Thermal-Dissociation Laser Induced Fluorescence

The UC Berkeley thermal-dissociation laser-induced fluorescence (TD- LIF) instrument detects NO2 directly and detects total peroxynitrates (ΣPNs ≡ PAN + PPN +N2O5 + HNO4. . .), total alkyl- and other thermally stable organic nitrates (ΣANs), and HNO3 following thermal dissociation of these NOy species to NO2. The sensitivity for NO2 at 1 Hz is 30 pptv (S/N=2) with a slope uncertainty of 5%. The uncertainties for the dissociated species are 10% for ΣPNs and 15% for ΣANs and HNO3.

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Langley Wideband Integrated Bioaerosol Sensor

Wideband Integrated Bioaerosol Sensor (WIBS-4A) - Droplet Measurement Technologies.  Dectection of Fluorescent Biological Aerosol Particle (FBAP) number concentrations.  Single particle analysis using dual wavelength (280nm and 370nm by xenon lamps) excitation on two parallel broadband visible-wavelength detectors (310-400nm and 420-650nm). Particles are classified by a combination of fluorescence excitation and emission characteristics, as well as their optical size measured by forward-scattering using a 635nm continuous-wave diode laser.    

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URI Peroxides and Formaldehyde Instrument

POPS measures CH2O, H2O2, and CH3OOH.

CH2O is measured by aqueous collection followed by enzyme fluorescence detection.

H2O2 and CH3OOH is measured by aqueous collection followed by HPLC separation and enzyme fluorescence detection.

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Georgia Tech Laser-Induced Fluorescence

The Georgia Tech Laser-Induced Fluorescence instrument measures nitric oxide (NO), formaldehyde (HCHO), and nitrogen dioxide (NO2). Each species is measured by laser-induced fluorescence at reduced pressure. Ambient air is drawn in through a pinhole orifice into a pair of multipass White cells. The pressure in the White cells is maintained at 5-10 mbar to extend the fluorescence lifetime, and the multiple passes (typically 32-40) effectively extends the probe interaction volume. The ambient air is probed at 90o from the flow and the fluorescence collected at 90o to the flow and probe.

NO is probed at the 226 absorption line and monitored at the 247 nm fluorescence. The laser pulse and scattering will be time-gated out using microchannel plate detectors. The expected 2-sigma limit of detection is 5 pptv/min. Formaldehyde is probed at 353 nm and the fluorescence monitored in a range from 400 to 450 nm. The expected performance is 10 pptv/min. NO2 will be probed near 435 nm and the fluorescence around 780 nm collected. Its expected performance is 15 pptv/min. In each case, the probe wavelength will be alternately switched from the absorption feature to a nearby “off-line” position to determine the background. The actual frequency will be monitored in reference cells. Calbration is done by standard addition to the airflow. The light sources used are custom-built cavities pumped by a diode-pumped Nd:YAG laser operating at ~10 kHz.

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Chlorine Nitrate Instrument

The NO2-ClO-ClONO2-BrO instrument is composed of two separate instruments: A laser-induced fluorescence instrument for the detection of NO2 and a thermal dissociation/resonance fluorescence instrument for the detection of ClO, ClONO2 and BrO.

The NO2 detection system uses laser-induced resonance fluorescence (LIF) for the direct detection of NO2. Ambient air passes through a detection axis where the output of a narrow bandwidth (0.06 cm-1), tunable dye laser operating near 585 nm is used to excite a rovibronic transition in NO2. The excited NO2 molecules are either quenched by collision with air or fluorescence. The NO2 fluorescence is strongly red-shifted, with emission occurring over a broad range of wavelengths from 585 nm to the mid-infrared. The specificity of the technique is accomplished by tuning the laser frequency on and off resonance with a narrow spectral feature (0.04 cm-1) in the NO2 absorption spectrum. The difference between the fluorescence signal on and off resonance is related to the mixing ratio of NO2 through laboratory and in-flight calibrations. The observations are determined with an accuracy (1 sigma) of ±10% ±50 pptv, precision (1 sigma) of ±40 pptv, and a reporting interval of 10 seconds. Higher resolution (0.25 sec) data available on request.

