Eladio M. Knipping

Isoprene Epoxydiols as Precursors to Secondary Organic Aerosol Formation: Acid-Catalyzed Reactive Uptake Studies with Authentic Compounds

Isoprene epoxydiols (IEPOX), formed from the photooxidation of isoprene under low-NO(x) conditions, have recently been proposed as precursors of secondary organic aerosol (SOA) on the basis of mass spectrometric evidence. In the present study, IEPOX isomers were synthesized in high purity (>99%) to investigate their potential to form SOA via reactive uptake in a series of controlled dark chamber studies followed by reaction product analyses. IEPOX-derived SOA was substantially observed only in the presence of acidic aerosols, with conservative lower-bound yields of 4.7-6.4% for β-IEPOX and 3.4-5.5% for δ-IEPOX, providing direct evidence for IEPOX isomers as precursors to isoprene SOA. These chamber studies demonstrate that IEPOX uptake explains the formation of known isoprene SOA tracers found in ambient aerosols, including 2-methyltetrols, C(5)-alkene triols, dimers, and IEPOX-derived organosulfates. Additionally, we show reactive uptake on the acidified sulfate aerosols supports a previously unreported acid-catalyzed intramolecular rearrangement of IEPOX to cis- and trans-3-methyltetrahydrofuran-3,4-diols (3-MeTHF-3,4-diols) in the particle phase. Analysis of these novel tracer compounds by aerosol mass spectrometry (AMS) suggests that they contribute to a unique factor resolved from positive matrix factorization (PMF) of AMS organic aerosol spectra collected from low-NO(x), isoprene-dominated regions influenced by the presence of acidic aerosols.

Real-Time Continuous Characterization of Secondary Organic Aerosol Derived from Isoprene Epoxydiols in Downtown Atlanta, Georgia, Using the Aerodyne Aerosol Chemical Speciation Monitor

Real-time continuous chemical measurements of fine aerosol were made using an Aerodyne Aerosol Chemical Speciation Monitor (ACSM) during summer and fall 2011 in downtown Atlanta, Georgia. Organic mass spectra measured by the ACSM were analyzed by positive matrix factorization (PMF), yielding three conventional factors: hydrocarbon-like organic aerosol (HOA), semivolatile oxygenated organic aerosol (SV-OOA), and low-volatility oxygenated organic aerosol (LV-OOA). An additional OOA factor that contributed to 33 ± 10% of the organic mass was resolved in summer. This factor had a mass spectrum that strongly correlated (r(2) = 0.74) to that obtained from laboratory-generated secondary organic aerosol (SOA) derived from synthetic isoprene epoxydiols (IEPOX). Time series of this additional factor is also well correlated (r(2) = 0.59) with IEPOX-derived SOA tracers from filters collected in Atlanta but less correlated (r(2) < 0.3) with a methacrylic acid epoxide (MAE)-derived SOA tracer, α-pinene SOA tracers, and a biomass burning tracer (i.e., levoglucosan), and primary emissions. Our analyses suggest IEPOX as the source of this additional factor, which has some correlation with aerosol acidity (r(2) = 0.3), measured as H(+) (nmol m(-3)), and sulfate mass loading (r(2) = 0.48), consistent with prior work showing that these two parameters promote heterogeneous chemistry of IEPOX to form SOA.

Characterization and Quantification of Isoprene-Derived Epoxydiols in Ambient Aerosol in the Southeastern United States

Isoprene-derived epoxydiols (IEPOX) are identified in ambient aerosol samples for the first time, together with other previously identified isoprene tracers (i.e., 2-methyltetrols, 2-methylglyceric acid, C(5)-alkenetriols, and organosulfate derivatives of 2-methyltetrols). Fine ambient aerosol collected in downtown Atlanta, GA and rural Yorkville, GA during the 2008 August Mini-Intensive Gas and Aerosol Study (AMIGAS) was analyzed using both gas chromatography/quadrupole mass spectrometry (GC/MS) and gas chromatography/time-of-flight mass spectrometry (GC/TOFMS) with prior trimethylsilylation. Mass concentrations of IEPOX ranged from approximately 1 to 24 ng m(-3) in the aerosol collected from the two sites. Detection of particle-phase IEPOX in the AMIGAS samples supports recent laboratory results that gas-phase IEPOX produced from the photooxidation of isoprene under low-NO(x) conditions is a key precursor of ambient isoprene secondary organic aerosol (SOA) formation. On average, the sum of the mass concentrations of IEPOX and the measured isoprene SOA tracers accounted for about 3% of the organic carbon, demonstrating the significance of isoprene oxidation to the formation of ambient aerosol in this region.

