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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 km2, 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.

The hydroxyl (OH), hydroperoxy (HO2), and organic peroxy (RO2) radicals play important roles in atmospheric chemistry. In the presence of nitrogen oxides (NOx), reactions between OH and volatile organic compounds (VOCs) can initiate a radical propagation cycle that leads to the production of ozone and secondary organic aerosols. Previous measurements of these radicals under low-NOx conditions in forested environments characterized by emissions of biogenic VOCs, including isoprene and monoterpenes, have shown discrepancies with modeled concentrations. During the summer of 2016, OH, HO2, and RO2 radical concentrations were measured as part of the Program for Research on Oxidants: Photochemistry, Emissions, and Transport – Atmospheric Measurements of Oxidants in Summer (PROPHET-AMOS) campaign in a midlatitude deciduous broadleaf forest. Measurements of OH and HO2 were made by laser-induced fluorescence–fluorescence assay by gas expansion (LIF-FAGE) techniques, and total peroxy radical (XO2) mixing ratios were measured by the Ethane CHemical AMPlifier (ECHAMP) instrument. Supporting measurements of photolysis frequencies, VOCs, NOx, O3, and meteorological data were used to constrain a zero-dimensional box model utilizing either the Regional Atmospheric Chemical Mechanism (RACM2) or the Master Chemical Mechanism (MCM). Model simulations tested the influence of HOx regeneration reactions within the isoprene oxidation scheme from the Leuven Isoprene Mechanism (LIM1). On average, the LIM1 models overestimated daytime maximum measurements by approximately 40 % for OH, 65 % for HO2, and more than a factor of 2 for XO2. Modeled XO2 mixing ratios were also significantly higher than measured at night. Addition of RO2 + RO2 accretion reactions for terpene-derived RO2 radicals to the model can partially explain the discrepancy between measurements and modeled peroxy radical concentrations at night but cannot explain the daytime discrepancies when OH reactivity is dominated by isoprene. The models also overestimated measured concentrations of isoprene-derived hydroxyhydroperoxides (ISOPOOH) by a factor of 10 during the daytime, consistent with the model overestimation of peroxy radical concentrations. Constraining the model to the measured concentration of peroxy radicals improves the agreement with the measured ISOPOOH concentrations, suggesting that the measured radical concentrations are more consistent with the measured ISOPOOH concentrations. These results suggest that the models may be missing an important daytime radical sink and could be overestimating the rate of ozone and secondary product formation in this forest.

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 that Arctic sea ice leads are 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 (3 April–7 May 2016). Blowing snow conditions were observed during 25 % of the 5-week study period and were overpredicted 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 6, 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 wind-dependent 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 sublimated would 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.

The FORCAsT (FORest Canopy Atmosphere Transfer) model version 1.0 is updated to FORCAsT 2.0 by implementing five major changes, including (1) a change to the operator splitting, separating chemistry from emission and dry deposition, which reduces the run time of the gas-phase chemistry by 70 % and produces a more realistic in-canopy profile for isoprene; (2) a modification of the eddy diffusivity parameterization to produce greater and more realistic vertical mixing in the boundary layer, which ameliorates the unrealistic simulated end-of-day peaks in isoprene under well-mixed conditions and improves daytime air temperature; (3) updates to dry deposition velocities with available measurements; (4) implementation of the Reduced Caltech Isoprene Mechanism (RCIM) to reflect the current knowledge of isoprene oxidation; and (5) extension of the aerosol module to include isoprene-derived secondary organic aerosol (iSOA) formation. Along with the operator splitting, modified vertical mixing, and dry deposition, RCIM improves the estimation of first-generation isoprene oxidation products (methyl vinyl ketone and methacrolein) and some second-generation products (such as isoprene epoxydiols). Inclusion of isoprene in the aerosol module in FORCAsT 2.0 leads to a 7 % mass yield of iSOA. The most important iSOA precursors are IEPOX and tetrafunctionals, which together account for >86 % of total iSOA. The iSOA formed from organic nitrates is more important in the canopy, accounting for 11 % of the total iSOA. The tetrafunctionals compose up to 23 % of the total iSOA formation, highlighting the importance of the fate (i.e., dry deposition and gas-phase chemistry) of later-generation isoprene oxidation products in estimating iSOA formation.

Cities represent a large and concentrated portion of global greenhouse gas emissions, including methane. Quantifying methane emissions from urban areas is difficult, and inventories made using bottom-up accounting methods often differ greatly from top-down estimates generated from atmospheric observations. Emissions from leaks in natural gas infrastructure are difficult to predict and are therefore poorly constrained in bottom-up inventories. Natural gas infrastructure leaks and emissions from end uses can be spread throughout the city, and this diffuse source can represent a significant fraction of a city's total emissions. We investigated diffuse methane emissions of the city of Indianapolis, USA, during a field campaign in May 2016. A network of five portable solar-tracking Fourier transform infrared (FTIR) spectrometers was deployed throughout the city. These instruments measure the mole fraction of methane in a total column of air, giving them sensitivity to larger areas of the city than in situ sensors at the surface. We present an innovative inversion method to link these total column concentrations to surface fluxes. This method combines a Lagrangian transport model with a Bayesian inversion framework to estimate surface emissions and their uncertainties, together with determining the concentrations of methane in the air flowing into the city. Variations exceeding 10 ppb were observed in the inflowing air on a typical day, which is somewhat larger than the enhancements due to urban emissions ( ppb downwind of the city). We found diffuse methane emissions of 73(±22) mol s−1, which is about 50 % of the urban total and 68 % higher than estimated from bottom-up methods, although it is somewhat smaller than estimates from studies using tower and aircraft observations. The measurement and model techniques developed here address many of the challenges present when quantifying urban greenhouse gas emissions and will help in the design of future measurement schemes in other cities.

