Arctic springtime observations of volatile organic compounds during the OASIS‐2009 campaign

Gas‐phase volatile organic compounds (VOCs) were measured at three vertical levels between 0.6 m and 5.4 m in the Arctic boundary layer in Barrow, Alaska, for the Ocean‐Atmosphere‐Sea Ice‐Snowpack (OASIS)‐2009 field campaign during March–April 2009. C4‐C8 nonmethane hydrocarbons (NMHCs) and oxygenated VOCs (OVOCs), including alcohols, aldehydes, and ketones, were quantified multiple times per hour, day and night, during the campaign using in situ fast gas chromatography‐mass spectrometry. Three canister samples were also collected daily and subsequently analyzed for C2‐C5 NMHCs. The NMHCs and aldehydes demonstrated an overall decrease in mixing ratios during the experiment, whereas acetone and 2‐butanone showed increases. Calculations of time‐integrated concentrations of Br atoms, ∫[Br]dt, yielded values as high as (1.34 ± 0.27) × 1014 cm−3 s during the longest observed ozone depletion event (ODE) of the campaign and were correlated with the steady state Br calculated at the site during this time. Both chlorine and bromine chemistry contributed to the large perturbations on the production and losses of VOCs. Notably, acetaldehyde, propanal, and butanal mixing ratios dropped below the detection limit of the instrument (3 parts per trillion by volume (pptv) for acetaldehyde and propanal, 2 pptv for butanal) during several ODEs due to Br chemistry. Chemical flux calculations of OVOC production and loss are consistent with localized high Cl‐atom concentrations either regionally or within a very shallow surface layer, while the deeper Arctic boundary layer provides a continuous source of precursor alkanes to maintain the OVOC mixing ratios.

[1]  M. Frey,et al.  Formaldehyde (HCHO) in air, snow, and interstitial air at Concordia (East Antarctic Plateau) in summer , 2015 .

[2]  T. Wallington,et al.  The Mechanisms of Reactions Influencing Atmospheric Ozone , 2015 .

[3]  J. Peischl,et al.  Upper tropospheric ozone production from lightning NOx‐impacted convection: Smoke ingestion case study from the DC3 campaign , 2015 .

[4]  R. Russo,et al.  Impact of Marcellus Shale natural gas development in southwest Pennsylvania on volatile organic compound emissions and regional air quality. , 2015, Environmental science & technology.

[5]  P. Shepson,et al.  Interactions of bromine, chlorine, and iodine photochemistry during ozone depletions in Barrow, Alaska , 2014 .

[6]  A. Stohl,et al.  Seasonal variability of atmospheric nitrogen oxides and non-methane hydrocarbons at the GEOSummit station, Greenland , 2014 .

[7]  Christopher W. Fairall,et al.  Boundary layer dynamics during the Ocean‐Atmosphere‐Sea‐Ice‐Snow (OASIS) 2009 experiment at Barrow, AK , 2014 .

[8]  D. Helmig,et al.  Seasonal behavior of non-methane hydrocarbons in the firn air at Summit, Greenland , 2014 .

[9]  P. Shepson,et al.  High levels of molecular chlorine in the Arctic atmosphere , 2014 .

[10]  R. Russo,et al.  Volatile organic compound distributions during the NACHTT campaign at the Boulder Atmospheric Observatory: Influence of urban and natural gas sources , 2013 .

[11]  J. McConnell,et al.  Air–snowpack exchange of bromine, ozone and mercury in the springtime Arctic simulated by the 1-D model PHANTAS – Part 1: In-snow bromine activation and its impact on ozone , 2013 .

[12]  P. Shepson,et al.  Photochemical production of molecular bromine in Arctic surface snowpacks , 2013 .

[13]  J. D. de Gouw,et al.  Source signature of volatile organic compounds from oil and natural gas operations in northeastern Colorado. , 2013, Environmental science & technology.

