The use of macro and micro proton beams to study the variation in PIXE yield from metal targets insulated with PTFE, glass and nylon

Proton beams of diameters of 3 mm and 3 μm, were used to observe the differences in PIXE yield from pure metal targets encapsulated with PTFE, glass (macor) and nylon. The beam energy was kept constant at 700 keV. Beam currents varied from about 200 pA with the microbeam and between 1–10 nA with the macrobeam. Considerable enhancement was observed mainly with the use of PTFE, up to about a factor of 18 with the macrobeam and 306 with the microbeam.     

A review and tutorial discussion of noise and signal-to-noise ratios in analytical spectrometry—II. Fundamental principles of signal-to-noise ratios

This part of the review links up with the tutorial discussion in Part I and gives general signal-to-noise expressions for emission and luminescence spectrometric systems. Tabular presentations are used for the expressions and for comparison of noise sources.     

A review and tutorial discussion of noise and signal-to-noise ratios in analytical spectrometry—I. Fundamental principles of signal-to-noise ratios

This review consists of two parts which discuss signal-to-noise in a tutorial manner. The sources of noise, the mathematical representation of noise, and the major types of noises in emission and luminescence spectrometry are discussed. An extensive treatment of noise and signal-to-noise ratios of paired readings is given using the relation between the auto-correlation function and the spectral noise power. These signal-to-noise expressions under optimized measurement conditions are given in terms of currents and count rates as well as in terms of charge and counts for the cases of d.c. and a.c. measurements; the present treatment is limited to the cases when the background shows only either shot noise or flicker noise. Finally, the consequences of the combination of these noise sources is considered. Signal expressions for optical spectrometry are also given. Tables give the expressions for signal-to-noise ratios in the various cases.     

Spinodal and ideal glass limits for metastable liquids

A spinodal line provides a high-temperature limit to the stability of a superheated liquid and a line of ideal glass transitions may provide a low-temperature limit for a supercooled liquid. For models in which the thermodynamic properties depend on only one independent external variable the line of ideal glass transition can be viewed as a second-order transition between two equilibrated phases and it meets the spinodal with the same slope at the maximum tension a stretched liquid can sustain. For real materials there are two independent external variables, temperature and pressure; the line of ideal glass transitions cannot be viewed as a second-order phase transition and the two lines need not have the same slope where they meet.     

Detection limits in inductively coupled plasma atomic emission spectrometry: an approach to the breakdown of the ratios of detection limits reported for different equipments

Potential OH band interferences were studied for over 100 prominent lines emitted by an inductively coupled plasma (ICP). The basic information was derived from stepped spectral scans obtained with a 1.5-m echelle monochromator with predisperser (Spectrochim. Acta39B 1239 (1984)). The scans were made at both “high resolution” (HR) and “medium resolution” (MR) corresponding to spectral bandwidths of 4–5 pm and 11–16 pm, respectively.The seriousness of OH band interferences was assessed on the basis of the ratio of the limit of determination (c_D) and the limit of detection (c_L) as defined in Parts I and II (Spectrochim. Acta40B, 1085,1107 (1985)). It is shown that the results of an assessment based on this criterion do not strongly depend on the ICP operating conditions.Results are presented for a conventional argon ICP operated under compromise conditions. Appraisals are stated in generalized form for spectral bandwidths of 5 and 15 pm, independent of the apparatus used in this work. Out of the more than 100 prominent lines examined 7 were found to experience very serious OH band interference (c_D/c_L 30) at 5 and/or 15 pm bandwidth. Serious interference (10 c_D/c_L 30) at 5 and/or 15 pm bandwidth was established for 18 lines. OH band interference turned out to be non-existent or negligible for 83 prominent lines.The study also revealed that generally in the case of line overlap it is the limit of determination rather than the limit of detection that should be used as the criterion for the optimization of the ICP parameters.     

Detectors and detection limits in INAA

The kinetic behavior of deuteriation of 2-chloro-, 3-chloro- and 4-chlorobenzoic acids in the presence of homogeneous platinum salt catalyst in a medium containing solution of deuteriated acetic acid in heavy water has been studied at 130°C. The quasiunimolecular H/D exchange rate constants for particular position of aromatic ring hydrogens were determined by¹H NMR integration signal.     

Detectors and detection limits in INAA

Expressions have been derived which link detection limits in INAA with the Ge-detector specifications, provided by the vendors: relative efficiency, peak-to-Compton ratio and resolution. Situations have been distinguished in which a peak has to be detected on a Compton background, or on a natural background. The expressions allow for a direct indication of the improvement in detection limits, or the shortening of tumaround-time to attain equal detection limits, when a given detector is replaced by a detector with better specifications.     

