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Methane emissions from oil and gas facilities can exhibit operation-dependent temporal variability; however, this variability has yet to be fully characterized. A field campaign was conducted in June 2014 in the Eagle Ford basin, Texas, to examine spatiotemporal variability of methane emissions using four methods. Clusters of methane-emitting sources were estimated from 14 aerial surveys of two ("East" or "West") 35 × 35 km grids, two aircraft-based mass balance methods measured emissions repeatedly at five gathering facilities and three flares, and emitting equipment source-types were identified via helicopter-based infrared camera at 13 production and gathering facilities. Significant daily variability was observed in the location, number (East: 44 ± 20% relative standard deviation (RSD), N = 7; West: 37 ± 30% RSD, N = 7), and emission rates (36% of repeat measurements deviate from mean emissions by at least ±50%) of clusters of emitting sources. Emission rates of high emitters varied from 150-250 to 880-1470 kg/h and regional aggregate emissions of large sources (>15 kg/h) varied up to a factor of ∼3 between surveys. The aircraft-based mass balance results revealed comparable variability. Equipment source-type changed between surveys and alterations in operational-mode significantly influenced emissions. Results indicate that understanding temporal emission variability will promote improved mitigation strategies and additional analysis is needed to fully characterize its causes.

Speciated particle-phase organic nitrates (pONs) were quantified using online chemical ionization MS during June and July of 2013 in rural Alabama as part of the Southern Oxidant and Aerosol Study. A large fraction of pONs is highly functionalized, possessing between six and eight oxygen atoms within each carbon number group, and is not the common first generation alkyl nitrates previously reported. Using calibrations for isoprene hydroxynitrates and the measured molecular compositions, we estimate that pONs account for 3% and 8% of total submicrometer organic aerosol mass, on average, during the day and night, respectively. Each of the isoprene- and monoterpenes-derived groups exhibited a strong diel trend consistent with the emission patterns of likely biogenic hydrocarbon precursors. An observationally constrained diel box model can replicate the observed pON assuming that pONs (i) are produced in the gas phase and rapidly establish gas-particle equilibrium and (ii) have a short particle-phase lifetime (∼2-4 h). Such dynamic behavior has significant implications for the production and phase partitioning of pONs, organic aerosol mass, and reactive nitrogen speciation in a forested environment.

The emission, dispersion, and photochemistry of isoprene (C5H8) and related chemical species in the convective boundary layer (CBL) during sunlit daytime were studied over a mixed forest in the southeastern United States by combining ground-based and aircraft observations. Fluxes of isoprene and monoterpenes were quantified at the top of the forest canopy using a high-resolution proton transfer reaction time-of-flight mass spectrometer (PTR-TOF-MS). Snapshot (2 min sampling duration) vertical profiles of isoprene, methyl vinyl ketone (MVK)Cmethacrolein (MACR), and monoterpenes were collected from aircraft every hour in the CBL (100-1000 m). Both ground-based and airborne collected volatile organic compound (VOC) data are used to constrain the initial conditions of a mixed-layer chemistry model (MXLCH), which is applied to examine the chemical evolution of the O3-NOx-HOx-VOC system and how it is affected by boundary layer dynamics in the CBL. The chemical loss rate of isoprene (1 h) is similar to the turbulent mixing timescale (0.1-0.5 h), which indicates that isoprene concentrations are equally dependent on both photooxidation and boundary layer dynamics. Analysis of a modelderived concentration budget suggests that diurnal evolution of isoprene inside the CBL is mainly controlled by surface emissions and chemical loss; the diurnal evolution of O3 is dominated by entrainment. The NO to HO2 ratio (NO :HO2) is used as an indicator of anthropogenic impact on the CBL chemical composition and spans a wide range (1-163). The fate of hydroxyl-substituted isoprene peroxyl radical (HOC5H8OO q; ISOPOO) is strongly affected by NO:HO2, shifting from NO-dominant to NO-HO2-balanced conditions from early morning to noontime. This chemical regime change is reflected in the diurnal evolution of isoprene hydroxynitrates (ISOPN) and isoprene hydroxy hydroperoxides (ISOPOOH).

