Showing papers by "Paul O. Wennberg published in 2006"

Measurement of gas-phase hydroperoxides by chemical ionization mass spectrometry.

Abstract: A new method for the detection of gas-phase hydroperoxides is described. The clustering chemistry of CF3O- is exploited to produce speciated measurements of several hydroperoxides with high sensitivity and fast time response. Correspondence of airborne observations made with this technique and the established HPLC method is illustrated. CF3O- appears to be a highly versatile reagent ion for measurements of both weak and strong acids in the atmosphere.

Carbon dioxide column abundances at the Wisconsin Tall Tower site

Abstract: We have developed an automated observatory for measuring atmospheric column abundances of CO_2 and O_2 using near-infrared spectra of the Sun obtained with a high spectral resolution Fourier Transform Spectrometer (FTS). This is the first dedicated laboratory in a new network of ground-based observatories named the Total Carbon Column Observing Network. This network will be used for carbon cycle studies and validation of spaceborne column measurements of greenhouse gases. The observatory was assembled in Pasadena, California, and then permanently deployed to northern Wisconsin during May 2004. It is located in the heavily forested Chequamegon National Forest at the WLEF Tall Tower site, 12 km east of Park Falls, Wisconsin. Under clear sky conditions, ∼0.1% measurement precision is demonstrated for the retrieved column CO_2 abundances. During the Intercontinental Chemical Transport Experiment–North America and CO_2 Boundary Layer Regional Airborne Experiment campaigns in summer 2004, the DC-8 and King Air aircraft recorded eight in situ CO_2 profiles over the WLEF site. Comparison of the integrated aircraft profiles and CO_2 column abundances shows a small bias (∼2%) but an excellent correlation.

Space‐based near‐infrared CO2 measurements: Testing the Orbiting Carbon Observatory retrieval algorithm and validation concept using SCIAMACHY observations over Park Falls, Wisconsin

Abstract: Space-based measurements of reflected sunlight in the near-infrared (NIR) region promise to yield accurate and precise observations of the global distribution of atmospheric CO_2. The Orbiting Carbon Observatory (OCO) is a future NASA mission, which will use this technique to measure the column-averaged dry air mole fraction of CO_2 (X_(CO)_2) with the precision and accuracy needed to quantify CO_2 sources and sinks on regional scales (∼1000 × 1000 km^2) and to characterize their variability on seasonal timescales. Here, we have used the OCO retrieval algorithm to retrieve (X_(CO)_2) and surface pressure from space-based Scanning Imaging Absorption Spectrometer for Atmospheric Chartography (SCIAMACHY) measurements and from coincident ground-based Fourier transform spectrometer (FTS) measurements of the O_2 A band at 0.76 μm and the 1.58 μm CO_2 band for Park Falls, Wisconsin. Even after accounting for a systematic error in our representation of the O_2 absorption cross sections, we still obtained a positive bias between SCIAMACHY and FTS (X_(CO)_2) retrievals of ∼3.5%. Additionally, the retrieved surface pressures from SCIAMACHY systematically underestimate measurements of a calibrated pressure sensor at the FTS site. These findings lead us to speculate about inadequacies in the forward model of our retrieval algorithm. By assuming a 1% intensity offset in the O_2 A band region for the SCIAMACHY (X_(CO)_2) retrieval, we significantly improved the spectral fit and achieved better consistency between SCIAMACHY and FTS (X_(CO)_2) retrievals. We compared the seasonal cycle of (X_(CO)_2)at Park Falls from SCIAMACHY and FTS retrievals with calculations of the Model of Atmospheric Transport and Chemistry/Carnegie-Ames-Stanford Approach (MATCH/CASA) and found a good qualitative agreement but with MATCH/CASA underestimating the measured seasonal amplitude. Furthermore, since SCIAMACHY observations are similar in viewing geometry and spectral range to those of OCO, this study represents an important test of the OCO retrieval algorithm and validation concept using NIR spectra measured from space. Finally, we argue that significant improvements in precision and accuracy could be obtained from a dedicated CO_2 instrument such as OCO, which has much higher spectral and spatial resolutions than SCIAMACHY. These measurements would then provide critical data for improving our understanding of the carbon cycle and carbon sources and sinks.