[14]  P. Shepson,et al.  Ozone dynamics and snow-atmosphere exchanges during ozone depletion events at Barrow, Alaska , 2012 .

[15]  P. Shepson,et al.  The relative importance of chlorine and bromine radicals in the oxidation of atmospheric mercury at Barrow, Alaska , 2012 .

[16]  J. Harris,et al.  Springtime boundary layer ozone depletion at Barrow, Alaska: Meteorological influence, year-to-year variation, and long-term change , 2012 .

[17]  W. Sturges,et al.  Evidence from firn air for recent decreases in non-methane hydrocarbons and a 20th century increase in nitrogen oxides in the northern hemisphere , 2012 .

[18]  D. Blake,et al.  Observations of nonmethane organic compounds during ARCTAS - Part 1: Biomass burning emissions and plume enhancements , 2011 .

[19]  A. Weinheimer,et al.  Nitrous acid (HONO) during polar spring in Barrow, Alaska: A net source of OH radicals? , 2011 .

[20]  A. Fried,et al.  Formaldehyde in the Alaskan Arctic snowpack: Partitioning and physical processes involved in air-snow exchanges , 2011 .

[21]  P. Shepson,et al.  A comparison of Arctic BrO measurements by chemical ionization mass spectrometry and long path‐differential optical absorption spectroscopy , 2011 .

[22]  D. Blake,et al.  Characterization of trace gases measured over Alberta oil sands mining operations: 76 speciated C 2 –C 10 volatile organic compounds (VOCs), CO 2 , CH 4 , CO, NO, NO 2 , NO y , O 3 and SO 2 , 2010 .

[23]  H. Mao,et al.  Multi-year (2004–2008) record of nonmethane hydrocarbons and halocarbons in New England: seasonal variations and regional sources , 2010 .

[24]  H. Mao,et al.  Temporal variability, sources, and sinks of C 1 -C 5 alkyl nitrates in coastal Ne , 2009 .

[25]  S. Madronich,et al.  Chemical evolution of volatile organic compounds in the outflow of the Mexico City Metropolitan area , 2009, Atmospheric Chemistry and Physics.

[26]  S. Reimann,et al.  Severe aromatic hydrocarbon pollution in the Arctic town of Longyearbyen (Svalbard) caused by snowmobile emissions. , 2009, Environmental science & technology.

[27]  J. Burrows,et al.  Intercomparison of oxygenated volatile organic compound measurements at the SAPHIR atmosphere simulation chamber , 2008 .

[28]  M. Hoffmann,et al.  HONO emissions from snow surfaces , 2008 .

[29]  A. Jones,et al.  Measurement and interpretation of gas phase formaldehyde concentrations obtained during the CHABLIS campaign in coastal Antarctica , 2008 .

[30]  D. Blake,et al.  Bromoform and dibromomethane measurements in the seacoast region of New Hampshire, 2002–2004 , 2008 .

[31]  C. Anastasio,et al.  Light absorption by soluble chemical species in Arctic and Antarctic snow , 2007 .

[32]  P. Shepson,et al.  An overview of snow photochemistry: evidence, mechanisms and impacts , 2007 .

[33]  Lars Kaleschke,et al.  Halogens and their role in polar boundary-layer ozone depletion , 2007 .

[34]  P. Shepson,et al.  Volatile organic compound ratios as probes of halogen atom chemistry in the Arctic , 2007 .

[35]  B. Lefer,et al.  Light penetration in the snowpack at Summit, Greenland: Part 1: Nitrite and hydrogen peroxide photolysis , 2007 .

[36]  P. Shepson,et al.  A study of the vertical scale of halogen chemistry in the Arctic troposphere during Polar Sunrise at Barrow, Alaska , 2007 .

[37]  Roger Atkinson,et al.  Evaluated kinetic and photochemical data for atmospheric chemistry: Volume III – gas phase reactions of inorganic halogens , 2006 .

[38]  R. Russo,et al.  Development of a cryogen-free concentration system for measurements of volatile organic compounds. , 2005, Analytical chemistry.

