Ship-based nitric acid measurements in the Gulf of Maine during New England Air Quality Study 2002

Gas phase nitric acid (HNO3) was measured at 5-min resolution on board the National Oceanographic and Atmospheric Administration (NOAA) research vessel Ronald H. Brown during the second leg (29 July to 10 August) of the New England Air Quality Study (NEAQS) 2002 cruise. A primary objective of the cruise was to improve understanding of the oxidation of NOx in, and removal of the oxidation products from, the polluted marine boundary layer east of northeastern North America. For the first 9 days of this leg the ship remained north of Cape Cod, and the cruise track did not extend much farther north than the New Hampshire-Maine border. During this period, HNO3 averaged 1.1 ppb and accounted for 19% of total reactive nitrogen oxides (measured NOy). On all days, peak HNO3 mixing ratios were observed in the early afternoon (average 2.3 ppb), at levels twofold to fourfold higher than the minima around sunrise and sunset. In these daytime peaks, HNO3/NOy averaged 28%. There were secondary nighttime peaks of HNO3 (0.9 ppb average), when HNO3 accounted for 16% of total reactive nitrogen oxides. This pronounced diurnal pattern confirms that production, and subsequent deposition, of HNO3 in the polluted marine boundary layer downwind of New England removes a significant fraction of the NOx exported to the atmosphere over the Gulf of Maine. Nitric acid was correlated with O3, particularly during the early afternoon interval when both molecules reached maximum mixing ratios (R2 = 0.66). The ozone production efficiency (OPE) inferred from the slope (10 ppb O3/ppb HNO3) was similar to the OPE of 9 estimated at the Atmospheric Investigation, Regional Modeling, Analysis and Prediction (AIRMAP) Thompson Farm station in coastal New Hampshire during the study period

Engineering Improved Photoswitches for the Control of Nucleocytoplasmic Distribution

Optogenetic techniques use light-responsive proteins to study dynamic processes in living cells and organisms. These techniques typically rely on repurposed naturally occurring light-sensitive proteins to control subcellular localization and activity. We previously engineered two optogenetic systems, the light activated nuclear shuttle (LANS) and the light-inducible nuclear exporter (LINX), by embedding nuclear import or export sequence motifs into the C-terminal helix of the light-responsive LOV2 domain of Avena sativa phototropin 1, thus enabling light-dependent trafficking of a target protein into and out of the nucleus. While LANS and LINX are effective tools, we posited that mutations within the LOV2 hinge-loop, which connects the core PAS domain and the C-terminal helix, would further improve the functionality of these switches. Here, we identify hinge-loop mutations that favorably shift the dynamic range (the ratio of the on- to off-target subcellular accumulation) of the LANS and LINX photoswitches. We demonstrate the utility of these new optogenetic tools to control gene transcription and epigenetic modifications, thereby expanding the optogenetic "tool kit" for the research community

Nighttime removal of NOx in the summer marine boundary layer

The nitrate radical, NO3, and dinitrogen pentoxide, N2O5, are two important components of nitrogen oxides that occur predominantly at night in the lower troposphere. Because a large fraction of NO2 reacts to form NO3 and N2O5 during the course of a night, their fate is an important determining factor to the overall fate of NOx (=NO and NO2). As a comprehensive test of nocturnal nitrogen oxide chemistry, concentrations of O3, NO, NO2, NO3, N2O5, HNO3 and a host of other relevant compounds, aerosol abundance and composition, and meteorological conditions were measured in the marine boundary layer from the NOAA research vessel Ronald H. Brown off the East Coast of the United States as part of the New England Air Quality Study (NEAQS) during the summer of 2002. The results confirm the prominent role of NO3 and N2O5 in converting NOx to HNO3 at night with an efficiency on par with daytime photochemical conversion. The findings demonstrate the large role of nighttime chemistry in determining the NOx budget and consequent production of ozone. INDEX TERMS: 0322 Atmospheric Composition and Structure: Constituent sources and sinks; 0345 Atmospheric Composition and Structure: Pollution—urban and regional (0305); 0365 Atmospheric Composition and Structure: Troposphere—composition and chemistry. Citation: Brown, S. S., et al. (2004), Nighttime removal of NOx in the summer marine boundary layer, Geophys. Res. Lett., 31, L07108, doi:10.1029/2004GL01941