Biogenic volatile organic compounds (BVOCs) emitted by plants represent the largest source of non-methane hydrocarbon emissions on Earth. Photochemical oxidation of BVOCs represents a significant pathway in the production of secondary organic aerosol (SOA), affecting Earth's radiative balance. Organic nitrates (RONO2), formed from the oxidation of BVOCs in the presence of NOx, represent important aerosol precursors and affect the oxidative capacity of the atmosphere, in part by sequestering NOx. In the aerosol phase, RONO2 hydrolyze to form nitric acid and numerous water-soluble products, thus contributing to an increase in aerosol mass. However, only a small number of studies have investigated the production of RONO2 from OH oxidation of terpenes, and among those, few have studied their hydrolysis. Here, we report a laboratory study of OH-initiated oxidation of β-ocimene, an acyclic, tri-olefinic monoterpene released during the daytime from vegetation, including forests, agricultural landscapes, and grasslands. We conducted studies of the OH oxidation of β-ocimene in the presence of NOx using a 5.5 m3 all-Teflon photochemical reaction chamber, during which we quantified the total (gas- and particle-phase) RONO2 yield and the SOA yields. We sampled the organic nitrates produced and measured their hydrolysis rate constants across a range of atmospherically relevant pH. The total organic nitrate yield was determined to be 38(±9) %, consistent with the available literature regarding the dependence of organic nitrate production (from RO2 + NO) on carbon number. We found the hydrolysis rate constants to be highly pH dependent, with a hydrolysis lifetime of 51(±13) min at pH = 4 and 24(±3) min at pH = 2.5, a typical pH for deliquesced aerosols. We also employed high-resolution mass spectrometry for preliminary product identification. The results indicate that the ocimene SOA yield (< 1 %) under relevant aerosol mass loadings in the atmosphere is significantly lower than reported yields from cyclic terpenes, such as α-pinene, likely due to alkoxy radical decomposition and formation of smaller, higher-volatility products. This is also consistent with the observed lower particle-phase organic nitrate yields of β-ocimene – i.e., 1.5(±0.5) % – under dry conditions. We observed the expected hydroxy nitrates by chemical ionization mass spectrometry (CIMS) and some secondary production of the dihydroxy dinitrates, likely produced by oxidation of the first-generation hydroxy nitrates. Lower RONO2 yields were observed under high relative humidity (RH) conditions, indicating the importance of aerosol-phase RONO2 hydrolysis under ambient RH. This study provides insight into the formation and fate of organic nitrates, β-ocimene SOA yields, and NOx cycling in forested environments from daytime monoterpenes not currently included in atmospheric models.

We use airborne measurements of water vapor (H2Ov) stable isotopologues and complementary meteorological observations to examine how boundary layer (BL) dynamics, cloud processing, and atmospheric mixing influence the vertical structure of δD, δ18O, and deuterium excess (d excess =δD–8×δ18O) in the BL, inversion layer (INV), and lower free troposphere (FT). Flights were conducted around two continental US cities in February–March 2016 and included vertical profiles extending from near the surface to ≤2 km. We examine observations from three unique case study flights in detail. One case study shows observations that are consistent with Rayleigh isotopic distillation theory coinciding with clear skies, dry adiabatic lapse rates within the boundary layer, and relatively constant vertical profiles of wind speed and wind direction. This suggests that the air mass retained the isotopic fingerprint of dehydration during moist adiabatic processes upwind of the study area. Also, observed d-excess values in the free troposphere were sometimes larger than Rayleigh theory predicts, which may indicate mixing of extremely dehydrated air from higher altitudes. The two remaining case studies show isotopic anomalies in the d-excess signature relative to Rayleigh theory and indicate cloud processes and complex boundary layer development. The most notable case study with stratocumulus clouds present had extremely low (negative) d-excess values at the interface of the inversion layer and the free troposphere, which is possibly indicative of cloud or rain droplet evaporation. We discuss how in situ H2Ov stable isotope measurements, and d excess in particular, could be useful for improving our understanding of water phase changes, transport, and mixing that occurs between the BL, INV, and FT.

The mechanisms of molecular halogen production from frozen saline surfaces remain incompletely understood, limiting our ability to predict atmospheric oxidation and composition in polar regions. In this laboratory study, condensed-phase hydroxyl radicals (OH) were photochemically generated in frozen saltwater solutions that mimicked the ionic composition of ocean water. These hydroxyl radicals were found to oxidize Cl−, Br−, and I−, leading to the release of Cl2, Br2, I2, and IBr. At moderately acidic pH (buffered between 4.5 and 4.8), irradiation of ice containing OH precursors (either of hydrogen peroxide or nitrite ion) produced elevated amounts of I2. Subsequent addition of O3 produced additional I2, as well as small amounts of Br2. At lower pH (1.7–2.2) and in the presence of an OH precursor, rapid dark conversion of I− to I2 occurred from reactions with hydrogen peroxide or nitrite, followed by substantial photochemical production of Br2 upon irradiation. Exposure to O3 under these low pH conditions also increased production of Br2 and I2; this likely results from direct O3 reactions with halides, as well as the production of gas-phase HOBr and HOI that subsequently diffuse to frozen solution to react with Br− and I−. Photochemical production of Cl2 was only observed when the irradiated sample was composed of high-purity NaCl and hydrogen peroxide (acting as the OH precursor) at pH = 1.8. Though condensed-phase OH was shown to produce Cl2 in this study, kinetics calculations suggest that heterogeneous recycling chemistry may be equally or more important for Cl2 production in the Arctic atmosphere. The condensed-phase OH-mediated halogen production mechanisms demonstrated here are consistent with those proposed from recent Arctic field observations of molecular halogen production from snowpacks. These reactions, even if slow, may be important for providing seed halogens to the Arctic atmosphere. Our results suggest the observed molecular halogen products are dependent on the relative concentrations of halides at the ice surface, as we only observe what diffuses to the air–surface interface.

Gas-phase atmospheric concentrations of peroxyacetyl nitrate (PAN), peroxypropionyl nitrate (PPN), and peroxymethacryloyl nitrate (MPAN) were measured on the ground using a gas chromatograph electron capture detector (GC-ECD) during the Southern Oxidants and Aerosols Study (SOAS) 2013 campaign (1 June to 15 July 2013) in Centreville, Alabama, in order to study biosphere–atmosphere interactions. Average levels of PAN, PPN, and MPAN were 169, 5, and 9 pptv, respectively, and the sum accounts for an average of 16 % of NOy during the daytime (10:00 to 16:00 local time). Higher concentrations were seen on average in air that came to the site from the urban NOx sources to the north. PAN levels were the lowest observed in ground measurements over the past two decades in the southeastern US. A multiple regression analysis indicates that biogenic volatile organic compounds (VOCs) account for 66 % of PAN formation during this study. Comparison of this value with a 0-D model simulation of peroxyacetyl radical production indicates that at least 50 % of PAN formation is due to isoprene oxidation. MPAN has a statistical correlation with isoprene hydroxynitrates (IN). Organic aerosol mass increases with gas-phase MPAN and IN concentrations, but the mass of organic nitrates in particles is largely unrelated to MPAN.

