Tunable Infrared Laser Differential Absorption Spectroscopy Research Articles

Rapid and Precise Analysis of Carbon Dioxide Clumped Isotopic Composition by Tunable Infrared Laser Differential Spectroscopy.

The high precision measurement of doubly substituted ("clumped") isotopologues in CO2 is a topic of significant interest in isotope geochemistry. Here we describe the performance of a new isotope ratio laser spectrometer using tunable infrared laser differential absorption spectroscopy (TILDAS). The TILDAS instrument has two continuous-wave lasers to simultaneously measure the four isotopologues involved in the 12C16O2 + 13C16O18O ⇆ 13C16O2 + 12C16O18O exchange reaction. CO2 samples are trapped in a low volume (∼250 mL) optical multipass cell with a path length of 36 m. Each sample is compared to a reference gas, and clumped isotopologue precision of 0.01‰ (SE) is achieved within 20 min for 15 μmol samples. Similar precision is also achieved for bulk isotopic composition. The degree of rare isotope clumping in excess of strictly random distribution (Δ16O13C18O) measured by this TILDAS instrument varies linearly with theoretically calculated values and shows a very weak dependence on bulk isotopic composition.

Effective line strengths of trans-nitrous acid near 1275 cm−1 and cis-nitrous acid at 1660 cm−1

We determined the effective line strengths of the trans conformer of nitrous acid (HONO) near 1275cm−1 (R-branch of ν3 mode, NOH bend) and of the cis conformer at 1660cm−1 (R-branch of ν2 mode, NO stretch), both at a spectral resolution of 0.001cm−1 by tunable infrared laser differential absorption spectroscopy (TILDAS) utilizing continuous-wave quantum cascade (cw-QC) lasers. Absorbance of one conformer was measured while simultaneously quantifying the mixing ratio of total HONO by catalytic conversion to nitric oxide (NO) followed by calibrated absorption spectroscopy. Line strengths obtained here are consistent with previously reported band strengths for the trans conformer but are lower by a factor of approximately 2.4 for the cis conformer.

Eddy covariance measurement of ammonia fluxes: Comparison of high frequency correction methodologies

Several methods are available for evaluating and correcting the underestimation of trace gas fluxes measured by eddy covariance (EC) method and due to the design and the setup of the employed equipment. Different frequency correction factors (CF) to apply to the measured EC ammonia (NH3) fluxes have been applied using the following approaches: (i) the spectral theoretical transfer function (CFTheor) with and without phase shift; (ii) the in situ ogive method (CFO); and (iii) the inductance correction method (CFL). The NH3 fluxes were measured in an experimental field located in south Italy, above a sorghum crop submitted to Mediterranean semi-arid climate and fertilized with urea. A fast analyser based on Tunable Infrared Laser Differential Absorption Spectroscopy (TILDAS) coupled with a quantum cascade (QC) laser was used to measure NH3 concentration at high frequency. The results showed that correction of the values of NH3 EC fluxes over natural surfaces are necessary for taking into account the dumping of high frequency contribution due to the coupling of ammonia fast analyser by QC-TILDAS and sonic anemometer. In particular, the calculated flux losses ranged between −23% (inductance method, with the CF threshold selected to 2.5) and −43% (experimental-ogive method); while the two theoretical transfer function approaches gave comparable loss estimates, i.e. −30 and −31% for the methods with time lag and phase shift, respectively.

Evaluation of nitrogen dioxide chemiluminescence monitors in a polluted urban environment

