Dissolved black carbon as a potential driver of surface water heating dynamics in wildfire-impacted regions: A case study from Pyramid Lake, NV, USA.

Black carbon (BC), pyrogenic residues resulting from the incomplete combustion of organics, are liberated from wildfires at high rates. Subsequent introduction to aqueous environments via atmospheric deposition or overland flow results in the formation of a dissolved fraction, called dissolved black carbon (DBC). As wildfire frequency and intensity increases along with a changing climate, it becomes imperative to understand the impact a concurrent increase in DBC load might have to aquatic ecosystems. In the atmosphere BC stimulates warming by absorbing solar radiation, and similar processes may occur with surface waters that contain DBC. In this work we investigated whether the addition of environmentally relevant levels of DBC could impact surface water heating dynamics in experimental settings. DBC was quantified at multiple locations and depths in Pyramid Lake (NV, USA) during peak fire season while two large, proximal wildfires burned. DBC was detected in Pyramid Lake water at all sampled locations at concentrations (3.6-18 ppb) significantly higher than those reported for other large inland lakes. DBC was positively correlated (R2 = 0.84) with chromophoric dissolved organic matter (CDOM) but not bulk dissolved or total organic carbon (DOC, TOC), suggesting that DBC is a significant component of the optically active organics in the lake. Subsequent lab-based experiments were conducted by adding environmentally relevant levels of DBC standards to pure water, exposing the system to solar spectrum radiation, and creating a numerical model of heat transfer based on observed temperatures. The addition of DBC at environmentally relevant orders of magnitude caused reductions to shortwave albedo when exposed to the solar spectrum, which resulted in 5-8 % more incident radiation being absorbed by water and changes to water heating dynamics. In environmental settings, this increase in energy absorption could translate to increased heating of the epilimnion in Pyramid Lake and other wildfire-impacted surface waters.

Emission factors for polycyclic aromatic hydrocarbons from laboratory biomass-burning and their chemical transformations during aging in an oxidation flow reactor.

Atmospheric polycyclic aromatic hydrocarbons (PAHs) can be emitted from different combustion sources including domestic biomass burning, internal combustion engines, and biomass burning (BB) in wild, prescribed, and agricultural fires. With climate warming and consequent global increases in frequency and severity of wildfires, BB is a dominant source of PAHs emitted into the atmosphere. In this study, six globally and regionally important and representative fuels (Alaskan peat, Moscow peat, Pskov peat, eucalyptus, Malaysian peat, and Malaysian agricultural peat) were burned under controlled conditions in the combustion chamber facility at the Desert Research Institute (DRI, Reno, NV, USA). Gas- and particle-phase BB emissions were aged in an oxidation flow reactor (OFR) to mimic five to sevendays of atmospheric aging. To sample gas- and particle-phase BB emissions, fresh and OFR-aged biomass-burning aerosols were collected on Teflon-impregnated glass fiber filters (TIGF) in tandem with XAD resin media for organic carbon speciation. The objectives of this study were to i) quantify the emission factors for 113 PAHs emitted from the combustion of the six selected fuels, ii) characterize the distribution of PAH compounds between gas and particle phases for these fuels, iii) identify the changes in PAHs during OFR-aging, and iv) evaluate toxicity potential with characterized compounds. We found that combustion emissions of gas-phase PAHs were more abundant (>80 % by mass) than particle-phase PAHs, for emissions from all combusted fuels. The mass fraction of substituted napthalenes in Moscow peat and Malaysian peat emissions were ∼70 % & 84 %, respectively, whereas in Eucalyptus the same fraction was <50 %, which indicates that these substituted compounds can be used as tracers for peat emissions. Mass concentrations of gas- and particle-phase PAHs were reduced by ∼70 % after OFR oxidation. However, the understanding of the fate of PAHs during OFR oxidation requires further investigations. Our results also indicate that the PAH toxicity of BB samples would be underestimated by 10-100 times if only the BaPeq for the 16 US EPA priority PAHs in the particle phase are included.

Relative abundance of saccharides, free amino acids, and other compounds in specific pollen species for source profiling of atmospheric aerosol.