Polyolefinic monoterpenes represent a potentially important but understudied source of organic nitrates (ONs) and secondary organic aerosol (SOA) following oxidation due to their high reactivity and propensity for multi-stage chemistry. Recent modeling work suggests that the oxidation of polyolefinic γ-terpinene can be the dominant source of nighttime ON in a mixed forest environment. However, the ON yields, aerosol partitioning behavior, and SOA yields from γ-terpinene oxidation by the nitrate radical (NO3), an important nighttime oxidant, have not been determined experimentally. In this work, we present a comprehensive experimental investigation of the total (gas + particle) ON, hydroxy nitrate, and SOA yields following γ-terpinene oxidation by NO3. Under dry conditions, the hydroxy nitrate yield = 4(+1/−3) %, total ON yield = 14(+3/−2) %, and SOA yield ≤ 10 % under atmospherically relevant particle mass loadings, similar to those for α-pinene + NO3. Using a chemical box model, we show that the measured concentrations of NO2 and γ-terpinene hydroxy nitrates can be reliably simulated from α-pinene + NO3 chemistry. This suggests that NO3 addition to either of the two internal double bonds of γ-terpinene primarily decomposes forming a relatively volatile keto-aldehyde, reconciling the small SOA yield observed here and for other internal olefinic terpenes. Based on aerosol partitioning analysis and identification of speciated particle-phase ON applying high-resolution liquid chromatography–mass spectrometry, we estimate that a significant fraction of the particle-phase ON has the hydroxy nitrate moiety. This work greatly contributes to our understanding of ON and SOA formation from polyolefin monoterpene oxidation, which could be important in the northern continental US and the Midwest, where polyolefinic monoterpene emissions are greatest.

The return of sunlight in the polar spring leads to the production of reactive halogen species from the surface snowpack, significantly altering the chemical composition of the Arctic near-surface atmosphere and the fate of long-range transported pollutants, including mercury. Recent work has shown the initial production of reactive bromine at the Arctic surface snowpack; however, we have limited knowledge of the vertical extent of this chemistry, as well as the lifetime and possible transport of reactive bromine aloft. Here, we present bromine monoxide (BrO) and aerosol particle measurements obtained during the March 2012 BRomine Ozone Mercury EXperiment (BROMEX) near Utqiaġvik (Barrow), AK. The airborne differential optical absorption spectroscopy (DOAS) measurements provided an unprecedented level of spatial resolution, over 2 orders of magnitude greater than satellite observations and with vertical resolution unable to be achieved by satellite methods, for BrO in the Arctic. This novel method provided quantitative identification of a BrO plume, between 500 m and 1 km aloft, moving at the speed of the air mass. Concurrent aerosol particle measurements suggest that this lofted reactive bromine plume was transported and maintained at elevated levels through heterogeneous reactions on colocated supermicron aerosol particles, independent of surface snowpack bromine chemistry. This chemical transport mechanism explains the large spatial extents often observed for reactive bromine chemistry, which impacts atmospheric composition and pollutant fate across the Arctic region, beyond areas of initial snowpack halogen production. The possibility of BrO enhancements disconnected from the surface potentially contributes to sustaining BrO in the free troposphere and must also be considered in the interpretation of satellite BrO column observations, particularly in the context of the rapidly changing Arctic sea ice and snowpack.

Ozone depletion events (ODEs) in the Arctic are primarily controlled by a bromine radical-catalyzed destruction mechanism that depends on the efficient production and recycling of Br atoms. Numerous laboratory and modeling studies have suggested the importance of heterogeneous recycling of Br through HOBr reaction with bromide on saline surfaces. On the other hand, the gas-phase regeneration of bromine atoms through BrO–BrO radical reactions has been assumed to be an efficient, if not dominant, pathway for Br reformation and thus ozone destruction. Indeed, it has been estimated that the rate of ozone depletion is approximately equal to twice the rate of the BrO self-reaction. Here, we use a zero-dimensional, photochemical model, largely constrained to observations of stable atmospheric species from the 2009 Ocean–Atmosphere–Sea Ice–Snowpack (OASIS) campaign in Barrow, Alaska, to investigate gas-phase bromine radical propagation and recycling mechanisms of bromine atoms for a 7-day period during late March. This work is a continuation of that presented in Thompson et al. (2015) and utilizes the same model construct. Here, we use the gas-phase radical chain length as a metric for objectively quantifying the efficiency of gas-phase recycling of bromine atoms. The gas-phase bromine chain length is determined to be quite small, at 3 concentrations. Furthermore, we find that Br atom production from photolysis of Br2 and BrCl, which is predominately emitted from snow and/or aerosol surfaces, can account for between 30 and 90 % of total Br atom production. This analysis suggests that condensed-phase production of bromine is at least as important as, and at times greater than, gas-phase recycling for the occurrence of Arctic ODEs. Therefore, the rate of the BrO self-reaction is not a sufficient estimate for the rate of O3 depletion.

The production of atmospheric organic nitrates (RONO2) has a large impact on air quality and climate due to their contribution to secondary organic aerosol and influence on tropospheric ozone concentrations. Since organic nitrates control the fate of gas phase NOx (NO + NO2), a byproduct of anthropogenic combustion processes, their atmospheric production and reactivity is of great interest. While the atmospheric reactivity of many relevant organic nitrates is still uncertain, one significant reactive pathway, condensed phase hydrolysis, has recently been identified as a potential sink for organic nitrate species. The partitioning of gas phase organic nitrates to aerosol particles and subsequent hydrolysis likely removes the oxidized nitrogen from further atmospheric processing, due to large organic nitrate uptake to aerosols and proposed hydrolysis lifetimes, which may impact long-range transport of NOx, a tropospheric ozone precursor. Despite the atmospheric importance, the hydrolysis rates and reaction mechanisms for atmospherically derived organic nitrates are almost completely unknown, including those derived from α-pinene, a biogenic volatile organic compound (BVOC) that is one of the most significant precursors to biogenic secondary organic aerosol (BSOA). To better understand the chemistry that governs the fate of particle phase organic nitrates, the hydrolysis mechanism and rate constants were elucidated for several organic nitrates, including an α-pinene-derived organic nitrate (APN). A positive trend in hydrolysis rate constants was observed with increasing solution acidity for all organic nitrates studied, with the tertiary APN lifetime ranging from 8.3 min at acidic pH (0.25) to 8.8 h at neutral pH (6.9). Since ambient fine aerosol pH values are observed to be acidic, the reported lifetimes, which are much shorter than that of atmospheric fine aerosol, provide important insight into the fate of particle phase organic nitrates. Along with rate constant data, product identification confirms that a unimolecular specific acid-catalyzed mechanism is responsible for organic nitrate hydrolysis under acidic conditions. The free energies and enthalpies of the isobutyl nitrate hydrolysis intermediates and products were calculated using a hybrid density functional (ωB97X-V) to support the proposed mechanisms. These findings provide valuable information regarding the organic nitrate hydrolysis mechanism and its contribution to the fate of atmospheric NOx, aerosol phase processing, and BSOA composition.

