Organic Emissions of Volatile Chemical Products in Canada: Emission Inventories, Indoor-to-Outdoor Transfer, and Regional Impacts.

The contribution of volatile chemical products (VCPs) to ambient air pollution has increased following decades of regulating combustion sources. There is a research gap concerning the impact of indoor physicochemical phenomena on VCP emissions. In this work, a bottom-up speciated VCP emission inventory with indoor-outdoor resolution was developed for Canada, an industrialized country with low air pollution levels, whose major cities are among the largest urban areas in North America. VCPs were estimated to account for about 290 kilotons of gaseous organic emissions for a typical year in the 2010s, with more than 60% of emissions occurring indoors. Coatings and cleaners were the most emissive VCP categories. Oxygenated species and saturated aliphatics dominated the chemical profiles of most emissions. Less than 5% of VCP emissions were impacted by indoor physicochemical phenomena. VCP emissions were predicted to account for 0.8-3.2 s-1 of OH reactivity and 0.22-0.52 µg/m3 of secondary organic aerosol formation potential in major urban areas in Canada. Our predictions aligned with previous measurements concerning indoor and outdoor organic pollutant levels, underscoring the important air quality impacts of VCPs relative to other sources. Our results provide helpful insights for future research regarding VCP emissions, especially from indoor spaces.

Particulate Matter and Volatile Organic Compound Emissions Generated from a Domestic Air Fryer.

Air frying has become a popular cooking method for domestic cooking, but the level of released indoor air pollutants is poorly understood. In this work, we compared particle and gas phase emission factors (EF) and particle size distributions between cooking with a domestic air fryer and a pan for a variety of foods. The PM10 EFs of air frying chicken wings and breast were higher than pan cooking by a factor of 2.1 and 5.4, respectively. On the other hand, a higher PM10 emission factor from air frying can be achieved by increasing the amount of oil to levels similar to or above those from pan-frying for French fries and asparagus. We propose that higher temperature and greater turbulence lead to higher PM10 EFs for cooking with the air fryer compared with the pan for the same mass of oil added. EFs of volatile organic compounds (VOCs) are also generally higher for cooking with the air fryer compared with the pan: 2.5 times higher for French fries and 4.8 times higher for chicken breast. Our study highlights the potential risk of higher indoor PM10 levels associated with domestic air frying under certain cases and proposes possible mitigation measures.

Multiphase Reactions between Organic Peroxides and Sulfur Dioxide in Internally Mixed Inorganic and Organic Particles: Key Roles of Particle Phase Separation and Acidity.

Organic peroxides (POs) are ubiquitous in the atmosphere and particularly reactive toward dissolved sulfur dioxide (SO2), yet the reaction kinetics between POs and SO2, especially in complex inorganic-organic mixed particles, remain poorly constrained. Here, we report the first investigation of the multiphase reactions between SO2 and POs in monoterpene-derived secondary organic aerosol internally mixed with different inorganic salts (ammonium sulfate, ammonium bisulfate, or sodium nitrate). We find that when the particles are phase-separated, the PO-S(IV) reactivity is consistent with that measured in pure SOA and depends markedly on the water content in the organic shell. However, when the organic and inorganic phases are miscible, the PO-S(IV) reactivity varies substantially among different aerosol systems, mainly driven by their distinct acidities (not by ionic strength). The second-order PO-S(IV) rate constant decreases monotonically from 5 × 105 to 75 M-1 s-1 in the pH range of 0.1-5.6. Both proton catalysis and general acid catalysis contribute to S(IV) oxidation, with their corresponding third-order rate constants determined to be (6.4 ± 0.7) × 106 and (6.9 ± 4.6) × 104 M-2 s-1 at pH 2-6, respectively. The measured kinetics imply that the PO-S(IV) reaction in aerosol is an important sulfate formation pathway, with the reaction kinetics dominated by general acid catalysis at pH > 3 under typical continental atmospheric conditions.