Though studies in bioaerosols are being conducted with increasing frequency over the past decade, the total breadth of knowledge on bioaerosols and their role in atmospheric processes is still minimal. In order to better characterize the chemical composition of fresh biological aerosol for purposes of source apportionment and tracing in the atmosphere, several plant pollen species were selected for detailed chemical analyses. For this purpose, different pollen species were purchased and collected around Reno, Nevada, USA, for further extraction and detailed chemical analysis. These species included aspen, corn, pecan, ragweed, eastern cottonwood, paper mulberry, rabbitbrush, bitterbrush, lodgepole pine, and Jeffrey pine. Saccharides, free amino acids, and various other polar compounds (e.g., anhydrosugars and resin acids) were quantitatively analyzed using gas chromatography and ultra-high performance liquid chromatography coupled with mass spectrometry techniques (GC-MS and UPLC-MS), with the purpose to identify differences and nuances in chemical composition of specific pollen species. The saccharides ß-d-fructose, α-d-glucose, and ß-d-glucose were ubiquitously found across all pollen samples (10), and sucrose was found in five samples. d-galactose was also found in pine species. Total saccharides were 4.0 to 29% of total dry weight across all samples. Total free amino acids were 0.29% to 15% of total dry weight across all samples, with the most common amino acid being proline. Chemical profiles (including both saccharides and amino acids) of surface-deposited aerosol in the Lake Tahoe area correlated most closely with pine pollen than other analyzed pollen species, indicating that chemical profiles of pollen can be used to infer its contribution to local aerosols.

Indoor Air Quality and Passive E-cigarette Aerosol Exposures in Vape-Shops.

INTRODUCTION: Direct emissions of nicotine and harmful chemicals from electronic cigarettes (e-cigarettes) have been intensively studied, but secondhand and thirdhand e-cigarette aerosol (THA) exposures in indoor environments are understudied. AIMS AND METHODS: Indoor CO2, NO2, particulate matter (PM2.5), aldehydes, and airborne nicotine were measured in five vape-shops to assess secondhand exposures. Nicotine and tobacco-specific nitrosamines were measured on vape-shop surfaces and materials (glass, paper, clothing, rubber, and fur ball) placed in the vape-shops (14 days) to study thirdhand exposures. RESULTS: Airborne PM2.5, formaldehyde, acetaldehyde, and nicotine concentrations during shop opening hours were 21, 3.3, 4.0, and 3.8 times higher than the levels during shop closing hours, respectively. PM2.5 concentrations were correlated with the number of e-cigarette users present in vape-shops (ρ = 0.366-0.761, p < .001). Surface nicotine, 4-(N-methyl-N-nitrosamino)-4-(3-pyridyl)butanal (NNA), and 4-(methylnitrosamino)-1-(3-pyridyl)-1-butanone (NNK) were also detected at levels of 223.6 ± 313.2 µg/m2, 4.78 ± 11.8 ng/m2, and 44.8 ± 102.3 ng/m2, respectively. Substantial amounts of nicotine (up to 2073 µg/m2) deposited on the materials placed within the vape-shops, and NNA (up to 474.4 ng/m2) and NNK (up to 184.0 ng/m2) were also formed on these materials. The deposited nicotine concentrations were strongly correlated with the median number of active vapers present in a vape-shop per hour (ρ = 0.894-0.949, p = .04-.051). NNK levels on the material surfaces were significantly associated with surface nicotine levels (ρ=0.645, p = .037). CONCLUSIONS: Indoor vaping leads to secondhand and THA exposures. Thirdhand exposures induced by e-cigarette vaping are comparable or higher than that induced by cigarette smoking. Long-term studies in various microenvironments are needed to improve our understanding of secondhand and THA exposures. IMPLICATIONS: This study adds new convincing evidence that e-cigarette vaping can cause secondhand and THA exposures. Our findings can inform Occupational Safety and Health Administration, state authorities, and other government agencies regarding indoor air policies related to e-cigarette use, particularly in vape-shops. There is an urgent need to ensure that vape-shops maintain suitable ventilation systems and cleaning practices to protect customers, employees, and bystanders. Our study also demonstrates that nicotine can deposit or be adsorbed on baby's clothes and toys, and that tobacco-specific nitrosamines can form and retain on baby's clothes, highlighting children's exposure to environmental e-cigarette aerosol and THA at home is of a particular concern.