Sub-ppt detection limits for copper ions with Gly-Gly-His modified electrodes

An electrochemical metal ion sensor has been developed with a detection limit of less than 0.2 ppt by the covalent attachment of the tripeptide Gly-Gly-His as a recognition element to a 3-mercaptopropionic acid modified gold electrode.     

A comparison of signal-to-noise ratios for single channel methods (sequential and multiplex) vs multichannel methods in optical spectroscopy

Four major types of spectroscopic systems for quantitative analysis of one or more spectral components we compared, with regard to signal-to-noise ratio for constant analysis time. These four methods are based on sequential-linear scan, sequential-slew scan, multichannel, and multiplex approaches. The multiplex methods can generally be classified into two types, namely Fourier transform spectroscopy and Hadamard transform spectroscopy. It is shown that for the same spectral source, for the same resolving power luminosity product of the optical system, and the same detector, the multichannel approach is the best and the sequential slew scan system is nearly as good for relatively simple spectra in the u.v.- Visible region. Multiplex methods have little to offer in the u.v.- Visible region, where the detector noise limitation seldom applies and where background shot and/or fluctuation noise are dominant but could find considerable use in the u.v.- Visible region for atomic fluorescence or emission spectroscopy especially if the density of spectral lines in the measurement region is not too great and the background intensity is low.     

A review and tutorial discussion of noise and signal-to-noise ratios in analytical spectrometry—III. Multiplicative noises

In this review, signal-to-noise ratios are discussed in a tutorial fashion for the case of multiplicative noise. Multiplicative noise is introduced simultaneously with the analyte signal and is therefore much more difficult to reduce than additive noise. The sources of noise, the mathematical representation of noise, and the major types of noises in emission and luminescence spectrometry are discussed. If the limiting source of noise is multiplicative white noise, the signal-to-noise ratio for optimal sampling time τ_s increases as the square root of the response or integration time of the readout and is independent of the rate at which sample and reference are measured. The variation of multiplicative flicker noise with variation in sampling time, τ_s, time interval between sample and reference measurements, T, and response (τ_r) or integration (τ_i) time is discussed in some detail. The optimal system for the case of multiplicative noise is a dual channel approach in which the sample and reference are measured simultaneously and a ratio of signals is taken. Although the best reference in most cases of interest to analytical chemists is a calibration standard, it is often impossible to measure a sample and a calibration standard simultaneously and so an internal standard, a detector monitoring the source intensity, etc., may be useful.     

Signal processing and detection limits for graphite furnace atomic absorption with Zeeman background correction

The signal handling requirements for graphite furnace atomic absorption are much more demanding than those for flame atomic absorption. Graphite furnace signals change rapidly, background levels are higher, and signal interpretation needs are more extensive.We have identified a number of signal generation and processing factors that are important for success in graphite furnace analyses. These include: use of the transverse, a.c. Zeeman technique with the magnet on the analyte for background correction; production of a series of signal integrals at line frequency to accurately represent the shape of the furnace peak; use of interpolation techniques to better correct for rapidly changing background levels; use of integrated peak absorbance (A.s) signals rather than peak height absorbance for quantitative measurements; use of baseline correction to improve the accuracy of integrated peak absorbance signals; and use of graphical techniques to facilitate data interpretation and methods development.Examples are presented that illustrate the contribution of these factors to precision and detection limit performance. It is possible to improve detection limits over those previously reported by choosing appropriate signal handling parameters.     

Determination and prediction of transfer ratios for anions in capillary zone electrophoresis with indirect UV detection

Transfer ratios (i.e. the number of moles of the UV-absorbing probe anion displaced by one mole of analyte anion) were determined for the separation of inorganic and organic anions by capillary zone electrophoresis using indirect UV absorbance detection. When the electrolyte was buffered and contained only the probe anion and a single counter-cation, transfer ratios calculated from Kohlrausch theory were found to agree well with values obtained experimentally from accurately determined mobility data. However, these electrolyte systems gave long analysis times and were therefore considered impractical. More useful electrolytes were obtained by the addition of surfactants to suppress or reverse the electroosmotic flow but the co-anion introduced with the surfactant can reduce the value of the measured transfer ratio and hence adversely affect sensitivity. This problem was overcome by the use of a surfactant in the hydroxide from such as cetyltrimethylammonium hydroxide combined with a suitable buffering counter-cation such as protonated 1,3-bis[tris(hydroxymethyl)-methylamino]-propane or tris(hydroxymethyl)aminoethane. Four buffered electrolytes consisting of chromate, benzoate, phthalate, or trimellitate as probes and a suitable surfactant were used to determine transfer ratios. These systems were shown to give transfer ratios that were close to those calculated from Kohlrausch theory, thereby enabling prediction of experimental conditions giving maximum transfer ratios.     