We investigated the ability of three planetary boundary layer (PBL) schemes in the Weather Research and Forecasting (WRF) Model to simulate boundary layer turbulence in the "gray zone" (i.e., resolutions from 100 m to 1 km). The three schemes chosen are the well-established MYNN PBL scheme and the two newest PBL schemes added to WRF: the three-dimensional scale-adaptive turbulent kinetic energy scheme (SMS-3DTKE) and the E–ε parameterization scheme (EEPS). The SMS-3DTKE scheme is designed to be scale aware and avoid the double counting of TKE in simulations within the gray zone. We evaluated their performance using aircraft measurements obtained during three research flights immediately downwind of Manhattan, New York City, New York. The MYNN PBL scheme simulates TKE best, despite not being scale aware and slightly underestimating TKE from observations, whereas the SMS-3DTKE scheme appears to be overly scale aware for the three flights examined, in particular, when combined with the MM5 surface layer scheme. The EEPS scheme significantly underestimates TKE, mostly in the elevated layers of the boundary layer. In addition, we examined the impact of flow over tall buildings on observed TKE and found that only the windiest day showed a significant increase in TKE directly downwind of Manhattan. This impact was not reproduced by any of the model configurations, regardless of the land-use data selected, although the better resolved National Land Cover Database (NLCD) land use led to a slight improvement of the spatial distribution of TKE, implying that more explicit representation of the impact of tall buildings may be needed to fully capture their impact on boundary layer turbulence. Significance Statement: Because the majority of the world's population lives in cities, it is important to accurately simulate the atmosphere above and around these cities including the turbulence caused by tall buildings. This turbulence can significantly impact the mixing and dilution of air pollutants and other toxins in highly populated urban environments. The scale of cities often falls into what is known as the "gray zone" for turbulence modeling, which has been analyzed theoretically before but rarely in varied real-world conditions. Our analysis around New York City, New York, suggests that model turbulence schemes can match observations relatively well even at gray zone scales, although newer schemes require refinement, and all schemes tend to underestimate turbulence downwind of tall buildings. [ABSTRACT FROM AUTHOR]

Reactive halogen chemistry in the springtime Arctic causes ozone depletion events and alters the rate of pollution processing. There are still many uncertainties regarding this chemistry, including the multiphase recycling of halogens and how sea ice impacts the source strength of reactive bromine. Adding to these uncertainties are the impacts of a rapidly warming Arctic. We present observations from the CHACHA (CHemistry in the Arctic: Clouds, Halogens, and Aerosols) field campaign based out of Utqiaġvik, Alaska, from mid-February to mid-April of 2022 to provide information on the vertical distribution of bromine monoxide (BrO), which is a tracer for reactive bromine chemistry. Data were gathered using the Heidelberg Airborne Imaging DOAS (differential optical absorption spectroscopy) Instrument (HAIDI) on the Purdue University Airborne Laboratory for Atmospheric Research (ALAR) and employing a unique sampling technique of vertically profiling the lower atmosphere with the aircraft via "porpoising" maneuvers. Observations from HAIDI were coupled to radiative transfer model calculations to retrieve mixing ratio profiles throughout the lower atmosphere (below 1000 m), with unprecedented vertical resolution (50 m) and total information gathered (average of 17.5 degrees of freedom) for this region. A cluster analysis was used to categorize 245 retrieved BrO mixing ratio vertical profiles into four common profile shapes. We often found the highest BrO mixing ratios at the Earth's surface with a mean of nearly 30 pmol mol -1 in the lowest 50 m, indicating an important role for multiphase chemistry on the snowpack in reactive bromine production. Most lofted-BrO profiles corresponded with an aerosol profile that peaked at the same altitude (225 m above the ground), suggesting that BrO was maintained due to heterogeneous reactions on particle surfaces aloft during these profiles. A majority (11 of 15) of the identified lofted-BrO profiles occurred on a single day, 19 March 2022, over an area covering more than 24 000 km 2 , indicating that this was a large-scale lofted-BrO event. The clustered BrO mixing ratio profiles should be particularly useful for some MAX-DOAS (multi-axis DOAS) studies, where a priori BrO profiles and their uncertainties, used in optimal estimation inversion algorithms, are not often based on previous observations. Future MAX-DOAS studies (and past reanalyses) could rely on the profiles provided in this work to improve BrO retrievals. [ABSTRACT FROM AUTHOR]

