The preservation of atmospheric nitrate in snow at Summit, Greenland

There is great interest in using nitrate NO3 isotopic composition in ice cores to track the history of precursor nitrogen oxides (NOx = NO + NO2) in the atmosphere. Nitrate NO3 however can be lost from the snow by surface processes, such as photolysis back to NOx upon exposure to sunlight, making it difficult to interpret records of NO3 as a tracer of atmospheric NOx loading. In a campaign consisting of two field seasons (May–June) at Summit, Greenland, high temporal frequency surface snow samples were collected and analyzed for the oxygen isotopic composition of NO3. The strong, linear relationship observed between the oxygen isotopes of NO3 in both 2010 and 2011, is difficult to explain in the presence of significant post depositional processing of NO3 unless several unrelated variables change in concert. Therefore, the isotopic signature of NO3 in the snow at Summit is most feasibly explained as preserved atmospheric NO3 deposition

Modeling chemistry in and above snow at Summit, Greenland – Part 2: Impact of snowpack chemistry on the oxidation capacity of the boundary layer

The chemical composition of the boundary layer in snow covered regions is impacted by chemistry in the snowpack via uptake, processing, and emission of atmospheric trace gases. We use the coupled one-dimensional (1-D) snow chemistry and atmospheric boundary layer model MISTRA-SNOW to study the impact of snowpack chemistry on the oxidation capacity of the boundary layer. The model includes gas phase photochemistry and chemical reactions both in the interstitial air and the atmosphere. While it is acknowledged that the chemistry occurring at ice surfaces may consist of a true quasi-liquid layer and/or a concentrated brine layer, lack of additional knowledge requires that this chemistry be modeled as primarily aqueous chemistry occurring in a liquid-like layer (LLL) on snow grains. The model has been recently compared with BrO and NO data taken on 10 June–13 June 2008 as part of the Greenland Summit Halogen-HOx experiment (GSHOX). In the present study, we use the same focus period to investigate the influence of snowpack derived chemistry on OH and HOx + RO2 in the boundary layer. We compare model results with chemical ionization mass spectrometry (CIMS) measurements of the hydroxyl radical (OH) and of the hydroperoxyl radical (HO2) plus the sum of all organic peroxy radicals (RO2) taken at Summit during summer 2008. Using sensitivity runs we show that snowpack influenced nitrogen cycling and bromine chemistry both increase the oxidation capacity of the boundary layer and that together they increase the midday OH concentrations. Bromine chemistry increases the OH concentration by 10–18 % (10 % at noon LT), while snow sourced NOx increases OH concentrations by 20–50 % (27 % at noon LT). We show for the first time, using a coupled one dimensional snowpack-boundary layer model, that air-snow interactions impact the oxidation capacity of the boundary layer and that it is not possible to match measured OH levels without snowpack NOx and halogen emissions. Model predicted HONO compared with mistchamber measurements suggests there may be an unknown HONO source at Summit. Other model predicted HOx precursors, H2O2 and HCHO, compare well with measurements taken in summer 2000, which had lower levels than other years. Over 3 days, snow sourced NOx contributes an additional 2 ppb to boundary layer ozone production, while snow sourced bromine has the opposite effect and contributes 1 ppb to boundary layer ozone loss

Measurements of pernitric acid at the South Pole during ISCAT 2000

The first measurements of pernitric acid at the South Pole were performed during the second Investigation of Sulfur Chemistry in the Antarctic Troposphere (ISCAT 2000). Observed HO2NO2 concentrations averaged 25 pptv. Simple steady-state calculations constrained by measurements show that the lifetime of pernitric acid was largely controlled by dry deposition, with thermal decomposition becoming increasingly important at warmer temperatures. We determined that the pernitric acid equilibrium constant is less uncertain than indicated in the literature. One consequence of pernitric acid deposition to the snow surface is that it is an important sink for both NOx and HOx. Another is that the photochemistry of HO2NO2 in the Antarctic snowpack may be a NOx source in addition to nitrate photolysis. This might be one of the important differences in snow photochemistry between the South Pole and warmer polar sites

