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.     

Determination of chlorinated hydrocarbons introduced into air/acetylene flames by Fourier transform infrared emission spectroscopy

A Fourier transform spectrometer is used to record the infrared emission from chlorinated hydrocarbons combusted in an air/acetylene flame. In this manner, the chlorinated hydrocarbons are determined by monitoring the infrared emission of hydrogen chloride at 2653 cm(-1). Discussion is presented of the air/acetylene flame background, and the potential spectral interference from the emission of deuterated species. Practical detection limits for chloroform, carbon tetrachloride and methylene chloride in acetone, methanol, and ethanol are solvent independent and are found to be 1.1, 0.80, and 1.0%, respectively. Calibration curves for these three analytes are linear from their detection limits to approximately 55% (v/v). In addition, evidence is presented that flame flicker-noise does not lead to a multiplex disadvantage when the Fourier transform instrument is used for data acquisition.     

Mechanical feed burner with total consumption for flame photometry and atomic absorption spectroscopy

A mechanical feed burner has been developed for use in flame photometry and atomic absorption spectroscopy. The optimum flame conditions for cinisaion and absorption are very different. These conditions are also modified when organic instead of aqueous solvents are used. When different organic solvents are used, the interference is eliminated with atomic absorption but not emission. Flame profiles of a.tomic absorption and emission signals indicate that the processes are independent; the best signal for each is obtained at different parts of the flame. With emission, it appears that line spectra and background emission originate from the same process e.g. chemiluminescence     

Study of quenching of S2 emission by addition of oxygen to a hydrogen flame in molecular emission cavity analysis

Interferences of oxygen on S₂ emission were measured for a hydrogen-oxgen flame in molecular emission cavity analysis and are discussed in terms of the emission intensities and temperatures in different regions of the flame. When a little oxygen is added to a hydrogen flame, S₂ emission is usually quenched. It also brings about a reduction in temperature in the lower region of the flame, where a cavity is introduced. However, in a “lower burnt hydrogen-oxygen flame”, in which hydrogen reacts instantly with added oxygen at the burner top, S₂ emission is not quenched by addition of oxygen, and the intensity and the flame temperature increase linearly with increasing oxygen flow-rate. Therefore, it is apparent that an increase in flame temperature is not responsible for the quenching. It is suggested that the existence of unburnt oxygen in the lower region of the flame can cause the quenching owing to the destruction of S₂ molecules to form sulphur-oxygen compounds.     

Emission spectra of nitrous oxide supported acetylene flames at atmospheric pressure

The emission spectra of a premixed flame of acetylene supported by nitrous oxide have been recorded under different fuel-gas mixture conditions. The emission spectra in these flames of a series of metals, for which it is difficult to obtain a significant population of ground state atoms for atomic absorption spectroscopy in more conventional flames, have also been studied. The red secondary zone which is present in the fuel-rich flames shows emission attributable to long-lived CN and NH species which form a strongly reducing atmosphere to inhibit refractory oxide formation from elements such as molybdenum, titanium and aluminium introduced into the flame. An attempt has also been made to explain some of the reactions which may occur between the flame species above the primary reaction zone.     

Improvements in thermospray flame furnace atomic absorption spectrometry

In thermospray flame furnace atomic absorption spectrometry (TS-FF-AAS) a nickel atomization tube is placed in the acetylene/air flame on a holder built onto a standard AAS burner head. The liquid to be analyzed is transported by a low or high-pressure pump through a very hot, simple, inexpensive ceramic capillary tip acting as a flame-heated thermospray into the flame furnace. This results in complete sample introduction and increases the residence time of the sample in the absorption volume. This leads for 17 elements to a 3-110-fold improvement in the power of detection compared to conventional flame AAS. The absolute detection limits (3s values, N=25) lie between 0.2 μg l⁻¹ (Zn) and 310 μg l⁻¹ (Se) according to the element. The R.S.D. (N=15) is 1.4-5.5% according to the element and applied concentration. TS-FF-AAS can easily be incorporated on any standard flame AAS instrument and can be automated with a standard autosampler.     

Improvements in derivative-corrected nitrous oxide-acetylene flame emission spectrometry

The use of repetitive optical scanning in the derivative mode has been thoroughly evaluated for flame emission spectrometry with a nitrous oxide-acetylene flame. Most of the detection limits obtained were the best reported for flame emission spectrometry. A comparison has been made between atomic absorption and inductively coupled plasma spectrometry. The flame emission technique was found to be complementary to and highly competitive with both techniques.     