Reactive halogen chemistry in the springtime Arctic causes ozone depletion events and alters the rate of pollution processing. There are still many uncertainties regarding this chemistry, including the multiphase recycling of halogens and how sea ice impacts the source strength of reactive bromine. Adding to these uncertainties are the impacts of a rapidly warming Arctic. We present observations from the CHemistry in the Arctic: Clouds, Halogens, and Aerosols (CHACHA) field campaign based out of Utqiag ̇vik, Alaska from mid-February to mid-April of 2022 to provide information on the vertical distribution of bromine monoxide (BrO), which is a tracer for reactive bromine chemistry. Data was gathered using the Heidelberg Airborne Imaging DOAS Instrument (HAIDI) on the Purdue University Airborne Laboratory for Atmospheric Research (ALAR) and employing a unique sampling technique of vertically profiling the lower atmosphere with the aircraft via "porpoising" ma- neuvers. Observations from HAIDI were coupled with radiative transfer model calculations to retrieve mixing ratio profiles throughout the lower atmosphere (below 1000 m), with unprecedented vertical resolution (50 m) and total information gathered (average of 17.5 degrees of freedom) for this region. A cluster analysis was used to categorize 245 retrieved BrO mixing ratio vertical profiles into four common profile shapes. We often found the highest BrO mixing ratios at the Earth’s surface with a mean of nearly 30 pmol mol−1 in the lowest 50 m, indicating an important role for multiphase chemistry on the snowpack in reactive bromine production. Most lofted BrO profiles corresponded with an aerosol profile that peaked at the same altitude (225 m above the ground), suggesting that BrO was maintained due to heterogeneous reactions on particle surfaces aloft during these cases. A majority, 11 of 15, of the identified lofted BrO cases occurred on a single day, March 19, 2022, over an area covering more than 24,000 km2, indicating that this was a large scale lofted BrO event. The clustered BrO mixing ratio profiles should be particularly useful for MAX-DOAS studies, where prior BrO profiles, needed for the optimal estimation retrieval, are not often based on previous observations. Future MAX-DOAS studies (and past reanalyses) could rely on the profiles provided in this work to improve BrO retrievals. [ABSTRACT FROM AUTHOR]

Although oxidation of biogenic volatile organic compounds (BVOCs) plays an important role in tropospheric ozone and secondary organic aerosol production, significant uncertainties remain in our understanding of the impacts of BVOCs on ozone, aerosols, and climate. To quantify BVOCs, the proton-transfer reaction linear ion trap (PTR-LIT) mass spectrometer was previously developed. The PTR-LIT represents an improvement over more traditional techniques (including the proton-transfer reaction mass spectrometer), providing the capability to directly quantify and differentiate isomeric compounds by MS/MS analysis, with better lime resolution and minimal sample handling, compared to gas chromatography techniques. Herein, we present results from the first field deployment of the PTR-LIT. During the Program for Research on Oxidants: Photochemistry, Emissions and Transport (PROPHET) summer 2008 study in northern Michigan, the PTR-LIT successfully quantified isoprene, total monoterpenes, and isomeric isoprene oxidation products methyl vinyl ketone and methacrolein at sub-parts per billion (nmol/mol) levels in a complex forest atmosphere. The utility of the fast lime response of the PTR-LIT was shown by the measurement of rapid changes in isoprene, methyl vinyl ketone, and methacrolein, concurrent with changing ozone mole fractions. Overall, the PTR-LIT was shown to be a viable field instrument with the necessary sensitivity, selectivity, and lime response to provide detailed measurements of BVOC mole fractions in complex atmospheric samples, at trace levels. 10.1021/ac1014244