Harmful chemicals emitted from electronic cigarettes and potential deleterious effects in the oral cavity.

Use of electronic nicotine delivery systems (ENDS), such as electronic cigarettes (e-cigs), is increasing across the US population and is particularly troubling due to their adoption by adolescents, teens, and young adults. The industry's marketing approach for these instruments of addiction has been to promote them as a safer alternative to tobacco, a behavioral choice supporting smoking cessation, and as the 'cool' appearance of vaping with flavored products (e.g. tutti frutti, bubble gum, and buttered popcorn etc.). Thus, there is a clear need to better document the health outcomes of e-cig use in the oral cavity of the addicted chronic user. There appears to be an array of environmental toxins in the vapors, including reactive aldehydes and carbonyls resulting from the heating elements action on fluid components, as well as from the composition of chemical flavoring agents. The chemistry of these systems shows that the released vapors from the e-cigs frequently contain levels of environmental toxins that considerably exceed federal occupational exposure limits. Additionally, the toxicants in the vapors appear to be retained in the host fluids/tissues at levels often approximating 90% of the levels in the e-cig vapors. These water-soluble reactive toxins can challenge the oral cavity constituents, potentially contributing to alterations in the autochthonous microbiome and host cells critical for maintaining oral homeostasis. This review updates the existing chemistry/environmental aspects of e-cigs, as well as providing an overview of the somewhat limited data on potential oral health effects that could occur across the lifetime of daily e-cig users.

Carbonyls and Carbon Monoxide Emissions from Electronic Cigarettes Affected by Device Type and Use Patterns.

Dangerous levels of harmful chemicals in electronic cigarette (e-cigarette) aerosols were reported by several studies, but variability in e-cigarette design and use patterns, and a rapid development of new devices, such as JUUL, hamper efforts to develop standardized testing protocols and understand health risks associated with e-cigarette use. In this study, we investigated the relative importance of e-cigarette design, power output, liquid composition, puff topography on e-cigarette emissions of carbonyl compounds, carbon monoxide (CO), and nicotine. Four popular e-cigarette devices representing the most common e-cigarette types (e.g., cig-a-like, top-coil, 'mod', and 'pod') were tested. Under the tested vaping conditions, a top-coil device generated the highest amounts of formaldehyde and CO. A 'pod' type device (i.e., JUUL) emitted the highest amounts of nicotine, while generating the lowest levels of carbonyl and CO as compared to other tested e-cigarettes. Emissions increased nearly linearly with puff duration, while puff flow had a relatively small effect. Flavored e-liquids generated more carbonyls and CO than unflavored liquids. Carbonyl concentrations and CO in e-cigarette aerosols were found to be well correlated. While e-cigarettes emitted generally less CO and carbonyls than conventional cigarettes, daily carbonyl exposures from e-cigarette use could still exceed acute exposure limits, with the top-coil device potentially posing more harm than conventional cigarettes.

Dominant volatile organic compounds (VOCs) measured at four Cannabis growing facilities: Pilot study results.

In recent years, sale of recreational marijuana products has been permitted in several states and countries resulting in rapid growth of the commercial cannabis cultivation and processing industry. As previous research has shown, biogenic volatile organic compounds (BVOCs) emitted from plants can react with other urban air constituents (e.g., NOx, HO radical) and thus negatively affect regional air quality. In this pilot study, BVOC emissions from Cannabis plants were analyzed at four grow facilities. The concentrations of measured BVOCs inside the facilities were between 110 and 5,500 µg m-3. One adult Cannabis plant emits hundreds of micrograms of BVOCs per day and thus can trigger the formation of tropospheric ozone (approximately 2.6 g day-1 plant-1) and other toxic air pollutants. In addition, high concentrations of butane (1,080- 43,000 µg m-3), another reactive VOC, were observed at the facilities equipped with Cannabis oil extraction stations. Implications: High concentrations of VOCs emitted from Cannabis grow facilities can lead to the formation of ozone, secondary VOCs (e.g., formaldehyde and acrolein), and particulate matter. Our results highlight that further assessment of VOC emissions from Cannabis facilities is needed, and this assessment is one of the key factors for developing policies for optimal air pollution control.

