Theoretical multiplex gain in a UV/VIS Hadamard transform spectrometer utilizing a uniformly imperfect encoding mask

The effect of a uniformly imperfect (non-ideal) encoding mask on the signal-to-noise ratio improvement in a Hadamard transform spectrometer utilizing photon detection is theoretically studied. General equations are developed for the calculation of the multiplex gain (the Fellgett advantage) under conditions of limitation by shot noise and source-fluctuation noise. It is shown that for both cases, the multiplex gain depends on the transmission properties of the encoding mask, the UV/VIS spectrum impinging upon the mask, and the multiplex size, N. It is demonstrated that a uniformly imperfect encoding mask allows sufficient multiplex gain, and that photon-detection in Hadamard transform spectrometry can have advantages in some spectroscopic applications. In addition, comparisons are made between the multiplex gain advantages present in UV/VIS FTS and those present in UV/VIS HTS.     

Atomic fluorescence and atomic emission measurements with an image dissector echelle spectrometer

This paper deals with the investigation of an image dissector echelle spectrometer as an analytical instrument for flame atomic fluorescence spectrometry and for flame atomic emission spectroscopy. The fluorescence was induced by high-pressure xenon arc lamps, which emitted continuum spectra and had higher power ratings, i.e. 1.6 and 2.5 kW, than those normally used for the same purpose. The experimental set-up included two different types of premix burners and one type of total consumption burner. A spherical reflector was applied to improve the utilization of the fluorescence radiation. Two different coatings were tested. None gave the expected enhancement.Detection limits and growth curves were measured for 8 different elements (Ca, Co, Cu, Fe, K, Mg, Na and Ni) in a non-separated air/acetylene flame. The attained detection limits were found to be equally good or somewhat better in flame atomic fluorescence excited with continuum sources than previously reported in the literature, i.e. using similar flames. In flame atomic emission spectroscopy better detection limits have been reported before.     

Limits of detection for an AOTF-FFP spectrometer in ICP atomic emission spectroscopy

Limits of detection for a number of elements both in air and in argon inductively coupled plasma atomic emission spectroscopy (ICPAES) have been determined using a high-resolution interferometric spectrometer (HiRIS) that consists of an acousto-optic tunable filter, a fiber-optic Fabry-Perot interferometer, and a photon-counting PMT detector. Detection limits using the HiRIS are comparable to those determined using a 1.5 m focal-length grating spectrometer, which has resolution similar to that of the HiRIS. Differences between the two spectrometer systems and the two plasma systems are discussed. The portability and versatility of the HiRIS make it a useful alternative for field or on-line measurements using ICPAES. The high-resolution capabilities allow the HiRIS to replace large grating spectrometers for resolution of isotopic and complex spectra.     

Low power capacitively coupled plasma microtorch for simultaneous multielemental determination by atomic emission using microspectrometers

A new, low power capacitively coupled plasma microtorch (30 W, 13.56 MHz, 0.5 L min^?1 Ar) was investigated in conjunction with commercially available microspectrometers for the simultaneous multielemental analysis by atomic emission spectrometry of liquid samples without desolvation. Emission spectrum is simpler than in ICP-AES, the resonance lines are the most intense, so that a microspectrometer with FWHM of at least 1.5 nm is satisfactory for the record. The deviation from the Boltzmann distribution for Fe I has demonstrated the departure from the LTE in plasma. The non-spectral matrix effects of Li, Na, K, Ca and Mg on analytes emission are depressive and depend on matrix volatility, ionization potential of the interferent and analyte excitation energy. The detection limits (μg mL^?1) are in the range 0.003 (Li) and 1.5 (Mn). The use of the standard additions method allowed the simultaneous determination of elements in environmental certified reference materials with overall recovery of 95 ± 10% and relative standard deviation of 1.7–8.2%. Compared to the traditional ICP, the microtorch has a simple construction, runs at low argon flow and can be integrated in a portable system suitable for in-situ simultaneous determination of elements.     

Interfacing an atomic absorption spectrometer with an inexpensive desktop computer

A Commodore PET microcomputer and a Duoprint electro-sensitive printer are employed, with little additional equipment, to control a Varian-Techtron AA6 spectrometer in conjunction with power supplies, and to process and record the results of atomic absorption and emission measurements.     

