Formaldehyde Distribution over North America: Implications for Satellite Retrievals of Formaldehyde Columns and Isoprene Emission

Formaldehyde (HCHO) columns measured from space provide constraints on emissions of volatile organic compounds (VOCs). Quantitative interpretation requires characterization of errors in HCHO column retrievals and relating these columns to VOC emissions. Retrieval error is mainly in the air mass factor (AMF) which relates fitted backscattered radiances to vertical columns and requires external information on HCHO, aerosols, and clouds. Here we use aircraft data collected over North America and the Atlantic to determine the local relationships between HCHO columns and VOC emissions, calculate AMFs for HCHO retrievals, assess the errors in deriving AMFs with a chemical transport model (GEOS-Chem), and draw conclusions regarding space-based mapping of VOC emissions. We show that isoprene drives observed HCHO column variability over North America; HCHO column data from space can thus be used effectively as a proxy for isoprene emission. From observed HCHO and isoprene profiles we find an HCHO molar yield from isoprene oxidation of 1.6 ± 0.5, consistent with current chemical mechanisms. Clouds are the primary error source in the AMF calculation; errors in the HCHO vertical profile and aerosols have comparatively little effect. The mean bias and 1σ uncertainty in the GEOS-Chem AMF calculation increase from <1% and 15% for clear skies to 17% and 24% for half-cloudy scenes. With fitting errors, this gives an overall 1σ error in HCHO satellite measurements of 25–31%. Retrieval errors, combined with uncertainties in the HCHO yield from isoprene oxidation, result in a 40% (1σ) error in inferring isoprene emissions from HCHO satellite measurements.Earth and Planetary SciencesEngineering and Applied Science

Formaldehyde over North America and the North Atlantic during the summer 2004 INTEX campaign: Methods, observed distributions, and measurement‐model comparisons

A tunable diode laser absorption spectrometer (TDLAS) was operated on the NASA DC‐8 aircraft during the summer INTEX‐NA study to acquire ambient formaldehyde (CH2O) measurements over North America and the North Atlantic Ocean from ∼0.2 km to ∼12.5 km altitude spanning 17 science flights. Measurements of CH2O in the boundary layer and upper troposphere over the southeastern United States were anomalously low compared to studies in other years, and this was attributed to the record low temperatures over this region during the summer of 2004. Formaldehyde is primarily formed over the southeast from isoprene, and isoprene emissions are strongly temperature‐dependent. Despite this effect, the median upper tropospheric (UT) CH2O mixing ratio of 159 pptv from the TDLAS over continental North America is about a factor of 4 times higher than the median UT value of 40 pptv observed over remote regions during TRACE‐P. These observations together with the higher variability observed in this study all point to the fact that continental CH2O levels in the upper troposphere were significantly perturbed during the summer of 2004 relative to more typical background levels in the upper troposphere over more remote regions. The TDLAS measurements discussed in this paper are employed together with box model results in the companion paper by Fried et al. to further examine enhanced CH2O distributions in the upper troposphere due to convection. Measurements of CH2O on the DC‐8 were also acquired by a coil enzyme fluorometric system and compared with measurements from the TDLAS system

Modeling NH4NO3 over the San Joaquin Valley During the 2013 DISCOVER-AQ Campaign

The San Joaquin Valley (SJV) of California experiences high concentrations of PM2.5 (particulate matter with aerodynamic diameter 2.5 m) during episodes of meteorological stagnation in winter. Modeling PM2.5 NH4NO3 during these episodes is challenging because it involves simulating meteorology in complex terrain under low wind speed and vertically stratified conditions, representing complex pollutant emissions distributions, and simulating daytime and nighttime chemistry that can be influenced by the mixing of urban and rural air masses. A rich dataset of observations related to NH4NO3 formation was acquired during multiple periods of elevated NH4NO3 during the DISCOVER-AQ (Deriving Information on Surface Conditions from Column and Vertically Resolved Observations Relevant to Air Quality) field campaign in SJV in January and February 2013. Here, NH4NO3 is simulated during the SJV DISCOVER-AQ study period with the Community Multiscale Air Quality (CMAQ) model version 5.1, predictions are evaluated with the DISCOVER-AQ dataset, and process analysis modeling is used to quantify HNO3 production rates. Simulated NO3- generally agrees well with routine monitoring of 24-h average NO3-, but comparisons with hourly average NO3- measurements in Fresno revealed differences at higher time resolution. Predictions of gas-particle partitioning of total nitrate (HNO3 + NO3-) and NHx (NH3 + NH4+) generally agreed well with measurements in Fresno, although partitioning of total nitrate to HNO3 was sometimes overestimated at low relative humidity in afternoon. Gas-particle partitioning results indicate that NH4NO3 formation is limited by HNO3 availability in both the model and ambient. NH3 mixing ratios are underestimated, particularly in areas with large agricultural activity, and the spatial allocation of NH3 emissions could benefit from additional work, especially near Hanford. HNO3 production via daytime and nighttime pathways is reasonably consistent with the conceptual model of NH4NO3 formation in SJV, and production peaked aloft between about 160 and 240 m in the model. During a period of elevated NH4NO3, the model predicted that the OH + NO2 pathway contributed 46% to total HNO3 production in SJV and the N2O5 heterogeneous hydrolysis pathway contributed 54%. The relative importance of the OH + NO2 pathway for HNO3 production is predicted to increase as NOx emissions decrease