Overview of the 2007 and 2008 campaigns conducted as part of the Greenland Summit Halogen-HO\u3csub\u3ex\u3c/sub\u3e Experiment (GSHOX)

From 10 May through 17 June 2007 and 6 June through 9 July 2008 intensive sampling campaigns at Summit, Greenland confirmed that active bromine chemistry is occurring in and above the snow pack at the highest part of the Greenland ice sheet (72°36´ N, 38°25´ W and 3.2 km above sea level). Direct measurements found BrO and soluble gas phase Br− mixing ratios in the low pptv range on many days (maxima \u3c 10 pptv). Conversion of up to 200 pg m−3 of gaseous elemental mercury (GEM) to reactive gaseous mercury (RGM) and enhanced OH relative to HO2 plus RO2 confirm that active bromine chemistry is impacting chemical cycles even at such low abundances of reactive bromine species. However, it does not appear that Bry chemistry can fully account for observed perturbations to HOx partitioning, suggesting unknown additional chemical processes may be important in this unique environment, or that our understanding of coupled NOx-HOx-Brychemistry above sunlit polar snow is incomplete. Rapid transport from the north Atlantic marine boundary layer occasionally caused enhanced BrO at Summit (just two such events observed during the 12 weeks of sampling over the two seasons). In general observed reactive bromine was linked to activation of bromide (Br−) in, and release of reactive bromine from, the snowpack. A coupled snow-atmosphere model simulated observed NO and BrO at Summit during a three day interval when winds were weak. The source of Br− in surface and near surface snow at Summit is not entirely clear, but concentrations were observed to increase when stronger vertical mixing brought free tropospheric air to the surface. Reactive Bry mixing ratios above the snow often increased in the day or two following increases in snow concentration, but this response was not consistent. On seasonal time scales concentrations of Br− in snow and reactive bromine in the air were directly related

The impact of local sources and long-range transport on aerosol properties over the northeast U.S. region during INTEX-NA

We use data collected aboard the NASA DC-8 aircraft during the summer 2004, Intercontinental Transport and Chemical Evolution Experiment over North America (INTEX-NA) field campaign to examine the origin, composition, physical and optical properties of aerosols within air masses sampled over and downwind of the northeastern U.S. We note that aerosol concentrations within the region exhibited steep vertical gradients and significant variability in both time and space. An examination of air mass chemical signatures and backward trajectories indicates that transport from four, significantly different source regions contributed to the variability: the subtropical Atlantic Ocean (AO); the U.S. west coast and eastern Pacific (WCP); the U.S. east coast and Midwestern states (EC); and northwest Canada and Alaska (CA). AO air masses were typically confined to below 2 km altitude, exhibited low pollutant contents, contained enhanced levels of sea salt, and were typically observed when the Bermuda High strengthened. The most common air mass present in the upper troposphere, WCP air often contained weak dust and aged pollution enhances from convective input occurring over the central part of the continent. CA air exhibited enhancements in anthropogenic pollution tracers below 2 km and contained some black-carbon rich haze layers between 3 and 5 km that could be traced to forest fires burning in western Canada and Alaska. EC air was prevalent at lower elevations throughout the study area and exhibited enhanced scattering along with elevated levels of sulfate aerosols and combustion tracers. There is an overall balance between the observed cations and anions for all cases, except EC air mass below 4 km

Multi-scale modeling study of the source contributions to near-surface ozone and sulfur oxides levels over California during the ARCTAS-CARB period