Studies in atomic-fluorescence spectroscopy-VII Fluorescence and analytical characteristics of arsenic, with a microwave excited electrodeless discharge tube as source

The construction of an electrodeless arsenic discharge tube and its use for atomic-fluorescence studies is described. Cool nitrogen-hydrogen and argon-hydrogen diffusion flames as well as normal premixed flames are considered as atom reservoirs and the atomic-fluorescence emission at 15 different wavelengths is evaluated. The diffusion flames give the largest emission signals at arsenic concentrations below 200 ppm, but show a premature curvature at higher concentrations because of the presence of an abnormally high density of arsenic atoms. Above 200 ppm of arsenic, the premixed air-acetylene flame is superior. The limit of detection at 1890 A is 0.2 ppm of arsenic in the nitrogen-hydrogen diffusion flame and 1.0 ppm in the airacetylene flame. A long path-length diffusion flame is also particularly useful in atomic-absorption measurements because it absorbs very little radiation in the far ultraviolet region and gives an abundance of arsenic atoms.     

Statistical evaluation of the performance of a new programmed-scan monochromator for multielement determinations by atomic emission

The reproducibility of a programmed-scan monochromator with stationary dispersion optics was evaluated by means of analysis of variance (ANOVA). The spectrometer used an optical multiplexer coupled with glass-fiber optic light-guides to a multiple entrance-slit spectrometer employing a photomultiplier as the detector. With this spectrometer, 15 emission intensity measurements at the lithium resonance line wavelength (670.7 nm) were collected for five rotations of the optiplexer mirror under four different emission situations: flame background emission at 670.7 nm, lithium emission from an acetylene-air flame in the absence of an ionization buffer, lithium emission from an acetylene-air flame in the presence of an ionization buffer, and tungsten lamp emission at 670.7 nm. For all four situations, the ANOVA results showed that instrumental changes which occurred during mirror rotation in the optiplexer were a significant source of signal variation compared with factors not associated with mirror rotation, i.e., photon shot noise, source fluctuation noise, and electronic drift. The actual magnitude of the signal variability introduced during mirror rotation, however, was found to be quite small, producing an average relative standard deviation of only 0.76% for the signal.     

Construction and performance of a time-multiplex multiple-slit flame atomic fluorescence spectrometer for multi-element analysis

The design and performance characteristics of a new multi-element flame atomic fluorescence spectrometer are presented. Radiation from four hollow-cathode tubes is directed onto an unsheathed air—hydrogen flame. The resulting atomic fluorescence is viewed by a special monochromator with a separate exit slit for each element. The light exiting from all slits is directed to a single photomultiplier tube. The fluorescence signals from different elements are distinguished by a time multiplex approach. Single-element detection limits for ten elements and multi-element detection limits for four elements are presented. The degradation of detection limits by flame background emission noise and effect of flame composition on performance are discussed. Better than 1% precision is obtained for moderate analyte concentrations.     

Qualitative and quantitative sensitivity in flame photometry

Concepts of sensitivity in flame photometry are discussed. A distinction is made between sensitivity itself, concentration limits and dilution limits applied to qualitative and quantitative analysis by flame photometry. Sensitivity values, as well as the concentration limits, are considered from two different aspects: as a function of the slope of calibration curves-percentual values-and as a function of fluctutions-fluctuational values. The concepts are applied to the two main branches of flame photometry, emission and absorption.     

Atomic spectrometry and flow injection analysis: a synergic combination

The combination of flow-injection techniques with atomic spectrometry (flame atomic absorption and emission spectrometry and inductively-coupled plasma/atomic emission spectrometry) is reviewed, with particular reference to the more recent contributions. The considerable growth in the number of directly couple pre-concentration and matrix isolation is noted, together with the increasing number of reports of indirect methods for metals, inorganic anions and even drug molecules. Many developments are motivated by a desire to increase the performance of the spectrometry over that obtained with conventional methods of sample introduction. Conflicting statements concerning the possible benefits of reduced uptake rate, of air compensation and of peak-area measurement are examined critically. The conflicting requirements of obtaining freedom from stable-compound interferences coupled with god detection limits are discussed, as are means of obtaining the best detection limits. Modifications to nebuliser and spray-chamber design are suggested for maximising peak height (to obtain detection limits) and for working with reduced uptake rates (to reduce stable-compound interferences in flame-based spectrometries). The single well-stirred tank model is used to model nebuliser response and results are presented for the flow-injection behaviour of a Philips Scientific SP9 instrument under conditions of low flow rate which show reasonable agreement with the model. With the instrument, the best detection limits are obtained on the basis of peak-height measurements at the flow rate producing maximum signal-to-noise ratio.     