[39]  R. A. Cox,et al.  Evaluated kinetic and photochemical data for atmospheric chemistry: Volume II – reactions of organic species , 2005 .

[40]  J. Dibb,et al.  Soluble reactive nitrogen oxides at South Pole during ISCAT 2000 , 2004 .

[41]  Roger Atkinson,et al.  Evaluated kinetic and photochemical data for atmospheric chemistry: Volume I - gas phase reaxtions of Ox, HOx, NOx and SOx species , 2004 .

[42]  R. Lueb,et al.  A fast‐GC/MS system to measure C2 to C4 carbonyls and methanol aboard aircraft , 2003 .

[43]  R. Koppmann,et al.  Seasonal variability and trends of volatile organic compounds in the lower polar troposphere , 2003 .

[44]  D. Blake,et al.  Seasonal variations of C2–C4 nonmethane hydrocarbons and C1–C4 alkyl nitrates at the Summit research station in Greenland , 2003 .

[45]  S. Madronich,et al.  Calculation of actinic fluxes with a coupled atmosphere-snow radiative transfer model , 2002 .

[46]  J. Fuentes,et al.  NOx during background and ozone depletion periods at Alert: Fluxes above the snow surface , 2002 .

[47]  Paul B. Shepson,et al.  Air-Snow Interactions and Atmospheric Chemistry , 2002, Science.

[48]  Sébastien Perrier,et al.  Distribution and trends of oxygenated hydrocarbons in the high Arctic derived from measurements in the atmospheric boundary layer and interstitial snow air during the ALERT2000 field campaign , 2002 .

[49]  Sébastien Perrier,et al.  Acetaldehyde and acetone in the Arctic snowpack during the ALERT2000 campaign. Snowpack composition, incorporation processes and atmospheric impact , 2002 .

[50]  Hacene Boudries,et al.  A study of photochemical and physical processes affecting carbonyl compounds in the Arctic atmospheric boundary layer , 2002 .

[51]  J. Dibb,et al.  Shouldn’t snowpacks be sources of monocarboxylic acids? , 2002 .

[52]  K. Steffen,et al.  Measurements of hydrogen peroxide and formaldehyde exchange between the atmosphere and surface snow at Summit, Greenland , 2002 .

[53]  K. Steffen,et al.  Vertical fluxes of NOx, HONO, and HNO3 above the snowpack at Summit, Greenland , 2002 .

[54]  P. Shepson,et al.  Snowpack processing of acetaldehyde and acetone in the Arctic atmospheric boundary layer , 2002 .

[55]  A. Volz-Thomas,et al.  Quality Assurance of Hydrocarbon Measurements for the German Tropospheric Research Focus (TFS) , 2002 .

[56]  J. McConnell,et al.  HCHO in Antarctic snow: Preservation in ice cores and air‐snow exchange , 2002 .

[57]  P. Shepson,et al.  The role of Br2 and BrCl in surface ozone destruction at polar sunrise. , 2001, Science.

[58]  J. Bottenheim,et al.  Cl and Br atom concentrations during a surface boundary layer ozone depletion event in the Canadian High Arctic , 2000 .

[59]  F. Fehsenfeld,et al.  The Nonmethane Hydrocarbon Intercomparison Experiment (NOMHICE): Task 3 , 1999 .

[60]  J. Rudolph,et al.  Halogen atom concentrations in the Arctic Troposphere derived from hydrocarbon measurements: Impact on the budget of formaldehyde , 1999 .

[61]  R. Röthlisberger,et al.  Atmosphere‐to‐snow‐to‐firn transfer studies of HCHO at Summit, Greenland , 1999 .

[62]  Martin D. Müller,et al.  Photolysis frequency measurements using actinic flux spectroradiometry during the PEM‐Tropics mission: Instrumentation description and some results , 1999 .

