Roderic L. Jones

Cavity enhanced absorption spectroscopy of multiple trace gas species using a supercontinuum radiation source

Supercontinuum radiation sources are attractive for spectroscopic applications owing to their broad wavelength coverage, which enables spectral signatures of multiple species to be detected simultaneously. Here we report the first use of a supercontinuum radiation source for broadband trace gas detection using a cavity enhanced absorption technique. Spectra were recorded at bandwidths of up to 100 nm, encompassing multiple absorption bands of H(2)O, O(2) and O(2)-O(2). The same instrument was also used to make quantitative measurements of NO(2) and NO(3). For NO(3) a detection limit of 3 parts-per-trillion in 2 s was achieved, which corresponds to an effective 3sigma sensitivity of 2.4 x 10(-9) cm(-1)Hz(-1/2). Our results demonstrate that a conceptually simple and robust instrument is capable of highly sensitive broadband absorption measurements.

Rotational Raman scattering and the ring effect in zenith‐sky spectra

The technique of zenith-sky spectroscopy is widely used to measure the vertical columns of O3, NO2, OClO and BrO in the atmosphere. In this paper, a model to simulate the effect of rotational Raman scattering by O2 and N2 on zenith-sky spectra is presented. The model is used to calculate the Raman-scattering cross-section for zenith-sky measurements and this cross-section is shown to correspond closely to the measured Ring cross-section, supporting the case that Raman scattering is the major cause of the Ring effect. Raman scattering is also shown to reduce the depths of structured molecular absorptions in scattered light spectra, leading to a general underestimation of the slant columns of molecules measured by zenith-sky spectroscopy which can be significant in some cases. This effect varies with solar zenith angle, so will affect particularly attempts to retrieve the vertical profile of an absorber from the variation of slant column with zenith angle. The calculated Ring cross-section is used to infer the proportion of multiply-scattered light which enters a zenith-sky spectrometer at twilight, and thus to estimate the magnitude of the corresponding underestimation of measured slant columns.

Broadband cavity ringdown spectroscopy of the NO3 radical.

Abstract Cavity ringdown spectroscopy (CRDS) has been demonstrated using a broadband (20 nm) laser source and a two-dimensional clocked detector array. Absorption spectra of dilute samples (50–500 parts per trillion) of the nitrate radical, NO 3 , have been obtained between 650 and 670 nm by monitoring simultaneously the time and wavelength resolved output of a ringdown cavity. The potential of broadband CRDS for making measurements on samples containing multiple absorbers (e.g., atmospheric samples) is shown by applying analysis methods from differential optical absorption spectroscopy to quantify the NO 3 concentration in the presence of nitrogen dioxide impurities.

Slant column measurements of O3 and NO2 during the NDSC intercomparison of zenith-sky UV-visible spectrometers in June 1996

In June 1996, 16 UV-visible sensors from 11 institutes measured spectra of the zenith sky for more than 10 days. Spectra were analysed in real-time to determine slant column amounts of O3 and NO2. Spectra of Hg lamps and lasers were measured, and the amount of NO2 in a cell was determined by each spectrometer. Some spectra were re-analysed after obvious errors were found. Slant columns were compared in two ways: by examining regression analyses against comparison instruments over the whole range of solar zenith angles; and by taking fractional differences from a comparison instrument at solar zenith angles between 85° and 91°. Regression identified which pairs of instruments were most consistent, and so which could be used as universal comparison instruments. For O3, regression slopes for the whole campaign agreed within 5% for most instruments despite the use of different cross-sections and wavelength intervals, whereas similar agreement was only achieved for NO2 when the same cross-sections and wavelength intervals were used and only one half-days data was analysed. Mean fractional differences in NO2 from a comparison instrument fall within ±7% (1-sigma) for most instruments, with standard deviations of the mean differences averaging 4.5%. Mean differences in O3 fall within ±2.5% (1- sigma) for most instruments, with standard deviations of the mean differences averaging 2%. Measurements of NO2 in the cell had similar agreement to measurements of NO2 in the atmosphere, but for some instruments measurements with cell and atmosphere relative to a comparison instrument disagreed by more than the error bars.