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) + methacrolein (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 model-derived 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·; 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).

In isoprene-impacted environments, carbonyl nitrates are produced from NO3-initiated isoprene oxidation, which constitutes a potentially important NOx reservoir. To better understand the fate of isoprene carbonyl nitrates, we synthesized a model compound, trans-2-methyl-4-nitrooxy-2-buten-1-al (4,1-isoprene carbonyl nitrate, or 4,1-isoprene nitrooxy enal), and investigated its photochemical degradation process. The measured OH and O3 oxidation rate constants (298 K) for this nitrooxy enal are 4.1(±0.7) × 10−11 cm3 molecules−1 s−1 and 4.4(±0.3) × 10−18 cm3 molecules−1 s−1, respectively. Its UV absorption spectrum was determined, and the result is consistent with TDDFT calculations. Based on its UV absorption cross section and photolysis frequency in a reaction chamber, we estimate that the ambient photolysis frequency for this compound is 3.1(±0.8) × 10−4 s−1 for a solar zenith angle of 45°. The fast photolysis rate and high reactivity toward OH lead to a lifetime of less than 1 h for the isoprene nitrooxy enal, with photolysis being a dominant daytime sink. The nitrate products derived from the OH oxidation and the photolysis of the nitrooxy enal were identified with an iodide-based chemical ionization mass spectrometer. For the OH oxidation reaction, we quantified the yields of two nitrate products, methyl vinyl ketone nitrate and ethanal nitrate, which together contributed to 36(±5) % of the first-generation products.

Formation of organic nitrates (RONO2) during oxidation of biogenic volatile organic compounds (BVOCs: isoprene, monoterpenes) is a significant loss pathway for atmospheric nitrogen oxide radicals (NOx), but the chemistry of RONO2 formation and degradation remains uncertain. Here we implement a new BVOC oxidation mechanism (including updated isoprene chemistry, new monoterpene chemistry, and particle uptake of RONO2) in the GEOS-Chem global chemical transport model with ∼ 25 × 25 km2 resolution over North America. We evaluate the model using aircraft (SEAC4RS) and ground-based (SOAS) observations of NOx, BVOCs, and RONO2 from the Southeast US in summer 2013. The updated simulation successfully reproduces the concentrations of individual gas- and particle-phase RONO2 species measured during the campaigns. Gas-phase isoprene nitrates account for 25–50 % of observed RONO2 in surface air, and we find that another 10 % is contributed by gas-phase monoterpene nitrates. Observations in the free troposphere show an important contribution from long-lived nitrates derived from anthropogenic VOCs. During both campaigns, at least 10 % of observed boundary layer RONO2 were in the particle phase. We find that aerosol uptake followed by hydrolysis to HNO3 accounts for 60 % of simulated gas-phase RONO2 loss in the boundary layer. Other losses are 20 % by photolysis to recycle NOx and 15 % by dry deposition. RONO2 production accounts for 20 % of the net regional NOx sink in the Southeast US in summer, limited by the spatial segregation between BVOC and NOx emissions. This segregation implies that RONO2 production will remain a minor sink for NOx in the Southeast US in the future even as NOx emissions continue to decline.

Isoprene hydroxynitrates (IN) are tracers of the photochemical oxidation of isoprene in high NOx environments. Production and loss of IN have a significant influence on the NOx cycle and tropospheric O3 chemistry. To better understand IN chemistry, a series of photochemical reaction chamber experiments was conducted to determine the IN yield from isoprene photooxidation at high NO concentrations (> 100 ppt). By combining experimental data and calculated isomer distributions, a total IN yield of 9(+4/−3) % was derived. The result was applied in a zero-dimensional model to simulate production and loss of ambient IN observed in a temperate forest atmosphere, during the Southern Oxidant and Aerosol Study (SOAS) field campaign, from 27 May to 11 July 2013. The 9 % yield was consistent with the observed IN/(MVK+MACR) ratios observed during SOAS. By comparing field observations with model simulations, we identified NO as the limiting factor for ambient IN production during SOAS, but vertical mixing at dawn might also contribute (~ 27 %) to IN dynamics. A close examination of isoprene's oxidation products indicates that its oxidation transitioned from a high-NO dominant chemical regime in the morning into a low-NO dominant regime in the afternoon. A significant amount of IN produced in the morning high NO regime could be oxidized in the low NO regime, and a possible reaction scheme was proposed.

The springtime depletion of tropospheric ozone in the Arctic is known to be caused by active halogen photochemistry resulting from halogen atom precursors emitted from snow, ice, or aerosol surfaces. The role of bromine in driving ozone depletion events (ODEs) has been generally accepted, but much less is known about the role of chlorine radicals in ozone depletion chemistry. While the potential impact of iodine in the High Arctic is more uncertain, there have been indications of active iodine chemistry through observed enhancements in filterable iodide, probable detection of tropospheric IO, and recently, observation of snowpack photochemical production of I2. Despite decades of research, significant uncertainty remains regarding the chemical mechanisms associated with the bromine-catalyzed depletion of ozone, as well as the complex interactions that occur in the polar boundary layer due to halogen chemistry. To investigate this, we developed a zero-dimensional photochemical model, constrained with measurements from the 2009 OASIS field campaign in Barrow, Alaska. We simulated a 7-day period during late March that included a full ozone depletion event lasting 3 days and subsequent ozone recovery to study the interactions of halogen radicals under these different conditions. In addition, the effects of iodine added to our Base Model were investigated. While bromine atoms were primarily responsible for ODEs, chlorine and iodine were found to enhance the depletion rates and iodine was found to be more efficient per atom at depleting ozone than Br. The interaction between chlorine and bromine is complex, as the presence of chlorine can increase the recycling and production of Br atoms, while also increasing reactive bromine sinks under certain conditions. Chlorine chemistry was also found to have significant impacts on both HO2 and RO2, with organic compounds serving as the primary reaction partner for Cl atoms. The results of this work highlight the need for future studies on the production mechanisms of Br2 and Cl2, as well as on the potential impact of iodine in the High Arctic.