Indoor and outdoor air quality impacts of cooking and cleaning emissions from a commercial kitchen.

Gas and particulate emissions from commercial kitchens are important contributors to urban air quality. Not only are these emissions important for occupational exposure of kitchen staff, but they can also be vented to outdoors, causing uncertain health and environmental impacts. In this study, we chemically speciated volatile organic compounds and measured particulate matter mass concentrations in a well-ventilated commercial kitchen for two weeks, including during typical cooking and cleaning operations. From cooking, we observed a complex mixture of volatile organic gases dominated by oxygenated compounds commonly associated with the thermal degradation of cooking oils. Gas-phase chemicals existed at concentrations 2-7 orders of magnitude lower than their exposure limits, due to the high ventilation in the room (mean air change rate of 28 h-1 during operating hours). During evening kitchen cleaning, we observed an increase in the signal of chlorinated gases from 1.1-9.0 times their values during daytime cooking. Particulate matter mass loadings tripled at these times. While exposure to cooking emissions in this indoor environment was reduced effectively by the high ventilation rate, exposure to particulate matter and chlorinated gases was elevated during evening cleaning periods. This emphasizes the need for careful consideration of ventilation rates and methods in commercial kitchen environments during all hours of kitchen operation.

Dynamic Wood Smoke Aerosol Toxicity during Oxidative Atmospheric Aging.

Wildfires are a major source of biomass burning aerosol to the atmosphere, with their incidence and intensity expected to increase in a warmer future climate. However, the toxicity evolution of biomass burning organic aerosol (BBOA) during atmospheric aging remains poorly understood. In this study, we report a unique set of chemical and toxicological metrics of BBOA from pine wood smoldering during multiphase aging by gas-phase hydroxyl radicals (OH). Both the fresh and OH-aged BBOA show activity relevant to adverse health outcomes. The results from two acellular assays (DTT and DCFH) show significant oxidative potential (OP) and reactive oxygen species (ROS) formation in OH-aged BBOA. Also, radical concentrations in the aerosol assessed by electron paramagnetic resonance (EPR) spectroscopy increased by 50% following heterogeneous aging. This enhancement was accompanied by a transition from predominantly carbon-centered radicals (85%) in the fresh aerosol to predominantly oxygen-centered radicals (76%) following aging. Both the fresh and aged biomass burning aerosols trigger prominent antioxidant defense during the in vitro exposure, indicating the induction of oxidative stress by BBOA in the atmosphere. By connecting chemical composition and toxicity using an integrated approach, we show that short-term aging initiated by OH radicals can produce biomass burning particles with a higher particle-bound ROS generation capacity, which are therefore a more relevant exposure hazard for residents in large population centers close to wildfire regions than previously studied fresh biomass burning emissions.

Organic Peroxides in Aerosol: Key Reactive Intermediates for Multiphase Processes in the Atmosphere.

Organic peroxides (POs) are organic molecules with one or more peroxide (-O-O-) functional groups. POs are commonly regarded as chemically labile termination products from gas-phase radical chemistry and therefore serve as temporary reservoirs for oxidative radicals (HOx and ROx) in the atmosphere. Owing to their ubiquity, active gas-particle partitioning behavior, and reactivity, POs are key reactive intermediates in atmospheric multiphase processes determining the life cycle (formation, growth, and aging), climate, and health impacts of aerosol. However, there remain substantial gaps in the origin, molecular diversity, and fate of POs due to their complex nature and dynamic behavior. Here, we summarize the current understanding on atmospheric POs, with a focus on their identification and quantification, state-of-the-art analytical developments, molecular-level formation mechanisms, multiphase chemical transformation pathways, as well as environmental and health impacts. We find that interactions with SO2 and transition metal ions are generally the fast PO transformation pathways in atmospheric liquid water, with lifetimes estimated to be minutes to hours, while hydrolysis is particularly important for α-substituted hydroperoxides. Meanwhile, photolysis and thermolysis are likely minor sinks for POs. These multiphase PO transformation pathways are distinctly different from their gas-phase fates, such as photolysis and reaction with OH radicals, which highlights the need to understand the multiphase partitioning of POs. By summarizing the current advances and remaining challenges for the investigation of POs, we propose future research priorities regarding their origin, fate, and impacts in the atmosphere.