Hydroxyl Radicals in E-Cigarette Vapor and E-Vapor Oxidative Potentials under Different Vaping Patterns.

Available studies, while limited in number, suggest that e-cigarette vaping induces oxidative stress, with one potential mechanism being the direct formation of reactive oxygen species (ROS) in e-vapor. In the present studies, we measured the formation of hydroxyl radical (•OH), the most destructive ROS, in e-vapor under a range of vaping patterns (i.e., power settings, solvent concentrations, flavorings). Study results show that increased power output and puff volume correspond with the formation of significantly higher amounts of •OH in e-vapor because of elevated coil temperature and oxygen supply. Vegetable glycerin (VG) e-liquids generated higher •OH levels than propylene glycol (PG) e-liquids, as did flavored e-liquids relative to nonflavored e-liquids. E-vapor in combination with ascorbic acid, which is an abundant biological molecule in human epithelial lining fluid, can also induce •OH formation. The dose of radical per puff associated with e-cigarette vaping was 10-1000 times lower than the reported dose generated by cigarette smoking. However, the daily average •OH dose can be comparable to that from cigarette smoking depending on vaping patterns. Overall, e-cigarette users who use VG-based flavored e-cigarettes at higher power output settings may be at increased risk for •OH exposures and related health consequences such as asthma and chronic obstructive pulmonary disease.

Aldehydes in Exhaled Breath during E-Cigarette Vaping: Pilot Study Results.

Several studies have shown the presence of aldehydes (i.e., formaldehyde, acrolein) in mainstream emissions of some e-cigarettes. For this reason, concerns have been raised regarding potential toxicity. The purpose of this research was to measure levels of carbonyls in exhaled breath of e-cigarette users during "vaping" sessions and estimate the respiratory tract (RT) uptake of specific aldehydes, including formaldehyde and acetaldehyde. We measured concentrations of 12 carbonyls in e-cigarette aerosols produced directly by e-cigarettes and in the exhaled breath of 12 participants (19 sessions). Carbonyls were sampled on 2,4-dinitrophenylhydrazine (DNPH) cartridges and analyzed with high performance liquid chromatography (HPLC) coupled with a UV/Vis photodiode detector. We found that in most cases, levels of aldehydes and methyl ethyl ketone (MEK) were significantly higher (2⁻125 times) in exhaled e-cigarette breaths than in pre-exposed breath. Exposure levels for the most abundant individual carbonyls in e-cigarette emissions-formaldehyde, acetaldehyde, acrolein-were between the limit of quantification (LOQ) and 24.4 µg·puff-1. The mean retention of formaldehyde in the respiratory tract was 99.7 ± 0.9% for all participants, while acetaldehyde retention was 91.6 ± 9.9%. Within the limitation of a small number of participants, our results showed that there is an increase in breath carbonyls during e-cigarette use.

Comment on "Do flavouring compounds contribute to aldehyde emissions in e-cigarettes?" by Farsalinos and Voudris.

This letter is in response to a paper "Do flavouring compounds contribute to aldehyde emissions in e-cigarettes?" authored by Farsalinos and Voudris in the May 2018 edition of FCT. Our purpose is to point out and/or correct inconsistencies and inaccuracies in that paper. Using evidence from several independent studies, we demonstrate that experimental methods used by Farsalinos and Voudris do not fully account for neither particle nor gas-phase aldehydes in e-cigarette aerosols, leading to significant underestimation of aldehyde emissions and risks associated with e-cigarette use.

Do 16 Polycyclic Aromatic Hydrocarbons Represent PAH Air Toxicity?

