Thomas J. Pongetti

Validation of Ozone Monitoring Instrument nitrogen dioxide columns

[1] We review the standard nitrogen dioxide (NO2) data product (Version 1.0.), which is based on measurements made in the spectral region 415–465 nm by the Ozone Monitoring Instrument (OMI) on the NASA Earth Observing System-Aura satellite. A number of ground- and aircraft-based measurements have been used to validate the data product’s three principal quantities: stratospheric, tropospheric, and total NO2 column densities under nearly or completely cloud-free conditions. The validation of OMI NO2 is complicated by a number of factors, the greatest of which is that the OMI observations effectively average the NO2 over its field of view (minimum 340 km 2 ), while a ground-based instrument samples at a single point. The tropospheric NO2 field is often very inhomogeneous, varying significantly over tens to hundreds of meters, and ranges from 10 16 cm � 2 over urban and industrial areas. Because of OMI’s areal averaging, when validation measurements are made near NO2 sources the OMI measurements are expected to underestimate the ground-based, and this is indeed seen. Further, we use several different instruments, both new and mature, which might give inconsistent NO2 amounts; the correlations between nearby instruments is 0.8–0.9. Finally, many of the validation data sets are quite small and span a very short length of time; this limits the statistical conclusions that can be drawn from them. Despite these factors, good agreement is generally seen between the OMI and ground-based measurements, with OMI stratospheric NO2 underestimated by about 14% and total and tropospheric columns underestimated by 15–30%. Typical correlations between OMI NO2 and ground-based measurements are generally >0.6.

Midlatitude atmospheric OH response to the most recent 11-y solar cycle

The hydroxyl radical (OH) plays an important role in middle atmospheric photochemistry, particularly in ozone (O3) chemistry. Because it is mainly produced through photolysis and has a short chemical lifetime, OH is expected to show rapid responses to solar forcing [e.g., the 11-y solar cycle (SC)], resulting in variabilities in related middle atmospheric O3 chemistry. Here, we present an effort to investigate such OH variability using long-term observations (from space and the surface) and model simulations. Ground-based measurements and data from the Microwave Limb Sounder on the National Aeronautics and Space Administration’s Aura satellite suggest an ∼7–10% decrease in OH column abundance from solar maximum to solar minimum that is highly correlated with changes in total solar irradiance, solar Mg-II index, and Lyman-α index during SC 23. However, model simulations using a commonly accepted solar UV variability parameterization give much smaller OH variability (∼3%). Although this discrepancy could result partially from the limitations in our current understanding of middle atmospheric chemistry, recently published solar spectral irradiance data from the Solar Radiation and Climate Experiment suggest a solar UV variability that is much larger than previously believed. With a solar forcing derived from the Solar Radiation and Climate Experiment data, modeled OH variability (∼6–7%) agrees much better with observations. Model simulations reveal the detailed chemical mechanisms, suggesting that such OH variability and the corresponding catalytic chemistry may dominate the O3 SC signal in the upper stratosphere. Continuing measurements through SC 24 are required to understand this OH variability and its impacts on O3 further.

Direct Sun measurements of NO2 column abundances from Table Mountain, California: Intercomparison of low- and high-resolution spectrometers

