Surface Emissions Modulate Indoor SVOC Concentrations through Volatility-Dependent Partitioning.

Measurements by semivolatile thermal desorption aerosol gas chromatography (SV-TAG) were used to investigate how semivolatile organic compounds (SVOCs) partition among indoor reservoirs in (1) a manufactured test house under controlled conditions (HOMEChem campaign) and (2) a single-family residence when vacant (H2 campaign). Data for phthalate diesters and siloxanes suggest that volatility-dependent partitioning processes modulate airborne SVOC concentrations through interactions with surface-laden condensed-phase reservoirs. Airborne concentrations of SVOCs with vapor pressures in the range of C13 to C23 alkanes were observed to be correlated with indoor air temperature. Observed temperature dependencies were quantitatively similar to theoretical predictions that assumed a surface-air boundary layer with equilibrium partitioning maintained at the air-surface interface. Airborne concentrations of SVOCs with vapor pressures corresponding to C25 to C31 alkanes correlated with airborne particle mass concentration. For SVOCs with higher vapor pressures, which are expected to be predominantly gaseous, correlations with particle mass concentration were weak or nonexistent. During primary particle emission events, enhanced gas-phase emissions from condensed-phase reservoirs partitioned to airborne particles, contributing substantially to organic particulate matter. An emission event related to oven-usage was inferred to deposit siloxanes in condensed-phase reservoirs throughout the house, leading to the possibility of reemission during subsequent periods with high particle loading

Thermally Evolved & Separated Composition of Atmospheric Aerosols: Development and Application of Advanced Data Analysis Techniques for a Thermal Desorption Aerosol Gas Chromatograph (TAG)

Atmospheric organic aerosols are composed of thousands of individual compounds, interacting with climate through changes in aerosol optical properties and cloud interactions, and can be detrimental to human health. Aerosol mass spectrometry (MS) and gas chromatography (GC)-separated MS measurements have been utilized to better characterize the chemical composition of this material that comes from a variety of sources and experiences continuous oxidation while in the atmosphere. This dissertation describes the development of a novel rapid data analysis method for grouping of major components within chromatography-separated measurements and first application using thermal desorption aerosol gas chromatograph (TAG) – MS data. Chromatograms are binned and inserted directly into a positive matrix factorization (PMF) analysis to determine major contributing components, eliminating the need for manual compound integrations of hundreds of resolved molecules, and incorporating the entirety of the eluting MS signal, including Unresolved Complex Mixtures (UCM) and decomposition products that are often ignored in traditional GC-MS analysis. Binned GC-MS data has three dimensions: (1) mass spectra index m/z, (2) bin number, and (3) sample number. PMF output is composed of two dimensions; factor profiles and factor time series. The specific arrangement of the input data (three dimensions of variation structured as a two dimensional matrix) in a two dimensional PMF analysis affects the structure of the PMF profiles and time series output. If mass spectra index is in the profile dimension, and bin number and sample number are in the time series dimension, PMF groups components into factors with similar mass spectra, such as major contributing individual compounds, UCM with similar functional composition, and homologous compound series. This type of PMF analysis is described as the binning method for chromatogram deconvolution, and is presented in Chapter 2. If the sample number is in the time series dimension, and the bin number and mass spectra index, arranged as mass spectra resolved retention time/chromatogram (bin number), are in the profile dimension, PMF groups components with similar time series trends. This type of PMF analysis is described as binning method for source apportionment, and is described in Chapter 3. The binning methods are compared to traditional compound integration methods using previously-collected hourly ambient samples from Riverside, CA during the 2005 Study of Organic Aerosols at Riverside (SOAR) field campaign, as discussed in Chapters 2-3. Further application of the binning method for source apportionment is performed on newly acquired hourly TAG data from East St. Louis, IL, operated as part of the 2013 St. Louis Air Quality Regional Study (SLAQRS). Major sources of biogenic secondary organic aerosol (SOA), anthropogenic primary organic aerosol (POA) were identified, as described in detail in Chapter 4. Finally, our PMF separation method was tested for reliability using primary and secondary sources in a controlled laboratory system. As shown in Chapter 5, we find that for application of PMF on receptor measurements, high signal intensity and unique measurement profiles, like those found in TAG chromatograms, are keys to successful source apportionment. The binning method with component separation by PMF may be a valuable analysis technique for other complex data sets that incorporate measurements (e.g., mass spectrometry, spectroscopy, etc.) with additional separations (e.g., volatility, hygroscopicity, electrical mobility, etc.)

