Showing papers by "Paul O. Wennberg published in 2003"

Extreme deuterium enrichment in stratospheric hydrogen and the global atmospheric budget of H2

Abstract: Molecular hydrogen (H_2) is the second most abundant trace gas in the atmosphere after methane (CH_4). In the troposphere, the D/H ratio of H_2 is enriched by 120‰ relative to the world's oceans. This cannot be explained by the sources of H_2 for which the D/H ratio has been measured to date (for example, fossil fuels and biomass burning). But the isotopic composition of H_2 from its single largest source—the photochemical oxidation of methane—has yet to be determined. Here we show that the D/H ratio of stratospheric H2 develops enrichments greater than 440‰, the most extreme D/H enrichment observed in a terrestrial material. We estimate the D/H ratio of H_2 produced from CH_4 in the stratosphere, where production is isolated from the influences of non-photochemical sources and sinks, showing that the chain of reactions producing H_2 from CH_4 concentrates D in the product H_2. This enrichment, which we estimate is similar on a global average in the troposphere, contributes substantially to the D/H ratio of tropospheric H_2.

Measured HDO/H2O ratios across the tropical tropopause

Abstract: We present the first simultaneous measurements of HDO and H_2O in the tropical upper troposphere (UT) and lower stratosphere (LS) as derived from infrared solar absorption spectra acquired by the Atmospheric Trace Molecule Spectroscopy (ATMOS) experiment. We find, surprisingly, that the observed HDO/H_2O ratio does not decrease with altitude in this region despite a factor of 4–5 decrease in the water vapor mixing ratio. This observation is inconsistent with the view that dehydration in the tropical UT/LS is by gradual processes, and suggests a major role by convective processes.

Tropospheric methane retrieved from ground-based near-IR solar absorption spectra

Abstract: High-resolution near-infrared solar absorption spectra recorded between 1977 and 1995 at the Kitt Peak National Solar Observatory are analyzed to retrieve column abundances of methane (CH_4), hydrogen fluoride (HF), and oxygen (O_2). Employing a stratospheric “slope equilibrium” relationship between CH_4 and HF, the varying contribution of stratospheric CH_4 to the total column is inferred. Variations in the CH_4 column due to changes in surface pressure are determined from the O_2 column abundances. By this technique, CH_4 tropospheric volume mixing ratios are determined with a precision of ∼0.5%. These display behavior similar to Mauna Loa in situ surface measurements, with a seasonal peak-to-peak amplitude of approximately 30 ppbv and a nearly linear increase between 1977 and 1983 of 18.0 ± 0.8 ppbv yr^(−1), slowing significantly after 1990.

Novel Aerosol/Gas Inlet for Aircraft-Based Measurements

Abstract: A novel inlet has been designed for selective sampling of gas and aerosol phases of volatile species from high-speed aircraft. A multistage flow system brings the flow nearly isokinetically towards the sampling port. Two small airfoil-shaped "blades" are placed close to the sample port to provide the flow conditions required for aerosol and gas sampling. Aerosols are sampled when these blades are positioned to operate the inlet as a counterflow virtual impactor (CVI). The design enables sampling of particles as small as 0.1 w m from a high-speed aircraft under stratospheric conditions, a substantial improvement over that possible with previous CVI designs. For gas sampling, one of the blades is moved by a stepper motor to occlude the inlet opening and gas is sampled perpendicular to the bulk flow. Boundary layer suction is used to prevent the sampled gas from coming in contact with the impactor walls. This is one of the first designs of an inlet that enables gas sampling free of wall contact. The inlet was flown on the NASA ER-2 aircraft during the SOLVE 2000 campaign to study aerosol/gas partitioning of nitric acid in the lower stratosphere. Data from the flight tests show that the inlet flow characteristics are broadly in agreement with computational fluid dynamics (CFD) simulations.

A compact, lightweight gas standards generator for permeation tubes

Abstract: A lightweight, compact gas standards generator for permeation tubes is described. This system provides reliable temperature control during periods of intermittent power and is ideal for field measurements. A eutectic alloy with a high heat of fusion is used as a phase change material. This thermal source allows the system to maintain a constant permeation tube temperature of 46.6 °C for over 5 h in the absence of external power. This permeation system is currently being used in an aircraft chemical ionization mass spectrometer to provide HNO3 calibration.