David E. Eckels

Spatiotemporal characteristics of the inductively coupled plasma

A previously unrecognised source of noise in inductively coupled plasma (ICP) atomic emission spectrometry was identified with a combination of high-speed motion picture photography and noise spectrum analysis. The noise mechanism is a fluid mechanics phenomenon and involves axisymmetric oscillations of the plasma as the plasma gases flow from the torch into the surrounding static atmosphere. The oscillations develop into vortex rings with increasing height above the torch. As these plasma oscillations pass through the optical axis of the measurement system they produce periodic variations in the analytical signal, typically in the 100–600 Hz range. The frequencies of the oscillations observed in the films agreed with the frequencies of the major noise peaks in the noise power spectra. Knowledge of this noise phenomenon is relevant to studies of the fundamental properties of the ICP and its applications.

Spectral line-diode registry effects with photodiode array detectors

A limitation of photodiode array detectors for spectroscopic intensity measurements relates to the spacing of the diodes and the errors generated when a spectral line is not in exact registry with the diode or diodes from which its intensity is being measured. These misregistry intensity errors, which may be as high as 25 to 30%, are documented for a range of spectral bandwidths and for single diode (pixel) intensities and multiple diode summations of intensities.

AOTF-echelle spectrometer for air-ICP-AES continuous emission monitoring of heavy metals and actinides

A spectrometer system consisting of a quartz acousto-optic tunable filter (AOTF) and an echelle grating has been assembled and tested for ICP-AES continuous emission monitoring of heavy metal and actinide elements in stack exhaust offgases introduced into an air plasma. The AOTF is a rapidly tunable bandpass filter that is used to select a small wavelength range (0.1 to 0.6 nm) of optical emission from the air plasma; the echelle grating provides high dispersion, yielding a spectral resolution of approximately 0.004 to 0.008 nm from 200 to 425 nm. The AOTF-echelle spectrometer, equipped with a photodiode array or CCD, provides rapid sequential multielement analysis capabilities. It is much more compact and portable than commercial ICP-AES echelle spectrometers, allowing use of the system in field and on-line process monitoring applications. Data will be presented that detail the resolution, detection limits, capabilities, and performance of the AOTF-echelle spectrometer for continuous emission monitoring of heavy metals (As, Be, Cd, Cr, Hg, and Pb) and actinides (including U isotopes). The potential use of the AOTF-echelle spectrometer with other emission sources and for other monitoring applications will be discussed.

Development of Mercury and Hydrogen Chloride Emission Monitors for Coal Gasifiers

The gas conditioning issues involved with coal gasification streams are very complex and do not have simple solutions. This is particularly true in view of the fact that the gas conditioning system must deal with tars, high moisture contents, and problems with NH{sub 3} without affecting low ppb levels of Hg, low levels (low ppm or less) of HCl, or the successful operation of conditioner components and analytical systems. Those issues are far from trivial. Trying to develop a non-chemical system for gas conditioning was very ambitious in view of the difficult sampling environment and unique problems associated with coal gasification streams. Although a great deal was learned regarding calibration, sample transport, instrumentation options, gas stream conditioning, and CEM design options, some challenging issues still remain. Sample transport is one area that is often not adequately considered. Because of the gas stream composition and elevated temperatures involved, special attention will need to be given to the choice of materials for the sample line and other plumbing components. When using gas stream oxidation, there will be sample transport regions under oxidizing as well as reducing conditions, and each of those regions will require different materials of construction for sample transport. The catalytic oxidation approach worked well for removal of tars and NH{sub 3} on a short term basis, but durability issues related to using the catalyst tube during extended testing periods still require study.

A continuous sampling air-ICP for metals emission monitoring

An air-inductively coupled plasma (air-ICP) system has been developed for continuous sampling and monitoring of metals as a continuous emission monitor (CEM). The plasma is contained in a metal enclosure to allow reduced-pressure operation. The enclosure and plasma are operated at a pressure slightly less than atmospheric using a Roots blower, so that sample gas is continuously drawn into the plasma. A Teflon sampling chamber, equipped with a sampling pump, is connected to the stack that is to be monitored to isokinetically sample gas from the exhaust line and introduce the sample into the air-ICP. Optical emission from metals in the sampled gas stream is detected and monitored using an acousto-optic tunable filter (AOTF)-echelle spectrometer system. A description of the continuous sampling air-ICP system is given, along with some preliminary laboratory data for continuous monitoring of metals.