Methyl Chavicol: Characterization of its Biogenic Emission Rate, Abundance, and Oxidation Products in the Atmosphere

We report measurements of ambient atmospheric mixing ratios for methyl chavicol and determine its biogenic emission rate. Methyl chavicol, a biogenic oxygenated aromatic compound, is abundant within and above Blodgett Forest, a ponderosa pine forest in the Sierra Nevada Mountains of California. Methyl chavicol was detected simultaneously by three in-situ instruments – a gas chromatograph with mass spectrometer detector (GC-MS), a proton transfer reaction mass spectrometer (PTR-MS), and a thermal desorption aerosol GC-MS (TAG) – and found to be abundant within and above Blodgett Forest. Methyl chavicol atmospheric mixing ratios are strongly correlated with 2-methyl-3-buten-2-ol (MBO), a light- and temperature-dependent biogenic emission from the ponderosa pine trees at Blodgett Forest. Scaling from this correlation, methyl chavicol emissions account for 4–68% of the carbon mass emitted as MBO in the daytime, depending on the season. From this relationship, we estimate a daytime basal emission rate of 0.72–10.2 μgCg−1 h−1, depending on needle age and seasonality. We also present the first observations of its oxidation products (4-methoxybenzaldehyde and 4-methyoxy benzene acetaldehyde) in the ambient atmosphere. Methyl chavicol is a major essential oil component of many plant species. This work suggests that methyl chavicol plays a significant role in the atmospheric chemistry of Blodgett Forest, and potentially other sites, and should be included explicitly in both biogenic volatile organic carbon emission and atmospheric chemistry models

Development & Testing of Novel Atmospheric Chemistry Technologies

Atmospheric aerosols play an important role in global atmospheric chemistry and climate and have a detrimental impact on human health. Advancements in measurement technologies allow for better monitoring of atmospheric composition and dynamics, creating better predictive models and understanding of atmospheric chemistry and physics. Gas and particle atmospheric oxidation is poorly understood. In order to create a better understanding of atmospheric oxidation, the following equipment was developed: 1) a Potential Aerosol Mass: PAM) flow reaction chamber was developed to create reproducible steady-state oxidation of organic species in a controlled laboratory setting, 2) a custom combustion chamber for introduction of realistic single source samples, and 3) a Thermal desorption Aerosol Gas chromatograph: TAG) for hourly speciation of hundreds of semi-volatile and non-volatile organic compounds. Development and construction of the Combustion Chamber, PAM Chamber, and TAG system are discussed as well as preliminary applications of this equipment. These instruments allow for the study of primary organic aerosol: POA) and secondary organic aerosol: SOA) formation. Due to the lack of knowledge concerning organic aerosol source chemical profiles and subsequent chemical evolution in the atmosphere, these studies are crucial for furthering the understanding of atmospheric chemistry and in developing accurate atmospheric models

Aerial drone furnished with miniaturized versatile air sampling systems for selective collection of nitrogen containing compounds in boreal forest

A wide variety of nitrogen-containing compounds are present in the environment, which contributes to air pollution and new particle formation, for example. These eventually affect human health and the climate. With all this consideration, there is a growing interest in the development of efficient and reliable methods to determine these compounds in the atmosphere. In this study, titanium hydrogen phosphate-modified Mobil Composition of Matter No. 41 was used as sorbent material for in-tube extraction (ITEX) sampling system, to selectively collect nitrogen-containing compounds from natural air samples. The effect of sampling accessories, based on adsorbent coatings (with Tenax-GR as an adsorbent material) and polytetrafluoroethylene filters, was studied to improve the selectivity of the sampling system and to remove particles. Aerial drone with miniaturized air sampling system was employed for the reliable collection of nitrogen-containing compounds in both gas phase and aerosol particles. A total of 170 air samples were collected in July 2020 at the SMEAR II station, Finland to evaluate nitrogen-containing compounds diurnal patterns and vertical profiles (0.25, 5, 50, and 150 m). More than twenty nitrogen-containing compounds, such as aliphatic amines, imines, imidazoles, and pyridines, were identified, quantified or semi-quantified. The average concentrations of detected aliphatic amines at the altitude of 50 m were up to 40.4 ng m−3 (dimethylamine) in gas phase and 128 ng m−3 (ethylamine) in aerosol particles. Among nitrogen-containing compounds detected, pyridine gave the highest average concentration of 746 ng m−3 in gas phase and 644 ng m−3 in particle phase.Peer reviewe