Comparison of atomic fluorescence power efficiencies for the helium-oxygen-acetylene and air-acetylene flames

Power efficiencies for five elements have been measured for the helium-oxygen-acetylene and air-acetylene flames. The increased power efficiencies found in this study for the helium-diluted flame, coupled with its enhanced atom-formation capabilities, suggest that lower atomic fluorescence detection limits should exist. However, in a comparison study with an air-acetylene flame using identical experimental conditions, a decreased atomic fluorescence signal-to-noise ratio was found for most elements in the helium-diluted flame. This decrease is ascribed to greater background emission noise in the hotter helium-diluted flame and decreased nebulization efficiency caused by the low density of the helium-containing nebulizer gas. A comparison of flame emission detection limits for the two flames confirms the increased sensitivity of the hotter helium-oxygen-acetylene flame, despite its lower nebulization efficiency.     

Emission intensity of cesium in flames of various gas compositions

The emission intensity of cesium at 852.1 nm has been studied in hydrogen flames burning with various mixtures of oxygen and nitrogen. A significant maximum was observed in the relative emission intensity of cesium at an oxygen to nitrogen ratio of 3:2 in the aspirating gas. The effect of Rb⁺, K⁺, Li⁺, Na⁺, and NH₄⁺ ions on cesium emission is much less pronounced in this optimum flame than in a pure oxy-hydrogen flame. The optimum flame (60% oxygen) yields a significantly better calibration curve than can be obtained in either the normal air-hydrogen or oxyhydrogen flame for 0–12 p.p.m. cesium concentrations; the graph is linear over this concentration range.     

Elimination of phosphate interference in flame photometric determination of strontium and barium

The interference of phosphate in the flame emission of calcium, strontium and barium was studied. The emission intensity decreases proportionally to the amount of interfering anion up to a maximum depression for equimolar amounts of phosphate to metal. A thermostable phosphate is formed before the cation enters the flame. Appropriate addition of lanthanum restores the three alkaline earth lines to their intensities in absence of phosphate, the lanthanum displacing, the alkaline earths from their phosphates before the hot region of the flame is reached.     

Flame atomic emission determination of rubidium in mineral and well waters using methane-air flame as excitation source

The rubidium content of some well and mineral waters has been determined by flame atomic emission spectrometry using the methane-air flame. Effects of the flame and of instrumental parameters (flame composition, the observation height, spectral bandpass of the monochromator) on the emission of rubidium in methane-air flame was studied and optimized. The best results were obtained using the 780.0 nm rubidium line at the observation height of 11 mm, with the flame composition of 1.12 (relative stoichiometric units, RSU) and the slitwidth of 0.6 mm. The effect of Na, K, Ca and Mg on the emission of rubidium was studied too. The detection limit of 2.3+/-0.9 mug l(-1) was obtained, in the presence of 200 mg l(-1) Cs, at a significance level of 0.05, using the two-step Neyman-Pearson criterion. The rubidium content of waters has been determined directly using both external calibration curve and standard addition method. With background correction results agree between these two methods.     

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.     

The suitability of a flame atomizer in a voigt effect optical filter

A Voigt effect optical filter is described which uses a small flame as a tuning device. The filter selectively transmits the atomic spectra of the element(s) introduced into the flame. Under favourable conditions, e.g., when an atomic spectrum is isolated from a hollow-cathode emission source, no additional wavelength discrimination is needed. The performance of the system is described for emission and absorption measurements.     

Excitation of Species in an Expanded Argon Microwave Plasma at Atmospheric Pressure

The excitation capability of an argon microwave plasma flame expanded at atmospheric pressure has been studied. For this purpose, argon with different proportions of nitrogen was introduced at the end of the expanded flame, where the population densities of the atomic argon levels were still high enough. Optical emission spectra allowed the identification of different excited species in the plasma. When argon containing nitrogen was added at the end of the plasma flame, all argon lines emitted in this region were highly quenched, emission due to species containing nitrogen (NH, CN) was enhanced and a noticeable increase in the emission of N₂ (C ³Π_u ? B ³Π_g) was observed. On the contrary, the weak emission of $ {\text{N}}_{2}^{ + } \left( {B^{ 2} \sum_{u}^{ + } - X^{ 2} \sum_{g}^{ + } } \right) $ was scarcely affected. According to these results it is possible to conclude that metastable argon atoms from the expanded flame are the main energy carriers when generating N₂ reactive species in this plasma zone.     

Some causes of bending of analytical curves in atomic absorption spectroscopy

Some factors affecting the shape of analytical curves in atomic absorption spectroscopy are considered and the influence of the emission and absorption line profiles is discussed in detail. An empirical equation expressing the analytical curves for different ratios of emission line width to absorption line width is given. The possible influence of resonance line broadening and resonance line shift in atomic absorption flame photometry is also discussed.