Estimation of carcinogenic potency based on analysis of 16 polycyclic aromatic hydrocarbons (PAHs) ranked by U.S. Environmental Protection Agency (EPA) is the most popular approach within scientific and environmental air quality management communities. The majority of PAH monitoring projects have been focused on particle-bound PAHs, ignoring the contribution of gas-phase PAHs to the toxicity of PAH mixtures in air samples. In this study, we analyzed the results of 13 projects in which 88 PAHs in both gas and particle phases were collected from different sources (biomass burning, mining operation, and vehicle emissions), as well as in urban air. The aim was to investigate whether 16 particle-bound U.S. EPA priority PAHs adequately represented health risks of inhalation exposure to atmospheric PAH mixtures. PAH concentrations were converted to benzo(a)pyrene-equivalent (BaPeq) toxicity using the toxic equivalency factor (TEF) approach. TEFs of PAH compounds for which such data is not available were estimated using TEFs of close isomers. Total BaPeq toxicities (∑88BaPeq) of gas- and particle-phase PAHs were compared with BaPeq toxicities calculated for the 16 particle-phase EPA PAH (∑16EPABaPeq). The results showed that 16 EPA particle-bound PAHs underrepresented the carcinogenic potency on average by 85.6% relative to the total (gas and particle) BaPeq toxicity of 88 PAHs. Gas-phase PAHs, like methylnaphthalenes, may contribute up to 30% of ∑88BaPeq. Accounting for other individual non-EPA PAHs (i.e., benzo(e)pyrene) and gas-phase PAHs (i.e., naphthalene, 1- and 2-methylnaphthalene) will make the risk assessment of PAH-containing air samples significantly more accurate.

Flavoring Compounds Dominate Toxic Aldehyde Production during E-Cigarette Vaping.

The growing popularity of electronic cigarettes (e-cigarettes) raises concerns about the possibility of adverse health effects to primary users and people exposed to e-cigarette vapors. E-Cigarettes offer a very wide variety of flavors, which is one of the main factors that attract new, especially young, users. How flavoring compounds in e-cigarette liquids affect the chemical composition and toxicity of e-cigarette vapors is practically unknown. Although e-cigarettes are marketed as safer alternatives to traditional cigarettes, several studies have demonstrated formation of toxic aldehydes in e-cigarette vapors during vaping. So far, aldehyde formation has been attributed to thermal decomposition of the main components of e-cigarette e-liquids (propylene glycol and glycerol), while the role of flavoring compounds has been ignored. In this study, we have measured several toxic aldehydes produced by three popular brands of e-cigarettes with flavored and unflavored e-liquids. We show that, within the tested e-cigarette brands, thermal decomposition of flavoring compounds dominates formation of aldehydes during vaping, producing levels that exceed occupational safety standards. Production of aldehydes was found to be exponentially dependent on concentration of flavoring compounds. These findings stress the need for a further, thorough investigation of the effect of flavoring compounds on the toxicity of e-cigarettes.

Polycyclic aromatic hydrocarbons in biomass-burning emissions and their contribution to light absorption and aerosol toxicity.

In recent years, brown carbon (BrC) has been shown to be an important contributor to light absorption by biomass-burning atmospheric aerosols in the blue and near-ultraviolet (UV) part of the solar spectrum. Emission factors and optical properties of 113 polycyclic aromatic hydrocarbons (PAHs) were determined for combustion of five globally important fuels: Alaskan, Siberian, and Florida swamp peat, cheatgrass (Bromus tectorum), and ponderosa pine (Pinus ponderosa) needles. The emission factors of total analyzed PAHs were between 1.9±0.43.0±0.6 and 9.6±1.2-42.2±5.4mgPAHkg(-1)fuel for particle- and gas phase, respectively. Spectrophotometric analysis of the identified PAHs showed that perinaphthenone, methylpyrenes, and pyrene contributed the most to the total PAH light absorption with 17.2%, 3.3 to 10.5%, and 7.6% of the total particle-phase PAH absorptivity averaged over analyzed emissions from the fuels. In the gas phase, the top three PAH contributors to BrC were acenaphthylene (32.6%), anthracene (8.2%), and 2,4,5-trimethylnaphthalene (8.0%). Overall, the identified PAHs were responsible for 0.087-0.16% (0.13% on average) and 0.033-0.15% (0.11% on average) of the total light absorption by dichloromethane-acetone extracts of particle and gas emissions, respectively. Toxic equivalency factor (TEF) analysis of 16 PAHs prioritized by the United States Environmental Protection Agency (EPA) showed that benzo(a)pyrene contributed the most to the PAH carcinogenic potency of particle phase emissions (61.8-67.4% to the total carcinogenic potency of Σ16EPA PAHs), while naphthalene played the major role in carcinogenicity of the gas phase PAHs in the biomass-burning emission analyzed here (35.4-46.0% to the total carcinogenic potency of Σ16EPA PAHs). The 16 EPA-prioritized PAHs contributed only 22.1±6.2% to total particle and 23.4±11% to total gas phase PAH mass, thus toxic properties of biomass-burning PAH emissions are most likely underestimated.