The NO_2 total column abundance, C_(NO_2) was measured with a direct Sun viewing technique using three different instruments at NASA Jet Propulsion Laboratorys (JPL) Table Mountain Facility in California during an instrument intercomparison campaign in July 2007. The instruments are a high‐resolution (∼0.001 nm) Fourier transform ultraviolet spectrometer (FTUVS) from JPL and two moderate‐resolution grating spectrometers, multifunction differential optical absorption spectroscopy (MF‐DOAS) (∼0.8 nm) from Washington State University and Pandora (∼0.4 nm) from NASA Goddard Space Flight Center. FTUVS uses high spectral resolution to determine the absolute NO_2 column abundance independently from the exoatmospheric solar irradiance using rovibrational NO_2 absorption lines. The NO_2 total column is retrieved after removing the solar background using Doppler‐shifted spectra from the east and west limbs of the Sun. The FTUVS measurements were used to validate the independently calibrated measurements of multifunction differential optical absorption spectroscopy (MF‐DOAS) and Pandora. The latter two instruments start with measured high‐Sun spectra as solar references to retrieve relative NO_2 columns and then apply modified Langley or “bootstrap” methods to determine the amounts of NO_2 in the references to obtain the absolute NO_2 columns. The calibration offset derived from the FTUVS measurements is consistent with the values derived from Langley and bootstrap calibration plots of the NO_2 slant column measured by the grating spectrometers. The calibrated total vertical column abundances of NO_2, C_(NO_2) from all three instruments are compared showing that MF‐DOAS and Pandora data agree well with each other, and both data sets agree with FTUVS data to within (1.5 ± 4.1)% and (6.0 ± 6.0)%, respectively.

Carbon dioxide and methane measurements from the Los Angeles Megacity Carbon Project – Part 1: calibration, urban enhancements, and uncertainty estimates

We report continuous surface observations of carbon dioxide (CO2) and methane (CH4) from the Los Angeles (LA) Megacity Carbon Project during 2015. We devised a calibration strategy, methods for selection of background air masses, calculation of urban enhancements, and a detailed algorithm for estimating uncertainties in urban-scale CO2 and CH4 measurements. These methods are essential for understanding carbon fluxes from the LA megacity and other complex urban environments globally. We estimate background mole fractions entering LA using observations from four “extra-urban” sites including two “marine” sites located south of LA in La Jolla (LJO) and offshore on San Clemente Island (SCI), one “continental” site located in Victorville (VIC), in the high desert northeast of LA, and one “continental/mid-troposphere” site located on Mount Wilson (MWO) in the San Gabriel Mountains. We find that a local marine background can be established to within ~1 ppm CO2 and ~10 ppb CH4 using these local measurement sites. Overall, atmospheric carbon dioxide and methane levels are highly variable across Los Angeles. “Urban” and “suburban” sites show moderate to large CO2 and CH4 enhancements relative to a marine background estimate. The USC (University of Southern California) site near downtown LA exhibits median hourly enhancements of ~20 ppm CO2 and ~150 ppb CH4 during 2015 as well as ~15 ppm CO2 and ~80 ppb CH4 during mid-afternoon hours (12:00–16:00 LT, local time), which is the typical period of focus for flux inversions. The estimated measurement uncertainty is typically better than 0.1 ppm CO2 and 1 ppb CH4 based on the repeated standard gas measurements from the LA sites during the last 2 years, similar to Andrews et al. (2014). The largest component of the measurement uncertainty is due to the single-point calibration method; however, the uncertainty in the background mole fraction is much larger than the measurement uncertainty. The background uncertainty for the marine background estimate is ~10 and ~15 % of the median mid-afternoon enhancement near downtown LA for CO2 and CH4, respectively. Overall, analytical and background uncertainties are small relative to the local CO2 and CH4 enhancements; however, our results suggest that reducing the uncertainty to less than 5 % of the median mid-afternoon enhancement will require detailed assessment of the impact of meteorology on background conditions.

Validation of Aura Microwave Limb Sounder OH measurements with Fourier Transform Ultra-Violet Spectrometer total OH column measurements at Table Mountain, California

The first seasonal and interannual validation of OH measurements from the Aura Microwave Limb Sounder (MLS) has been conducted using ground-based OH column measurements from the Fourier Transform Ultra-Violet Spectrometer (FTUVS) over the Jet Propulsion Laboratorys Table Mountain Facility (TMF) during 2004–2007. To compare with FTUVS total column measurements, MLS OH vertical profiles over TMF are integrated to obtain partial OH columns above 21.5 hPa, which covers nearly 90% of the total column. The tropospheric OH and the lower stratopheric OH not measured by MLS are estimated using GEOS (Goddard Earth Observing System)-Chem and a Harvard 2-D model implemented within GEOS-Chem, respectively. A number of field observations and calculations from a photochemical box model are compared to OH profiles from these models to estimate the variability in the lower atmospheric OH and thus the uncertainty in the combined total OH columns from MLS and models. In general, the combined total OH columns agree extremely well with TMF total OH columns, especially during seasons with high OH. In winter with low OH, the combined columns are often higher than TMF measurements. A slightly weaker seasonal variation is observed by MLS relative to TMF. OH columns from TMF and the combined total columns from MLS and models are highly correlated, resulting in a mean slope of 0.969 with a statistically insignificant intercept. This study therefore suggests that column abundances derived from MLS vertical profiles have been validated to within the mutual systematic uncertainties of the MLS and FTUVS measurements.