Multiple axis differential absorption spectroscopy (MAX-DOAS) measurements of bromine monoxide (BrO) probed the vertical structure of halogen activation events during March–May 2012 at Barrow, Alaska. An analysis of the BrO averaging kernels and degrees of freedom obtained by optimal-estimation-based inversions from raw MAX-DOAS measurements reveals the information is best represented by reducing the retrieved BrO profile to two quantities: the integrated column from the surface through 200 m (VCD200 m), and the lower tropospheric vertical column density (LT-VCD), which represents the integrated column of BrO from the surface through 2 km. The percentage of lower tropospheric BrO in the lowest 200 m was found to be highly variable ranging from shallow layer events, where BrO is present primarily in the lowest 200 m, to distributed column events where BrO is observed at higher altitudes. The highest observed LT-VCD events occurred when BrO was distributed throughout the lower troposphere, rather than concentrated near the surface. Atmospheric stability in the lowest 200 m influenced the percentage of LT-VCD that is in the lowest 200 m, with inverted temperature structures having a first-to-third quartile range (Q1–Q3) of VCD200 m/LT-VCD from 15–39%, while near-neutral-temperature structures had a Q1–Q3 range of 7–13%. Data from this campaign show no clear influence of wind speed on either lower tropospheric bromine activation (LT-VCD) or the vertical distribution of BrO, while examination of seasonal trends and the temperature dependence of the vertical distribution supported the conclusion that the atmospheric stability affects the vertical distribution of BrO.

Many relevant processes in tropospheric chemistry take place on rather small scales (e.g., tens to hundreds of meters) but often influence areas of several square kilometer. Thus, measurements of the involved trace gases with high spatial resolution are of great scientific interest. In order to identify individual sources and sinks and ultimately to improve chemical transport models, we developed a new airborne instrument, which is based on the well established Differential Optical Absorption Spectroscopy (DOAS) method. The Heidelberg Airborne Imaging DOAS Instrument (HAIDI) is a passive imaging DOAS spectrometer, which is capable of recording horizontal and vertical trace gas distributions with a resolution of better than 100 m. Observable species include NO2, HCHO, C2H2O2, H2O, O3, O4, SO2, IO, OClO and BrO. Here we give a technical description of the instrument including its custom-built spectrographs and CCD detectors. Also first results from measurements with the new instrument are presented. These comprise spatial resolved SO2 and BrO in volcanic plumes, mapped at Mt. Etna (Sicily, Italy), NO2 emissions in the metropolitan area of Indianapolis (Indiana, USA) as well as BrO and NO2 distributions measured during arctic springtime in context of the BRomine, Ozone, and Mercury EXperiment (BROMEX) campaign, which was performed 2012 in Barrow (Alaska, USA).

Urban environments are the primary contributors to global anthropogenic carbon emissions. Because much of the growth in CO2 emissions will originate from cities, there is a need to develop, assess, and improve measurement and modeling strategies for quantifying and monitoring greenhouse gas emissions from large urban centers. In this study the uncertainties in an aircraft-based mass balance approach for quantifying carbon dioxide and methane emissions from an urban environment, focusing on Indianapolis, IN, USA, are described. The relatively level terrain of Indianapolis facilitated the application of mean wind fields in the mass balance approach. We investigate the uncertainties in our aircraft-based mass balance approach by (1) assessing the sensitivity of the measured flux to important measurement and analysis parameters including wind speed, background CO2 and CH4, boundary layer depth, and interpolation technique, and (2) determining the flux at two or more downwind distances from a point or area source (with relatively large source strengths such as solid waste facilities and a power generating station) in rapid succession, assuming that the emission flux is constant. When we quantify the precision in the approach by comparing the estimated emissions derived from measurements at two or more downwind distances from an area or point source, we find that the minimum and maximum repeatability were 12 and 52%, with an average of 31%. We suggest that improvements in the experimental design can be achieved by careful determination of the background concentration, monitoring the evolution of the boundary layer through the measurement period, and increasing the number of downwind horizontal transect measurements at multiple altitudes within the boundary layer.

Following polar sunrise in the Arctic springtime, tropospheric ozone episodically decreases rapidly to near-zero levels during ozone depletion events (ODEs). Many uncertainties remain in our understanding of ODE characteristics, including the temporal and spatial scales, as well as environmental drivers. Measurements of ozone, bromine monoxide (BrO), and meteorology were obtained during several deployments of autonomous, ice-tethered buoys (O-Buoys) from both coastal sites and over the Arctic Ocean; these data were used to characterize observed ODEs. Detected decreases in surface ozone levels during the onset of ODEs corresponded to a median estimated apparent ozone depletion timescale (based on both chemistry and the advection of O3-depleted air) of 11 h. If assumed to be dominated by chemical mechanisms, these timescales would correspond to larger-than-observed BrO mole fractions based on known chemistry and assumed other radical levels. Using backward air mass trajectories and an assumption that transport mechanisms dominate observations, the spatial scales for ODEs (defined by time periods in which ozone levels ≤15 nmol mol−1) were estimated to be 877 km (median), while areas estimated to represent major ozone depletions (−1) had dimensions of 282 km (median). These observations point to a heterogeneous boundary layer with localized regions of active, ozone-destroying halogen chemistry, interspersed among larger regions of previously depleted air that retain reduced ozone levels through hindered atmospheric mixing. Based on the estimated size distribution, Monte Carlo simulations showed it was statistically possible that all ODEs observed could have originated upwind, followed by transport to the measurement site. Local wind speed averages were low during most ODEs (median of ~3.6 m s−1), and there was no apparent dependence on local temperature.

Hydroxyl (OH) and hydroperoxyl (HO2) radicals are key species driving the oxidation of volatile organic compounds that can lead to the production of ozone and secondary organic aerosols. Previous measurements of these radicals in forest environments with high isoprene, low NOx conditions have shown serious discrepancies with modeled concentrations, bringing into question the current understanding of isoprene oxidation chemistry in these environments. During the summers of 2008 and 2009, OH and peroxy radical concentrations were measured using a laser-induced fluorescence instrument as part of the PROPHET (Program for Research on Oxidants: PHotochemistry, Emissions, and Transport) and CABINEX (Community Atmosphere-Biosphere INteractions EXperiment) campaigns at a forested site in northern Michigan. Supporting measurements of photolysis rates, volatile organic compounds, NOx (NO + NO2 and other inorganic species were used to constrain a zero-dimensional box model based on the Regional Atmospheric Chemistry Mechanism, modified to include the Mainz Isoprene Mechanism (RACM-MIM). The CABINEX model OH predictions were in good agreement with the measured OH concentrations, with an observed-to-modeled ratio near one (0.70 ± 0.31) for isoprene mixing ratios between 1–2 ppb on average. The measured peroxy radical concentrations, reflecting the sum of HO2 and isoprene-based peroxy radicals, were generally lower than predicted by the box model in both years.

