phase HK concentrations were 25-50 microg/m3. The estimate of the dose from inhalation exposure of disinfection byproducts (DBPs) in the particulate phase indicate that they represent less than 1% of the ingestion dose, so inhalation is not expected to be an important exposure route to nonvolatile water contaminants or the portion of volatile DBPs that stay in the particulate phase, unless the lung is the target organ. The vapor-phase levels of volatile HKs, though, are significantly higher and can contribute greater than 10% of the ingestion dose during a shower. Thus, risk assessment to the these DBPs needs to consider the inhalation route.     

Studying the role of common membrane surface functionalities on adsorption and cleaning of organic foulants using QCM-D

Adsorption of organic foulants on nanofiltration (NF) and reverse osmosis (RO) membrane surfaces strongly affects subsequent fouling behavior by modifying the membrane surface. In this study, impact on organic foulant adsorption of specific chemistries including those in commercial thin-film composite membranes was investigated using self-assembled monolayers with seven different ending chemical functionalities (-CH(3), -O-phenyl, -NH(2), ethylene-glycol, -COOH, -CONH(2), and -OH). Adsorption and cleaning of protein (bovine serum albumin) and polysaccharide (sodium alginate) model foulants in two solution conditions were measured using quartz crystal microbalance with dissipation monitoring, and were found to strongly depend on surface functionality. Alginate adsorption correlated with surface hydrophobicity as measured by water contact angle in air; however, adsorption of BSA on hydrophilic -COOH, -NH(2), and -CONH(2) surfaces was high and dominated by hydrogen bond formation and electrostatic attraction. Adsorption of both BSA and alginate was the fastest on -COOH, and adsorption on -NH(2) and -CONH(2) was difficult to remove by surfactant cleaning. BSA adsorption kinetics was shown to be markedly faster than that of alginate, suggesting its importance in the formation of the conditioning layer. Surface modification to render -OH or ethylene-glycol functionalities are expected to reduce membrane fouling.     

Modeling aerosol formation from alpha-pinene + NOx in the presence of natural sunlight using gas-phase kinetics and gas-particle partitioning theory

A kinetic mechanism was used to link and model the gas-phase reactions and aerosol accumulation resulting from alpha-pinene reactions in the presence of sunlight, ozone (O3), and oxides of nitrogen (NOx). Reaction products and aerosol formation from the kinetic model were compared to outdoor smog chamber experiments conducted under natural sunlight in the presence of NOx and in the dark in the presence of O3. The gas-particle partitioning of semivolatile organics generated in the gas phase was treated as an equilibrium process between particle absorption and desorption. Models vs experimental aerosol yields illustrate that reasonable predictions of secondary aerosol formation are possible from both dark ozone and light NOx/alpha-pinene systems over a variety of different outdoor conditions. On average, measured gas- and particle-phase products accounted for approximately 54-72% of the reacted alpha-pinene carbon. Model predictions suggest that organic nitrates account for another approximately 25% of the reacted carbon, and most of this is in the gas phase. Measured particle-phase products accounted for 60-100% of the particle filter mass, with pinic acid and pinonic acid being the primary aerosol-phase products. In the gas phase, pinonaldehyde and pinonic acid are major products. Model simulations of these and other products show generally reasonable fits to the experimental data from the perspective of timing and concentrations. These results are very encouraging for a compound such as pinonaldehyde, since it is being formed from OH attack on alpha-pinene and is also simultaneously photolyzed and reacted with OH.     

Experimental study of the sampling artifact of chloride depletion from collected sea salt aerosols

