Doppler spectrum-based polar nephelometer.

The particle scattering asymmetry parameter of an ensemble of submicrometer particles, as well as the complete scattering phase function (angular distribution), is determined by measuring the Doppler spectrum of the scattered light. No calibration is required. The monitor incorporates a 532 nm laser with long coherence length, an integrating sphere to collect the scattered light, and a heterodyne (interferometric) detection scheme. Measurements of monodisperse polystyrene latex spheres and polydisperse ammonium sulfate particles indicate that the measured value of the asymmetry parameter is generally within ±0.03 of that calculated using Mie theory.

A practical alternative to chemiluminescence-based detection of nitrogen dioxide: cavity attenuated phase shift spectroscopy.

We present results obtained from a greatly improved version of a previously reported nitrogen dioxide monitor (Anal Chem. 2005, 77, 724-728) that utilizes cavity attenuated phase shift spectroscopy (CAPS). The sensor, which detects the optical absorption of nitrogen dioxide within a 20 nm bandpass centered at 440 nm, comprises a blue light emitting diode, an enclosed stainless steel measurement cell (26 cm length) incorporating a resonant optical cavity of near-confocal design and a vacuum photodiode detector. An analog heterodyne detection scheme is used to measure the phase shift in the waveform of the modulated light transmitted through the cell induced by the presence of nitrogen dioxide within the cell. The sensor, which operates at atmospheric pressure, fits into a 19 in.-rack-mounted instrumentation box, weighs 10 kg, and utilizes 70 W of electrical power with pump included. The sensor response to nitrogen dioxide (calculated as the cotangent of the phase shift) is demonstrated to be linear (r2 > 0.9999) within +/- 1 ppb over a range of 0-320 ppb (by volume). The device exhibits a detection limit (3sigma precision) of less than 60 parts per trillion (0.060 ppb) with 10 s integration, a value derived from measurements at NO2 concentration levels of both 0 and 20 ppb; the detection limit improves as the integration time is increased to several hundred seconds. The observed baseline drift is less than +/- 0.5 ppb overthe course of a month. An intercomparison of measurements of ambient NO2 concentrations over several days using this sensor with a quantum cascade laser-based infrared absorption spectrometer and a standard chemiluminescence-based NOx analyzer is presented. The data from the CAPS sensor are highly correlated (r2 > 0.99) with the other two instruments. The absolute agreement between the CAPS and each of the two other instruments is within the expected statistical noise associated with the infrared laser-based absorption spectrometer (+/- 0.3 ppb with 10 s sampling) and chemiluminescence analyzer (+/- 0.4 ppb with 60 s averaging). The major limitation concerning accuracy is a direct spectral interference with phototchemically produced 1,2-dicarbonyl species (e.g., glyoxal, methylglyoxal). However, this interference can be readily removed by shifting the detection band to a slightly longer wavelength and ensuring that the lower edge of the detection band is greater than 455 nm.

Optical extinction monitor using cw cavity enhanced detection.

We present details of an apparatus capable of measuring optical extinction (i.e., scattering and/or absorption) with high precision and sensitivity. The apparatus employs one variant of cavity enhanced detection, specifically cavity attenuated phase shift spectroscopy, using a near-confocal arrangement of two high reflectivity (R approximately 0.9999) mirrors in tandem with an enclosed cell 26 cm in length, a light emitting diode (LED), and a vacuum photodiode detector. The square wave modulated light from the LED passes through the absorption cell and is detected as a distorted wave form which is characterized by a phase shift with respect to the initial modulation. The amount of that phase shift is a function of fixed instrument properties-cell length, mirror reflectivity, and modulation frequency-and of the presence of a scatterer or absorber (air, particles, trace gases, etc.) within the cell. The specific implementation reported here employs a blue LED; the wavelength and spectral bandpass of the measurement are defined by the use of an interference filter centered at 440 nm with a 20 nm wide bandpass. The monitor is enclosed within a standard 19 in. rack-mounted instrumentation box, weighs 10 kg, and uses 70 W of electrical power including a vacuum pump. Measurements of the phase shift induced by Rayleigh scattering from several gases (which range in extinction coefficient from 0.4-32 Mm(-1)) exhibit a highly linear dependence (r(2)=0.999 97) when plotted as the co-tangent of the phase shift versus the expected extinction. Using heterodyne demodulation techniques, we demonstrate a detection limit of 0.04 Mm(-1) (4 x 10(-10) cm(-1)) (2sigma) in 10 s integration time and a base line drift of less than +/-0.1 Mm(-1) over a 24 h period. Detection limits decrease as the square root of integration time out to approximately 150 s.

Detection of nitrogen dioxide by cavity attenuated phase shift spectroscopy.

We present initial results obtained from an optical absorption sensor for the monitoring of ambient atmospheric nitrogen dioxide concentrations (0-200 ppb). This sensor utilizes cavity attenuated phase shift spectroscopy, a technology related to cavity ringdown spectroscopy. A modulated broadband incoherent light source (a 430-nm LED) is coupled to an optically resonant cavity formed by two high-reflectivity mirrors. The presence of NO(2) in the cell causes a phase shift in the signal received by a photodetector that is proportional to the NO(2) concentration. The sensor, which employed a 0.5-m cell, was shown to have a sensitivity of 0.3 ppb in the photon (shot) noise limit. Improvements in the optical coupling of the LED to the resonant cavity would allow the sensor to reach this limit with integration times of 10 s or less (corresponding to a noise equivalent absorption coefficient of <1 x 10(-8) cm(-1) Hz(-1/2)). Over a 2-day-long period of ambient atmospheric monitoring, a comparison of the sensor with an extremely accurate and precise tunable diode laser-based absorption spectrometer showed that the CAPS-based instrument was able to reliably and quantitatively measure both large and small fluctuations in the ambient nitrogen dioxide concentration.