Biogenic volatile organic compounds (BVOCs) can react in the atmosphere to form organic nitrates, which serve as NOx (NO + NO2) reservoirs, impacting ozone and secondary organic aerosol production, the oxidative capacity of the atmosphere, and nitrogen availability to ecosystems. To examine the contributions of biogenic emissions and the formation and fate of organic nitrates in a forest environment, we simulated the oxidation of 57 individual BVOCs emitted from a rural mixed forest in northern Michigan. Key BVOC-oxidant reactions were identified for future laboratory and field investigations into reaction rate constants, yields, and speciation of oxidation products. Of the total simulated organic nitrates, monoterpenes contributed ~70% in the early morning at ~12 m above the forest canopy when isoprene emissions were low. In the afternoon, when vertical mixing and isoprene nitrate production were highest, the simulated contribution of isoprene-derived organic nitrates was greater than 90% at all altitudes, with the concentration of secondary isoprene nitrates increasing with altitude. Notably, reaction of isoprene with NO3 leading to isoprene nitrate formation was found to be significant (~8% of primary organic nitrate production) during the daytime, and monoterpene reactions with NO3 were simulated to comprise up to ~83% of primary organic nitrate production at night. Lastly, forest succession, wherein aspen trees are being replaced by pine and maple trees, was predicted to lead to increased afternoon concentrations of monoterpene-derived organic nitrates. This further underscores the need to understand the formation and fate of these species, which have different chemical pathways and oxidation products compared to isoprene-derived organic nitrates and can lead to secondary organic aerosol formation.

Biological volatile organic compounds (BVOCs), such as isoprene and monoterpenes, are emitted in large amounts from forests. Quantification of the flux of BVOCs is critical in the evaluation of the impact of these compounds on the concentrations of atmospheric oxidants and on the production of secondary organic aerosol. A disjunct eddy accumulation (DEA) sampler system was constructed for the measurement of speciated BVOC fluxes. Unlike traditional eddy covariance (EC), the relatively new technique of disjunct sampling differs by taking short, discrete samples that allow for slower sampling frequencies. Disjunct sample airflow is directed into cartridges containing sorbent materials at sampling rates proportional to the magnitude of the vertical wind. Compounds accumulated on the cartridges are then quantified by thermal desorption and gas chromatography. Herein, we describe our initial tests to evaluate the disjunct sampler including the application of vertical wind measurements to create optimized sampling thresholds. Measurements of BVOC fluxes obtained from DEA during its deployment above a mixed hardwood forest at the University of Michigan Biological Station (Pellston, MI) during the 2009 CABINEX field campaign are reported. Daytime (09:00 a.m. to 05:00 p.m. LT) isoprene fluxes, when averaged over the footprint of the tower, were 1.31 mg m−2 h−1 which are comparable to previous flux measurements at this location. Speciated monoterpene fluxes are some of the first to be reported from this site. Daytime averages were 26.7 μg m−2 h−1 for α-pinene and 10.6 μg m−2 h−1 for β-pinene. These measured concentrations and fluxes were compared to the output of an atmospheric chemistry model, and were found to be consistent with our knowledge of the variables that control BVOCs fluxes at this site.

Vegetation emits large quantities of biogenic volatile organic compounds (BVOC). At remote sites, these compounds are the dominant precursors to ozone and secondary organic aerosol (SOA) production, yet current field studies show that atmospheric models have difficulty in capturing the observed HOx cycle and concentrations of BVOC oxidation products. In this manuscript, we simulate BVOC chemistry within a forest canopy using a one-dimensional canopy-chemistry model (Canopy Atmospheric CHemistry Emission model; CACHE) for a mixed deciduous forest in northern Michigan during the CABINEX 2009 campaign. We find that the base-case model, using fully-parameterized mixing and the simplified biogenic chemistry of the Regional Atmospheric Chemistry Model (RACM), underestimates daytime in-canopy vertical mixing by 50–70% and by an order of magnitude at night, leading to discrepancies in the diurnal evolution of HOx, BVOC, and BVOC oxidation products. Implementing observed micrometeorological data from above and within the canopy substantially improves the diurnal cycle of modeled BVOC, particularly at the end of the day, and also improves the observation-model agreement for some BVOC oxidation products and OH reactivity. We compare the RACM mechanism to a version that includes the Mainz isoprene mechanism (RACM-MIM) to test the model sensitivity to enhanced isoprene degradation. RACM-MIM simulates higher concentrations of both primary BVOC (isoprene and monoterpenes) and oxidation products (HCHO, MACR+MVK) compared with RACM simulations. Additionally, the revised mechanism alters the OH concentrations and increases HO2. These changes generally improve agreement with HOx observations yet overestimate BVOC oxidation products, indicating that this isoprene mechanism does not improve the representation of local chemistry at the site. Overall, the revised mechanism yields smaller changes in BVOC and BVOC oxidation product concentrations and gradients than improving the parameterization of vertical mixing with observations, suggesting that uncertainties in vertical mixing parameterizations are an important component in understanding observed BVOC chemistry.

Systems have been developed and deployed at a North Michigan forested site to measure ambient HONO and vertical HONO flux. The modified HONO measurement technique is based on aqueous scrubbing of HONO using a coil sampler, followed by azo dye derivatization and detection using a long-path absorption photometer (LPAP). A Na2CO3-coated denuder is used to generate "zero HONO" air for background correction. The lower detection limit of the method, defined by 3 times of the standard deviation of the signal, is 1 pptv for 1-min averages, with an overall uncertainty of ±(1 + 0.05 [HONO]) pptv. The HONO flux measurement technique has been developed based on the relaxed eddy accumulation approach, deploying a 3-D sonic anemometer and two HONO measurement systems. The overall uncertainty is estimated to be within ±(8 × 10−8 + 0.15 FHONO) mol m−2 h−1, with a 20-min averaged data point per 30 min. Ambient HONO and vertical HONO flux were measured simultaneously at the PROPHET site from 17 July to 7 August 2008. The forest canopy was found to be a net HONO source, with a mean upward flux of 0.37 × 10−6 moles m−2 h−1. The HONO flux reached a maximal mean of ~0.7 × 10−6 moles m−2 h−1 around solar noon, contributing a major fraction to the HONO source strength required to sustain the observed ambient concentration of ~70 pptv. There were no significant correlations between [NOx] and daytime HONO flux and between JNO2 × [NO2] and HONO flux, suggesting that NOx was not an important precursor responsible for HONO daytime production on the forest canopy surface in this low-NOx rural environment. Evidence supports the hypothesis that photolysis of HNO3 deposited on the forest canopy surface is a major daytime HONO source.