Abstract. Data from a recent field campaign in Mexico City are used to evaluate the performance of the EPA Federal Reference Method for monitoring the ambient concentrations of NO2. Measurements of NO2 from standard chemiluminescence monitors equipped with molybdenum oxide converters are compared with those from Tunable Infrared Laser Differential Absorption Spectroscopy (TILDAS) and Differential Optical Absorption Spectroscopy (DOAS) instruments. A significant interference in the chemiluminescence measurement is shown to account for up to 50% of ambient NO2 concentration during afternoon hours. As expected, this interference correlates well with non-NOx reactive nitrogen species (NOz) as well as with ambient O3 concentrations, indicating a photochemical source for the interfering species. A combination of ambient gas phase nitric acid and alkyl and multifunctional alkyl nitrates is deduced to be the primary cause of the interference. Observations at four locations at varying proximities to emission sources indicate that the percentage contribution of HNO3 to the interference decreases with time as the air parcel ages. Alkyl and multifunctional alkyl nitrate concentrations are calculated to reach concentrations as high as several ppb inside the city, on par with the highest values previously observed in other urban locations. Averaged over the MCMA-2003 field campaign, the chemiluminescence monitor interference resulted in an average measured NO2 concentration up to 22% greater than that from co-located spectroscopic measurements. Thus, this interference has the potential to initiate regulatory action in areas that are close to non-attainment and may mislead atmospheric photochemical models used to assess control strategies for photochemical oxidants.

Measurement of nitrogen dioxide in cigarette smoke using quantum cascade tunable infrared laser differential absorption spectroscopy (TILDAS)

Although nitrogen dioxide (NO 2) has been previously reported to be present in cigarette smoke, the concentration estimates were derived from kinetic calculations or from measurements of aged smoke, where NO 2 was formed some time after the puff was taken. The objective of this work was to use tunable infrared laser differential absorption spectroscopy (TILDAS) equipped with a quantum cascade (QC) laser to determine if NO 2 could be detected and quantified in a fresh puff of cigarette smoke. A temporal resolution of ∼0.16 s allowed measurements to be taken directly as the NO 2 was formed during the puff. Sidestream cigarette smoke was sampled to determine if NO 2 could be detected using TILDAS. Experiments were conducted using 2R4F Kentucky Reference cigarettes with and without a Cambridge filter pad. NO 2 was detected only in the lighting puff of whole mainstream smoke (without a Cambridge filter pad), with no NO 2 detected in the subsequent puffs. The measurement precision was ∼1.0 ppbV Hz −1/2, which allows a detection limit of ∼0.2 ng in a 35 ml puff volume. More NO 2 was generated in the lighting puff using a match or blue flame lighter (29 ± 21 ng) than when using an electric lighter (9 ± 3 ng). In the presence of a Cambridge filter pad, NO 2 was observed in the gas phase mainstream smoke for every puff (total of 200 ± 30 ng/cigarette) and is most likely due to smoke chemistry taking place on the Cambridge filter pad during the smoke collection process. Nitrogen dioxide was observed continuously in the sidestream smoke starting with the lighting puff.

Mobile Laboratory with Rapid Response Instruments for Real-Time Measurements of Urban and Regional Trace Gas and Particulate Distributions and Emission Source Characteristics

Recent technological advances have allowed the development of robust, relatively compact, low power, rapid response (approximately 1 s) instruments with sufficient sensitivity and specificity to quantify many trace gases and aerosol particle components in the ambient atmosphere. Suites of such instruments can be deployed on mobile platforms to study atmospheric processes, map concentration distributions of atmospheric pollutants, and determine the composition and intensities of emission sources. A mobile laboratory containing innovative tunable infrared laser differential absorption spectroscopy (TILDAS) instruments to measure selected trace gas concentrations at sub parts-per-billion levels and an aerosol mass spectrometer (AMS) to measure size resolved distributions of the nonrefractory chemical components of fine airborne particles as well as selected commercial fast response instruments and position/velocity sensors is described. Examples of the range of measurement strategies that can be undertaken using this mobile laboratory are discussed, and samples of measurement data are presented.

Tunable infrared laser detection of pyrolysis products of explosives in soils

A research program involving two applications of tunable infrared laser differential absorption spectroscopy (TILDAS) with multipass, long-path absorption cells to the detection of explosives contamination in soils is reported. In the first application, sensitive, specific real-time species concentration measurements by TILDAS have led to new understanding of the processes involved in explosives detection by the heating of contaminated soils and the quantification of the resulting pyrolysis gases. In the second, we present results of our calculations of the properties of astigmatic off-axis resonator absorption cells, which show that useful TILDAS path lengths can be achieved inside a cone penetrometer probe.