Chronic high surface ozone (O3) levels and the increasing sulfur oxides (SOx = SO2+SO4) ambient concentrations over South Coast (SC) and other areas of California (CA) are affected by both local emissions and long-range transport. In this paper, multi-scale tracer, full-chemistry and adjoint simulations using the STEM atmospheric chemistry model are conducted to assess the contribution of local emission sourcesto SC O3 and to evaluate the impacts of transported sulfur and local emissions on the SC sulfur budgetduring the ARCTAS-CARB experiment period in 2008. Sensitivity simulations quantify contributions of biogenic and fire emissions to SC O3 levels. California biogenic and fire emissions contribute 3–4 ppb to near-surface O3 over SC, with larger contributions to other regions in CA. During a long-range transport event from Asia starting from 22 June, high SOx levels (up to ~0.7 ppb of SO2 and ~1.3 ppb of SO4) is observed above ~6 km, but they did not affect CA surface air quality. The elevated SOx observed at 1–4 km is estimated to enhance surface SOx over SC by ~0.25 ppb (upper limit) on ~24 June. The near-surface SOx levels over SC during the flight week are attributed mostly to local emissions. Two anthropogenic SOx emission inventories (EIs) from the California Air Resources Board (CARB) and the US Environmental Protection Agency (EPA) are compared and applied in 60 km and 12 km chemical transport simulations, and the results are compared withobservations. The CARB EI shows improvements over the National Emission Inventory (NEI) by EPA, but generally underestimates surface SC SOx by about a factor of two. Adjoint sensitivity analysis indicated that SO2 levels at 00:00 UTC (17:00 local time) at six SC surface sites were influenced by previous day maritime emissions over the ocean, the terrestrial emissions over nearby urban areas, and by transported SO2 from the north through both terrestrial and maritime areas. Overall maritime emissions contribute 10–70% of SO2 and 20–60% fine SO4 on-shore and over the most terrestrial areas, with contributions decreasing with in-land distance from the coast. Maritime emissions also modify the photochemical environment, shifting O3 production over coastal SC to more VOC-limited conditions. These suggest an important role for shipping emission controls in reducing fine particle and O3concentrations in SC

Bromine measurements in ozone depleted air over the Arctic Ocean

In situ measurements of ozone, photochemically active bromine compounds, and other trace gases over the Arctic Ocean in April 2008 are used to examine the chemistry and geographical extent of ozone depletion in the arctic marine boundary layer (MBL). Data were obtained from the NOAA WP-3D aircraft during the Aerosol, Radiation, and Cloud Processes affecting Arctic Climate (ARCPAC) study and the NASA DC-8 aircraft during the Arctic Research of the Composition of the Troposphere from Aircraft and Satellites (ARCTAS) study. Fast (1 s) and sensitive (detection limits at the low pptv level) measurements of BrCl and BrO were obtained from three different chemical ionization mass spectrometer (CIMS) instruments, and soluble bromide was measured with a mist chamber. The CIMS instruments also detected Br2. Subsequent laboratory studies showed that HOBr rapidly converts to Br2 on the Teflon instrument inlets. This detected Br2 is identified as active bromine and represents a lower limit of the sum HOBr + Br2. The measured active bromine is shown to likely be HOBr during daytime flights in the arctic. In the MBL over the Arctic Ocean, soluble bromide and active bromine were consistently elevated and ozone was depleted. Ozone depletion and active bromine enhancement were confined to the MBL that was capped by a temperature inversion at 200–500 m altitude. In ozone-depleted air, BrO rarely exceeded 10 pptv and was always substantially lower than soluble bromide that was as high as 40 pptv. BrCl was rarely enhanced above the 2 pptv detection limit, either in the MBL, over Alaska, or in the arctic free troposphere

Chemical characterization of secondary organic aerosol at a rural site in the southeastern US: insights from simultaneous high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS) and FIGAERO chemical ionization mass spectrometer (CIMS) measurements

