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Atmospheric hydroperoxides are a significant component of the atmosphere's oxidizing capacity. Two of the most abundant hydroperoxides, hydrogen peroxide (H₂O₂) and methyl hydroperoxide (MHP, CH₃OOH), were measured in the remote atmosphere using chemical ionization mass spectrometry aboard the NASA DC-8 aircraft during the Atmospheric Tomography Mission. These measurements present a seasonal investigation into the global distribution of these two hydroperoxides, with near pole-to-pole coverage across the Pacific and Atlantic Ocean basins and from the marine boundary layer to the upper troposphere and lower stratosphere. H₂O₂ mixing ratios are highest between 2 and 4 km altitude in the equatorial region of the Atlantic Ocean basin, where they reach global maximums of 3.6–6.5 ppbv depending on season. MHP mixing ratios reach global maximums of 4.3–8.6 ppbv and are highest between 1 and 3 km altitude, but peak in different regions depending on season. A major factor contributing to the global H₂O₂ distribution is the influence of biomass burning emissions in the Atlantic Ocean basin, encountered in all four seasons, where the highest H₂O₂ mixing ratios were found to correlate strongly with increased mixing ratios of the biomass burning tracers hydrogen cyanide (HCN) and carbon monoxide (CO). This biomass burning enhanced H₂O₂ by a factor of 1.3–2.2, on average, in the Atlantic compared with the Pacific Ocean basin.

We evaluate the uncertainties of methane optimal estimation retrievals from single-footprint thermal infrared observations from the Atmospheric Infrared Sounder (AIRS). These retrievals are primarily sensitive to atmospheric methane in the mid-troposphere through the lower stratosphere (∼2 to ∼17 km). We compare them to in situ observations made from aircraft during the HIAPER Pole to Pole Observations (HIPPO) and Atmospheric Tomography Mission (ATom) campaigns, and from the NOAA GML aircraft network, between the surface and 5–13 km, across a range of years, latitudes between 60∘ S to 80∘ N, and over land and ocean. After a global, pressure-dependent bias correction, we find that the land and ocean have similar biases and that the reported observation error (combined measurement and interference errors) of ∼27 ppb is consistent with the SD between aircraft and individual AIRS observations. A single observation has measurement (noise related) uncertainty of ∼17 ppb, a ∼20 ppb uncertainty from radiative interferences (e.g., from water or temperature), and ∼30 ppb due to “smoothing error”, which is partially removed when making comparisons to in situ measurements or models in a way that accounts for this regularization. We estimate a 10 ppb validation uncertainty because the aircraft typically did not measure methane at altitudes where the AIRS measurements have some sensitivity, e.g., the stratosphere, and there is uncertainty in the truth that we validate against. Daily averaging only partly reduces the difference between aircraft and satellite observation, likely because of correlated errors introduced into the retrieval from temperature and water vapor. For example, averaging nine observations only reduces the aircraft–model difference to ∼17 ppb vs. the expected ∼10 ppb. Seasonal averages can reduce this ∼17 ppb uncertainty further to ∼10 ppb, as determined through comparison with NOAA aircraft, likely because uncertainties related to radiative effects of temperature and water vapor are reduced when averaged over a season.

Global observations and model studies indicate that new particle formation (NPF) in the upper troposphere (UT) and subsequent particles supply 40–60 % of cloud condensation nuclei (CCN) in the lower troposphere, thus affecting the Earth's radiative budget. There are several plausible nucleation mechanisms and precursor species in this atmospheric region, which, in the absence of observational constraints, lead to uncertainties in modeled aerosols. In particular, the type of nucleation mechanism and concentrations of nucleation precursors, in part, determine the spatial distribution of new particles and resulting spatial distribution of CCN from this source. Although substantial advances in understanding NPF have been made in recent years, NPF processes in the UT in pristine marine regions are still poorly understood and are inadequately represented in global models. Here, we evaluate commonly used and state-of-the-art NPF schemes in a Lagrangian box model to assess which schemes and precursor concentrations best reproduce detailed in situ observations. Using measurements of aerosol size distributions (0.003

