Formaldehyde column density measurements as a suitable pathway to estimate near‐surface ozone tendencies from space

In support of future satellite missions that aim to address the current shortcomings in measuring air quality from space, NASA's Deriving Information on Surface Conditions from Column and Vertically Resolved Observations Relevant to Air Quality (DISCOVER‐AQ) field campaign was designed to enable exploration of relationships between column measurements of trace species relevant to air quality at high spatial and temporal resolution. In the DISCOVER‐AQ data set, a modest correlation (r2 = 0.45) between ozone (O3) and formaldehyde (CH2O) column densities was observed. Further analysis revealed regional variability in the O3‐CH2O relationship, with Maryland having a strong relationship when data were viewed temporally and Houston having a strong relationship when data were viewed spatially. These differences in regional behavior are attributed to differences in volatile organic compound (VOC) emissions. In Maryland, biogenic VOCs were responsible for ~28% of CH2O formation within the boundary layer column, causing CH2O to, in general, increase monotonically throughout the day. In Houston, persistent anthropogenic emissions dominated the local hydrocarbon environment, and no discernable diurnal trend in CH2O was observed. Box model simulations suggested that ambient CH2O mixing ratios have a weak diurnal trend (±20% throughout the day) due to photochemical effects, and that larger diurnal trends are associated with changes in hydrocarbon precursors. Finally, mathematical relationships were developed from first principles and were able to replicate the different behaviors seen in Maryland and Houston. While studies would be necessary to validate these results and determine the regional applicability of the O3‐CH2O relationship, the results presented here provide compelling insight into the ability of future satellite missions to aid in monitoring near‐surface air quality.

[1]  Crystal B. Schaaf,et al.  A climatology of visible surface reflectance spectra , 2016 .

[2]  K. Chance,et al.  The role of OH production in interpreting the variability of CH2O columns in the southeast U.S. , 2016 .

[3]  Nicolas Theys,et al.  Diurnal, seasonal and long-term variations of global formaldehyde columns inferred from combined OMI and GOME-2 observations , 2015 .

[4]  A. Reitze The National Ambient Air Quality Standards for Ozone , 2015 .

[5]  J. Peischl,et al.  Formaldehyde production from isoprene oxidation across NOx regimes. , 2015, Atmospheric chemistry and physics.

[6]  I. D. Smedt,et al.  Inter-annual variations in satellite observations of nitrogen dioxide and formaldehyde over India , 2015 .

[7]  Tracey Holloway,et al.  Spatial and temporal variability of ozone sensitivity over China observed from the Ozone Monitoring Instrument , 2015 .

[8]  A. Fried,et al.  Compact highly sensitive multi-species airborne mid-IR spectrometer , 2015 .

[9]  Markus Müller,et al.  A compact PTR-ToF-MS instrument for airborne measurements of volatile organic compounds at high spatiotemporal resolution , 2014 .

[10]  D. Jacob,et al.  Anthropogenic emissions of highly reactive volatile organic compounds in eastern Texas inferred from oversampling of satellite (OMI) measurements of HCHO columns , 2014 .

[11]  J. Peñuelas,et al.  Remote sensing of atmospheric biogenic volatile organic compounds (BVOCs) via satellite-based formaldehyde vertical column assessments , 2014 .

[12]  D. Blake,et al.  Evidence of mixing between polluted convective outflow and stratospheric air in the upper troposphere during DC3 , 2014 .

[13]  Ernest Hilsenrath,et al.  Satellite Data of Atmospheric Pollution for U.S. Air Quality Applications: Examples of Applications, Summary of Data End-User Resources, Answers to FAQs, and Common Mistakes to Avoid , 2014 .

[14]  Elena Paoletti,et al.  Ozone levels in European and USA cities are increasing more than at rural sites, while peak values are decreasing. , 2014, Environmental pollution.

[15]  Xiong Liu,et al.  The added value of a visible channel to a geostationary thermal infrared instrument to monitor ozone for air quality , 2014 .

[16]  J. Lamarque,et al.  Global Distribution and Trends of Tropospheric Ozone: An Observation-Based Review , 2014 .

[17]  Glenn S. Diskin,et al.  Impact of Bay-Breeze Circulations on Surface Air Quality and Boundary Layer Export , 2014 .

[18]  A. Wisthaler,et al.  A compact PTR-ToF-MS instrument for airborne measurements of VOCs at high spatio-temporal resolution , 2014 .

[19]  A. Weinheimer,et al.  Ozone profiles in the Baltimore-Washington region (2006–2011): satellite comparisons and DISCOVER-AQ observations , 2014, Journal of Atmospheric Chemistry.

[20]  Xiong Liu,et al.  Relationship Between Column-Density and Surface Mixing Ratio: Statistical Analysis of O3 and NO2 Data from the July 2011 Maryland DISCOVER-AQ Mission , 2014 .

[21]  R. Dickerson,et al.  An elevated reservoir of air pollutants over the Mid-Atlantic States during the 2011 DISCOVER-AQ campaign: Airborne measurements and numerical simulations , 2014 .

