Limit atomic absorption spectroscopy

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. 

Atomic absorption spectroscopy is more suited to samples where the number of metals is small, because it is essentially a single-element technique. The conventional air—acetylene flame is used for most metals however, elements that form refractory compounds, eg, Al, Si, V, etc, require the hotter nitrous oxide—acetylene flame. The use of a graphite furnace provides detection limits much lower than either of the flames. A cold-vapor-generation technique combined with atomic absorption is considered the most suitable method for mercury analysis (34). 

Atomic absorption spectroscopy is an alternative to the colorimetric method. Arsine is stiU generated but is purged into a heated open-end tube furnace or an argon—hydrogen flame for atomi2ation of the arsenic and measurement. Arsenic can also be measured by direct sample injection into the graphite furnace. The detection limit with the air—acetylene flame is too high to be useful for most water analysis. 

Atomic absorption spectroscopy of VPD solutions (VPD-AAS) and instrumental neutron activation analysis (INAA) offer similar detection limits for metallic impurities with silicon substrates. The main advantage of TXRF, compared to VPD-AAS, is its multielement capability AAS is a sequential technique that requires a specific lamp to detect each element. Furthermore, the problem of blank values is of little importance with TXRF because no handling of the analytical solution is involved. On the other hand, adequately sensitive detection of sodium is possible only by using VPD-AAS. INAA is basically a bulk analysis technique, while TXRF is sensitive only to the surface. In addition, TXRF is fast, with an typical analysis time of 1000 s turn-around times for INAA are on the order of weeks. Gallium arsenide surfaces can be analyzed neither by AAS nor by INAA. 

Mullins [ 189] has described a procedure for determining the concentrations of dissolved chromium species in seawater. Chromium (III) and chromium (VI) separated by coprecipitation with hydrated iron (III) oxide and total dissolved chromium are determined separately by conversion to chromium (VI), extraction with ammonium pyrrolidine diethyl dithiocarbamate into methyl isobutyl ketone, and determination by atomic absorption spectroscopy. The detection limit is 40 ng/1 Cr. The dissolved chromium not amenable to separation and direct extraction is calculated by difference. In the waters investigated, total concentrations were relatively high, (1-5 pg/1), with chromium (VI) the predominant species in all areas sampled with one exception, where organically bound chromium was the major species. 

In contrast, the coupling of electrochemical and spectroscopic techniques, e.g., electrodeposition of a metal followed by detection by atomic absorption spectrometry, has received limited attention. Wire filaments, graphite rods, pyrolytic graphite tubes, and hanging drop mercury electrodes have been tested [383-394] for electrochemical preconcentration of the analyte to be determined by atomic absorption spectroscopy. However, these ex situ preconcentration methods are often characterised by unavoidable irreproducibility, contaminations arising from handling of the support, and detection limits unsuitable for lead detection at sub-ppb levels. 

Petit [563] has described a method for the determination of tellurium in seawater at picomolar concentrations. Tellurium (VI) was reduced to tellurium (IV) by boiling in 3 M hydrochloric acid. After preconcentration by coprecipitation with magnesium hydroxide, tellurium was reduced to the hydride by sodium borohydrate at 300 °C for 120 seconds, then 257 °C for 12 seconds. The hydride was then measured by atomic absorption spectroscopy. Recovery was 90 - 95% and the detection limit was 0.5 pmol/1. 

Agemian and Chau [55] have described an automated method for the determination of total dissolved mercury in fresh and saline waters by ultraviolet digestion and cold vapour atomic absorption spectroscopy. A flow-through ultraviolet digester is used to carry out photo-oxidation in the automated cold vapour atomic absorption spectrometric system. This removes the chloride interference. Work was carried out to check the ability of the technique to degrade seven particular organomercury compounds. The precision of the method at levels of 0.07 pg/1, 0.28 pg/1, and 0.55 pg/1 Hg was 6.0%, 3.8%, and 1.00%, respectively. The detection limit of the system is 0.02 pg/1. 

Limit of detection The method you choose must be able to detect the analyte at a concentration relevant to the problem. If the Co level of interest to the Bulging Drums was between 1 and 10 parts per trillion, would flame atomic absorption spectroscopy be the best method to use As you consider methods and published detection limits (LOD), remember that the LOD definition is the analyte concentration producing a signal that is three times the noise level of the blank, i.e., a S/N of 3. For real-world analysis, you will need to be at a level well above the LOD. Keep in mind that the LOD for the overall analytical method is often very different than the LOD for the instrumental analysis. 

High-performance liquid chromatography coupled with fluorescence detection [106, 107] or ion-exchange high-performance liquid chromatography with detection by graphite furnace atomic absorption spectroscopy [108] proved to be sensitive methods, but may lack from limitations in separation power and ease of identification of unknown products. 

The major anions and cations in seawater have a significant influence on most analytical protocols used to determine trace metals at low concentrations, so production of reference materials in seawater is absolutely essential. The major ions interfere strongly with metal analysis using graphite furnace atomic absorption spectroscopy (GFAAS) and inductively coupled plasma mass spectroscopy (ICP-MS) and must be eliminated. Consequently, preconcentration techniques used to lower detection limits must also exclude these elements. Techniques based on solvent extraction of hydrophobic chelates and column preconcentration using Chelex 100 achieve these objectives and have been widely used with GFAAS. 

