Brown, Steven G., authorHerckes, Pierre, authorKreidenweis, Sonia M., authorCollett, Jeffrey L., Jr., author2022-08-022022-08-022001-12https://hdl.handle.net/10217/235503December 2001.The Big Bend Regional Aerosol and Visibility Observational (BRAVO) study was a four month field campaign (July-October 1999) to investigate aerosol particle properties, sources, and impacts on regional visibility in Big Bend National Park, Texas. Daily PM2.5 aerosol samples were collected on pre-fired quartz fiber filters for detailed molecular analysis of the aerosol organic carbon fraction. Aerosol black carbon concentrations during BRAVO were measured with an aethalometer. The molecular characterization of the organic carbon fraction of aerosol present during the BRAVO study was performed using gas chromatography - mass spectroscopy (GC-MS). Organic carbon concentrations on individual days were too low for a detailed analysis by GC-MS. Therefore, multi-day composite samples, selected based on common air mass trajectories and temporal proximity, were extracted and analyzed for numerous compounds, including n-alkanes, polycyclic aromatic hydrocarbons (PAH), and alkanoic acids. Low alkane Carbon Preference Indices (CPIs) during July through September reflect similar concentrations of n-alkanes containing odd and even numbers of carbon atoms and indicate that anthropogenic emissions were important contributors to carbonaceous aerosol during this period, when air masses generally were advected from the east over Texas and Mexico. In October, CPIs increased, reflecting increased influence of odd carbon numbered alkanes and suggesting a predominant biogenic aerosol influence with air masses arriving from the north and the south. Plant wax contributions to odd carbon number alkanes (C25-C33) were estimated to range between 26% and 78%, with the highest contributions occurring in October with air masses arriving from the north and south. Periods with transport from eastern Texas and northeastern Mexico had much smaller plant wax contributions. Alkanoic acids were the most abundant compound class, with CPIs that were high throughout the study. The high acid CPI suggests that the alkanoic acids may be largely biogenic in origin, a finding consistent with other studies. Caution is required in interpreting the acid CPI, however, as alkanoic acids can also be formed as secondary products of atmospheric reactions. Polycyclic aromatic hydrocarbons (P AH) were usually not found in abundance, suggesting that upwind combustion emissions were not important contributors to carbonaceous aerosol or that P AH were removed by reaction or deposition in transit. Higher P AH concentrations during one period indicated a more significant contribution from fresh combustion emissions. Molecular source tracer (hopanes for vehicle emissions, levoglucosan for wood combustion, cholesterol for meat cooking) concentrations were generally not detected. Based on analytical detection limits for these species, it was estimated that wood smoke contributed no more than 1% of the total Organic Carbon (OC) present, vehicle exhaust contributed no more than 4%, and smoke from meat cooking contributed less than 13%. The presence of other wood smoke tracer molecules, however, suggests a possibly greater influence from wood combustion and possible chemical instability of levoglucosan during multi-day transport in an acidic atmosphere. Several observations suggest that secondary production contributed significantly to BRAVO carbonaceous aerosol. Examination of ratios of aerosol organic carbon to elemental carbon indicates that secondary organic aerosol may have contributed between 45% and 90% of the total BRAVO aerosol organic carbon. High ratios of saturated/unsaturated C18 acids, an abundance of nonanoic acid, and high concentrations of 6,10,14 trimethylpentadecan-2-one (an indicator of secondary aerosol production from vegetation emissions) all support the conclusion that secondary aerosol formation was important in the region. Total black carbon (BC) concentrations ranged from below detection limit (71 ng/m3) to 267 ng/m3, averaging 129 ng/m3. Fine (< 1 μm) aerosol BC concentrations averaged 114 ng/m3, and comprised 89% of the total BC. BC concentrations correlated reasonably well with aerosol sulfate concentrations, suggesting similar source regions for these species.reportsengCopyright and other restrictions may apply. User is responsible for compliance with all applicable laws. For information about copyright law, please see https://libguides.colostate.edu/copyright.Aerosols -- MeasurementAir -- Pollution -- Texas -- Big Bend National ParkText