An overview of the EASOE Campaign

The scientific planning of the EASOE campaign is outlined and the various constituent and meteorological data sets are described.

The vertical distribution of NO3 in the atmospheric boundary layer

Abstract Recent urban measurements suggest that NO 3 concentrations vary significantly with altitude in the lowest few hundred metres of the atmosphere. Calculations using a one-dimensional boundary layer model show that NO 3 concentrations are small near the ground and increase with altitude to a maximum near the top of the nocturnal boundary layer (NBL). These results show that the NBL is not well mixed, and that where there are surface sources and sinks two-box models of the NBL are inadequate, and surface measurements are not representative and may lead to an underestimate of the oxidising capacity of the atmosphere.

Ozone sensors based on WO3: a model for sensor drift and a measurement correction method

The use of a tungstic oxide semiconductor as a sensor for ozone at concentration levels relevant to atmospheric monitoring applications is an important advance in attempts to produce cheap, lightweight and reliable instruments. Problems of stability are a possible obstacle to this application. A model that describes the response of these sensors to ozone is proposed here and using it an explanation for the drift of resistance with time at constant concentrations of ozone is given. Consideration of this drift model enables a measurement routine to be employed that compensates for the drift observed experimentally, thus producing a reliable calibration of the sensor.

Temperature-dependent absorption cross-sections of gaseous nitric acid and methyl nitrate

Abstract Absorption cross-sections for HNO3 and CH3ONO2 were measured in the wavelength region 220–340 nm, using a dual-beam diode array spectrometer, with a spectral resoltuion of 0.3 nm. The results at room temperature were in good agreement with earlier measurements. Absorption over most of the range showed a distinct temperature dependence, with a similar decline in cross-section with decreasing temperature in the range 295-239 K for both molecules. The results have quite large effects on the calculated photodissociation rate of HNO3 in the lower stratosphere, especially at the low temperatures and high solar zenith angles (SZA) characteristics of the polar winter and spring. For example, at 20 km altitude, with an SZA of 80°, the photolysis rate at a temperature of 200 K is approximately a factor of 5 smaller than at 298 K.

Modelling the response of a tungsten oxide semiconductor as a gas sensor for the measurement of ozone

The behaviour of gas-sensitive resistors based on WO3 towards small concentrations of ozone in air can be understood with a simple model involving the reaction of ozone with surface oxygen vacancies. This model has been validated by comparison with experimental results for the effects of varying oxygen partial pressure on the ozone response. A complete description of the behaviour of devices constructed by printing WO3 as porous layers onto an impermeable substrate requires consideration of the effects of the microstructure of such a device upon its response. A very simple series-parallel equivalent circuit model captures the effects and allows a simple interpretation of the sensor behaviour, including the quadratic limiting steady state resistance response to ozone and the effects of variation of device thickness. An important fact that allows WO3 to be used at rather high temperatures as an effective ozone sensor is that ozone does not decompose at any discernible rate on the oxide surface. Saturation of the oxide surface at ambient temperature with water vapour inhibits the ozone response when the sensor is subsequently heated. The effect can be removed by heating at sufficiently high temperature. Water vapour also gives a high-temperature sensor response, but appears to act at sites different to those that mediate the response to ozone.

Interpolation errors in UV–visible spectroscopy for stratospheric sensing: implications for sensitivity, spectral resolution, and spectral range

UV-visible measurements of stratospheric constituents require the ratio of a pair of spectra to be determined. If their wavelength calibrations differ and if an array detector is used, at least one spectrum must be interpolated. This introduces error if the spectrum is undersampled; the error is smaller if wavelength stability is good. Increasing the sampling ratio by making the spectral resolution poorer reduces the optical depths of absorption by constituents. Exact values of interpolation errors from real spectra are a difficult topic, but with a theoretical study with a simulated spectrum we show that the sampling ratio should exceed ~4.5 pixels/FWHM but need not exceed 6.5 pixels/FWHM. To avoid significant reduction in the optical depth of NO(2), the resolution should be smaller than ~1.0 nm FWHM. Hence a spectrometer system that measures both OClO and NO(3) by observing one order from one stationary grating should have more than ~1500 pixels, more than many currently available array detectors.