Sampling artifact of chloride depletion from collected sea salt particles was studied, based on simultaneous measurements of size distribution measurements by a 10-stage Micro-Orifice Uniform Deposit Impactor (MOUDI) and of PM2.5 measurements by a Compact Porous Metal Denuder Sampler (PMDS) at a coastal site in Hong Kong on May 7, 8, 9, 11, and 29, 1998. The ambient concentrations of SO2, HNO3, HNO2, and NH3 were also measured by the PMDS. PM2.5 measurements by the PMDS, which is equipped with denuders and nylon back filters, are compared with the PM1.8 and PM3.1 measurements by the MOUDI. The percentages of chloride depletion from sea salt aerosols in PM1.8 and PM3.1 were 4-45% higher than that in PM2.5. This suggests that chloride evaporation in PM1.8 and PM3.1 collected on Teflon filters of the MOUDI during sampling was present. From the sum of the contributions of particles on the Teflon and nylon filters of the PMDS, nitrate formation almost completely accounts for chloride depletion in PM2.5 prior to collection since the equivalent ratio of [Na+] to ([NO3-] + [Cl-]) is close to the seawater ratio of 0.85. However, it was found that 22-74% of nitrate and 45-86% of chloride in the collected particles on the Teflon filter of the PMDS evaporated during sampling. Excess chloride depletion unexplained by NO3- and nss-SO4(2-) was found in the collected particles on the Teflon filter of the PMDS. Similarly, an amount of 3.7-27.2 nequiv m-3 of excess depleted chloride (equivalent to 8-55% of total chloride depletion) was found in supermicron particles collected by the MOUDI. In the 1.8-3.1 microns particles, the excess depleted chloride is positively correlated to the chloride evaporated from the deposited particles. Particle--particle interactions are proposed to explain the evaporation of nitrates and chlorides in the PMDS and MOUDI measurements. The observed chloride depletion from seasalt aerosols was partially attributed to sampling artifact due to particle--particle interactions.     

Atmospheric gas-particle partitioning of polycyclic aromatic hydrocarbons in high mountain regions of Europe

Atmospheric concentrations and gas-particle partitioning of polycyclic aromatic hydrocarbons (PAH) have been determined at three remote mountain areas in Europe. Gas-phase mean concentrations of total PAH (20 individual compounds) were very similar at all sites, ranging from 1.3-2.6 ng m(-3) in the Pyrenees (Spain) to 2.7-3.7 ng m(-3) in the Alps (Austria) and Caledonian mountains (Norway). A seasonal variability was observed, with the highest levels found in winter. The seasonal differences were reflected better in the particle-associated PAH, showing the increase of PAH emissions in the colder months and a temperature dependence of the gas-particle partitioning. Significant geographical differences were also observed for particulate PAH, indicating a greater influence of regional sources than in the gas phase. Partitioning of PAH between gas and particulate phases was well-correlated with the subcooled liquid vapor pressure in all samples, but with slopes significantly steeper than the expected value of -1. These steeper slopes may reflect the occurrence of a nonexchangeable PAH fraction in the aerosols, likely associated to the soot carbon phase. Comparison of absorption to organic matter and soot carbon using the octanol-air (Koa) and soot-air (Ksa) partitioning coefficients shows that, despite uncertainties on estimated organic matter and soot carbon contents in the sampled aerosols, Koa underpredicts aerosol PAH concentrations by a factor of 0.6-2 log units. In contrast, predicted and measured high mountain aerosol PAH differ by 0.2-0.6 log units when Ksa is considered. The results point to soot carbon as the main transport medium for the long-range distribution of aerosol-associated PAH.     

Measurements of isoprene-derived organosulfates in ambient aerosols by aerosol time-of-flight mass spectrometry - part 1: single particle atmospheric observations in Atlanta

Organosulfate species have recently been identified as a potentially significant class of secondary organic aerosol (SOA) species, yet little is known about their behavior in the atmosphere. In this work, organosulfates were observed in individual ambient aerosols using single particle mass spectrometry in Atlanta, GA during the 2002 Aerosol Nucleation and Characterization Experiment (ANARChE) and the 2008 August Mini-Intensive Gas and Aerosol Study (AMIGAS). Organosulfates derived from biogenically produced isoprene were detected as deprotonated molecular ions in negative-ion spectra measured by aerosol time-of-flight mass spectrometry; comparison to high-resolution mass spectrometry data obtained from filter samples corroborated the peak assignments. The size-resolved chemical composition measurements revealed that organosulfate species were mostly detected in submicrometer aerosols and across a range of aerosols from different sources, consistent with secondary reaction products. Detection of organosulfates in a large fraction of negative-ion ambient spectra - ca. 90-95% during ANARChE and ~65% of submicrometer particles in AMIGAS - highlights the ubiquity of organosulfate species in the ambient aerosols of biogenically influenced urban environments.