Total Observed Organic Carbon (TOOC): A synthesis of North American observations

Measurements of organic carbon compounds in both the gas and particle phases measured upwind, over and downwind of North America are synthesized to examine the total observed organic carbon (TOOC) over this region. These include measurements made aboard the NOAA WP-3 and BAe-146 aircraft, the NOAA research vessel Ronald H. Brown, and at the Thompson Farm and Chebogue Point surface sites during the summer 2004 ICARTT campaign. Both winter and summer 2002 measurements during the Pittsburgh Air Quality Study are also included. Lastly, the spring 2002 observations at Trinidad Head, CA, surface measurements made in March 2006 in Mexico City and coincidentally aboard the C-130 aircraft during the MILAGRO campaign and later during the IMPEX campaign off the northwestern United States are incorporated. Concentrations of TOOC in these datasets span more than two orders of magnitude. The daytime mean TOOC ranges from 4.0 to 456 μgC m^−3 from the cleanest site (Trinidad Head) to the most polluted (Mexico City). Organic aerosol makes up 3–17% of this mean TOOC, with highest fractions reported over the northeastern United States, where organic aerosol can comprise up to 50% of TOOC. Carbon monoxide concentrations explain 46 to 86% of the variability in TOOC, with highest TOOC/CO slopes in regions with fresh anthropogenic influence, where we also expect the highest degree of mass closure for TOOC. Correlation with isoprene, formaldehyde, methyl vinyl ketene and methacrolein also indicates that biogenic activity contributes substantially to the variability of TOOC, yet these tracers of biogenic oxidation sources do not explain the variability in organic aerosol observed over North America. We highlight the critical need to develop measurement techniques to routinely detect total gas phase VOCs, and to deploy comprehensive suites of TOOC instruments in diverse environments to quantify the ambient evolution of organic carbon from source to sink.

[1]  I. Galbally,et al.  The Production of Methanol by Flowering Plants and the Global Cycle of Methanol , 2002 .

[2]  D. Blake,et al.  Summertime measurements of selected nonmethane hydrocarbons in the Arctic and Subarctic during the 1988 Arctic Boundary Layer Expedition (ABLE 3A) , 1992 .

[3]  J. A. de Gouw,et al.  Airborne measurements of carbonaceous aerosol soluble in water over northeastern United States: Method development and an investigation into water-soluble organic carbon sources , 2006 .

[4]  Corinne Le Quéré,et al.  Climate Change 2013: The Physical Science Basis , 2013 .

[5]  Jonathan Crosier,et al.  Chemical composition observed over the mid-Atlantic and the detection of pollution signatures far from source regions , 2007 .

[6]  A. Goldstein,et al.  Emissions of ethene, propene, and 1-butene by a midlatitude forest , 1996 .

[7]  A. Weinheimer,et al.  On the Measurement of PANs by Gas Chromatography and Electron Capture Detection , 2005 .

[8]  A. Stohl,et al.  Impacts of sources and aging on submicrometer aerosol properties in the marine boundary layer across the Gulf of Maine , 2006 .

[9]  Allen L Robinson,et al.  Rethinking Organic Aerosols: Semivolatile Emissions and Photochemical Aging , 2007, Science.

[10]  D. Jacob,et al.  Formaldehyde, glyoxal, and methylglyoxal in air and cloudwater at a rural mountain site in central Virginia , 1995 .

[11]  John H. Seinfeld,et al.  Photochemical modeling of the Southern California air quality study , 1993 .

[12]  A. Stohl,et al.  Volatile organic compounds composition of merged and aged forest fire plumes from Alaska and western Canada , 2006 .

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

[14]  Cliff I. Davidson,et al.  Pittsburgh air quality study overview , 2004 .

[15]  J. A. de Gouw,et al.  No evidence for acid‐catalyzed secondary organic aerosol formation in power plant plumes over metropolitan Atlanta, Georgia , 2007 .

[16]  S. Paulson,et al.  An investigation of the relationship between total non-methane organic carbon and the sum of speciated hydrocarbons and carbonyls measured by standard GC/FID: measurements in the Los Angeles air basin , 2003 .

