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Pamela M Chu

Publications and source records attributed to Pamela M Chu.

5 recordsLinked to original sources

Quantitative vapor-phase infrared spectrometry of ammonia.

Reference spectra of ammonia from four sources are compared. Low-resolution spectra (i.e., spectra for which the spectrometer resolution is numerically greater than the full-width at half-height of the rotational lines) were obtained from the Environmental Protection Agency (EPA) web site and from Infrared Analysis, Inc. High-resolution (0.12 cm-1) spectra were obtained from the National Institute for Standards and Technology (NIST) and Pacific Northwest National Laboratory (PNNL). Two protocols were used to validate the EPA and Infrared Analysis spectra, with one requiring that Beer's law be obeyed by the low-resolution spectrum and the other that Beer's law be obeyed by the high-resolution spectrum. In all cases, the second protocol gave a significantly better spectral match. It is shown that the path-integrated concentrations for the low-resolution reference spectra were in error by as little as 4% to as much as an order of magnitude, presumably because of the effect of adsorption on the cell walls. Measured absorptivities of the NIST and PNNL spectra were different by approximately 2.6% and it is believed that the effect of adsorption on these spectra is small. When the same protocols were used to test the reference spectrum of methane, the calculated path-integrated concentration was only approximately 2% different from the one that was calculated from the NIST reference spectrum, suggesting that the data processing protocols provide accurate data.

Ammonia↗

Consistency of ozone and nitrogen oxides standards at tropospherically relevant mixing ratios.

The absolute accuracy and long-term precision of atmospheric measurements hinge on the quality of the instrumentation and calibration standards. To assess the consistency of the ozone (O3) and nitrogen oxides (NO(x)) standards maintained at the National Institute of Standards and Technology (NIST), these standards were compared through the gas-phase titration of O3 with nitric oxide (NO). NO and O3 were monitored using chemiluminescence and UV absorption, respectively. Nitrogen dioxide (NO2) was monitored directly by laser-induced fluorescence and indirectly by catalytic conversion to NO, followed by chemiluminescence. The observed equivalent loss of both NO and O3 and the formation of NO2 in these experiments was within 1% on average over the range of 40-200 nmol mol(-1) of NO in excess O3, indicating that these instruments, when calibrated with the NIST O3 and NO standards and the NO2 permeation calibration system, are consistent to within 1% at tropospherically relevant mixing ratios of O3. Experiments conducted at higher initial NO mixing ratios or in excess NO are not in as good agreement. The largest discrepancies are associated with the chemiluminescence measurements. These results indicate the presence of systematic biases under these specific conditions. Prospects for improving these experiments are discussed.

Air Pollutants, Occupational↗

Gas-phase databases for quantitative infrared spectroscopy.

The National Institute of Standards and Technology (NIST) and the Pacific Northwest National Laboratory (PNNL) are each creating quantitative databases containing the vapor-phase infrared spectra of pure chemicals. The digital databases have been created with both laboratory and remote-sensing applications in mind. A spectral resolution of approximate, equals 0.1 cm(-1) was selected to avoid degrading sharp spectral features, while also realizing that atmospheric broadening typically limits line widths to 0.1 cm(-1). Calculated positional (wave- number, cm(-1)) uncertainty is </=0.005 cm(-1), while the 1sigma statistical uncertainty in absorbance values is <2% for most compounds. The latter was achieved by measuring multiple (typically >/=9) path length-concentration burdens and fitting a weighted Beer's law plot to each wavenumber channel. The two databases include different classes of compounds and were compared using 12 samples. Though these 12 samples span a range of polarities, absorption strengths, and vapor pressures, the data agree to within experimental uncertainties with only one exception.

Calibration↗

Removing aperture-induced artifacts from Fourier transform infrared intensity values.

Two Fourier transform infrared intensity artifacts have been observed at moderately high (0.1 cm(-1)) spectral resolution: Light reflected off the aperture was double modulated by the interferometer, producing a 2f alias, and the warm (approximately 310 K) annulus of the aperture seen by a cooled detector resulted in distorted line shapes and anomalous intensities in the fingerprint region. Although the second artifact has been alluded to previously, we report corrections to remove both of these anomalies and to demonstrate the efficacy of these corrections. Prior to correction, integrated-band intensities were found to be in error by up to 12%.

Journal Article↗