Detection limit, electrons

High-resolution compositional measurements are possible through use of a variety of microanalytical methods. Ideally, these should be non-destructive, can be targeted on small areas of sample, and have low minimum detection limits. Electron-probe X-ray microanalysis (EPXMA) and proton-induced X-ray emission (PIXE) techniques have both been used successfully on archaeological sediment thin sections (19, 20). Both techniques yield elemental composition data for a range of elements. EPXMA has the advantage of being nondestructive, whereas PIXE when used on thin-section samples is typically destructive conversely the detection limit for PIXE is lower than EPXMA. 

The section on Spectroscopy has been expanded to include ultraviolet-visible spectroscopy, fluorescence, Raman spectroscopy, and mass spectroscopy. Retained sections have been thoroughly revised in particular, the tables on electronic emission and atomic absorption spectroscopy, nuclear magnetic resonance, and infrared spectroscopy. Detection limits are listed for the elements when using flame emission, flame atomic absorption, electrothermal atomic absorption, argon ICP, and flame atomic fluorescence. Nuclear magnetic resonance embraces tables for the nuclear properties of the elements, proton chemical shifts and coupling constants, and similar material for carbon-13, boron-11, nitrogen-15, fluorine-19, silicon-29, and phosphorus-31. 

The analysis of mefloquine in blood, using packed-column sfc, a mobile phase consisting of / -pentane modified with 1% methanol and 0.15% -butylamine, and electron capture detection has been reported (92). The method compares favorably to a previously pubflshed hplc-based procedure having a detection limit of 7.5 ng/mLin 0.1 mL blood sample. 

The complex of the following destmctive and nondestmctive analytical methods was used for studying the composition of sponges inductively coupled plasma mass-spectrometry (ICP-MS), X-ray fluorescence (XRF), electron probe microanalysis (EPMA), and atomic absorption spectrometry (AAS). Techniques of sample preparation were developed for each method and their metrological characteristics were defined. Relative standard deviations for all the elements did not exceed 0.25 within detection limit. The accuracy of techniques elaborated was checked with the method of additions and control methods of analysis. 

The method of detecting dimethylterephthalate (DMTP), dibuthyl-phthalate (DBP) and diocthylphthalate (DOP) in aqueous extract is based on their extraction with an organic solvent (hexane) and subsequent concentration using gas-liquid chromatography and an electron-absorbing detector. The detection limit is 0.05 mg/dirf for DMTP and DBP, and 0,01 mg/dm for DOP. 

With modern detectors and electronics most Enei -Dispersive X-Ray Spectroscopy (EDS) systems can detect X rays from all the elements in the periodic table above beryllium, Z= 4, if present in sufficient quantity. The minimum detection limit (MDL) for elements with atomic numbers greater than Z = 11 is as low as 0.02% wt., if the peaks are isolated and the spectrum has a total of at least 2.5 X 10 counts. In practice, however, with EDS on an electron microscope, the MDL is about 0.1% wt. because of a high background count and broad peaks. Under conditions in which the peaks are severely overlapped, the MDL may be only 1—2% wt. For elements with Z < 10, the MDL is usually around 1—2% wt. under the best conditions, especially in electron-beam instruments. 

In summary, CL can provide contactless and nondestructive analysis of a wide range of electronic properties of a variety of luminescent materials. Spatial resolution of less than 1 pm in the CL-SEM mode and detection limits of impurity concentrations down to 10 at/cm can be attained. CL depth profiling can be performed by varying the range of electron penetration that depends on the electron-beam energy the excitation depth can be varied from about 10 nm to several pm for electron-beam energies ranging between about 1 keV and 40 keV. 

One should compare capabilities to the electron beam X-ray emission methods of Chapter 3. The major difference is the higher lateral resolution with electron beams and the associated mapping capabilides. Another difference is the shorter probing depth possible with electrons, except when compared to the specialized TXRF method. Comparing electron-beam EDS to X-ray/particle EDS or electron-beam WDS to X-ray/particle WDS, the electron beams have poorer detection limits because of the greater X-ray bacl ound associated with electron... 

Compared to EDS, which uses 10-100 keV electrons, PEXE provides orders-of-magnitude improvement in the detection limits for trace elements. This is a consequence of the much reduced background associated with the deceleration of ions (called bremsstrahlun compared to that generated by the stopping of the electrons, and of the similarity of the cross sections for ioiuzing atoms by ions and electrons. Detailed comparison of PIXE with XRF showed that PDCE should be preferred for the analysis of thin samples, surfrce layers, and samples with limited amounts of materials. XRF is better (or bulk analysis and thick specimens because the somewhat shallow penetration of the ions (e.g., tens of pm for protons) limits the analytical volume in PIXE. 

