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Abstract. The Arctic is a climatically sensitive region that has experienced warming at almost 3 times the global average rate in recent decades, leading to an increase in Arctic greenness and a greater abundance of plants that emit biogenic volatile organic compounds (BVOCs). These changes in atmospheric emissions are expected to significantly modify the overall oxidative chemistry of the region and lead to changes in VOC composition and abundance, with implications for atmospheric processes. Nonetheless, observations needed to constrain our current understanding of these issues in this critical environment are sparse. This work presents novel atmospheric in situ proton-transfer-reaction time-of-flight mass spectrometry (PTR-ToF-MS) measurements of VOCs at Toolik Field Station (TFS; 68∘38′ N, 149∘36' W), in the Alaskan Arctictundra during May–June 2019. We employ a custom nested grid version of theGEOS-Chem chemical transport model (CTM), driven with MEGANv2.1 (Model ofEmissions of Gases and Aerosols from Nature version 2.1) biogenic emissionsfor Alaska at 0.25∘ × 0.3125∘ resolution, to interpret the observations in terms of their constraints onBVOC emissions, total reactive organic carbon (ROC) composition, andcalculated OH reactivity (OHr) in this environment. We find total ambientmole fraction of 78 identified VOCs to be 6.3 ± 0.4 ppbv (10.8 ± 0.5 ppbC), with overwhelming (> 80 %) contributions are from short-chain oxygenated VOCs (OVOCs) includingmore »methanol, acetone and formaldehyde. Isoprene was the most abundant terpene identified. GEOS-Chem captures the observed isoprene (and its oxidation products), acetone and acetaldehyde abundances within the combined model and observation uncertainties (±25 %), but underestimates other OVOCs including methanol, formaldehyde, formic acid and acetic acid by a factor of 3 to 12. The negative model bias for methanol is attributed to underestimated biogenic methanol emissions for the Alaskan tundra in MEGANv2.1. Observed formaldehyde mole fractions increase exponentially with air temperature, likely reflecting its biogenic precursors and pointing to a systematic model underprediction of its secondary production. The median campaign-calculated OHr from VOCs measured at TFS was 0.7 s−1, roughly 5 % of the values typically reported in lower-latitude forested ecosystems. Ten species account for over 80 % of the calculated VOC OHr, with formaldehyde, isoprene and acetaldehyde together accounting for nearly half of the total. Simulated OHr based on median-modeled VOCs included in GEOS-Chem averages 0.5 s−1 and is dominated by isoprene (30 %) and monoterpenes (17 %). The data presented here serve as a critical evaluation of our knowledge of BVOCs and ROC budgets in high-latitude environments and represent a foundation for investigating and interpreting future warming-driven changes in VOC emissions in the Alaskan Arctic tundra.« less

Abstract. We apply airborne measurements across three seasons(summer, winter and spring 2017–2018) in a multi-inversion framework toquantify methane emissions from the US Corn Belt and Upper Midwest, a keyagricultural and wetland source region. Combing our seasonal results withprior fall values we find that wetlands are the largest regional methanesource (32 %, 20 [16–23] Gg/d), while livestock (enteric/manure; 25 %,15 [14–17] Gg/d) are the largest anthropogenic source. Naturalgas/petroleum, waste/landfills, and coal mines collectively make up theremainder. Optimized fluxes improve model agreement with independentdatasets within and beyond the study timeframe. Inversions reveal coherentand seasonally dependent spatial errors in the WetCHARTs ensemble meanwetland emissions, with an underestimate for the Prairie Pothole region butan overestimate for Great Lakes coastal wetlands. Wetland extent andemission temperature dependence have the largest influence on predictionaccuracy; better representation of coupled soil temperature–hydrologyeffects is therefore needed. Our optimized regional livestock emissionsagree well with the Gridded EPA estimates during spring (to within 7 %) butare ∼ 25 % higher during summer and winter. Spatial analysisfurther shows good top-down and bottom-up agreement for beef facilities (withmainly enteric emissions) but larger (∼ 30 %) seasonaldiscrepancies for dairies and hog farms (with > 40 % manureemissions). Findings thus support bottom-up enteric emission estimates butsuggest errors for manure; we propose that the latter reflects inadequatetreatment of managementmore »factors including field application. Overall, ourresults confirm the importance of intensive animal agriculture for regionalmethane emissions, implying substantial mitigation opportunities throughimproved management.« less

We report on the sensitivity of enhanced ozone (O3) production, observed during lake breeze circulation along the coastline of Lake Michigan, to the concentrations of nitrogen oxides (NOx = NO + NO2) and volatile organic compounds (VOCs). We assess the sensitivity of O3 production to NOx and VOC on a high O3 day during the Lake Michigan Ozone Study 2017 (LMOS 2017) using an observationally-constrained chemical box model that implements the Master Chemical Mechanism (MCM v3.3.1) and recent emission inventories for NOx and VOCs. The MCM model is coupled to a backward air mass trajectory analysis from a ground supersite in Zion, IL where an extensive series of measurements of O3 precursors and their oxidation products, including hydrogen peroxide (H2O2), nitric acid (HNO3), and particulate nitrates (NO3-) serve as model constraints. We evaluate the chemical evolution of the Chicago-Gary urban plume as it advects over Lake Michigan and demonstrate how modeled indicators of VOC- vs. NOx- sensitive regimes can be constrained by measurements at the trajectory endpoint. Using the modeled ratio of the instantaneous H2O2 and HNO3 production rates (PH2O2 / PHNO3), we suggest that O3 production over the urban source region is strongly VOC-sensitive and progresses towards a moremore »NOx-sensitive regime as the plume advects north along the Lake Michigan coastline on this day. We also demonstrate that ground-based measurements of the mean concentration ratio of H2O2 to HNO3 describe the sensitivity of O3 production to VOC and NOx as the integral of chemical production along the plume path.« less