High-and low-temperature pyrolysis profiles describe volatile organic compound emissions from western US wildfire fuels

Biomass burning is a large source of volatile organic compounds (VOCs) and many other trace species to the atmosphere, which can act as precursors to secondary pollutants such as ozone and fine particles. Measurements performed with a proton-transfer-reaction time-of-flight mass spectrometer during the FIREX 2016 laboratory intensive were analyzed with positive matrix factorization (PMF), in order to understand the instantaneous variability in VOC emissions from biomass burning, and to simplify the description of these types of emissions. Despite the complexity and variability of emissions, we found that a solution including just two emission profiles, which are mass spectral representations of the relative abundances of emitted VOCs, explained on average 85% of the VOC emissions across various fuels representative of the western US (including various coniferous and chaparral fuels). In addition, the profiles were remarkably similar across almost all of the fuel types tested. For example, the correlation coefficient r2 of each profile between ponderosa pine (coniferous tree) and manzanita (chaparral) is higher than 0.84. The compositional differences between the two VOC profiles appear to be related to differences in pyrolysis processes of fuel biopolymers at high and low temperatures. These pyrolysis processes are thought to be the main source of VOC emissions. High-temperature and low-temperature pyrolysis processes do not correspond exactly to the commonly used flaming and smoldering categories as described by modified combustion efficiency (MCE). The average atmospheric properties (e.g., OH reactivity, volatility, etc) of the high-and low-temperature profiles are significantly different. We also found that the two VOC profiles can describe previously reported VOC data for laboratory and field burns

Sources and characteristics of summertime organic aerosol in the Colorado Front Range: perspective from measurements and WRF-Chem modeling

Abstract. The evolution of organic aerosols (OAs) and their precursors in the boundary layer (BL) of the Colorado Front Range during the Front Range Air Pollution and Photochemistry Éxperiment (FRAPPÉ, July–August 2014) was analyzed by in situ measurements and chemical transport modeling. Measurements indicated significant production of secondary OA (SOA), with enhancement ratio of OA with respect to carbon monoxide (CO) reaching 0.085±0.003 µg m−3 ppbv−1. At background mixing ratios of CO, up to  ∼  1.8 µg m−3 background OA was observed, suggesting significant non-combustion contribution to OA in the Front Range. The mean concentration of OA in plumes with a high influence of oil and natural gas (O&G) emissions was  ∼  40 % higher than in urban-influenced plumes. Positive matrix factorization (PMF) confirmed a dominant contribution of secondary, oxygenated OA (OOA) in the boundary layer instead of fresh, hydrocarbon-like OA (HOA). Combinations of primary OA (POA) volatility assumptions, aging of semi-volatile species, and different emission estimates from the O&G sector were used in the Weather Research and Forecasting model coupled with Chemistry (WRF-Chem) simulation scenarios. The assumption of semi-volatile POA resulted in greater than a factor of 10 lower POA concentrations compared to PMF-resolved HOA. Including top-down modified O&G emissions resulted in substantially better agreements in modeled ethane, toluene, hydroxyl radical, and ozone compared to measurements in the high-O&G-influenced plumes. By including emissions from the O&G sector using the top-down approach, it was estimated that the O&G sector contributed to  <  5 % of total OA, but up to 38 % of anthropogenic SOA (aSOA) in the region. The best agreement between the measured and simulated median OA was achieved by limiting the extent of biogenic hydrocarbon aging and consequently biogenic SOA (bSOA) production. Despite a lower production of bSOA in this scenario, contribution of bSOA to total SOA remained high at 40–54 %. Future studies aiming at a better emissions characterization of POA and intermediate-volatility organic compounds (IVOCs) from the O&G sector are valuable

Non-methane organic gas emissions from biomass burning: Identification, quantification, and emission factors from PTR-ToF during the FIREX 2016 laboratory experiment