[22]  L. Gu,et al.  Observed and modeled ecosystem isoprene fluxes from an oak-dominated temperate forest and the influence of drought stress , 2014 .

[23]  Kelly Chance,et al.  Monitoring high-ozone events in the US Intermountain West using TEMPO geostationary satellite observations , 2013 .

[24]  D. Jacob,et al.  Sources contributing to background surface ozone in the US Intermountain West , 2013 .

[25]  R. Martin,et al.  Emissions estimation from satellite retrievals: A review of current capability , 2013 .

[26]  Ronald C. Cohen,et al.  Chemical feedback effects on the spatial patterns of the NO x weekend effect: a sensitivity analysis , 2013 .

[27]  A. Weinheimer,et al.  Ozone correlations between mid-tropospheric partial columns and the near-surface at two mid-atlantic sites during the DISCOVER-AQ campaign in July 2011 , 2013, Journal of Atmospheric Chemistry.

[28]  J. Herman,et al.  Effects of local meteorology and aerosols on ozone and nitrogen dioxide retrievals from OMI and pandora spectrometers in Maryland, USA during DISCOVER-AQ 2011 , 2013, Journal of Atmospheric Chemistry.

[29]  Hilke Oetjen,et al.  The CU Airborne MAX-DOAS instrument: vertical profiling of aerosol extinction and trace gases , 2013 .

[30]  L. Horowitz,et al.  Springtime high surface ozone events over the western United States: Quantifying the role of stratospheric intrusions , 2012 .

[31]  Nicola J. Blake,et al.  Long-term decline of global atmospheric ethane concentrations and implications for methane , 2012, Nature.

[32]  D. Jacob,et al.  Isoprene emissions in Africa inferred from OMI observations of formaldehyde columns. , 2012, Atmospheric chemistry and physics.

[33]  M. Chin,et al.  Satellite contributions to the quantitative characterization of biomass burning for climate modeling , 2012 .

[34]  Qi Zhang,et al.  Summertime formaldehyde observations in New York City: Ambient levels, sources and its contribution to HOx radicals , 2012 .

[35]  Dirk Richter,et al.  Primary and secondary sources of formaldehyde in urban atmospheres: Houston Texas region , 2012 .

[36]  Annmarie Eldering,et al.  Multi-spectral sensitivity studies for the retrieval of tropospheric and lowermost tropospheric ozone from simulated clear-sky GEO-CAPE measurements , 2011 .

[37]  Annmarie Eldering,et al.  Ozone air quality measurement requirements for a geostationary satellite mission , 2011 .

[38]  D. Blake,et al.  Detailed comparisons of airborne formaldehyde measurements with box models during the 2006 INTEX-B and MILAGRO campaigns: potential evidence for significant impacts of unmeasured and multi-generation volatile organic carbon compounds , 2011 .

[39]  D. Blake,et al.  Impact of the deep convection of isoprene and other reactive trace species on radicals and ozone in the upper troposphere , 2011 .

[40]  D. Blake,et al.  Detailed comparisons of airborne formaldehyde measurements with box models during the 2006 INTEX-B campaign: potential evidence for unmeasured and multi-generation volatile organic carbon oxidation processing , 2011 .

[41]  A. Fried,et al.  Difference frequency generation spectrometer for simultaneous multispecies detection. , 2010, Optics express.

[42]  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 .

[43]  Yongtao Hu,et al.  Application of OMI observations to a space-based indicator of NO x and voe controls on surface ozone formation , 2011 .

[44]  W. Junkermann On the distribution of formaldehyde in the western Po-Valley, Italy, during FORMAT 2002/2003 , 2009 .

[45]  Neha Sharma,et al.  Quantifying the seasonal and interannual variability of the formation and migration pattern of North Brazil Current Rings , 2009, OCEANS 2009.

[46]  Henk Eskes,et al.  Validation of urban NO 2 concentrations and their diurnal and seasonal variations observed from the SCIAMACHY and OMI sensors using in situ surface measurements in Israeli cities , 2009 .

[47]  J. Seinfeld,et al.  Isoprene photooxidation: new insights into the production of acids and organic nitrates , 2009 .

[48]  R. Martin Satellite remote sensing of surface air quality , 2008 .

[49]  Byeong-Uk Kim,et al.  Modeling ozone formation from industrial emission events in Houston, Texas , 2008 .

[50]  D. Blake,et al.  Role of convection in redistributing formaldehyde to the upper troposphere over North America and the North Atlantic during the summer 2004 INTEX campaign , 2008 .

[51]  Henk Eskes,et al.  Intercomparison of SCIAMACHY and OMI Tropospheric NO2 Columns: Observing the Diurnal Evolution of Chemistry and Emissions from Space , 2008 .

[52]  J. Lelieveld,et al.  Mainz Isoprene Mechanism 2 (MIM2): an isoprene oxidation mechanism for regional and global atmospheric modelling , 2008 .