Formation pathways of aldehydes from heated cooking oils.

Cooking emissions account for a major fraction of urban volatile organic compounds and organic aerosol. Aldehyde species, in particular, are important exposure hazards in indoor residential and occupational environments, and precursors to particulate matter and ozone formation in outdoor air. Formation pathways of aldehydes from oils that lead to their emissions are not well understood. In this work, we investigate the underlying mechanisms involved in the formation of aldehydes from heated cooking oil emissions, through studying how antioxidants and oil composition modulate oxidation chemistry. Our results demonstrate that gaseous emissions are driven by radical-mediated autoxidation reactions in cooking oil, and the composition of cooking oils strongly influences the reaction mechanisms. Antioxidants have a dual effect on aldehyde emissions depending on the rates of radical propagation reactions. We propose a mechanistic framework that can be used to understand and predict cooking emissions under different cooking conditions. Our results highlight the need to understand the rates and mechanisms of autoxidation and other reactions in cooking oils in order to accurately predict the gas- and particle-phase emissions from food cooking in urban atmospheres.

Gas- and Particle-Phase Amide Emissions from Cooking: Mechanisms and Air Quality Impacts.

The high-temperature cooking of protein-rich foods represents an important but poorly constrained source of nitrogen-containing gases and particles to indoor and outdoor atmospheres. For example, panfrying meat may form and emit these nitrogen-containing compounds through complex chemistry occurring between heated proteins and cooking oils. Here, we simulate this cooking process by heating amino acids together with triglycerides. We explore their interactions across different temperatures, triglyceride types, and amino acid precursors to form amide-containing products. Ammonia, arising from the thermal degradation of amino acids, may react with a triglyceride's ester linkages, forming amides and promoting de-esterification reactions that break the triglyceride into volatilizable products. Additionally, triglycerides may thermally oxidize and fragment as they are heated, and the resulting oxygenated breakdown products may react with ammonia to form amides. We observed evidence for amide formation through both of these pathways, including gas-phase emissions of C2-11H5-23NO species, whose emission factors ranged from 33 to 813 µg total gas-phase amides per gram of amino acid precursor. Comparable quantities of particle-phase oleamide (C18H35NO) were emitted, ranging from 45 to 218 µg/g. The observed amide products had variable predicted toxicities, highlighting the importance of understanding their emissions from cooking and their ultimate inhalation exposure risks.

Isomer-Resolved Reactivity of Organic Peroxides in Monoterpene-Derived Secondary Organic Aerosol.

Organic peroxides play a vital role in the formation, evolution, and health impacts of atmospheric aerosols, yet their molecular composition and fate in the particle phase remain poorly understood. Here, we identified, using iodometry-assisted liquid chromatography mass spectrometry, a large suite of isomer-resolved peroxide monomers (C8-10H12-18O5-8) and dimers (C15-20H22-34O5-14) in secondary organic aerosol formed from ozonolysis of the most abundant monoterpene (α-pinene). Combining aerosol isothermal evaporation experiments and multilayer kinetic modeling, bulk peroxides were found to undergo rapid particle-phase chemical transformation with an average lifetime of several hours under humid conditions, while the individual peroxides decompose on timescales of half an hour to a few days. Meanwhile, the majority of isomeric peroxides exhibit distinct particle-phase behaviors, highlighting the importance of the characterization of isomer-resolved peroxide reactivity. Furthermore, the reactivity of most peroxides increases with aerosol water content faster in a low relative humidity (RH) range than in a high RH range. Such non-uniform water effects imply a more important role of water as a plasticizer than as a reactant in influencing the peroxide reactivity. The high particle-phase reactivity of organic peroxides and its striking dependence on RH should be considered in atmospheric modeling of their fate and impacts on aerosol chemistry and health effects.