Development of a United States-Mexico emissions inventory for the big bend regional aerosol and visibility observational (BRAVO) study

Abstract The Big Bend Regional Aerosol and Visibility Observational (BRAVO) Study was commissioned to investigate the sources of haze at Big Bend National Park in southwest Texas. The modeling domain of the BRAVO Study includes most of the continental United States and Mexico. The BRAVO emissions inventory was constructed from the 1999 National Emission Inventory for the United States, modified to include finer-resolution data for Texas and 13 U.S. states in close proximity. The first regional-scale Mexican emissions inventory designed for air-quality modeling applications was developed for 10 northern Mexican states, the Tula Industrial Park in the state of Hidalgo, and the Popocatépetl volcano in the state of Puebla. Emissions data were compiled from numerous sources, including the U.S. Environmental Protection Agency (EPA), the Texas Natural Resources Conservation Commission (now Texas Commission on Environmental Quality), the Eastern Research Group, the Minerals Management Service, the Instituto Nacional de Ecología, and the Instituto Nacional de Estadistica Geografía y Informática. The inventory includes emissions for CO, nitrogen oxides, sulfur dioxide, volatile organic compounds (VOCs), ammonia, particulate matter (PM) <10 μm in aerodynamic diameter, and PM <2.5 μm in aerodynamic diameter. Wind-blown dust and biomass burning were not included in the inventory, although high concentrations of dust and organic PM attributed to biomass burning have been observed at Big Bend National Park. The SMOKE modeling system was used to generate gridded emissions fields for use with the Regional Modeling System for Aerosols and Deposition (REMSAD) and the Community Multiscale Air Quality model modified with the Model of Aerosol Dynamics, Reaction, Ionization and Dissolution (CMAQ-MADRID). The compilation of the inventory, supporting model input data, and issues encountered during the development of the inventory are documented. A comparison of the BRAVO emissions inventory for Mexico with other emerging Mexican emission inventories illustrates their uncertainty.

A comparison of vascular effects from complex and individual air pollutants indicates a role for monoxide gases and volatile hydrocarbons.

Background Emerging evidence suggests that the systemic vasculature may be a target of inhaled pollutants of vehicular origin. We have identified several murine markers of vascular toxicity that appear sensitive to inhalation exposures to combustion emissions. Objective We sought to examine the relative impact of various pollutant atmospheres and specific individual components on these markers of altered vascular transcription and lipid peroxidation. Methods Apolipoprotein E knockout (ApoE−/−) mice were exposed to whole combustion emissions (gasoline, diesel, coal, hardwood), biogenically derived secondary organic aerosols (SOAs), or prominent combustion-source gases [nitric oxide (NO), NO2, carbon monoxide (CO)] for 6 hr/day for 7 days. Aortas were assayed for transcriptional alterations of endothelin-1 (ET-1), matrix metalloproteinase-9 (MMP-9), tissue inhibitor of metalloproteinase-2 (TIMP-2), and heme oxygenase-1 (HO-1), along with measures of vascular lipid peroxides (LPOs) and gelatinase activity. Results We noted transcriptional alterations with exposures to gasoline and diesel emissions. Interestingly, ET-1 and MMP-9 transcriptional effects could be recreated by exposure to CO and NO, but not NO2 or SOAs. Gelatinase activity aligned with levels of volatile hydrocarbons and also monoxide gases. Neither gases nor particles induced vascular LPO despite potent effects from whole vehicular emissions. Conclusions In this head-to-head comparison of the effects of several pollutants and pollutant mixtures, we found an important contribution to vascular toxicity from readily bioavailable monoxide gases and possibly from volatile hydrocarbons. These data support a role for traffic-related pollutants in driving cardiopulmonary morbidity and mortality.