The formation and evolution of secondary organic aerosol (SOA) were investigated at Yorkville, GA, in late summer (mid-August to mid-October 2016). The organic aerosol (OA) composition was measured using two online mass spectrometry instruments, the high-resolution time-of-flight aerosol mass spectrometer (AMS) and the Filter Inlet for Gases and AEROsols coupled to a high-resolution time-of-flight iodide-adduct chemical ionization mass spectrometer (FIGAERO-CIMS). Through analysis of speciated organics data from FIGAERO-CIMS and factorization analysis of data obtained from both instruments, we observed notable SOA formation from isoprene and monoterpenes during both day and night. Specifically, in addition to isoprene epoxydiol (IEPOX) uptake, we identified isoprene SOA formation from non-IEPOX pathways and isoprene organic nitrate formation via photooxidation in the presence of NO_x and nitrate radical oxidation. Monoterpenes were found to be the most important SOA precursors at night. We observed significant contributions from highly oxidized acid-like compounds to the aged OA factor from FIGAERO-CIMS. Taken together, our results showed that FIGAERO-CIMS measurements are highly complementary to the extensively used AMS factorization analysis, and together they provide more comprehensive insights into OA sources and composition

Chemical characterization of secondary organic aerosol at a rural site in the southeastern US: insights from simultaneous high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS) and FIGAERO chemical ionization mass spectrometer (CIMS) measurements

The formation and evolution of secondary organic aerosol (SOA) were investigated at Yorkville, GA, in late summer (mid-August to mid-October 2016). The organic aerosol (OA) composition was measured using two online mass spectrometry instruments, the high-resolution time-of-flight aerosol mass spectrometer (AMS) and the Filter Inlet for Gases and AEROsols coupled to a high-resolution time-of-flight iodide-adduct chemical ionization mass spectrometer (FIGAERO-CIMS). Through analysis of speciated organics data from FIGAERO-CIMS and factorization analysis of data obtained from both instruments, we observed notable SOA formation from isoprene and monoterpenes during both day and night. Specifically, in addition to isoprene epoxydiol (IEPOX) uptake, we identified isoprene SOA formation from non-IEPOX pathways and isoprene organic nitrate formation via photooxidation in the presence of NO_x and nitrate radical oxidation. Monoterpenes were found to be the most important SOA precursors at night. We observed significant contributions from highly oxidized acid-like compounds to the aged OA factor from FIGAERO-CIMS. Taken together, our results showed that FIGAERO-CIMS measurements are highly complementary to the extensively used AMS factorization analysis, and together they provide more comprehensive insights into OA sources and composition

Integration of airborne and ground observations of nitryl chloride in the Seoul metropolitan area and the implications on regional oxidation capacity during KORUS-AQ 2016

Nitryl chloride (ClNO2) is a radical reservoir species that releases chlorine radicals upon photolysis. An integrated analysis of the impact of ClNO2 on regional photochemistry in the Seoul metropolitan area (SMA) during the Korea-United States Air Quality Study (KORUS-AQ) 2016 field campaign is presented. Comprehensive multiplatform observations were conducted aboard the NASA DC-8 and at two ground sites (Olympic Park, OP; Taehwa Research Forest, TRF), representing an urbanized area and a forested suburban region, respectively. Positive correlations between daytime Cl2 and ClNO2 were observed at both sites, the slope of which was dependent on O3 levels. The possible mechanisms are explored through box model simulations constrained with observations. The overall diurnal variations in ClNO2 at both sites appeared similar but the nighttime variations were systematically different. For about half of the observation days at the OP site the level of ClNO2 increased at sunset but rapidly decreased at around midnight. On the other hand, high levels were observed throughout the night at the TRF site. Significant levels of ClNO2 were observed at both sites for 4-5 h after sunrise. Airborne observations, box model calculations, and back-trajectory analysis consistently show that these high levels of ClNO2 in the morning are likely from vertical or horizontal transport of air masses from the west. Box model results show that chlorine-radical-initiated chemistry can impact the regional photochemistry by elevating net chemical production rates of ozone by 25% in the morning