[17]  Kenneth A. Smith,et al.  Development of an Aerosol Mass Spectrometer for Size and Composition Analysis of Submicron Particles , 2000 .

[18]  Qi Zhang,et al.  Ubiquity and dominance of oxygenated species in organic aerosols in anthropogenically‐influenced Northern Hemisphere midlatitudes , 2007 .

[19]  Maria Cristina Facchini,et al.  Source attribution of water-soluble organic aerosol by nuclear magnetic resonance spectroscopy. , 2007, Environmental science & technology.

[20]  J. Seinfeld,et al.  Organic atmospheric particulate material. , 2003, Annual review of physical chemistry.

[21]  Allen B. White,et al.  Chemical speciation of organic aerosol during the International Consortium for Atmospheric Research on Transport and Transformation 2004: Results from in situ measurements , 2007 .

[22]  R. Hirsch,et al.  METHODS OF FITTING A STRAIGHT LINE TO DATA: EXAMPLES IN WATER RESOURCES , 1984 .

[23]  M. Molina,et al.  Secondary organic aerosol formation from anthropogenic air pollution: Rapid and higher than expected , 2006 .

[24]  A. Goldstein,et al.  Submicron aerosol composition at Trinidad Head, California, during ITCT 2K2: Its relationship with gas phase volatile organic carbon and assessment of instrument performance , 2004 .

[25]  P. A. Tanner,et al.  Organic Acids in the Atmosphere and Bulk Deposition of Hong Kong , 2003 .

[26]  Thomas P. Kurosu,et al.  Mapping isoprene emissions over North America using formaldehyde column observations from space , 2003 .

[27]  Jay R. Turner,et al.  A method for on‐line measurement of water‐soluble organic carbon in ambient aerosol particles: Results from an urban site , 2004 .

[28]  W. B. Knighton,et al.  Multi-model simulations of the impact of international shipping on atmospheric chemistry and climate in 2000 and 2030 , 2006 .

[29]  A. Sullivan,et al.  Fine Aerosol Bulk Composition Measured on WP-3D Research Aircraft in Vicinity of the Northeastern United States - Results from NEAQS , 2007 .

[30]  Joost A. de Gouw,et al.  A study of secondary organic aerosol formation in the anthropogenic-influenced southeastern United States , 2007 .

[31]  John H. Seinfeld,et al.  Secondary organic aerosol formation from m-xylene, toluene, and benzene , 2007 .

[32]  D. R. Worsnop,et al.  Hydrocarbon-like and oxygenated organic aerosols in Pittsburgh: insights into sources and processes of organic aerosols , 2005 .

[33]  D. Jacob,et al.  Global budget of methanol : Constraints from atmospheric observations , 2005 .

[34]  A. Lewis,et al.  A two-column method for long-term monitoring of non-methane hydrocarbons (NMHCs) and oxygenated volatile organic compounds (o-VOCs). , 2003, Journal of environmental monitoring : JEM.

[35]  Thomas P. Kurosu,et al.  Satellite observations of formaldehyde over North America from GOME , 2000 .

[36]  H. Niki,et al.  Measurement of total nonmethane organic carbon (Cy): development and application at Chebogue Point, Nova Scotia, during the 1993 North Atlantic Regional Experiment campaign , 1998 .

[37]  D. Jacob,et al.  Atmospheric acetylene and its relationship with CO as an indicator of air mass age , 2007 .

[38]  P. Solomon,et al.  Semicontinuous aerosol carbon measurements: Comparison of Atlanta Supersite measurements , 2003 .

[39]  J. Hearn,et al.  Reactions and mass spectra of complex particles using Aerosol CIMS , 2006 .

[40]  A. Goldstein,et al.  Known and Unexplored Organic Constituents in the Earth's Atmosphere , 2007 .

[41]  B. Anderson,et al.  On the flux of oxygenated volatile organic compounds from organic aerosol oxidation , 2006 .

[42]  D. Blake,et al.  Distributions of brominated organic compounds in the troposphere and lower stratosphere , 1999 .

[43]  A. Goldstein,et al.  Volatile Organic Compound Measurements at Trinidad Head, California, during Itct 2k2: Analysis of Sources, Atmospheric Composition, and Aerosol Residence Times , 2004 .