Autonomous airborne mid-infrared spectrometer for high-precision measurements of ethane during the NASA ACT-America studies

An airborne trace gas sensor based on mid-infrared technology is presented for fast (1&thinsp;s) and high-precision ethane measurements during the Atmospheric Carbon and Transport-America (ACT-America) study. The ACT-America campaign is a multiyear effort to better understand and quantify sources and sinks for the two major greenhouse gases carbon dioxide and methane. Simultaneous airborne ethane and methane measurements provide one method by which sources of methane can be identified and quantified. The instrument described herein was operated on NASA's B200 King Air airplane spanning five separate field deployments. As this platform has limited payload capabilities, considerable effort was devoted to minimizing instrument weight and size without sacrificing airborne ethane measurement performance. This paper describes the numerous features designed to achieve these goals. Two of the key instrument features that were realized were autonomous instrument control with no onboard operator and the implementation of direct absorption spectroscopy based on fundamental first principles. We present airborne measurement performance for ethane based upon the precisions of zero air background measurements and ambient precision during quiescent stable periods. The airborne performance was improved with each successive deployment phase, and we summarize the major upgraded design features to achieve these improvements. During the fourth deployment phase in the spring of 2018, the instrument achieved 1&thinsp;s (1&sigma;) airborne ethane precisions reproducibly in the 30&ndash;40 parts per trillion by volume (pptv) range in both the boundary layer and the less turbulent free troposphere. This performance is among some of the best reported to date for fast (1&thinsp;Hz) airborne ethane measurements. In both the laboratory conditions and at times during calm and level airborne operation, these precisions were as low as 15&ndash;20&thinsp;pptv. </div

Airborne formaldehyde and volatile organic compound measurements over the Daesan petrochemical complex on Korea’s northwest coast during the Korea-United States Air Quality study

The U.S. National Aeronautics and Space Administration in partnership with Korea’s National Institute of Environmental Research embarked on the Korea-United States Air Quality (KORUS-AQ) study to address air quality issues over the Korean peninsula. Underestimation of volatile organic compound (VOC) emissions from various large facilities on South Korea’s northwest coast may contribute to this problem, and this study focuses on quantifying top-down emissions of formaldehyde (CH₂O) and VOCs from the largest of these facilities, the Daesan petrochemical complex, and comparisons with the latest emission inventories. To accomplish this and additional goals discussed herein, this study employed a number of measurements acquired during KORUS-AQ onboard the NASA DC-8 aircraft during three Daesan overflights on June 2, 3, and 5, 2016, in conjunction with a mass balance approach. The measurements included fast airborne measurements of CH₂O and ethane from an infrared spectrometer, additional fast measurements from other instruments, and a suite of 33 VOC measurements acquired by the whole air sampler. The mass balance approach resulted in consistent top-down yearly Daesan VOC emission flux estimates, which averaged (61 ± 14) × 10³ MT/year for the 33 VOC compounds, a factor of 2.9 ± 0.6 (±1.0) higher than the bottom-up inventory value. The top-down Daesan emission estimate for CH₂O and its four primary precursors averaged a factor of 4.3 ± 1.5 (± 1.9) times higher than the bottom-up inventory value. The uncertainty values in parentheses reflect upper limits for total uncertainty estimates. The resulting averaged top-down Daesan emission estimate for sulfur dioxide (SO₂) yielded a ratio of 0.81–1.0 times the bottom-up SO₂ inventory, and this provides an important cross-check on the accuracy of our mass balance analysis

Formaldehyde Distribution over North America: Implications for Satellite Retrievals of Formaldehyde Columns and Isoprene Emission