Novel potentiometric and optical silver ion-selective sensors with subnanomolar detection limits

Ten Ag⁺-selective ionophores have been characterized in terms of their potentiometric selectivities and complex formation constants in solvent polymeric membranes. The compounds with π-coordination show much weaker interactions than those with thioether or thiocarbamate groups as the coordinating sites. Long-term studies with the best ionophores show that the lower detection limit of the best Ag⁺ sensors can be maintained in the subnanomolar range for at least 1 month. The best ionophores have also been characterized in fluorescent microspheres. The so far best lower detection limits of 3 × 10⁻¹¹ M (potentiometrically) and 2 × 10⁻¹¹ M Ag⁺ (optically) are found with bridged thiacalixarenes.     

A three-layer PMMA electrophoresis microchip with Pt microelectrodes insulated by a thin film for contactless conductivity detection

A three-layer poly (methyl methacrylate) (PMMA) electrophoresis microchip integrated with Pt microelectrodes for contactless conductivity detection is presented. A 50 μm-thick PMMA film is used as the insulating layer and placed between the channel plate (containing the microchannel) and the electrode plate (containing the microelectrode). The three-layer structure facilitates the achievement of a thin insulating layer, obviates the difficulty of integrating microelectrodes on a thin film, and does not compromise the integration of microchips. To overcome the thermal and chemical incompatibilities of polymers and photolithographic techniques, a modified lift-off process was developed to integrate Pt microelectrodes onto the PMMA substrate. A novel two-step bonding method was created to assemble the complete PMMA microchip. A low limit of detection of 1.25 μg ml(-1) for Na(+) and high separation efficiency of 77,000 and 48,000 plates/m for Na(+) and K(+) were obtained when operating the detector at a low excitation frequency of 60 kHz.     

Silver- and Coomassie-staining protocols: detection limits and compatibility with ESI MS

Staining protocols for PAGE have to be sensitive and should not impair further MS analysis of selected samples. In this study, the MS compatibility of different silver- and Coomassie-staining protocols with a nano-LC-MS/MS system was systematically elucidated. Altogether, 13 different silver-staining, 1 imidazole-staining and 2 Coomassie-staining protocols were used and compared to each other for their achieved sequence coverage and their detection sensitivity. Three proteins were used as model proteins (bovine serum albumin, rabbit L-lactate dehydrogenase, bovine milk beta-lactoglobulin) in decreasing concentration (12 pmol down to 30 fmol) and different staining protocols were applied. The conclusion of this study is that two silver-staining protocols (Blum, H. et al.,. Electrophoresis 1987, 8, 93-99 and Shevchenko, A. et al.,. Anal. Chem. 1996, 68, 850-858) combine good sequence coverage and good sensitivity and are recommended for nano-LC-MS/MS analysis.     

Methodologies for the practical determination and use of method detection limits

Underwater NaI(T1) and HPGe detectors are used in the environmental measurements programs at the Savannah River Site (SRS). A 22.9 cm × 10.2 cm NaI(T1) detector on the Savannah River continuously monitors effluent releases from both SRS (DOE) and Plant Vogtle (Georgia Power). Correlations with known releases indicate a sensitivity of 4 mBq/l for⁵⁸Co with 1500 min spectra; such levels are well below those of hazardous or legal concern. A 30%-efficient HPGe detector has appraised radionuclides in SRS cooling pond sediments; the dominant gamma-emitting radionuclide detected was¹³⁷Cs, at levels ranging up to 2.0 MBq/m². The pond activities were adequately quantified by 1 min counts with the HPGe detector; resulting contour maps of sediment¹³⁷Cs provided guidance for partially draining the ponds for dam repairs.     

Computer code for detection limits and type II errors with unequal sample and blank counting times

This paper extends previous work for decision levels to detection limits. After transforming the net count to an integer, the probability density function for the transformed net count can be readily determined when the transformed net count is greater than zero. The right tail of the distribution is summed and the detection limit is determined to four decimal places. The code under discussion works well when the product of the ratio of the blank count time to the sample count time with the expected blank count in the sample count time is not greater than 100.0.     

Comparison of approximate formulas for decision levels and detection limits for paired counting with the exact results

Summary Traceable non-destructive assay standards containing mixtures of well characterized americium and plutonium oxides were prepared by blending weighed quantities with a diatomaceous earth matrix and encapsulating in welded zirconium cylinders. Am and Pu retained in fabrication process materials (e.g., emptied blend bottles), termed holdup, was quantified by gamma-spectroscopy in order to accurately state the total nuclear material content of the standards. The observed holdup data indicate that the common assumption that Am and Pu holdup behavior is similar does not hold up well in the case of mixed oxides.