[44]  Bernard Aumont,et al.  Modelling the Evolution of Organic Carbon Modelling the Evolution of Organic Carbon during Its Gas-phase Tropospheric Oxidation: Development of an Explicit Model Based on a Self Generating Approach Acpd Modelling the Evolution of Organic Carbon , 2022 .

[45]  John H. Seinfeld,et al.  Regional variation of organic functional groups in aerosol particles on four U.S. east coast platforms during the International Consortium for Atmospheric Research on Transport and Transformation 2004 campaign , 2007 .

[46]  Barbara J. Turpin,et al.  Species Contributions to PM2.5 Mass Concentrations: Revisiting Common Assumptions for Estimating Organic Mass , 2001 .

[47]  J. A. de Gouw,et al.  Effects of mixing on evolution of hydrocarbon ratios in the troposphere , 2005 .

[48]  A. Robinson,et al.  Local and Regional Secondary Organic Aerosol: Insights from a Year of Semi-Continuous Carbon Measurements at Pittsburgh , 2006 .

[49]  H. Mao,et al.  Diurnal characteristics of surface level O3 and other important trace gases in New England , 2005 .

[50]  A. Goldstein,et al.  Secondary Atmospheric Photooxidation Products: Evidence for Biogenic and Anthropogenic Sources , 2001 .

[51]  D. Salcedo,et al.  A missing sink for gas‐phase glyoxal in Mexico City: Formation of secondary organic aerosol , 2007 .

[52]  Philip B. Russell,et al.  International Consortium for Atmospheric Research on Transport and Transformation (ICARTT): North America to Europe—Overview of the 2004 summer field study , 2006 .

[53]  C. J. Hahn,et al.  Measurements of aromatic hydrocarbon ratios and NOx concentrations in the rural troposphere: Observation of air mass photochemical aging and NOx removal , 1984 .

[54]  A. Goldstein,et al.  Biogenic versus anthropogenic sources of CO in the United States , 2008 .

[55]  Judith C. Chow,et al.  Comparison and evaluation of in situ and filter carbon measurements at the Fresno Supersite , 2002 .

[56]  J. Slowik,et al.  Heterogeneous oxidation of saturated organic aerosols by hydroxyl radicals: uptake kinetics, condensed-phase products, and particle size change , 2007 .

[57]  James M. Roberts,et al.  Budget of organic carbon in a polluted atmosphere: Results from the New England Air Quality Study in 2002 , 2005 .

[58]  New Directions☆: Novel separation techniques in VOC analysis pose new challenges to atmospheric chemistry , 2000 .

[59]  D. Jacob,et al.  Atmospheric budget of acetone , 2002 .

[60]  M. Johnston,et al.  On-line analysis of organic components in fine and ultrafine particles by photoionization aerosol mass spectrometry. , 2004, Analytical chemistry.

[61]  Erik Swietlicki,et al.  Organic aerosol and global climate modelling: a review , 2004 .

[62]  Annmarie G. Carlton,et al.  Link between isoprene and secondary organic aerosol (SOA): Pyruvic acid oxidation yields low volatility organic acids in clouds , 2006 .

[63]  A. Goldstein,et al.  Emission, oxidation, and secondary organic aerosol formation of volatile organic compounds as observed at Chebogue Point, Nova Scotia , 2007 .

[64]  Kenneth A. Smith,et al.  Aerosol mass spectrometer for size and composition analysis of submicron particles , 1998 .

[65]  S. Herndon,et al.  Separation of emitted and photochemical formaldehyde in Mexico City using a statistical analysis and a new pair of gas-phase tracers , 2005 .

[66]  D. Blake,et al.  Hydrocarbon ratios during PEM‐WEST A: A model perspective , 1996 .

[67]  Ann M. Middlebrook,et al.  Single-particle mass spectrometry of tropospheric aerosol particles , 2006 .

[68]  W. Malm,et al.  Relative contributions of fossil and contemporary carbon sources to PM 2.5 aerosols at nine Interagency Monitoring for Protection of Visual Environments (IMPROVE) network sites , 2007 .

[69]  P. M. Lang,et al.  Atmospheric methane levels off: Temporary pause or a new steady‐state? , 2003 .