Formaldehyde (HCHO) columns measured from space provide constraints on emissions of volatile organic compounds (VOCs). Quantitative interpretation requires characterization of errors in HCHO column retrievals and relating these columns to VOC emissions. Retrieval error is mainly in the air mass factor (AMF) which relates fitted backscattered radiances to vertical columns and requires external information on HCHO, aerosols, and clouds. Here we use aircraft data collected over North America and the Atlantic to determine the local relationships between HCHO columns and VOC emissions, calculate AMFs for HCHO retrievals, assess the errors in deriving AMFs with a chemical transport model (GEOS-Chem), and draw conclusions regarding space-based mapping of VOC emissions. We show that isoprene drives observed HCHO column variability over North America; HCHO column data from space can thus be used effectively as a proxy for isoprene emission. From observed HCHO and isoprene profiles we find an HCHO molar yield from isoprene oxidation of 1.6 +/- 0.5, consistent with current chemical mechanisms. Clouds are the primary error source in the AMF calculation; errors in the HCHO vertical profile and aerosols have comparatively little effect. The mean bias and 1Q uncertainty in the GEOS-Chem AMF calculation increase from <1% and 15% for clear skies to 17% and 24% for half-cloudy scenes. With fitting errors, this gives an overall 1 Q error in HCHO satellite measurements of 25-31%. Retrieval errors, combined with uncertainties in the HCHO yield from isoprene oxidation, result in a 40% (1sigma) error in inferring isoprene emissions from HCHO satellite measurements

Top-down estimates of anthropogenic VOC emissions in South Korea using formaldehyde vertical column densities from aircraft during the KORUS-AQ campaign

Nonmethane volatile organic compounds (NMVOCs) result in ozone and aerosol production that adversely affects the environment and human health. For modeling purposes, anthropogenic NMVOC emissions have been typically compiled using the “bottom-up” approach. To minimize uncertainties of the bottom-up emission inventory, “top-down” NMVOC emissions can be estimated using formaldehyde (HCHO) observations. In this study, HCHO vertical column densities (VCDs) obtained from the Geostationary Trace gas and Aerosol Sensor Optimization spectrometer during the Korea–United States Air Quality campaign were used to constrain anthropogenic volatile organic compound (AVOC) emissions in South Korea. Estimated top-down AVOC emissions differed from those of the up-to-date bottom-up inventory over major anthropogenic source regions by factors of 1.0 ± 0.4 to 6.9 ± 3.9. Our evaluation using a 3D chemical transport model indicates that simulated HCHO mixing ratios using the top-down estimates were in better agreement with observations onboard the DC-8 aircraft during the campaign relative to those with the bottom-up emission, showing a decrease in model bias from –25% to –13%. The top-down analysis used in this study, however, has some limitations related to the use of HCHO yields, background HCHO columns, and AVOC speciation in the bottom-up inventory, resulting in uncertainties in the AVOC emission estimates. Our attempt to constrain diurnal variations of the AVOC emissions using the aircraft HCHO VCDs was compromised by infrequent aircraft observations over the same source regions. These limitations can be overcome with geostationary satellite observations by providing hourly HCHO VCDs

Observing atmospheric formaldehyde (HCHO) from space: validation and intercomparison of six retrievals from four satellites (OMI, GOME2A, GOME2B, OMPS) with SEAC4RS aircraft observations over the southeast US

Formaldehyde (HCHO) column data from satellites are widely used as a proxy for emissions of volatile organic compounds (VOCs), but validation of the data has been extremely limited. Here we use highly accurate HCHO aircraft observations from the NASA SEAC4RS (Studies of Emissions, Atmospheric Composition, Clouds and Climate Coupling by Regional Surveys) campaign over the southeast US in August-September 2013 to validate and intercompare six retrievals of HCHO columns from four different satellite instruments (OMI, GOME2A, GOME2B and OMPS; for clarification of these and other abbreviations used in the paper, please refer to Appendix A) and three different research groups. The GEOS-Chem chemical transport model is used as a common intercomparison platform. All retrievals feature a HCHO maximum over Arkansas and Louisiana, consistent with the aircraft observations and reflecting high emissions of biogenic isoprene. The retrievals are also interconsistent in their spatial variability over the southeast US (r Combining double low line 0.4-0.8 on a 0.5° x 0.5° grid) and in their day-to-day variability (r Combining double low line 0.5-0.8). However, all retrievals are biased low in the mean by 20-51 %, which would lead to corresponding bias in estimates of isoprene emissions from the satellite data. The smallest bias is for OMI-BIRA, which has high corrected slant columns relative to the other retrievals and low scattering weights in its air mass factor (AMF) calculation. OMI-BIRA has systematic error in its assumed vertical HCHO shape profiles for the AMF calculation, and correcting this would eliminate its bias relative to the SEAC4RS data. Our results support the use of satellite HCHO data as a quantitative proxy for isoprene emission after correction of the low mean bias. There is no evident pattern in the bias, suggesting that a uniform correction factor may be applied to the data until better understanding is achieved