On the flux of oxygenated volatile organic compounds from organic aerosol oxidation

Abstract: Previous laboratory and field studies suggest that oxidation of organic aerosols can be a source of oxygenated volatile organic compounds (OVOC). Using measurements of atmospheric oxidants and aerosol size distributions performed on the NASA DC-8 during the INTEX-NA campaign, we estimate the potential magnitude of the continental summertime OVOC flux from organic aerosol oxidation by OH to be as large as ∼70 pptv C/day in the free troposphere. Contributions from O_3, H_2O_2, photolysis, and other oxidants may increase this estimate. These processes may provide a large, diffuse source of OVOC that has not been included in current atmospheric models, and thus have a significant impact on our understanding of organic aerosol, OVOC, PAN, and HO_x chemistry. The potential importance and highly uncertain nature of our estimate highlights the need for more field and laboratory studies on organic aerosol composition and aging.

On the Stratospheric Chemistry of Hydrogen Cyanide

Abstract: HCN profiles measured by solar occultation spectrometry during 10 balloon flights of the JPL MkIV instrument are presented. The HCN profiles reveal a compact correlation with stratospheric tracers. Calculations with a 2D-model using established rate coefficients for the reactions of HCN with OH and O(1D) severely underestimate the measured HCN in the middle and upper stratosphere. The use of newly available rate coefficients for these reactions gives reasonable agreement of measured and modeled HCN. An HCN yield of approx.30% from the reaction of CH3CN with OH is consistent with the measurements.

Near-UV photolysis cross sections of CH 3 OOH and HOCH 2 OOH determined via action spectroscopy

Abstract: Knowledge of molecular photolysis cross sections is important for determining atmospheric lifetimes and fates of many species. A method and laser apparatus for measurement of these cross sections in the near-ultraviolet (UV) region is described. The technique is based on action spectroscopy, where the yield of a photodissociation product (in this case OH) is measured as a function of excitation energy. For compounds yielding OH, this method can be used to measure near-UV photodissociation cross section as low as 10^−23 cm^2 molecule−1. The method is applied to determine the photodissociation cross sections for methyl hydroperoxide (CH3OOH; MHP) and hydroxymethyl hydroperoxide (HOCH2OOH; HMHP) in the 305–365 nm wavelength range. The measured cross sections are in good agreement with previous measurements of absorption cross sections.

Atmospheric chemistry: radicals follow the Sun.

Abstract: Hydroxyl free radicals are part of a complex network of atmospheric chemical reactions. But a long-term study shows that their concentration can be predicted by the intensity of ultraviolet sunlight alone.

OH-Stretch Vibrational Spectroscopy of Hydroxymethyl Hydroperoxide

Abstract: We report measurement and analysis of the photodissociation spectrum of hydroxymethyl hydroperoxide (HOCH2OOH) and its partially deuterated analogue, HOCD2OOH, in the OH-stretching region. Spectra are obtained by Fourier transform infrared spectroscopy in the 1νOH and 2νOH regions, and by laser induced fluorescence detection of the OH fragment produced from dissociation of HOCH2OOH initiated by excitation of the 4νOH and 5νOH overtone regions (action spectroscopy). A one-dimensional local-mode model of each OH chromophore is used with ab initio calculated OH-stretching potential energy and dipole moment curves at the coupled-cluster level of theory. Major features in the observed absorption and photodissociation spectra are explained by our local-mode model. In the 4νOH region, explanation of the photodissocation spectrum requires a nonuniform quantum yield, which is estimated by assuming statistical energy distribution in the excited state. Based on the estimated dissociation threshold, overtone photodis...