Sources and composition of metals in indoor house dust in a mid-size Canadian city.

House dust is an important medium for exposure to persistent pollutants, such as metals. Detailed characterization of metal composition is needed to identify sources and potential health impacts of exposure. In this study we show that specific metals in dust dominate in different locations within residential homes in a mid-size Canadian city (Fort McMurray, Alberta), up to two years after a major wildfire event in 2016. Dust samples were collected in high-traffic (e.g. bedroom, N = 186), low-traffic (e.g. basement, N = 158), and entranceway areas (N = 171) of residential homes (N = 125), and analyzed for 25 trace metal elements using Inductively Coupled Plasma Mass Spectrometry (ICP-MS). The profile of metal concentrations in the entranceway resembled that of outdoor soils, especially for crustal elements. On the other hand, Cu, Zn, and Pb concentrations in dust sampled in indoor living areas were on average three to six times higher than in other indoor locations indicating indoor sources for these elements. In general, Pb concentrations were similar or lower than in an average Canadian residence, but a substantial fraction showed anomalously high concentrations in the low-traffic areas, particularly on concrete surfaces in basements. Notably, the 2016 wildfires showed limited influence on metal concentrations in indoor dust, despite the widespread concerns in the community about long term exposure. Enrichment factor ratio calculations and principal component analysis showed two classes of sources of metals in dust that represent geogenic-outdoor sources and anthropogenic-indoor sources. Overall, we demonstrate that outdoor and indoor sources of dust impact its composition, and these influences are reflected in the different areas of a home.

Multiphase Oxidation of Sulfur Dioxide in Aerosol Particles: Implications for Sulfate Formation in Polluted Environments.

Atmospheric oxidation of sulfur dioxide (SO2) forms sulfate-containing aerosol particles that impact air quality, climate, and human and ecosystem health. It is well-known that in-cloud oxidation of SO2 frequently dominates over gas-phase oxidation on regional and global scales. Multiphase oxidation involving aerosol particles, fog, and cloud droplets has been generally thought to scale with liquid water content (LWC) so multiphase oxidation would be negligible for aerosol particles due to their low aerosol LWC. However, recent field evidence, particularly from East Asia, shows that fast sulfate formation prevails in cloud-free environments that are characterized by high aerosol loadings. By assuming that the kinetics of cloud water chemistry prevails for aerosol particles, most atmospheric models do not capture this phenomenon. Therefore, the field of aerosol SO2 multiphase chemistry has blossomed in the past decade, with many oxidation processes proposed to bridge the difference between modeled and observed sulfate mass loadings. This review summarizes recent advances in the fundamental understanding of the aerosol multiphase oxidation of SO2, with a focus on environmental conditions that affect the oxidation rate, experimental challenges, mechanisms and kinetics results for individual reaction pathways, and future research directions. Compared to dilute cloud water conditions, this paper highlights the differences that arise at the molecular level with the extremely high solute strengths present in aerosol particles.

HVAC filtration of particles and trace metals: Airborne measurements and the evaluation of quantitative filter forensics.

Filters installed in the heating, ventilation, and air-conditioning (HVAC) systems can serve as air-cleaning and sampling devices for indoor particles. The purpose of this article is to evaluate these dual roles. An occupied home with a central HVAC system equipped with a Minimum Efficiency Reporting Value (MERV, from ASHRAE Standard 52.2) 11 filter was monitored for six weeks. Weekly airborne gravimetric and real-time sampling was performed to measure the particle size distribution and the concentration of total suspended particles (TSP), PM10, PM2.5, PM1, and 12 trace metals. The weekly system runtimes were intentionally changed to provide a wide range of weekly filtration volumes. The quantitative filter forensics (QFF) concentrations of particulate matter (PM) and trace metals were calculated using the analysis of the dust collected on the HVAC filter, the filtration volume, and filter in-situ efficiency. The results indicated that filtration was not influential to remove PM and trace metals as the concentrations during the weeks with continuous HVAC operation were not consistently lower than those during the other weeks. This suggests the dominance of other particle and trace metal source and loss mechanisms weakens the influence of filtration in this home. The QFF evaluation results indicated that the concentration of TSP and over half of the tested trace metals (e.g., Pb, Cd, Ni, V, Sb, K, and Sr) could be estimated by QFF within a factor of two when compared to airborne sampling results. PM10, PM2.5, and PM1 concentrations were significantly underestimated by QFF potentially due to the limitations of size distribution analysis by a laser diffraction particle sizer (LDPS) for the detection of <1 µm particles. Overall, while QFF was promising for TSP and some trace metals, improvement in size distribution analysis could extend the application of QFF for airborne sampling.