Secondary organic aerosol formation from methacrolein photooxidation: roles of NOx level, relative humidity and aerosol acidity

Environmental context Secondary organic aerosols formed from the oxidation of volatile organic compounds make a significant contribution to atmospheric particulate matter, which in turn affects both global climate change and human health. We investigate the mechanisms of formation and the chemical properties of secondary organic aerosols derived from isoprene, the most abundant non-methane-based, volatile organic compound emitted into the Earth’s atmosphere. However, the exact manner in which these aerosols are formed, and how they are affected by environmental conditions, remains unclear. Abstract Secondary organic aerosol (SOA) formation from the photooxidation of methacrolein (MACR) was examined in a dual outdoor smog chamber under varied initial nitric oxide (NO) levels, relative humidities (RHs) and seed aerosol acidities. Aerosol sizing measurements and off-line chemical analyses by gas chromatography/mass spectrometry and ultra performance liquid chromatography/electrospray ionisation high-resolution quadrupole time-of-flight mass spectrometry (UPLC/ESI-HR-Q-TOFMS) were used to characterise MACR SOA formation. Results indicate that both SOA mass and chemical composition largely depend on the initial MACR/NO ratio and RH conditions. Specifically, at lower initial NO levels (MACR/NO = ~2.7) more substantial SOA is formed under dry conditions (5–20 % RH) compared to wet conditions (30–80 % RH). However, at higher initial NO levels (MACR/NO = ~0.9), the maximum SOA formation was marginally higher under wet conditions. Furthermore, UPLC/ESI-HR-Q-TOFMS data suggest that most particle-phase oligomers, which have been previously observed to form from the oxidation of methacryloylperoxynitrate, were enhanced under dry conditions. In addition to 2-methylglyceric acid and organosulfates derived from MACR oxidation, a nitrogen-containing organic tracer compound was found to form substantially in both chamber-generated and ambient aerosol samples collected from downtown Atlanta, GA, during the 2008 August Mini-Intensive Gas and Aerosol Study (AMIGAS). Moreover, increasing aerosol acidity because of additional sulfuric acid appears to have a negligible effect on both SOA mass and most SOA constituents. Nevertheless, increased RH and aerosol acidity were both observed to enhance organosulfate formation; however, elevating RH mediates organosulfate formation, suggesting that wet sulfate aerosols are necessary to form organosulfates in atmospheric aerosols.

Toward Effective Source Apportionment Using Positive Matrix Factorization: Experiments with Simulated PM2.5 Data

Abstract To elucidate the relationship between factors resolved by the positive matrix factorization (PMF) receptor model and actual emission sources and to refine the PMF modeling strategy, speciated PM2.5 (particulate matter with aerodynamic diameter <2.5 μm) data generated from a state-of-the-art chemical transport model for two rural sites in the eastern United States are subjected to PMF analysis. In addition to χ-2 and R 2 used to infer the quality of fitting, the interpretability of PMF factors with respect to known primary and secondary sources is evaluated using a root mean square difference analysis. For the most part, factors are found to represent imperfect combinations of sources, and the optimal number of factors should be just adequate to explain the input data (e.g., R 2 > 0.95). Retaining more factors in the model does not help resolve minor sources, unless temporal resolution of the data is increased, thus allowing more information to be used by the model. If guided with a priori knowledge of source markers and/or special events, rotation of factors leads to more interpretable PMF factors. The choice of uncertainty weighting coefficients greatly influences the PMF modeling results, but it cannot usually be determined for simulated or real-world data. A simple test is recommended to check whether the weighting coefficients are suitable. However, uncertainties in the data divert PMF solutions even when the optimal weighting coefficients and number of factors are in place.

