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We describe an approach for determining limited information about the vertical distribution of carbon monoxide (CO) and carbon dioxide (CO2) from total column ground-based Total Carbon Column Observation Network (TCCON) observations. For CO and CO2 , it has been difficult to retrieve information about their vertical distribution from spectral line shapes because of the errors in the spectroscopy and the atmospheric temperature profile that mask the effects of variations in their mixing ratio with altitude. For CO2 the challenge is especially difficult given that these variations are typically 2 % or less. Nevertheless, if sufficient accuracy can be obtained, such information would be highly valuable for evaluation of retrievals from satellites and more generally for improving the estimate of surface sources and sinks of these trace gases. We present here the Temporal Atmospheric Retrieval Determining Information from Secondary Scaling (TARDISS) retrieval algorithm. TARDISS uses several simultaneously obtained total column observations of the same gas from different absorption bands with distinctly different vertical averaging kernels. The different total column retrievals are combined in TARDISS using a Bayesian approach where the weights and temporal covariance applied to the different retrievals include additional constraints on the diurnal variation in the vertical distribution for these gases. We assume that the near-surface part of the column varies rapidly over the course of a day (from surface sources and sinks, for example) and that the upper part of the column has a larger temporal covariance over the course of a day. Using measurements from the five North American TCCON sites, we find that the retrieved lower partial column (between the surface and ∼ 800 hPa) of the CO and CO2 dry mole fractions (DMFs) have slopes of 0.999 ± 0.002 and 1.001 ± 0.003 with respect to lower column DMF from integrated in situ data measured directly from aircraft and in AirCores. The average error for our lower column CO retrieval is 1.51 ppb (∼ 2 %) while the average error for our CO2 retrieval is 5.09 ppm (∼ 1.25 %). Compared with classical line-shape-derived vertical profile retrievals, our algorithm reduces the influence of forward model errors such as imprecision in spectroscopy (line shapes and intensities) and in the instrument line shape. In addition, because TARDISS uses the existing retrieved column abundances from TCCON (which themselves are computationally much less intensive than profile retrieval algorithms), it is very fast and processes years of data in minutes. We anticipate that this approach will find broad application for use in carbon cycle science. [ABSTRACT FROM AUTHOR]

Four in situ cavity ring-down spectrometers (G2132-i, Picarro, Inc.) measuring methane dry mole fraction (CH4), carbon dioxide dry mole fraction (CO2), and the isotopic ratio of methane (δ13CH4) were deployed at four towers in the Marcellus Shale natural gas extraction region of Pennsylvania. In this paper, we describe laboratory and field calibration of the analyzers for tower-based applications and characterize their performance in the field for the period January-December 2016. Prior to deployment, each analyzer was tested using bottles with various isotopic ratios, from biogenic to thermogenic source values, which were diluted to varying degrees in zero air, and an initial calibration was performed. Furthermore, at each tower location, three field tanks were employed, from ambient to high mole fractions, with various isotopic ratios. Two of these tanks were used to adjust the calibration of the analyzers on a daily basis. We also corrected for the cross-interference from ethane on the isotopic ratio of methane. Using an independent field tank for evaluation, the standard deviation of 4-h means of the isotopic ratio of methane difference from the known value was found to be 0.26-‰ δ13CH4. Following improvements in the field tank testing scheme, the standard deviation of 4-h means was 0.11-‰, well within the target compatibility of 0.2-‰. Round-robin style testing using tanks with near-ambient isotopic ratios indicated mean errors of -0.14 to 0.03-‰ for each of the analyzers. Flask to in situ comparisons showed mean differences over the year of 0.02 and 0.08-‰, for the east and south towers, respectively. Regional sources in this region were difficult to differentiate from strong perturbations in the background. During the afternoon hours, the median differences of the isotopic ratio measured at three of the towers, compared to the background tower, were &minus0.15 to 0.12-‰ with standard deviations of the 10-min isotopic ratio differences of 0.8-‰. In terms of source attribution, analyzer compatibility of 0.2-‰ δ13CH4 affords the ability to distinguish a 50-ppb CH4 peak from a biogenic source (at -60-‰, for example) from one originating from a thermogenic source (-35-‰), with the exact value dependent upon the source isotopic ratios. Using a Keeling plot approach for the non-afternoon data at a tower in the center of the study region, we determined the source isotopic signature to be -31.2-±-1.9-‰, within the wide range of values consistent with a deep-layer Marcellus natural gas source. [ABSTRACT FROM AUTHOR]