[63]  D. Tanner,et al.  Measurements of OH during PEM‐Tropics A , 1999 .

[64]  P. Shepson,et al.  Snowpack production of formaldehyde and its effect on the Arctic troposphere , 1999, Nature.

[65]  R. Koppmann,et al.  Hydrocarbon measurements during tropospheric ozone depletion events : Evidence for halogen atom chemistry , 1999 .

[66]  P. Shepson,et al.  Measurements comparison of oxygenated volatile organic compounds at a rural site during the 1995 SOS Nashville Intensive , 1998 .

[67]  B. Jobson,et al.  Measurements of C2-C7 hydrocarbons during the Polar Sunrise Experiment 1994: Further evidence for halogen chemistry in the troposphere , 1998 .

[68]  A. Guenther,et al.  Eddy covariance measurement of isoprene fluxes , 1998 .

[69]  Glenn Rolph,et al.  Real-time Environmental Applications and Display sYstem: READY , 2017, Environ. Model. Softw..

[70]  M. Rodgers,et al.  Hydrocarbon measurements during the 1992 Southern Oxidants Study Atlanta Intensive: Protocol and quality assurance , 1995 .

[71]  Y. Yokouchi,et al.  Serial gas chromatographic/mass spectrometric measurements of some volatile organic compounds in the Arctic atmosphere during the 1992 Polar Sunrise Experiment , 1994 .

[72]  Y. Yokouchi,et al.  Measurements of C2‐C6 hydrocarbons during the Polar Sunrise1992 Experiment: Evidence for Cl atom and Br atom chemistry , 1994 .

[73]  F. Fehsenfeld,et al.  The Nonmethane Hydrocarbon Intercomparison Experiment (NOMHICE): Tasks 1 and 2 , 1994 .

[74]  D. Jacob,et al.  Surface ozone depletion in Arctic spring sustained by bromine reactions on aerosols , 1992, Nature.

[75]  F. E. Grahek,et al.  A small, high-sensitivity, medium-response ozone detector suitable for measurements from light aircraft , 1992 .

[76]  P. Doskey,et al.  Non‐methane hydrocarbons in the Arctic atmosphere at Barrow, Alaska , 1992 .

[77]  Shao-Meng Li,et al.  Measurements of nitrogen oxides at Barrow, Alaska during spring: Evidence for regional and northern hemispheric sources of pollution , 1991 .

[78]  F. E. Grahek,et al.  A Small, Low Flow, High Sensitivity Reaction Vessel for NO Chemiluminescence Detectors , 1990 .

[79]  F. E. Livingston,et al.  Ozone destruction and bromine photochemistry at ground level in the Arctic spring , 1990, Nature.

[80]  P. Crutzen,et al.  Ozone destruction and photochemical reactions at polar sunrise in the lower Arctic atmosphere , 1988, Nature.

[81]  S. Oltmans,et al.  Surface ozone distributions and variations from 1973–1984: Measurements at the NOAA Geophysical Monitoring for Climatic Change Baseline Observatories , 1986 .

[82]  J. Bottenheim,et al.  Measurements of NO Y species and O 3 at 82° N latitude , 1986 .

[83]  R. Honrath,et al.  Evidence of NOx production within or upon ice particles in the Greenland snowpack , 2023 .

[84]  J. Peischl,et al.  Upper tropospheric ozoneproduction from lightning NO x-impacted convection : Smoke ingestion case study from the DC 3 campaign , 2015 .

[85]  J. Orlando,et al.  Temperature‐dependent rate coefficient measurements for the reaction of bromine atoms with a series of aldehydes , 2000 .

[86]  Sasha Madronich,et al.  The Role of Solar Radiation in Atmospheric Chemistry , 1999 .

[87]  H. Lenschow Micrometeorological techniques for measuring biosphere-atmosphere trace gas exchange , 1995 .

[88]  L. Barrie,et al.  Photochemical bromine production implicated in Arctic boundary-layer ozone depletion , 1992, Nature.