Cardiopulmonary response to inhalation of biogenic secondary organic aerosol

An irradiation chamber designed for reproducible generation of inhalation test atmospheres of secondary organic aerosol (SOA) was used to evaluate cardiopulmonary responses in rodents exposed to SOA derived from the oxidation of α-pinene. SOA atmospheres were produced with 10:1 ratios of α-pinene:nitrogen oxides (NOx) and 10:1:1 ratios of α-pinene:nitrogen oxides:sulfur dioxide (SO2). SOA atmospheres were produced to yield 200 μg m−3 of particulate matter (PM). Exposures were conducted downstream of honeycomb denuders employed to remove the gas-phase precursors and reaction products. Nose-only exposures were conducted with both rats (pulmonary effects) and mice (pulmonary and cardiovascular effects). Composition of the atmospheres was optimized to ensure that the SOA generated resembled SOA observed in previous irradiation studies, and contained specific SOA compounds of interest (e.g., organosulfates) identified in ambient air. Pulmonary and cardiovascular toxicity were measured in two different rodent species. In situ chemiluminescence and thiobarbituric acid– reactive substances (TBARS) were used to evaluate oxidative reactions in the F344 rats. ApoE−/− mice were exposed for 7 days and measurements of TBARS and gene expression of heme oxygenase-1 (HO-1), endothelin-1 (ET-1), matrix metalloproteinase-9 (MMP-9) were made in aorta. Pulmonary inflammatory responses in both species were measured by bronchoalveolar lavage fluid (BALF) cell counts. No pulmonary inflammation was observed in either species. A mild response was observed in mouse aorta for the upregulation of HO-1 and MMP-9, but was not seen for ET-1. Overall, α-pinene–derived SOA, including SOA that included organosulfate compounds, revealed limited biological response after short-term inhalation exposures

Modeling surface-mediated renoxification of the atmosphere via reaction of gaseous nitric oxide with deposited nitric acid

Abstract Air quality models consider the formation and deposition of nitric acid (HNO3) on surfaces to be an irreversible sink of atmospheric nitrogen oxides (NOx) and therefore an effective termination step in the ozone formation cycle. However, experimental evidence suggests that the reaction of gaseous nitric oxide with nitric acid on surfaces may convert HNO3 to photochemically active NOx. A first-order simulation of this surface-mediated renoxification process is performed using an air quality model of the South Coast Air Basin of California. Peak ozone concentrations are predicted closer to observed values in regions regularly underpredicted by base case models. In certain regions, ozone predictions are enhanced by as much as ∼30 ppb or ∼20% compared to the baseline simulation. These results suggest that renoxification processes may be a key to resolving long-standing shortcomings of air quality models, in addition to reconciling [HNO3]/[NOx] ratios in remote regions. This study also illustrates that the surface terrain may play a more active chemical role than hitherto considered in air quality models.

Modeling regional haze in the BRAVO study using CMAQ-MADRID: 1. Model evaluation

The Big Bend Regional Aerosol and Visibility Observational (BRAVO) study was a multiyear monitoring and assessment study of the causes of regional haze in Big Bend National Park (BBNP), Texas. The Community Multiscale Air Quality model augmented with the Model of Aerosol Dynamics, Reaction, Ionization and Dissolution (CMAQ-MADRID) was used to simulate tracers and regional haze in Big Bend National Park for the full BRAVO period of July-October 1999. The BRAVO monitoring network provided an opportunity to conduct a comprehensive evaluation of CMAQ-MADRID over a 4-month period. Tracer simulations revealed uncertainties in tlie model representation of advection and diffusion processes and the effects of uncertainties in meteorological fields on transport simulations. Results improved with the implementation of a more diffusive horizontal diffusion scheme. The 12-km resolution provided better results than the 4- and 36-km resolution simulations for 15-25 August 1999 and the 36-km resolution provided better results for 5-15 October. Model performance for tracers suggests that as currently formulated, grid-based Eulerian models are not well suited to simulate the impacts of long-range transport of individual point source emissions at specific receptors. Nonetheless, they are suitable for resolving the contributions of source regions that may contain multiple area and point sources. Using a 36-km resolution for a 4-month simulation, the model performance was good in comparison with contemporary models for sulfate (the major PM 2.5 component) in the region of interest (i.e., BBNP), with a low bias and coefficient of determination better than 0.5. However, the model overestimated sulfate and total sulfur significantly in other parts of the modeling domain. For organic particulate matter (OM, the second most prevalent PM 2.5 component at BBNP), the model correctly reproduced the dominance of secondary organic aerosols and explained most of the variance in the OM concentrations; however, it underestimated OM concentrations consistently. Model performance was poor for the less prevalent components of PM 2.5 (i.e., nitrate and black carbon) at BBNP. Diagnostic analyses suggest that the discrepancies between model simulation results and observations are due not only to limitations in the model formulation but also to uncertainties in the model inputs, including emissions, meteorology, and boundary conditions.