Aerial drone as a carrier for miniaturized air sampling systems

The applicability of an aerial drone as a carrier for new passive and active miniaturized air sampling systems, including solid phase microextration Arrow (SPME Arrow) and in-tube extraction (ITEX), was studied in this research. Thermal desorption, gas chromatography and mass spectrometry were used for the determination of volatile organic compounds (VOCs) collected by the sampling systems. The direct comparison of the profiles of VOCs, simultaneously sampled in air by SPME Arrow system including four different coatings, allowed the elucidation of their adsorption selectivity. A more complex experimental design, involving 20 samples (10 flights) and non-supervised pattern recognition techniques, was needed for the clarification of the same sampling parameters in the case of five ITEX sorbent materials. In addition, ITEX sampling accessories, such as particle, water and ozone traps, were evaluated by comparing the results obtained for air samples simultaneously collected by two ITEX systems, packed with the same sorbent and furnished or not with sampling accessories. The effect of the aerial drone horizontal displacement (HD) on the sampling efficiency was clear in the case of SPME Arrow. The number of detected compounds and their relative peak area values (RPA) revealed a clear increase (4 and 43%, respectively) in comparison with samples collected without drone HD. However, just minor differences were observed in the case of ITEX (2 compounds and 9% of the Sigma RPA). In addition, the system was able to provide almost simultaneous passive (SPME Arrow) and active (ITEX) samplings at different altitudes (5 and 50 m), being a good tool for low cost vertical profiling studies (Sigma RPA decreased over 35% for the samples collected at 50 m). Finally, the successful simultaneous air sampling by SPME Arrow and ITEX systems in two difficult access places, such as boreal forest and wetlands, was demonstrated, resulting in 21 and 31 detected compounds in forest and wetlands by SPME Arrow, and 27 and 39 compounds by ITEX. (C) 2019 The Authors. Published by Elsevier B.V.Peer reviewe

Continuous Measurement of Reactive Oxygen Species Inside and Outside of a Residential House during Summer

Reactive oxygen species (ROS) are an important contributor to adverse health effects associated with ambient air pollution. Despite infiltration of ROS from outdoors, and possible indoor sources (eg, combustion), there are limited data available on indoor ROS. In this study, part of the second phase of Air Composition and Reactivity from Outdoor aNd Indoor Mixing campaign (ACRONIM-2), we constructed and deployed an online, continuous, system to measure extracellular gas- and particle-phase ROS during summer in an unoccupied residence in St. Louis, MO, USA. Over a period of one week, we observed that the non-denuded outdoor ROS (representing particle-phase ROS and some gas-phase ROS) concentration ranged from 1 to 4 nmol/m3 (as H2O2). Outdoor concentrations were highest in the afternoon, coincident with peak photochemistry periods. The indoor concentrations of particle-phase ROS were nearly equal to outdoor concentrations, regardless of window-opening status or air exchange rates. The indoor/outdoor ratio of non-denuded ROS (I/OROS) was significantly less than 1 with windows open and even lower with windows closed. Combined, these observations suggest that gas-phase ROS are efficiently removed by interior building surfaces and that there may be an indoor source of particle-phase ROS

Simultaneous measurement of monoaromatic hydrocarbons and dicarboxylic acids in ambient air

Atmospheric aromatic hydrocarbons and dicarboxylic acids were measured simultaneously in this work. A method was developed for aromatic hydrocarbons: collection on Tenax and charcoal, thermal desorption, and gas chromatographic analysis. Another method was verified for diacids: collection on quartz filter, conversion to dibutylesters, and analysis by capillary gas chromatography; Results of aromatic hydrocarbon measurements show a very strong linear relation among all aromatic hydrocarbons, and a significant correlation between aromatic hydrocarbons and CO measured at a nearby location. This result strongly suggests that aromatic hydrocarbons originate from automobiles. After correcting for dilution effects by normalizing hydrocarbon concentrations by CO concentration, the observed decrease in the normalized daytime concentrations indicates that atmospheric aromatic hydrocarbons undergo photochemical destruction during the daytime; Results of diacid measurements show a complex diurnal variation in concentrations. The diacids measured possibly came from either local production and/or emissions, resuspension, or from long-range transport from other areas