Multielement atomic absorption analysis using Hadamard transform spectroscopy with a new computation and superposition procedure

The application of Hadamard transform spectroscopy (HTS) to analytical atomic spectroscopy has been investigated. A theoretical examination of the signal to noise ratio indicates that HTS offers a slight multiplex advantage over single slit scanning of the spectrum for the measurement of intense lines, as in atomic absorption, but is disadvantageous for measuring small signals in atomic emission and fluorescence. Using a simple HT spectrometer Mg and Pb were determined simultaneously by flame atomic absorption spectrometry. Sensitivities similar to those of conventional systems were obtained but, owing to instrumental imperfections and a short data collection time, detection limits were worse. Optimum system performance was obtained when the mask interval width was equal to the width of the image of the spectrometer entrance slit. Greater spectral detail was revealed by superposition of a set of computed spectra in which the starting point of each spectrum was displaced from the others by a distance less than the interval width of the Hadamard mask. This approach gave improved spectra without increased instrumental complexity.     

A radiometrie fourier transform spectrometer for the measurement of downwelling atmospheric emission

Radiometrically accurate downwelling emission from the atmosphere has been measured using a ground-based ambient temperature Michelson interferometer with a liquid-helium-cooled SiAs detector. Measurements were made under a wide range of atmospheric conditions covering very-cold, very-dry, very-clear sky conditions to heavy overcast with traces of sleet. Spectral resolutions of 0.5 and 0,1 cm^–1 were obtained with a radiometric accuracy of less than 0.5 K and a noise level on the order of 0.25 K rms.Overflights were made with the NASA ER2 high altitude research aircraft carrying a similar instrument [1, 2]. Aircraft and ground based LIDAR, radiosonde and other cloud physics experiments were also made at the same time to provide a data set complete enough to enable a much better understanding of the role of thin high clouds in the Earth's radiation balance.Measurements were made over the period from 10/24/86 to 11/21/86 in support of the NOAA/NASA/NSF project FIRE (First ISCCP Regional Experiment).     

Selective ionization for elemental analysis with an ion trap mass spectrometer

The ion storage capacity (<10⁶) of ion trap mass spectrometers (ITMS) can sometimes limit the ability to analyze trace components in complex mixtures. We demonstrate here that resonant laser ablation (RLA) can offer a degree of selectivity in the ionization process, thus allowing the preferential accumulation of analyte ions in the trap. Selectivities of 75 and 50, for chromium and iron, respectively, are reported here for RLA of stainless steel in an ITMS. We offer suggestions to improve both the selectivity and the ionization efficiency, relative to the results reported here.     

Hadamard transform CE-UV detection for biological samples

A Hadamard transform-capillary electrophoresis-UV (HT-CE-UV) detection technique is described for the analysis of biological samples. Pseudorandom injections of sample and buffer according to a simplex matrix obtained from the corresponding Hadamard matrix is performed with conventional capillaries. Alternating injections are achieved with a novel capillary "T" connector created by drilling conventional capillary dimensions through a 1-cm diameter polycarbonate disc. This connector design coupled with a switching system allows for rapid, electrokinetic injections of solution into alternating sample and buffer capillary arms for UV detection. The standard mixtures of nitric oxide (NO) metabolites, nitrite and nitrate, dissolved in physiological saline solution are injected into the separation capillary according to an 83-element injection sequence to obtain a signal-to-noise ratio (S/N) enhancement of ca. 4.5 over a single injection. Nitrite, being the less concentrated metabolite in NO detection and thereby more difficult to detect, was calibrated with the HT-CE-UV method and a limit of detection (LOD) of 0.56 microM was obtained. Rat blood plasma was analyzed with this detection system and demonstrated to be comparable with NO metabolite concentrations of previously published results. This HT-CE-UV method is described where a unique reservoir tube design that contains 8-microL standard nitrite sample volumes is placed over the end of the capillary arm to explore low volume limits for biological samples.     

Automated standardization technique for an inductively-coupled plasma emission spectrometer

The manifold assembly subsystem described permits real-time computer-controlled standardization and quality control of a commercial inductively-coupled plasma atomic emission spectrometer. The manifold assembly consists of a branch-structured glass manifold, a series of microcomputer-controlled solenoid valves, and a reservoir for each standard. Automated standardization involves selective actuation of each solenoid valve that permits a specific mixed standard solution to be pumped to the nebulizer of the spectrometer. Quality control is based on the evaluation of results obtained for a mixed standard containing 17 analytes, that is measured periodically with unknown samples. An inaccurate standard evaluation triggers restandardization of the instrument according to a predetermined protocol. Interaction of the computer-controlled manifold assembly hardware with the spectrometer system is outlined. Evaluation of the automated standardization system with respect to reliability, simplicity, flexibility, and efficiency is compared to the manual procedure.     