The halogen detection system uses gas-phase thermal dissociation of ambient ClONO2 to produce ClO and NO2 radicals. The pyrolysis is accomplished by passing the air sampled in a 5-cm-square duct through a grid of resistively heated silicon strips at 10 to 20 m/sec, rapidly heating the air to 520 K. The ClO fragment from ClONO2 is converted to Cl atoms by reaction with added NO, and Cl atoms are detected using ultra-violet resonance fluorescence at 118.9 nm. A similar detection axis upstream of the heater provides simultaneous detection of ambient ClO. An identical twin sampling duct provides the capability for diagnostic checks. The flight instrument is calibrated in a laboratory setting with known addition of ClONO2 as a function of pressure, heater temperature and flow velocity. The concentration of ClONO2 is measured with an accuracy and detection limit of ±20% and 10 pptv, respectively, in 35 seconds (all error estimates are 1 sigma). The concentration of ClO is measured with an accuracy and detection limit of ±17% and 3 pptv, respectively, in 35 seconds.

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Harvard Lyman-α Photofragment Fluorescence Hygrometer

The Harvard Water Vapor (HWV) instrument combines two independent measurement methods for the simultaneous in situ detection of ambient water vapor mixing ratios in a single duct. This dual axis instrument combines the heritage of the Harvard Lyman-α photo-fragment fluorescence instrument (LyA) with the newly designed tunable diode laser direct absorption instrument (HHH). The Lyman-α detection axis functions as a benchmark measurement, and provides a requisite link to the long measurement history of Harvard Lyman-α aboard NASA’s WB-57 and ER-2 aircraft [Weinstock et al., 1994; Hintsa et al., 1999; Weinstock et al., 2009]. The inclusion of HHH provides a second high precision measurement that is more robust than LyA to changes in its measurement sensitivity [Smith et al., in preparation]. The simultaneous utilization of radically different measurement techniques facilitates the identification, diagnosis, and constraint of systematic errors both in the laboratory and in flight. As such, it constitutes a significant step toward resolving the controversy surrounding water vapor measurements in the upper troposphere and lower stratosphere.

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Harvard Total Water

The design of the newly developed total water instrument is based on the same principles as the water vapor instrument, and is intended to fly in conjunction with it. Conceptually, the total water instrument can be thought of as containing four subsystems:
1. An inlet through which liquid and/or solid water particles can be brought into an instrument duct without perturbing the ambient particle density.
2. A heater that efficiently evaporates the liquid/solid water before it reaches the detection axis.
3. Ducting through which the air flows to the detection axis without perturbing the (total) water vapor mixing ratio.
4. A water vapor detection axis that accurately and precisely measures the total water content of the ambient air.

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Harvard Hydroxyl Experiment

OH is detected by direct laser induced fluorescence in the (0-1) band of the 2?-2? electronic transition. A pulsed dye-laser system produces frequency tunable laser light at 282 nm. An on-board frequency reference cell is used by a computer to lock the laser to the appropriate wavelength. Measurement of the signal is then made by tuning the laser on and off resonance with the OH transition.

Stratospheric air is channeled into the instrument using a double-ducted system that both maintains laminar flow through the detection region and slows the flow from free stream velocity (200 m/s) to 40 m/s. The laser light is beam-split and directed to two detection axes where it passes through the stratospheric air in multipass White cells.

Fluorescence from OH (centered at 309 nm) is detected orthogonal to both the flow and the laser propagation using a filtered PMT assembly. Optical stability is checked periodically by exchanging the 309 nm interference filter with a filter centered at 302 nm, where Raman scattering of N2 is observed.

HO2 is measured as OH after chemical titration with nitric oxide: HO2 + NO → OH + NO2. Variation of added NO density and flow velocity as well as the use of two detection axes aid in diagnosis of the kinetics of this titration. Measurements of ozone (by uv absorption) and water vapor (by photofragment fluorescence) are made as diagnostics of potential photochemical interference from the mechanism: O3 + hv (282 nm) → O(1D) + O2, followed by: O(1D) + H2O → OH + OH

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Berkeley Nitrogen Oxides Detector

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Airborne Tropospheric Hydrogen Oxides Sensor

ATHOS uses laser-induced fluorescence (LIF) to measure OH and HO2 simultaneously. OH is both excited and detected with the A2Σ+ (v’=0) → X2π (v”=0) transition near 308 nm. HO2 is reacted with reagent NO to form OH and is then detected with LIF. The laser is tuned on and off the OH wavelength to determine the fluorescence and background signals. ATHOS can detect OH and HO2 in clear air and light clouds from Earth's surface to the lower stratosphere. The ambient air is slowed from the aircraft speed of 240 m/s to 8-40 m/s in an aerodynamic nacelle. It is then pulled by a vacuum pump through a small inlet, up a sampling tube, and into two low-pressure detection cells - the first for OH and the second for HO2. Detection occurs in each cell at the intersection of the airflow, the laser beam, and the detector field-of-view.

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