Li or a Li compound in the flame gives a bright crimson color due to its emission of670.8 nm photons produced by the short-lived species LiOH. This is the property that allows for the spectrophotometric determination of Li by atomic absorption spectroscopy (AAS) down to 20 ppb. Inductively-coupled plasma emission spectroscopy (ICPAES), inductively-coupled plasma mass spectroscopy (ICPMS), and ion chromatography (IC) improve this limit to about 0.1 ppb. A spot test for detection of Li down to 2 ppm is provided by basic KIO4 plus FeCl3. 

ICP offers good detection limits and a wide linear range for most elements. With a direct reading instrument multi-element analysis is extremely fast. Chemical and ionization interferences frequently found in atomic absorption spectroscopy are suppressed in ICP analysis. Since all samples are converted to simple aqueous or organic matrices prior to analysis, the need for standards matched to the matrix of the original sample is eliminated. 

Howlett and Taylor (1978) used an atomic absorption spectroscopy fitted with a micro-cup assembly (MCAAS) for determining silver levels in human whole blood. The MCAAS technique affords a rapid, precise, and relatively simple method for the measurement of silver in blood. Furthermore, this technique requires no sample preparation prior to analysis except pipetting and drying. A detection limit level of 0.27 pg/100 ml of blood sample was measured. Flowlett and Taylor (1978) noted that repeated measurement of silver in blood using a single nickel cup showed a gradual decrease in sensitivity. 

In EMEP, ICP-MS is dehned as the reference technique. The exception is mercury, where cold vapor atomic fluorescence spectroscopy (CV-AFS) is chosen. Other techniques may be used, if they are shown to yield results of a quality equivalent to that obtainable with the recommended method. These other methods include graphite furnace atomic absorption spectroscopy (GF-AAS), flame-atomic absorption spectroscopy (F-AAS), and CV-AFS. The choice of technique depends on the detection limits desired. ICP-MS has the lowest detection limit for most elements and is therefore suitable for remote areas. The techniques described in this manual are presented with minimum detection limits. Table 17.2 lists the detection limits for the different methods. 

To date, there is limited published material concerning the pharmacokinetics of vanadium compounds in humans. The concentration of vanadium in humans not dosed with the metal is extremely low and at the limits of detection of many of the analytical techniques used. It is not possible to ascertain if the large differences observed in different populations are the result of environmental exposure or experimental variability. Studies using blood have shown vanadium levels of 0.4 to 2.8 pg/L in normal people. The serum contains the largest amount of vanadium with concentration values ranging from 2 to 4 pg/L using atomic absorption spectroscopy [90], The upper limit of vanadium in the urine of normal people was reported to be 22 pg/L, with excretion values averaging below 8 pg/24 h. Vanadium is widely available in nutrition stores for athletes, who believe it to be a nonsteroidal compound that increases muscle mass at a dose of approximately 7 to 10 mg day, without any reports of toxicity [91]. 

Belal et al [40] reported on the use of flame atomic absorption spectroscopy (FAAS), coupled with ion-exchange, to determine EDTA in dosage forms. EDTA is complexed with either Ca(II) or Mg(II) at pH 10, and the excess cations retained on an ion-exchange resin. At the same time, the Ca(II) or Mg(III) EDTA complexes are eluted and determined by AAS. Calibration curves were found to be linear over the range of 4-160 and 2-32 pg/mL EDTA when using Ca(II) or Mg(II), respectively. The method could be applied to eye drops and ampoules containing pharmaceuticals. Another combined AAS flow injection system was proposed for the determination of EDTA based on its reaction with Cu(II). The calibration curve was linear over the range of 5-50 pg/mL, with a limit of detection of 0.1 pg/mL [41]. 

The base promotes the formation of a phenolate ion, which undergoes a one-electron oxidation to form Cu(I) and a phenoxy radical. Two of these radicals combine to give the 4,4/-dihydroxybiphenyl compound, which can be further dehydrogenated to give the diphenoquinone. Within the detection limit of atomic absorption spectroscopy no Cu was observed in solution. Cu retention on the molecular sieve in this case is favored by the apolarity of the solvent, the absence of competing anions (e.g., acetate in solution), and the presence of base, with the latter promoting formation of copper hydroxides. 

Until now we have used the database for a very simple purpose, namely to extract information from a single file. However, it is also possible to connect several files. Let us suppose that we want to use dBASE for the following problem. In atomic absorption spectroscopy (AAS), one has to choose between the flame and the (flameless) graphite tube methods. The flame methods does not have such a low detection limit as the graphite tube, but it is easier to handle, less prone to interferences and more robust. For that reason the user s strategy will often be to apply the flame method above a certain concentration limit and the flameless method below it. The flame method has its own experimental characteristics and we suppose that we have another database file in which the characteristics for flame methods are given per element. In that case, we would like the consultation to go like this ... 

Table 11.5 Detection Limits (ng/mL = ppb) for Selected Elements by Atomic Absorption Spectroscopy (AAS), Atomic Emission Spectroscopy (AES), and Atomic Fluorescence Spectroscopy (AFS) [6]...

Barrier-layer cells and photomultipher tubes have both been used for photodetection in atomic absorption spectroscopy. The use of barrier-layer cells of course is limited by their sensitivity and the diflBculty encountered in amplifying their output. They will suflBce where determination of the alkali elements is desired only. For most other work photomultiplier tubes are necessary. These are available for a broad spectral... 

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