Proteome-wide effects of naphthalene-derived secondary organic aerosol in BEAS-2B cells are caused by short-lived unsaturated carbonyls.

Exposure to air pollution causes adverse health outcomes, but the toxicity mechanisms remain unclear. Here, we investigated the dynamic toxicities of naphthalene-derived secondary organic aerosol (NSOA) in a human bronchial epithelial cell line (BEAS-2B) and identified the chemical components responsible for toxicities. The chemical composition of NSOA was found to vary with six simulated atmospheric aging conditions (C1-C6), as characterized by high-resolution mass spectrometry and ion mobility mass spectrometry. Global proteome profiling reveals dynamic evolution in toxicity: Stronger proteome-wide impacts were detected in fresh NSOA, but the effects declined along with atmospheric aging. While Nrf2-regulated proteins (e.g., NQO1) were significantly up-regulated, the majority (78 to 97%) of proteins from inflammation and other pathways were down-regulated by NSOA exposure (e.g., Rho GTPases). This pattern is distinct from the reactive oxygen species (ROS)-mediated toxicity pathway, and an alternative cysteine reaction pathway was revealed by the decreased abundance of proteins (e.g., MT1X) prone to posttranslational thiol modification. This pathway was further validated by observing decreased Nrf2 response in reporter cells, after preincubating NSOA with cysteine. Ethynyl-naphthalene probe was employed to confirm the alkylation of cellular proteome thiols on the proteome-wide level by fresh NSOA via in-gel fluorescence imaging. Nontarget analysis identified several unsaturated carbonyls, including naphthoquinones and hydroxylated naphthoquinones, as the toxic components responsible for cysteine reactivity. Our study provides insights into the dynamic toxicities of NSOA during atmospheric aging and identifies short-lived unsaturated carbonyls as the predominant toxic components at the posttranslational level.

Organic Peroxides and Sulfur Dioxide in Aerosol: Source of Particulate Sulfate.

Sulfur oxides (SOx) are important atmospheric trace species in both gas and particulate phases, and sulfate is a major component of atmospheric aerosol. One potentially important source of particulate sulfate formation is the oxidation of dissolved SO2 by organic peroxides, which comprises a major fraction of secondary organic aerosol (SOA). In this study, we investigated the reaction kinetics and mechanisms between SO2 and condensed-phase peroxides. pH-dependent aqueous phase reaction rate constants between S(IV) and organic peroxide standards were measured. Highly oxygenated organic peroxides with O/C > 0.6 in α-pinene SOA react rapidly with S(IV) species in the aqueous phase. The reactions between organic peroxides and S(IV) yield both inorganic sulfate and organosulfates (OS), as observed by electrospray ionization ion mobility mass spectrometry. For the first time, 34S-labeling experiments in this study revealed that dissolved SO2 forms OS via direct reactions without forming inorganic sulfate as a reactive intermediate. Kinetics of OS formation was estimated semiquantitatively, and such reaction was found to account for 30-60% of sulfur reacted. The photochemical box model GAMMA was applied to assess the implications of the measured SO2 consumption and OS formation rates. Our findings indicate that this novel pathway of SO2-peroxide reaction is important for sulfate formation in submicron aerosol.