Modeling NH4NO3 Over the San Joaquin Valley During the 2013 DISCOVER‐AQ Campaign

The San Joaquin Valley (SJV) of California experiences high concentrations of particulate matterNH4NO3during episodes of meteorological stagnation in winter. A rich data set of observations related toNH4NO3formation was acquired during multiple periods of elevated NH4NO3during the DerivingInformation on Surface Conditions from Column and Vertically Resolved Observations Relevant to Air Quality(DISCOVER-AQ)field campaign in SJV in January and February 2013. Here NH4NO3is simulated during the SJVDISCOVER-AQ study period with the Community Multiscale Air Quality (CMAQ) model, diagnostic modelevaluation is performed using the DISCOVER-AQ data set, and integrated reaction rate analysis is used toquantify HNO3production rates. Simulated NO3 generally agrees well with routine monitoring of 24-hraverage NO3 , but comparisons with hourly average NO3 measurements in Fresno revealed differences athigher time resolution. Predictions of gas-particle partitioning of total nitrate (HNO3+NO3 ) and NHx(NH3+NH4+) generally agree well with measurements in Fresno, although partitioning of total nitrate toHNO3is sometimes overestimated at low relative humidity in afternoon. Gas-particle partitioning resultsindicate that NH4NO3formation is limited by HNO3availability in both the model and ambient. NH3mixingratios are underestimated, particularly in areas with large agricultural activity, and additional work on thespatial allocation of NH3emissions is warranted. During a period of elevated NH4NO3, the model predictedthat the OH + NO2pathway contributed 46% to total HNO3production in SJV and the N2O5heterogeneoushydrolysis pathway contributed 54%. The relative importance of the OH + NO2pathway for HNO3productionis predicted to increase as NOx emissions decrease

On the sources and sinks of atmospheric VOCs: an integratedanalysis of recent aircraft campaigns over North America

We apply a high-resolution chemical transport model (GEOS-Chem CTM) with updated treatment of volatile organic compounds (VOCs) and a comprehensive suite of airborne datasets over North America to (i) characterize the VOC budget and (ii) test the ability of current models to capture the distribution and reactivity of atmospheric VOCs over this region. Biogenic emissions dominate the North American VOC budget in the model, accounting for 70 % and 95 % of annually emitted VOC carbon and reactivity, respectively. Based on current inventories anthropogenic emissions have declined to the point where biogenic emissions are the dominant summertime source of VOC reactivity even in most major North American cities. Methane oxidation is a 2× larger source of nonmethane VOCs (via production of formaldehyde and methyl hydroperoxide) over North America in the model than are anthropogenic emissions. However, anthropogenic VOCs account for over half of the ambient VOC loading over the majority of the region owing to their longer aggregate lifetime. Fires can be a significant VOC source episodically but are small on average. In the planetary boundary layer (PBL), the model exhibits skill in capturing observed variability in total VOC abundance (R2=0.36) and reactivity (R2=0.54). The same is not true in the free troposphere (FT), where skill is low and there is a persistent low model bias (∼ 60 %), with most (27 of 34) model VOCs underestimated by more than a factor of 2. A comparison of PBL : FT concentration ratios over the southeastern US points to a misrepresentation of PBL ventilation as a contributor to these model FT biases. We also find that a relatively small number of VOCs (acetone, methanol, ethane, acetaldehyde, formaldehyde, isoprene + oxidation products, methyl hydroperoxide) drive a large fraction of total ambient VOC reactivity and associated model biases; research to improve understanding of their budgets is thus warranted. A source tracer analysis suggests a current overestimate of biogenic sources for hydroxyacetone, methyl ethyl ketone and glyoxal, an underestimate of biogenic formic acid sources, and an underestimate of peroxyacetic acid production across biogenic and anthropogenic precursors. Future work to improve model representations of vertical transport and to address the VOC biases discussed are needed to advance predictions of ozone and SOA formation