Evaluation of assumptions for estimating chemical light extinction at U.S. national parks.

UNLABELLED: Studies were conducted at Great Smoky Mountains National Park (NP) (GRSM), Tennessee, Mount Rainier NP (MORA), Washington, and Acadia NP (ACAD), Maine, to evaluate assumptions used to estimate aerosol light extinction from chemical composition. The revised IMPROVE equation calculates light scattering from concentrations of PM2.5 sulfates, nitrates, organic carbon mass (OM), and soil. Organics are assumed to be nonhygroscopic. Organic carbon (OC) is converted to OM with a multiplier of 1.8. Experiments were conducted to evaluate assumptions on aerosol hydration state, the OM/OC ratio, OM hygroscopicity, and mass scattering efficiencies. Sulfates were neutralized by ammonium during winter at GRSM (W, winter) and at MORA during summer but were acidic at ACAD and GRSM (S, summer) during summer. Hygroscopic growth was mostly smooth and continuous, rarely exhibiting hysteresis. Deliquescence was not observed except infrequently during winter at GRSM (W). Water-soluble organic carbon (WSOC) was separated from bulk OC with solid-phase absorbents. The average OM/OC ratios were 2.0, 2.7, 2.1, and 2.2 at GRSM (S), GRSM (W), MORA, and ACAD, respectively. Hygroscopic growth factors (GF) at relative humidity (RH) 90% for aerosols generated from WSOC extracts averaged 1.19, 1.06, 1.13, and 1.16 at GRSM (S), GRSM (W), MORA, and ACAD, respectively. Thus, the assumption that OM is not hygroscopic may lead to underestimation of its contribution to light scattering. IMPLICATIONS: Studies at IMPROVE sites conducted in U.S. national parks showed that aerosol organics comprise more PM2.5 mass and absorb more water as a function of relative humidity than is currently assumed by the IMPROVE equation for calculating chemical light extinction. Future strategies for reducing regional haze may therefore need to focus more heavily on understanding the origins and control of anthropogenic sources of organic aerosols.

Impact of emissions from natural gas production facilities on ambient air quality in the Barnett Shale area: a pilot study.

Rapid and extensive development of shale gas resources in the Barnett Shale region of Texas in recent years has created concerns about potential environmental impacts on water and air quality. The purpose of this study was to provide a better understanding of the potential contributions of emissions from gas production operations to population exposure to air toxics in the Barnett Shale region. This goal was approached using a combination of chemical characterization of the volatile organic compound (VOC) emissions from active wells, saturation monitoring for gaseous and particulate pollutants in a residential community located near active gas/oil extraction and processing facilities, source apportionment of VOCs measured in the community using the Chemical Mass Balance (CMB) receptor model, and direct measurements of the pollutant gradient downwind of a gas well with high VOC emissions. Overall, the study results indicate that air quality impacts due to individual gas wells and compressor stations are not likely to be discernible beyond a distance of approximately 100 m in the downwind direction. However, source apportionment results indicate a significant contribution to regional VOCs from gas production sources, particularly for lower-molecular-weight alkanes (< C6). Although measured ambient VOC concentrations were well below health-based safe exposure levels, the existence of urban-level mean concentrations of benzene and other mobile source air toxics combined with soot to total carbon ratios that were high for an area with little residential or commercial development may be indicative of the impact of increased heavy-duty vehicle traffic related to gas production. Implications: Rapid and extensive development of shale gas resources in recent years has created concerns about potential environmental impacts on water and air quality. This study focused on directly measuring the ambient air pollutant levels occurring at residential properties located near natural gas extraction and processing facilities, and estimating the relative contributions from gas production and motor vehicle emissions to ambient VOC concentrations. Although only a small-scale case study, the results may be useful for guidance in planning future ambient air quality studies and human exposure estimates in areas of intensive shale gas production.