Soluble Wood Smoke Extract Promotes Barrier Dysfunction in Alveolar Epithelial Cells through a MAPK Signaling Pathway.

Wildfire smoke induces acute pulmonary distress and is of particular concern to risk groups such as the sick and elderly. Wood smoke (WS) contains many of the same toxic compounds as those found in cigarette smoke (CS) including polycyclic aromatic hydrocarbons, carbon monoxide, and free radicals. CS is a well-established risk factor for respiratory diseases such as asthma and COPD. Limited studies investigating the biological effects of WS on the airway epithelium have been performed. Using a cell culture-based model, we assessed the effects of a WS-infused solution on alveolar epithelial barrier function, cell migration, and survival. The average geometric mean of particles in the WS was 178 nm. GC/MS analysis of the WS solution identified phenolic and cellulosic compounds. WS exposure resulted in a significant reduction in barrier function, which peaked after 24 hours of continuous exposure. The junctional protein E-cadherin showed a prominent reduction in response to increasing concentrations of WS. Furthermore, WS significantly repressed cell migration following injury to the cell monolayer. There was no difference in cell viability following WS exposure. Mechanistically, WS exposure induced activation of the p44/42, but not p38, MAPK signaling pathway, and inhibition of p44/42 phosphorylation prevented the disruption of barrier function and loss of E-cadherin staining. Thus, WS may contribute to the breakdown of alveolar structure and function through a p44/42 MAPK-dependent pathway and may lead to the development and/or exacerbation of respiratory pathologies with chronic exposure.

Improved molecular level identification of organic compounds using comprehensive two-dimensional chromatography, dual ionization energies and high resolution mass spectrometry.

A new analytical methodology combining comprehensive two-dimensional gas chromatography (GC×GC), dual ionization energies and high resolution time of flight mass spectrometry has been developed that improves molecular level identification of organic compounds in complex environmental samples. GC×GC maximizes compound separation providing cleaner mass spectra by minimizing erroneous fragments from interferences and co-eluting peaks. Traditional electron ionization (EI, 70 eV) provides MS fragmentation patterns that can be matched to published EI MS libraries while vacuum ultraviolet photoionization (VUV, 10.5 eV) yields MS with reduced fragmentation enhancing the abundance of the molecular ion providing molecular formulas when combined with high resolution mass spectrometry. We demonstrate this new approach by applying it to a sample of organic aerosol. In this sample, 238 peaks were matched to EI MS library data with FM ≥ 800 but a fifth (42 compounds) were determined to be incorrectly identified because the molecular formula was not confirmed by the VUV MS data. This highlights the importance of using a complementary technique to confirm compound identifications even for peaks with very good matching statistics. In total, 171 compounds were identified by EI MS matching to library spectra with confirmation of the molecular formula from the high resolution VUV MS data and were not dependent on the matching statistics being above a threshold value. A large number of unidentified peaks were still observed with FM < 800, which in routine analysis would typically be neglected. Where possible, these peaks were assigned molecular formulas from the VUV MS data (211 in total). In total, the combination of EI and VUV MS data provides more than twice as much molecular level peak information than traditional approaches and improves confidence in the identification of individual organic compounds. The molecular formula data from the VUV MS data was used, in conjunction with GC×GC retention times and the observed EI MS, to generate a new, searchable EI MS library compatible with the standard NIST MS search program. This library is deliberately dynamic and editable so that other end users can add new entries and update existing entries as new information becomes available.

Development of a Novel Simulation Reactor for Chronic Exposure to Atmospheric Particulate Matter.