Volatile and intermediate-volatility non-methane organic gases (NMOGs) released from biomass burning were measured during laboratory-simulated wildfires by proton-transfer-reaction time-of-flight mass spectrometry (PTR-ToF). We identified NMOG contributors to more than 150 PTR ion masses using gas chromatography (GC) pre-separation with electron ionization, H3O+ chemical ionization, and NO+ chemical ionization, an extensive literature review, and time series correlation, providing higher certainty for ion identifications than has been previously available. Our interpretation of the PTR-ToF mass spectrum accounts for nearly 90ĝ€-% of NMOG mass detected by PTR-ToF across all fuel types. The relative contributions of different NMOGs to individual exact ion masses are mostly similar across many fires and fuel types. The PTR-ToF measurements are compared to corresponding measurements from open-path Fourier transform infrared spectroscopy (OP-FTIR), broadband cavity-enhanced spectroscopy (ACES), and iodide ion chemical ionization mass spectrometry (Iĝ\u27 CIMS) where possible. The majority of comparisons have slopes near 1 and values of the linear correlation coefficient, R2, ofĝ€ & ĝ€-0.8, including compounds that are not frequently reported by PTR-MS such as ammonia, hydrogen cyanide (HCN), nitrous acid (HONO), and propene. The exceptions include methylglyoxal and compounds that are known to be difficult to measure with one or more of the deployed instruments. The fire-integrated emission ratios to CO and emission factors of NMOGs from 18 fuel types are provided. Finally, we provide an overview of the chemical characteristics of detected species. Non-aromatic oxygenated compounds are the most abundant. Furans and aromatics, while less abundant, comprise a large portion of the OH reactivity. The OH reactivity, its major contributors, and the volatility distribution of emissions can change considerably over the course of a fire

Non-methane organic gas emissions from biomass burning: identification, quantification, and emission factors from PTR-ToF during the FIREX 2016 laboratory experiment

Volatile and intermediate-volatility non-methane organic gases (NMOGs) released from biomass burning were measured during laboratory-simulated wildfires by proton-transfer-reaction time-of-flight mass spectrometry (PTR-ToF). We identified NMOG contributors to more than 150 PTR ion masses using gas chromatography (GC) pre-separation with electron ionization, H3O+ chemical ionization, and NO+ chemical ionization, an extensive literature review, and time series correlation, providing higher certainty for ion identifications than has been previously available. Our interpretation of the PTR-ToF mass spectrum accounts for nearly 90ĝ€-% of NMOG mass detected by PTR-ToF across all fuel types. The relative contributions of different NMOGs to individual exact ion masses are mostly similar across many fires and fuel types. The PTR-ToF measurements are compared to corresponding measurements from open-path Fourier transform infrared spectroscopy (OP-FTIR), broadband cavity-enhanced spectroscopy (ACES), and iodide ion chemical ionization mass spectrometry (Iĝ\u27 CIMS) where possible. The majority of comparisons have slopes near 1 and values of the linear correlation coefficient, R2, ofĝ€ & ĝ€-0.8, including compounds that are not frequently reported by PTR-MS such as ammonia, hydrogen cyanide (HCN), nitrous acid (HONO), and propene. The exceptions include methylglyoxal and compounds that are known to be difficult to measure with one or more of the deployed instruments. The fire-integrated emission ratios to CO and emission factors of NMOGs from 18 fuel types are provided. Finally, we provide an overview of the chemical characteristics of detected species. Non-aromatic oxygenated compounds are the most abundant. Furans and aromatics, while less abundant, comprise a large portion of the OH reactivity. The OH reactivity, its major contributors, and the volatility distribution of emissions can change considerably over the course of a fire

Emissions of nitrogen-containing organic compounds from the burning of herbaceous and arboraceous biomass: Fuel composition dependence and the variability of commonly used nitrile tracers

Volatile organic compounds (VOCs) emitted from residential wood and crop residue burning were measured in Colorado, U.S. When compared to the emissions from crop burning, residential wood burning exhibited markedly lower concentrations of acetonitrile, a commonly used biomass burning tracer. For both herbaceous and arboraceous fuels, the emissions of nitrogen-containing VOCs (NVOCs) strongly depend on the fuel nitrogen content; therefore, low NVOC emissions from residential wood burning result from the combustion of low-nitrogen fuel. Consequently, the emissions of compounds hazardous to human health, such as HNCO and HCN, and the formation of secondary pollutants, such as ozone generated by NOx, are likely to depend on fuel nitrogen. These results also demonstrate that acetonitrile may not be a suitable tracer for domestic burning in urban areas. Wood burning emissions may be best identified through analysis of the emissions profile rather than reliance on a single tracer species