PIXE detection limits for surface layers on bulk specimens are sufficiendy low to permit calibradon of true surfe.ce analysis techniques (e.g., Auger electron spectroscopy). 

The detection limit of each element depends upon the electron affinity or ionization potential of the element itself, the chemical nature of the sample in which it is contained, and the type and intensity of the primary ion beam used in the sputtering process. 

Molecular ion mass interferences are not as prevalent for the simpler matrices, as is clear from the mass spectrum obtained for the Pechiney 11630 A1 standard sample by electron-gas SNMSd (Figure 4). For metals like high-purity Al, the use of the quadrupole mass spectrometer can be quite satisfiictory. The dopant elements are present in this standard at the level of several tens of ppm and are quite evident in the mass spectrum. While the detection limit on the order of one ppm is comparable to that obtained from optical techniques, the elemental coverage by SNMS is much more comprehensive. 

Laser ionization mass spectrometry or laser microprobing (LIMS) is a microanalyt-ical technique used to rapidly characterize the elemental and, sometimes, molecular composition of materials. It is based on the ability of short high-power laser pulses (-10 ns) to produce ions from solids. The ions formed in these brief pulses are analyzed using a time-of-flight mass spectrometer. The quasi-simultaneous collection of all ion masses allows the survey analysis of unknown materials. The main applications of LIMS are in failure analysis, where chemical differences between a contaminated sample and a control need to be rapidly assessed. The ability to focus the laser beam to a diameter of approximately 1 mm permits the application of this technique to the characterization of small features, for example, in integrated circuits. The LIMS detection limits for many elements are close to 10 at/cm, which makes this technique considerably more sensitive than other survey microan-alytical techniques, such as Auger Electron Spectroscopy (AES) or Electron Probe Microanalysis (EPMA). Additionally, LIMS can be used to analyze insulating sam-... 

Typical elemental detection limits are listed in Table 1. The detection limit is the concentration that produces the smallest signal that can be distinguished from background emission fluctuations. The continuum background is produced via radiative recombination of electrons and ions e — M+ hv or M + e + e — ... 

The first bioanalytical application of LC-GC was presented by Grob et al. (119). These authors proposed this coupled system for the determination of diethylstilbe-strol in urine as a replacement for GC-MS. After hydrolysis, clean-up by solid-phase extraction and derivatization by pentafluorobenzyl bromide, the extract was separated with normal-phase LC by using cyclohexane/1 % tetrahydrofuran (THE) at a flow-rate of 260 p.l/min as the mobile phase. The result of LC-UV analysis of a urine sample and GC with electron-capture detection (ECD) of the LC fraction are shown in Ligures 11.8(a) and (b), respectively. The practical detection limits varied between about 0.1 and 0.3 ppb, depending on the urine being analysed. By use of... 

Electron paramagnetic resonance spectroscopy (HER), also called electron spin resonance spectroscopy (ESR), may be used for direct detection and conformational and structural characterization of paramagnetic species. Good introductions to F.PR have been provided by Fischer8 and I.effler9 and most books on radical chemistry have a section on EPR. EPR detection limits arc dependent on radical structure and the signal complexity. However, with modern instrumentation, radical concentrations > 1 O 9 M can be detected and concentrations > I0"7 M can be reliably quantified. 

A very sensitive method for the determination of MCA in surfactants is a gas chromatographic one [249]. The method is based on the derivatization of the sample with ethanol and subsequent extraction of the derived ester with cyclohexane. The acids are identified and qualified gas chromatographically by the use of an electron capture detector and two capillary columns of varying polarities. The detection limit is 0.2 ppm. 

The presence of redox catalysts in the electrode coatings is not essential in the c s cited alx)ve because the entrapped redox species are of sufficient quantity to provide redox conductivity. However, the presence of an additional redox catalyst may be useful to support redox conductivity or when specific chemical redox catalysis is used. An excellent example of the latter is an analytical electrode for the low level detection of alkylating agents using a vitamin 8,2 epoxy polymer on basal plane pyrolytic graphite The preconcentration step involves irreversible oxidative addition of R-X to the Co complex (see Scheme 8, Sect. 4.4). The detection by reductive voltammetry, in a two electron step, releases R that can be protonated in the medium. Simultaneously the original Co complex is restored and the electrode can be re-used. Reproducible relations between preconcentration times as well as R-X concentrations in the test solutions and voltammetric peak currents were established. The detection limit for methyl iodide is in the submicromolar range. 

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