Epidemiological studies have shown that air pollution is associated with the morbidity and mortality from cardiopulmonary diseases. Currently, limited experimental models are available to evaluate the physiological and cellular pathways activated by chronic multi-pollutant exposures. This manuscript describes an atmospheric simulation reactor (ASR) that was developed to investigate the health effects of air pollutants by permitting controlled chronic in vivo exposure of mice to combined particulate and gaseous pollutants. BALB/c mice were exposed for 1 hr/day for 3 consecutive days to secondary organic aerosol (SOA, a common particulate air pollutant) at 10-150 µg/m3, SOA (30 µg/m3) + ozone (65 ppb) or SOA + ozone (65 ppb) + nitrogen dioxide (NO2; 100 ppb). Daily exposure to SOA alone led to increased airway hyperresponsiveness (AHR) to methacholine with increasing SOA concentrations. Multi-pollutant exposure with ozone and/or NO2 in conjunction with a sub-toxic concentration of SOA resulted in additive effects on AHR to methacholine. Inflammatory cell recruitment to the airways was not observed in any of the exposure conditions. The ASR developed in this study allows us to evaluate the chronic health effects of relevant multi-pollutant exposures at 'real-life' levels under controlled conditions and permits repeated-exposure studies.

Enhancement in Secondary Organic Aerosol Formation in the Presence of Preexisting Organic Particle.

Atmospheric models of secondary organic aerosol (SOA) typically assume organic species form a well-mixed phase. As a result, partitioning of semivolatile oxidation products into the particle phase to form SOA is thought to be enhanced by preexisting organic particles. In this work, the physicochemical properties that govern such enhancement in SOA yield were examined. SOA yields from α-pinene ozonolysis were measured in the presence of a variety of organic seeds which were chosen based on polarity and phase state at room temperature. Yield enhancement was only observed with seeds of medium polarities (tetraethylene glycol and citric acid). Solid hexadecanol seed was observed to enhance SOA yields only in chamber experiments with longer mixing time scales, suggesting that the mixing process for SOA and hexadecanol may be kinetically limited at shorter time scales. Our observations indicate that, in addition to kinetic limitations, intermolecular interactions also play a significant role in determining SOA yields. Here we propose for the first time to use the Hansen solubility framework to determine aerosol miscibility and predict SOA yield enhancement. These results highlight that current models may overestimate SOA formation, and parametrization of intermolecular forces is needed for accurate predictions of SOA formation.

Comprehensive Chemical Characterization of Hydrocarbons in NIST Standard Reference Material 2779 Gulf of Mexico Crude Oil.

Comprehensive chemical information is needed to understand the environmental fate and impact of hydrocarbons released during oil spills. However, chemical information remains incomplete because of the limitations of current analytical techniques and the inherent chemical complexity of crude oils. In this work, gas chromatography (GC)-amenable C9-C33 hydrocarbons were comprehensively characterized from the National Institute of Standards and Technology Standard Reference Material (NIST SRM) 2779 Gulf of Mexico crude oil by GC coupled to vacuum ultraviolet photoionization mass spectrometry (GC/VUV-MS), with a mass balance of 68 ± 22%. This technique overcomes one important limitation faced by traditional GC and even comprehensive 2D gas chromatography (GC×GC): the necessity for individual compounds to be chromatographically resolved from one another in order to be characterized. VUV photoionization minimizes fragmentation of the molecular ions, facilitating the characterization of the observed hydrocarbons as a function of molecular weight (carbon number, NC), structure (number of double bond equivalents, NDBE), and mass fraction (mg kg(-1)), which represent important metrics for understanding their fate and environmental impacts. Linear alkanes (8 ± 1%), branched alkanes (11 ± 2%), and cycloalkanes (37 ± 12%) dominated the mass with the largest contribution from cycloalkanes containing one or two rings and one or more alkyl side chains (27 ± 9%). Linearity and good agreement with previous work for a subset of >100 components and for the sum of compound classes provided confidence in our measurements and represents the first independent assessment of our analytical approach and calibration methodology. Another crude oil collected from the Marlin platform (35 km northeast of the Macondo well) was shown to be chemically identical within experimental errors to NIST SRM 2779, demonstrating that Marlin crude is an appropriate surrogate oil for researchers conducting laboratory research into impacts of the DeepWater Horizon disaster.