[53]  Jassim A. Al-Saadi,et al.  REMOTE SENSING OF TROPOSPHERIC POLLUTION FROM SPACE , 2008 .

[54]  Louisa Emmons,et al.  Contribution of isoprene to chemical budgets: A model tracer study with the NCAR CTM MOZART-4 , 2008 .

[55]  K. F. Boersma,et al.  Spatial distribution of isoprene emissions from North America derived from formaldehyde column measurements by the OMI satellite sensor , 2008 .

[56]  D. Jacob,et al.  Formaldehyde Distribution over North America: Implications for Satellite Retrievals of Formaldehyde Columns and Isoprene Emission , 2006 .

[57]  D. Jacob,et al.  Quantifying the seasonal and interannual variability of North American isoprene emissions using satellite observations of the formaldehyde column , 2006 .

[58]  Francis J. Schmidlin,et al.  Long-term changes in tropospheric ozone , 2006 .

[59]  W. Brune,et al.  A reevaluation of airborne HOx observations from NASA field campaigns , 2006 .

[60]  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 .

[61]  D. Allen,et al.  Hydrocarbon emissions from industrial release events in the Houston-Galveston area and their impact on ozone formation , 2005 .

[62]  Alan Fried,et al.  Evaluation of GOME satellite measurements of tropospheric NO2 and HCHO using regional data from aircraft campaigns in the southeastern United States , 2004 .

[63]  D. Jacob,et al.  Ozone production in transpacific Asian pollution plumes and implications for ozone air quality in California , 2004, Journal of Geophysical Research: Atmospheres.

[64]  E. Atlas,et al.  Effect of petrochemical industrial emissions of reactive alkenes and NOx on tropospheric ozone formation in Houston, Texas , 2003 .

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

[66]  E. Atlas,et al.  Signatures of terminal alkene oxidation in airborne formaldehyde measurements during TexAQS 2000 , 2003 .

[67]  Glenn S. Diskin,et al.  Open-path airborne tunable diode laser hygrometer , 2002, SPIE Optics + Photonics.

[68]  P. Makar,et al.  Summertime formaldehyde at a high‐elevation site in Quebec , 2001 .

[69]  D. Blake,et al.  Seasonal differences in the photochemistry of the South Pacific: A comparison of observations and model results from PEM-Tropics A and B , 2001 .

[70]  P. Shepson,et al.  A study of formaldehyde chemistry above a forest canopy , 2001 .

[71]  C. Geron,et al.  Isoprene emission capacity for US tree species , 2001 .

[72]  D. Blake,et al.  Description of the analysis of a wide range of volatile organic compounds in whole air samples collected during PEM-tropics A and B. , 2001, Analytical chemistry.

[73]  D. Blake,et al.  Assessment of upper tropospheric HOx sources over the tropical Pacific based on NASA GTE/PEM data: Net effect on HOx and other photochemical parameters , 1999 .

[74]  G. W. Sachse,et al.  Airborne observations of the tropospheric CO2 distribution and its controlling factors over the South Pacific Basin , 1999 .

[75]  M. Holdren,et al.  Atmospheric chemistry and distribution of formaldehyde and several multioxygenated carbonyl compounds during the 1995 Nashville/Middle Tennessee Ozone Study , 1998 .

[76]  R. Mukund,et al.  Source attribution of ambient air toxic and other VOCs in Columbus, Ohio , 1996 .

[77]  G. W. Sachse,et al.  Airborne observations of spatial and temporal variability of tropospheric carbon dioxide , 1996 .

[78]  Michael O. Rodgers,et al.  Photochemistry of ozone formation in Atlanta, GA-Models and measurements☆ , 1995 .

[79]  D. Blake,et al.  Meridional distributions of NOx, NOy, and other species in the lower stratosphere and upper troposphere during AASE II , 1994 .

[80]  L. Kleinman Low and high NOx tropospheric photochemistry , 1994 .

[81]  Shao-Meng Li,et al.  Estimating primary and secondary production of HCHO in eastern North America based on gas phase measurements and principal component analysis , 1994 .

[82]  Glen W. Sachse,et al.  Airborne tunable diode laser sensor for high-precision concentration and flux measurements of carbon monoxide and methane , 1991, Photonics West - Lasers and Applications in Science and Engineering.

[83]  Sanford Sillman,et al.  The sensitivity of ozone to nitrogen oxides and hydrocarbons in regional ozone episodes , 1990 .

[84]  C. Flynn RELATIONSHIP BETWEEN COLUMN DENSITY AND SURFACE MIXING RATIO FOR O3 AND NO2: IMPLICATIONS FOR SATELLITE OBSERVATIONS AND THE IMPACTS OF VERTICAL MIXING , 2016 .

[85]  T. Sakulyanontvittaya,et al.  Emission reductions and urban ozone responses under more stringent US standards , 2015 .

[86]  D. Blake,et al.  Assessment of upper tropospheric HOsources over the tropical , 1999 .

[87]  C. Brunner National Ambient Air Quality Standards , 1985 .