Improving precision for laser solid sampling for ICP emission with an array spectrometer

An Excimer laser operating at the wavelength of 308 nm has been used to ablate soil for bulk analysis. The ablated material has been transferred to an array ICP emission spectrometer. In order to avoid a degraded reproducibility due to imhomogeneity, repetitive firings along a sampling line have been done at a firing frequency of 3 Hz. Effects of line length, read delay and internal standardization have been studied.     

Improving precision for laser solid sampling for ICP emission with an array spectrometer

An Excimer laser operating at the wavelength of 308 nm has been used to ablate soil for bulk analysis. The ablated material has been transferred to an array ICP emission spectrometer. In order to avoid a degraded reproducibility due to imhomogeneity, repetitive firings along a sampling line have been done at a firing frequency of 3 Hz. Effects of line length, read delay and internal standardization have been studied.     

Design and evaluation of a new programmed-scan spectrometer for multielement determinations by atomic emission

A new type of programmed-scan monochromator that employs a multiple entrance-slit dispersion system with stationary dispersion optics has been assembled and tested. The instrument uses an optical multiplexer, connected to the multiple entrance-slit spectrometer (MESS) by means of fiber-optic light guides, to illuminate up to eight entrance slits sequentially. A single high-sensitivity relatively inexpensive photomultiplier tube is used as the detector. A microcomputer interfaced with the detector is used to acquire data at a rate of approximately 4 sec per element and to control the optical multiplexer. Detection limits obtained from atomic emission measurements with an acetylene/air flame excitation source are reported for lithium, sodium, calcium, barium and strontium. The influence of signal averaging and sampling rate on system performance has been studied, and it was found that the delay time had essentially no influence on the measured signal-to-noise ratio.     

Applications of gas chromatography with an atomic emission detector

An atomic emission detector for gas chromatography has been developed which is, in principle, capable of detecting selectively any element (except helium) which can elute from a gas chromatographic column. Software methods have been developed so far for 23 elements and on isotope, including all of the organic elements along with mercury, lead, tin, silicon, and deuterium. Element-specific analyses are shown for several petroleum, environmental, and aroma samples. A table for the detector's element-specific detection limits, selectivities, and linear dynamic ranges is given for 12 elements and deuterium.     

Determination of arsenic by continuous hydride generation with direct introduction into an O2-argon microwave plasma torch atomic emission spectrometer

The determination of arsenic was studied with a simple and economic method. A continuous hydride generation system is interfaced to a microwave plasma torch atomic emission spectrometer (MPT-AES). Arsenic hydride is transferred directly and continuously by the carrier gas into the plasma torch without separation of hydrogen. When oxygen is introduced into the outer tube of the plasma torch, the plasma is more stable and has a higher tolerance to hydrogen. The detection limit (3σ) is 5.2 μg/L when the forward power is 100 W with argon as support gas. Application to the standard sample coal fly ash showed a comparable result to the certified quantity.     

Application of generalized standard additions method to inductively coupled plasma atomic emission spectroscopy with an echelle spectrometer and segmented-array charge-coupled detectors

Simultaneous correction for both spectral interferences and matrix effects in inductively coupled plasma atomic emission spectrometry can be accomplished by using the generalized standard additions method (GSAM). Results obtained with the application of the GSAM to the Perkin-Elmer Optima 3000 ICP atomic emission spectrometer are presented. The echelle-based polychromator with segmented-array charge-coupled device detectors enables the direct, visual examination of the overlapping lines Cd(I) 228.802 nm and As(I)228.812 nm. The slit translation capability allows a large number of data points to be sampled; therefore, the advantage of noise averaging is gained. Pure spectra of each of the spectrally active components in the sample can be extracted through the GSAM calculation.     

Instrument for Hadamard transform three-dimensional fluorescence microscope image analysis

An instrument combining fluorescence microscopy with Hadamard transform multiplexed imaging was designed by which a three-dimensional Hadamard transform fluorescence microscopic cell image was obtained. The image can provide useful information including, simultaneously, the apparent dimensions and the shape of the analytical sample, the content and the distribution of some species in it.