Recent studies show conflicting estimates of trends in methane (CH4) emissions from oil and natural gas (ONG) operations in the United States. We analyze atmospheric CH4 measurements from 20 North American sites in the National Oceanic and Atmospheric Administration Global Greenhouse Gas Reference Network and determined trends for 2006–2015. Using CH4 vertical gradients as an indicator of regional surface emissions, we find no significant increase in emissions at most sites and modest increases at three sites heavily influenced by ONG activities. Our estimated increases in North American ONG CH4 emissions (on average approximately 3.4 ± 1.4 %/year for 2006–2015, ±σ) are much smaller than estimates from some previous studies and below our detection threshold for total emissions increases at the east coast sites that are sensitive to U.S. outflows. We also find an increasing trend in ethane/methane emission ratios, which has resulted in major overestimation of oil and gas emissions trends in some previous studies.

The Orbiting Carbon Observatory-2 has been on orbit since 2014, and its global coverage holds the potential to reveal new information about the carbon cycle through the use of top-down atmospheric inversion methods combined with column average CO2 retrievals. We employ a large ensemble of atmospheric inversions utilizing different transport models, data assimilation techniques and prior flux distributions in order to quantify the satellite-informed fluxes from OCO-2 Version 7r land observations and their uncertainties at continental scales. Additionally, we use in situ measurements to provide a baseline against which to compare the satellite-constrained results. We find that within ensemble spread, in situ observations and satellite retrievals constrain a similar global total carbon sink of 3.7 ± 0.5 PgC, and 1.5 ± 0.6 PgC per year for global land, for the 2015–2016 annual mean. This agreement breaks down on smaller regions, and we discuss the differences between the experiments. Of particular interest is the difference between the different assimilation constraints in the tropics, with the largest differences occurring in tropical Africa, which could be an indication of the global perturbation from the 2015–2016 El Niño. Evaluation of posterior concentrations using TCCON and aircraft observations gives some limited insight into the quality of the different assimilation constraints, but the lack of such data in the tropics inhibits our ability to make strong conclusions there.

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.

This paper provides an overview of the validation of National Oceanic and Atmospheric Administration (NOAA) operational retrievals of atmospheric carbon trace gas profiles, specifically carbon monoxide (CO), methane (CH4) and carbon dioxide (CO2), from the NOAA-Unique Combined Atmospheric Processing System (NUCAPS), a NOAA enterprise algorithm that retrieves atmospheric profile environmental data records (EDRs) under global non-precipitating (clear to partly cloudy) conditions. Vertical information about atmospheric trace gases is obtained from the Cross-track Infrared Sounder (CrIS), an infrared Fourier transform spectrometer that measures high resolution Earth radiance spectra from NOAA operational low earth orbit (LEO) satellites, including the Suomi National Polar-orbiting Partnership (SNPP) and follow-on Joint Polar Satellite System (JPSS) series beginning with NOAA-20. The NUCAPS CO, CH4, and CO2 profile EDRs are rigorously validated in this paper using well-established independent truth datasets, namely total column data from ground-based Total Carbon Column Observing Network (TCCON) sites, and in situ vertical profile data obtained from aircraft and balloon platforms via the NASA Atmospheric Tomography (ATom) mission and NOAA AirCore sampler, respectively. Statistical analyses using these datasets demonstrate that the NUCAPS carbon gas profile EDRs generally meet JPSS Level 1 global performance requirements, with the absolute accuracy and precision of CO 5% and 15%, respectively, in layers where CrIS has vertical sensitivity; CH4 and CO2 product accuracies are both found to be within ±1%, with precisions of ≈1.5% and ⪅0.5%, respectively, throughout the tropospheric column.