Accounting for aerosol scattering in the CLARS retrieval of column averaged CO2 mixing ratios

The California Laboratory for Atmospheric Remote Sensing Fourier transform spectrometer (CLARS‐FTS) deployed at Mount Wilson, California, has been measuring column abundances of greenhouse gases in the Los Angeles (LA) basin in the near‐infrared spectral region since August 2011. CLARS‐FTS measures reflected sunlight and has high sensitivity to absorption and scattering in the boundary layer. In this study, we estimate the retrieval biases caused by aerosol scattering and present a fast and accurate approach to correct for the bias in the CLARS column averaged CO2 mixing ratio product, X_(CO2). The high spectral resolution of 0.06 cm^(−1) is exploited to reveal the physical mechanism for the bias. We employ a numerical radiative transfer model to simulate the impact of neglecting aerosol scattering on the CO_2 and O_2 slant column densities operationally retrieved from CLARS‐FTS measurements. These simulations show that the CLARS‐FTS operational retrieval algorithm likely underestimates CO_2 and O_2 abundances over the LA basin in scenes with moderate aerosol loading. The bias in the CO_2 and O_2 abundances due to neglecting aerosol scattering cannot be canceled by ratioing each other in the derivation of the operational product of X_(CO2). We propose a new method for approximately correcting the aerosol‐induced bias. Results for CLARS X_(CO2) are compared to direct‐Sun X_(CO2) retrievals from a nearby Total Carbon Column Observing Network (TCCON) station. The bias‐correction approach significantly improves the correlation between the X_(CO2) retrieved from CLARS and TCCON, demonstrating that this approach can increase the yield of useful data from CLARS‐FTS in the presence of moderate aerosol loading.

MAPPING THE WORLD’S LARGEST NATURAL GAS LEAK AND OTHER METHANE SOURCES USING HIGH RESOLUTION SPECTROSCOPY

CH4 is a potent greenhouse gas with a 100-year Global Warming Potential more than thirty times larger than CO2 if carbon-climate feedbacks are considered. In urban areas such as Los Angeles, anthropogenic methane emissions are poorly characterized because of the large diversity of sources: landfills, sewage treatment plants, agriculture, leaks in the natural gas distribution system, cattle and dairy farms, thermogenic emissions from oil fields and seeps. The California Laboratory for Atmospheric Remote Sensing (CLARS), operated by the Jet Propulsion Laboratory, is a mountaintop facility overlooking most of the Los Angeles basin, equipped with JPL-built Fourier transform spectrometers for measurements of the slant column abundances of several greenhouse gases including methane with high spatial and temporal resolution. This presentation will cover several topics including the design features of the two FTS instruments, spectroscopic issues associated with the retrieval of slant column abundances, and uncertainty analysis. One FTS has been in continuous operation since 2011, providing sufficient data to identify several CH4 emission hot spots in the LA basin. On October 23, 2015, a well pipe suffered a failure in a natural gas storage facility in Aliso Canyon, northwest of downtown Los Angeles resulting in a massive CH4 plume transported by winds throughout the LA basin. The CLARS FTS captured the plume propagation throughout the 4-month duration of the leak. We will show how the emission ratio method may be employed to derive a lower bound to the CH4 emission rate from the leaking well without the use of complex atmospheric transport models. The CLARS measurement system provides a small-scale example of the data that would be acquired by an imaging FTS on a geostationary space platform.a