[70]  Paul J. Webb,et al.  Partially oxidised organic components in urban aerosol using GCXGC-TOF/MS , 2004 .

[71]  R. Fall,et al.  Sensitivity and specificity of atmospheric trace gas detection by proton-transfer-reaction mass spectrometry , 2003 .

[72]  Qi Zhang,et al.  Submicron particles at Thompson Farm during ICARTT measured using aerosol mass spectrometry , 2008 .

[73]  P. Crutzen,et al.  High concentrations and photochemical fate of oxygenated hydrocarbons in the global troposphere , 1995, Nature.

[74]  J. Rudolph,et al.  The tropospheric distribution and budget of ethane , 1995 .

[75]  Herbert J. Tobias,et al.  Effect of Relative Humidity on the Chemical Composition of Secondary Organic Aerosol Formed from Reactions of 1-Tetradecene and O3 , 2000 .

[76]  D. Jacob,et al.  Impact of Asian emissions on observations at Trinidad Head, California, during ITCT 2K2 , 2004 .

[77]  C E Kolb,et al.  Guest Editor: Albert Viggiano CHEMICAL AND MICROPHYSICAL CHARACTERIZATION OF AMBIENT AEROSOLS WITH THE AERODYNE AEROSOL MASS SPECTROMETER , 2022 .

[78]  Amy P. Sullivan,et al.  Source Apportionment of Fine Organic Aerosol during Milagro Source Apportionment of Fine Organic Aerosol in Mexico City during the Milagro Experiment 2006 Acpd Source Apportionment of Fine Organic Aerosol during Milagro , 2022 .

[79]  M. Molina,et al.  Atmospheric evolution of organic aerosol , 2004 .

[80]  J. A. de Gouw,et al.  summer: 1. Direct emissions and secondary formation of organic matter in urban plumes , 2008 .

[81]  A. Goldstein,et al.  Atmospheric volatile organic compound measurements during the Pittsburgh Air Quality Study: Results, interpretation, and quantification of primary and secondary contributions , 2005 .

[82]  Charles E. Kolb,et al.  Air quality in North America's most populous city - overview of the MCMA-2003 campaign , 2007 .

[83]  A. Goldstein,et al.  Chemical characteristics of North American surface layer outflow: Insights from Chebogue Point, Nova Scotia , 2006 .

[84]  P. DeCarlo,et al.  Elemental analysis of organic species with electron ionization high-resolution mass spectrometry. , 2007, Analytical chemistry.

[85]  C. N. Hewitt,et al.  A global model of natural volatile organic compound emissions , 1995 .

[86]  James F. Meagher,et al.  Nonmethane hydrocarbon and oxy hydrocarbon measurements during the 2002 New England Air Quality Study , 2004 .

[87]  Robert McLaren,et al.  Reactive uptake of glyoxal by particulate matter , 2005 .

[88]  R. Russo,et al.  Coastal water source of short‐lived halocarbons in New England , 2005 .

[89]  A. Hansel,et al.  On-line monitoring of volatile organic compounds at pptv levels by means of proton-transfer-reaction mass spectrometry (PTR-MS) medical applications, food control and environmental research , 1998 .

[90]  J. D. de Gouw,et al.  Online volatile organic compound measurements using a newly developed proton-transfer ion-trap mass spectrometry instrument during New England Air Quality Study--Intercontinental Transport and Chemical Transformation 2004: performance, intercomparison, and compound identification. , 2005, Environmental science & technology.

[91]  Barry J. Huebert,et al.  A large organic aerosol source in the free troposphere missing from current models , 2005 .

[92]  Qi Zhang,et al.  A case study of urban particle acidity and its influence on secondary organic aerosol. , 2007, Environmental science & technology.

[93]  A. Goldstein,et al.  In situ measurements of C2‐C10 volatile organic compounds above a Sierra Nevada ponderosa pine plantation , 1999 .

[94]  J. Seinfeld,et al.  Concentrations and sources of organic carbon aerosols in the free troposphere over North America , 2006 .

[95]  Allen H. Goldstein,et al.  Seasonal variations of nonmethane hydrocarbons in rural New England: Constraints on OH concentrations in northern midlatitudes , 1995 .