The role of ice in the formation of chemically active halogens in the environment requires a full understanding because of its role in atmospheric chemistry, including controlling the regional atmospheric oxidizing capacity in specific situations. In particular, ice and snow are important for facilitating multiphase oxidative chemistry and as media upon which marine algae live. This paper reviews the nature of environmental ice substrates that participate in halogen chemistry, describes the reactions that occur on such substrates, presents the field evidence for ice-mediated halogen activation, summarizes our best understanding of ice-halogen activation mechanisms, and describes the current state of modeling these processes at different scales. Given the rapid pace of developments in the field, this paper largely addresses advances made in the past five years, with emphasis given to the polar boundary layer. The integrative nature of this field is highlighted in the presentation of work from the molecular to the regional scale, with a focus on understanding fundamental processes. This is essential for developing realistic parameterizations and descriptions of these processes for inclusion in larger scale models that are used to determine their regional and global impacts.

We performed an atmospheric inversion of the CO2 fluxes over Iowa and the surrounding states, from June to December 2007, at 20 km resolution and weekly timescale. Eight concentration towers were used to constrain the carbon balance in a 1000×1000 km2 domain in this agricultural region of the US upper midwest. The CO2 concentrations of the boundaries derived from CarbonTracker were adjusted to match direct observations from aircraft profiles around the domain. The regional carbon balance ends up with a sink of 183 Tg C±35 Tg C over the area for the period June–December, 2007. Potential bias from incorrect boundary conditions of about 0.55 ppm over the 7 months was corrected using mixing ratios from four different aircraft profile sites operated at a weekly time scale, acting as an additional source of uncertainty of 24 Tg C. We used two different prior flux estimates, the SiBCrop model and the inverse flux product from the CarbonTracker system. We show that inverse flux estimates using both priors converge to similar posterior estimates (20 Tg C difference), in our reference inversion, but some spatial structures from the prior fluxes remain in the posterior fluxes, revealing the importance of the prior flux resolution and distribution despite the large amount of atmospheric data available. The retrieved fluxes were compared to eddy flux towers in the corn and grassland areas, revealing an improvement in the seasonal cycles between the two compared to the prior fluxes, despite large absolute differences due to representation errors. The uncertainty of 34 Tg C (or 34 g C m2) was derived from the posterior uncertainty obtained with our reference inversion of about 25 to 30 Tg C and from sensitivity tests of the assumptions made in the inverse system, for a mean carbon balance over the region of −183 Tg C, slightly weaker than the reference. Because of the potential large bias (~24 Tg C in this case) due to choice of background conditions, proportional to the surface but not to the regional flux, this methodology seems limited to regions with a large signal (sink or source), unless additional observations can be used to constrain the boundary inflow.

The biogenic volatile organic compound α-pinene is one of the dominant monoterpenes emitted to the Earth's atmosphere at an estimated rate of ~50 Tg C yr−1. Its atmospheric oxidation products in the presence of NO can lead to ozone production, as well as production of secondary organic aerosol (SOA). The major oxidation pathway of α-pinene is reaction with OH, which in the presence of NO can form either α-pinene nitrates or convert NO to NO2, which can photolyze to form ozone. In this work, we successfully synthesized four α-pinene hydroxy nitrates through three different routes, and have identified these 4 individual isomers in α-pinene/OH/NO reaction chamber experiments. From the experiments, we determined their individual production yields, estimated the total RONO2 yield, and calculated the relative branching ratios of the nitrate precursor peroxy radicals (RO2). The combined yield of the four α-pinene nitrates was found to be 0.130 (±0.035) at atmospheric pressure and 296 K, and the total organic nitrate yield was estimated to be 0.19 (+0.10/−0.06). We also determined the OH rate constants for two of the isomers, and have calculated their overall atmospheric lifetimes, which range between 22 and 38 h.

Isoprene is an important atmospheric volatile organic compound involved in ozone production and NOx (NO+NO2) sequestration and transport. Isoprene reaction with OH in the presence of NO can form either isoprene hydroxy nitrates ("isoprene nitrates") or convert NO to NO2 which can photolyze to form ozone. While it has been shown that isoprene nitrate production can represent an important sink for NOx in forest impacted environments, there is little experimental knowledge of the relative importance of the individual isoprene nitrate isomers, each of which has a different fate and reactivity. In this work, we have identified the 8 individual isomers and determined their total and individual production yields. The overall yield of isoprene nitrates at atmospheric pressure and 295 K was found to be 0.070(+0.025/−0.015). Three isomers, representing nitrates resulting from OH addition to a terminal carbon, represent 90% of the total IN yield. We also determined the ozone rate constants for three of the isomers, and have calculated their atmospheric lifetimes, which range from ~1–2 h, making their oxidation products likely more important as atmospheric organic nitrates and sinks for nitrogen.

A buoy based instrument platform (the "O-buoy") was designed, constructed, and field tested for year-round measurement of ozone, bromine monoxide, carbon dioxide, and meteorological variables over Arctic sea ice. The O-buoy operated in an autonomous manner with daily, bi-directional data transmissions using Iridium satellite communication. The O-buoy was equipped with three power sources: primary lithium-ion battery packs, rechargeable lead acid packs, and solar panels that recharge the lead acid packs, and can fully power the O-buoy during summer operation. This system was designed to operate under the harsh conditions present in the Arctic, with minimal direct human interaction, to aid in our understanding of the atmospheric chemistry that occurs in this remote region of the world. The current design requires approximately yearly maintenance limited by the lifetime of the primary power supply. The O-buoy system was field tested in Elson Lagoon, Barrow, Alaska from February to May 2009, and deployed in the Beaufort Sea in October 2009. Here, we describe the design and present preliminary data.