Sea salt aerosols play an important role in the radiation budget and atmospheric composition over the Arctic, where the climate is rapidly changing. Previous observational studies have shown Arctic sea ice leads to be an important source of sea salt aerosols, and modeling efforts have also proposed blowing snow sublimation as a source. In this study, size-resolved atmospheric particle number concentrations and chemical composition were measured at the Arctic coastal tundra site of Utqiaġvik, Alaska during spring (April 3 - May 7, 2016). Blowing snow conditions were observed during 25% of the five-week study period and were over-predicted by a commonly used blowing snow parameterization based solely on wind speed and temperature. Throughout the study, open leads were present locally. During periods when blowing snow was observed, significant increases in the number concentrations of 0.01-0.06 µm particles (factor of six, on average) and 0.06-0.3 µm particles (67%, on average), and a significant decrease (82%, on average) in 1-4 µm particles, were observed, compared to low wind speed periods. These size distribution changes were likely caused by the generation of ultrafine particles from leads and/or blowing snow, with scavenging of supermicron particles by blowing snow. At elevated wind speeds, both submicron and supermicron sodium and chloride mass concentrations were enhanced, consistent with winddependent local sea salt aerosol production. At moderate wind speeds below the threshold for blowing snow, as well as during observed blowing snow, individual sea spray aerosol particles were measured. These individual salt particles were enriched in calcium relative to sodium in seawater, due to the binding of this divalent cation with organic matter in the sea surface microlayer and subsequent enrichment during seawater bubble bursting. The chemical composition of the surface snowpack also showed contributions from sea spray aerosol deposition. Overall, these results show the contribution of sea spray aerosol production from leads on both aerosols and the surface snowpack. Therefore, if blowing snow sublimation contributed to the observed sea salt aerosol, the snow being sublimed must have been impacted by sea spray aerosol deposition, rather than upward brine migration through the snowpack. Sea spray aerosol production from leads is expected to increase, with thinning and fracturing of sea ice in the rapidly warming Arctic. [ABSTRACT FROM AUTHOR]

Currently, proton-transfer reaction mass spectrometry (PTR-MS) allows for quantitative determination of volatile organic compounds in real time at concentrations in the low ppt range, but cannot differentiate isomers or isobaric molecules, using the conventional quadrupole mass filter. Here we pursue the application of linear quadrupole ion trap (LIT) mass spectrometry in combination with proton-transfer reaction chemical ionization to provide the advantages of specificity from MS/MS. A commercial PTR-MS platform composed of a quadrupole mass filter with the addition of end cap electrodes enabled the mass filter to operate as a linear ion trap. The rf drive electronics were adapted to enable the application of dipolar excitation to opposing rods, for collision-induced dissociation (CID) of trapped ions. This adaptation enabled ion isolation, ion activation, and mass analysis. The utility of the PTR-LIT was demonstrated by distinguishing between the isomeric isoprene oxidation pair, methyl vinyl ketone (MVK) and methacrolein (MACR). The CID voltage was adjusted to maximize the m/z 41 to 43 fragment ratio of MACR while still maintaining adequate sensitivity. Linear calibration curves for MVK and MACR fragments at m/z 41 and 43 were obtained with limits of detection of ~100 ppt, which should enable ambient measuremerits. Finally, the PTR-LIT method was compared to an established GC/MS method by quantifying MVK and MACR production during a smog chamber isopreneN[O.sub.x] irradiation experiment.

A compact commercial Doppler lidar has been deployed in Indianapolis for two years to measure wind profiles and mixing layer properties as part of project to improve greenhouse measurements from large area sources. The lidar uses vertical velocity variance and aerosol structure to measure mixing layer depth. Comparisons with aircraft and the NOAA HRDL lidar generally indicate good performance, although sensitivity might be an issue under low aerosol conditions.

An ion trap mass spectrometric technique using negative ion chemical ionization has been developed for the quantitative determination of the molecular halogen species [Br.sub.2], [Cl.sub.2], and BrCl. The technique utilizes N[O.sub.2.sup.-] as a chemical ionization reagent in an electron-transfer reaction to form the corresponding molecular anions of the halogen species, lending excellent selectivity to the measurement. Reaction rate experiments performed in the ion trap yield a rate constant for [Br.sub.2] + N[O.sub.2.sup.-] [right arrow] [Br.sub.2.sup.-] + N[O.sub.2] of (1.4 [+ or -] 0.6) x [10.sup.-9] [cm.sup.3] [molecule.sup.-1] [s.sup.-1], determined relative to published data for [Cl.sub.2] + N[O.sub.2.sup.-] [right arrow] [Cl.sub.2.sup.-]- + N[O.sub.2]. This paper describes a mass spectrometer pinhole inlet design and cryogenic preconcentration system for detection of the molecular halogens at atmospherically relevant concentrations. Linear calibration curves were obtained for [Cl.sub.2] and [Br.sub.2] over 3 orders of magnitude and indicate limits of detection of 50 and 8 pmol for 3.8- and 5.1-L samples, respectively, corresponding to 220 and 50 parts per trillion (mole/mole). Quantitation is based on the total signal at m/z values of 70, 72, and 74 for [Cl.sub.2] and 158, 160, and 162 for [Br.sub.2]. The effects of water vapor on the cryogenic preconcentration step are quatitatively assessed.