Molecular size evolution of oligomers in organic aerosols collected in urban atmospheres and generated in a smog chamber.

Only a minor fraction of the total organic aerosol mass can be resolved on a molecular level. High molecular weight compounds in organic aerosols have recently gained much attention because this class of compound potentially explains a major fraction of the unexplained organic aerosol mass. These compounds have been identified with different mass spectrometric methods, and compounds with molecular masses up to 1000 Da are found in secondary organic aerosols (SOA) generated from aromatic and terpene precursors in smog chamber experiments. Here, we apply matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS) to SOA particles from two biogenic precursors, alpha-pinene and isoprene. Similar oligomer patterns are found in these two SOA systems, but also in SOA from trimethylbenzene, an anthropogenic SOA precursor. However, different maxima molecular sizes were measured for these three SOA systems. While oligomers in alpha-pinene and isoprene have sizes mostly below 600-700 Da, they grow up to about 1000 Da in trimethylbenzene-SOA. The final molecular size of the oligomers is reached early during the particle aging process, whereas other particle properties related to aging, such as the overall acid concentration or the oligomer concentration, increase continuously over a much longer time scale. This kinetic behavior of the oligomer molecular size growth can be explained by a chain growth kinetic regime. Similar oligomer mass patterns were measured in aqueous extracts of ambient aerosol samples (measured with the same technique). Distinct differences between summer and winter were observed. In summer a few single mass peaks were measured with much higher intensity than in winter, pointing to a possible difference in the formation processes of these compounds in winter and summer.

High time resolution and size-segregated analysis of aerosol bound polycyclic aromatic hydrocarbons.

Polycyclic aromatic hydrocarbons (PAHs) are an ubiquitous class of compounds in the environment, mostly generated by anthropogenic processes. High time resolution measurements are necessary to gain further knowledge on the fate and diurnal pattern of these often carcinogenic and mutagenic compounds in the atmosphere. It is expected to find a strong correlation of the PAH levels with the strength and proximity to sources, as well as with meteorological parameters. To determine the fate of particle-bound PAHs, they were sampled in this study at an urban background site in Zurich, Switzerland, during summer 2002 and winter 2003. Particle-bound PAHs were collected with a rotating drum impactor and subsequently analyzed with two-step laser mass spectrometry. Using this combination of sampling and measurement, size-segregated (10-1.1, 1.1-0.3, and 0.3-0.1 microm) and high time resolution (20 min) data were obtained. The pronounced diurnal cycle (with day/night ratios of 0.1) was only altered during intensive atmospheric mixing periods (resulting in day/night ratios of up to 8) by cleaner air from upper atmospheric layers which was mixed into the boundary layer. During summer, signal intensities due to particle-bound PAHs were about a factor of 2-10 lower than during winter.

Analysis of size-segregated aerosol-bound polycyclic aromatic hydrocarbons with high time resolution using two-step laser mass spectrometry.

Polycyclic aromatic hydrocarbons are known for their mutagenic and carcinogenic properties. They are mainly emitted into the atmosphere by anthropogenic, incomplete combustion sources. Their trends over the course of a day are of interest in air quality management. A new combination of methods has been developed for the qualitative monitoring of polycyclic aromatic hydrocarbons in ambient aerosols with high time and size resolution. This has been accomplished by combining sampling with a rotating drum impactor and the analysis two-step laser mass spectrometry (L2MS). A validation for this method was carried out. Essential features of these combined techniques are (i) continuous, automatic sampling and (ii) selective as well as sensitive analysis due to the low detection limits which can be achieved with the L2MS analysis instrument. Analysis of a field sample taken in downtown Zurich, Switzerland, underlines the usefulness of this combined method, for example for following diurnal cycles of polycyclic aromatic hydrocarbons.