We performed MS/MS investigations of biogenic volatile organic compounds (BVOC) using a triple quadrupole tandem mass spectrometer (QqQ-MS) equipped with a Townsend Discharge ion source and a Proton Transfer Reaction Linear Ion Trap (PTR-LIT) mass spectrometer. Both instruments use H2O chemical ionization to produce protonated molecules. Here we report a study of the application of these instruments to determine methyl vinyl ketone (MVK) and methacrolein (MACR) and a series of monoterpenes (α-pinene, β-pinene, 3-carene, limonene, myrcene, ocimene) and sesquiterpenes (humulene and farnesene). Both instruments achieved sub-ppb detection limits in the single MS mode and in the MS/MS mode for differentiating MVK and MACR. Collision induced dissociation (CID) of protonated monoterpenes and sesquiterpenes was studied under the relatively high-energy, single-to-few collision conditions of the QqQ-MS instrument and under the low-energy, multiple collision conditions of the PTR-LIT. Differences and similarities in the breakdown curves obtained are discussed. In addition, we performed MS4 of protonated limonene to illustrate the analytical power of the PTR-LIT. In spite of the progress we have made, the selective on-line mass-spectrometric detection of individual monoterpenes or sesquiterpenes in complex mixtures currently does not yet seem to be possible.

A chamber was constructed within which snow crystals were grown on a string at various temperatures, relative humidities, and acetic acid gas phase mole fractions. The temperature, relative humidity, and acid mole fraction were measured for the first time at the point of crystal growth. Snow crystal morphological transition temperature shifts were recorded as a function of acid mole fraction, and interpreted according to the calculated acid concentration in the crystal's quasi-liquid layer, which is believed to have increased in thickness as a function of acid mole fraction, thereby affecting the crystal's morphology consistent with the hypothesis of Kuroda and Lacmann. Deficiencies in the understanding of the quasi-liquid layer and its role in determining snow crystal morphology are briefly discussed.

Oxidation of isoprene through reaction with NO3 radicals is a significant sink for isoprene that persists after dark. The main products of the reaction are multifunctional nitrates. These nitrates constitute a significant NOx sink in the nocturnal boundary layer and they likely play an important role in formation of secondary organic aerosol. Products of the isoprene+NO3 reaction will, in many locations, be abundant enough to affect nighttime radical chemistry and to persist into daytime where they may represent a source of NOx. Product formation in the isoprene + NO3 reaction was studied in a smog chamber at Purdue University. Isoprene nitrates and other hydrocarbon products were observed using Proton Transfer Reaction-Mass Spectrometry (PTR-MS) and reactive nitrogen products were observed using Thermal Dissociation–Laser Induced Fluorescence (TD-LIF). The organic nitrate yield is found to be 65±12% of which the majority was nitrooxy carbonyls and the combined yield of methacrolein and methyl vinyl ketone (MACR+MVK) is found to be ∼10%. PTR-MS measurements of nitrooxy carbonyls and TD-LIF measurements of total organic nitrates agreed well. The PTR-MS also observed a series of minor oxidation products which were tentatively identified and their yields quantified These other oxidation products are used as additional constraints on the reaction mechanism.

Volatile organic compound concentration ratios can be used as indicators of halogen chemistry that occurs during ozone depletion events in the Arctic during spring. Here we use a combination of modeling and measurements of [acetone]/[propanal] as an indicator of bromine chemistry, and [isobutane]/[n-butane] and [methyl ethyl ketone]/[n-butane] are used to study the extent of chlorine chemistry during four ozone depletion events during the Polar Sunrise Experiment of 1995. Using a 0-D photochemistry model in which the input of halogen atoms is controlled and varied, the approximate ratio of [Br]/[Cl] can be estimated for each ozone depletion event. It is concluded that there must be an additional source of propanal (likely from the snowpack) to correctly simulate the VOC chemistry of the Arctic, and further evidence that the ratio of Br atoms to Cl atoms can vary greatly during ozone depletion events is presented.

It has been shown that sunlit snow and ice plays an important role in processing atmospheric species. Photochemical production of a variety of chemicals has recently been reported to occur in snow/ice and the release of these photochemically generated species may significantly impact the chemistry of the overlying atmosphere. Nitrogen oxide and oxidant precursor fluxes have been measured in a number of snow covered environments, where in some cases the emissions significantly impact the overlying boundary layer. For example, photochemical ozone production (such as that occurring in polluted mid-latitudes) of 3–4 ppbv/day has been observed at South Pole, due to high OH and NO levels present in a relatively shallow boundary layer. Field and laboratory experiments have determined that the origin of the observed NOx flux is the photochemistry of nitrate within the snowpack, however some details of the mechanism have not yet been elucidated. A variety of low molecular weight organic compounds have been shown to be emitted from sunlit snowpacks, the source of which has been proposed to be either direct or indirect photo-oxidation of natural organic materials present in the snow. Although myriad studies have observed active processing of species within irradiated snowpacks, the fundamental chemistry occurring remains poorly understood. Here we consider the nature of snow at a fundamental, physical level; photochemical processes within snow and the caveats needed for comparison to atmospheric photochemistry; our current understanding of nitrogen, oxidant, halogen and organic photochemistry within snow; the current limitations faced by the field and implications for the future.

Abstract We report the CH4 emission flux from the city of Indianapolis, IN, the site of the Indianapolis Flux Experiment (INFLUX) project for developing, assessing, and improving top-down and bottom-up approaches for quantifying urban greenhouse gas emissions. Using an aircraft-based mass balance approach, we find that the average CH4 emission rate from five flight experiments in 2011 is 135 ± 58 (1σ) moles s-1 (7800 ± 3300 kg hr-1). The effective per capita CH4 emission rate for Indianapolis is 77 kg CH4 person-1 yr-1, a figure that is less than the national anthropogenic CH4 emission (∼91 kg CH4 person-1 yr-1) but considerably larger than the global figure (∼48 kg CH4 person-1 yr-1). We consistently observed elevated CH4 concentrations at specific coordinates along our flight transects downwind of the city. Inflight investigations as well as back trajectories using measured wind directions showed that the elevated concentrations originated from the southwest side of the city where a landfill and a natural gas transmission regulating station (TRS) are located. Street level mobile measurements downwind of the landfill and the TRS supported the results of aircraft-based data, and were used to quantify the relative contributions from the two sources. We find that the CH4 emission from the TRS was negligible relative to the landfill, which was responsible for 33 ± 10% of the citywide emission flux. A regression of propane versus methane from aircraft flask samples suggests that the remaining citywide CH4 emissions (∼67%) derive from the natural gas distribution system. We discuss the combination of surface mobile observations and aircraft city-wide flux measurements to determine the total flux and apportionment to important sources.