Traffic, transport, and vegetation drive VOC concentrations in a major urban area in Texas.

The population of Texas has increased rapidly in the past decade. The San Antonio Field Study (SAFS) was designed to investigate ozone (O3) production and precursors in this rapidly changing, sprawling metropolitan area. There are still many questions regarding the sources and chemistry of volatile organic compounds (VOCs) in urban areas like San Antonio which are affected by a complex mixture of industry, traffic, biogenic sources and transported pollutants. The goal of the SAFS campaign in May 2017 was to measure inorganic trace gases, VOCs, methane (CH4), and ethane (C2H6). The SAFS field design included two sites to better assess air quality across the metro area: an urban site (Traveler's World; TW) and a downwind/suburban site (University of Texas at San Antonio; UTSA). The results indicated that acetone (2.52 ± 1.17 and 2.39 ± 1.27 ppbv), acetaldehyde (1.45 ± 1.02 and 0.93 ± 0.45 ppbv) and isoprene (0.64 ± 0.49 and 1.21 ± 0.85 ppbv; TW and UTSA, respectively) were the VOCs with the highest concentrations. Additionally, positive matrix factorization showed three dominant factors of VOC emissions: biogenic, aged urban mixed source, and acetone. Methyl vinyl ketone and methacrolein (MVK + MACR) exhibited contributions from both secondary photooxidation of isoprene and direct emissions from traffic. The C2H6:CH4 demonstrated potential influence of oil and gas activities in San Antonio. Moreover, the high O3 days during the campaign were in the NOx-limited O3 formation regime and were preceded by evening peaks in select VOCs, NOx and CO. Overall, quantification of the concentration and trends of VOCs and trace gases in a major city in Texas offers vital information for general air quality management and supports strategies for reducing O3 pollution. The SAFS campaign VOC results will also add to the growing body of literature on urban sources and concentrations of VOCs in major urban areas.

Bouncier Particles at Night: Biogenic Secondary Organic Aerosol Chemistry and Sulfate Drive Diel Variations in the Aerosol Phase in a Mixed Forest.

Aerosol phase state is critical for quantifying aerosol effects on climate and air quality. However, significant challenges remain in our ability to predict and quantify phase state during its evolution in the atmosphere. Herein, we demonstrate that aerosol phase (liquid, semisolid, solid) exhibits a diel cycle in a mixed forest environment, oscillating between a viscous, semisolid phase state at night and liquid phase state with phase separation during the day. The viscous nighttime particles existed despite higher relative humidity and were independently confirmed by bounce factor measurements and atomic force microscopy. High-resolution mass spectrometry shows the more viscous phase state at night is impacted by the formation of terpene-derived and higher molecular weight secondary organic aerosol (SOA) and smaller inorganic sulfate mass fractions. Larger daytime particulate sulfate mass fractions, as well as a predominance of lower molecular weight isoprene-derived SOA, lead to the liquid state of the daytime particles and phase separation after greater uptake of liquid water, despite the lower daytime relative humidity. The observed diel cycle of aerosol phase should provoke rethinking of the SOA atmospheric lifecycle, as it suggests diurnal variability in gas-particle partitioning and mixing time scales, which influence aerosol multiphase chemistry, lifetime, and climate impacts.

Bidirectional Ecosystem-Atmosphere Fluxes of Volatile Organic Compounds Across the Mass Spectrum: How Many Matter?

Terrestrial ecosystems are simultaneously the largest source and a major sink of volatile organic compounds (VOCs) to the global atmosphere, and these two-way fluxes are an important source of uncertainty in current models. Here, we apply high-resolution mass spectrometry (proton transfer reaction-quadrupole interface time-of-flight; PTR-QiTOF) to measure ecosystem-atmosphere VOC fluxes across the entire detected mass range (m/z 0-335) over a mixed temperate forest and use the results to test how well a state-of-science chemical transport model (GEOS-Chem CTM) is able to represent the observed reactive carbon exchange. We show that ambient humidity fluctuations can give rise to spurious VOC fluxes with PTR-based techniques and present a method to screen for such effects. After doing so, 377 of the 636 detected ions exhibited detectable gross fluxes during the study, implying a large number of species with active ecosystem-atmosphere exchange. We introduce the reactivity flux as a measure of how Earth-atmosphere fluxes influence ambient OH reactivity and show that the upward total VOC (∑VOC) carbon and reactivity fluxes are carried by a far smaller number of species than the downward fluxes. The model underpredicts the ∑VOC carbon and reactivity fluxes by 40-60% on average. However, the observed net fluxes are dominated (90% on a carbon basis, 95% on a reactivity basis) by known VOCs explicitly included in the CTM. As a result, the largest CTM uncertainties in simulating VOC carbon and reactivity exchange for this environment are associated with known rather than unrepresented species. This conclusion pertains to the set of species detectable by PTR-TOF techniques, which likely represents the majority in terms of carbon mass and OH reactivity, but not necessarily in terms of aerosol formation potential. In the case of oxygenated VOCs, the model severely underpredicts the gross fluxes and the net exchange. Here, unrepresented VOCs play a larger role, accounting for ~30% of the carbon flux and ~50% of the reactivity flux. The resulting CTM biases, however, are still smaller than those that arise from uncertainties for known and represented compounds.

Source attribution and quantification of benzene event emissions in a Houston ship channel community based on real-time mobile monitoring of ambient air.

UNLABELLED: A mobile laboratory equipped with a proton transfer reaction mass spectrometer (PTR-MS) operated in Galena Park, Texas, near the Houston Ship Channel during the Benzene and other Toxics Exposure Study (BEE-TEX). The mobile laboratory measured transient peaks of benzene of up to 37 ppbv in the afternoon and evening of February 19, 2015. Plume reconstruction and source attribution were performed using the four-dimensional (4D) variational data assimilation technique and a three-dimensional (3D) micro-scale forward and adjoint air quality model based on mobile PTR-MS data and nearby stationary wind measurements at the Galena Park Continuous Air Monitoring Station (CAMS). The results of inverse modeling indicate that significant pipeline emissions of benzene may at least partly explain the ambient concentration peaks observed in Galena Park during BEE-TEX. Total pipeline emissions of benzene inferred within the 16-km(2) model domain exceeded point source emissions by roughly a factor of 2 during the observational episode. Besides pipeline leaks, the model also inferred significant benzene emissions from marine, railcar, and tank truck loading/unloading facilities, consistent with the presence of a tanker and barges in the Kinder Morgan port terminal during the afternoon and evening of February 19. Total domain emissions of benzene exceeded corresponding 2011 National Emissions Inventory (NEI) estimates by a factor of 2-6. IMPLICATIONS: Port operations involving petrochemicals may significantly increase emissions of air toxics from the transfer and storage of materials. Pipeline leaks, in particular, can lead to sporadic emissions greater than in emission inventories, resulting in higher ambient concentrations than are sampled by the existing monitoring network. The use of updated methods for ambient monitoring and source attribution in real time should be encouraged as an alternative to expanding the conventional monitoring network.