Spectrometric technique

Until the last War, variants of optical emission spectroscopy ( spectrometry when the technique became quantitative) were the principal supplement to wet chemical analysis. In fact, university metallurgy departments routinely employed resident analytical chemists who were primarily experts in wet methods, qualitative and quantitative, and undergraduates received an elementary grounding in these techniques. This has completely vanished now. 

Raman spectrometry is another variant which has become important. To quote one expert (Purcell 1993), In 1928, the Indian physicist C.V. Raman (later the first Indian Nobel prizewinner) reported the discovery of frequency-shifted lines in the scattered light of transparent substances. The shifted lines, Raman announced, were independent of the exciting radiation and characteristic of the sample itself. It appears that Raman was motivated by a passion to understand the deep blue colour of the Mediterranean. The many uses of this technique include examination of polymers and of silicon for microcircuits (using an exciting wavelength to which silicon is transparent). 

In addition to the wet and optical spectrometric methods, which are often used to analyse elements present in very small proportions, there are also other techniques which can only be mentioned here. One is the method of mass spectrometry, in which the proportions of separate isotopes can be measured this can be linked to an instrument called a field-ion microscope, in which as we have seen individual atoms can be observed on a very sharp hemispherical needle tip through the mechanical action of a very intense electric field. Atoms which have been ionised and detached can then be analysed for isotopic mass. This has become a powerful device for both curiosity-driven and applied research. 

Another family of techniques is chromatography (Carnahan 1993), which can be applied to gases, liquids or gels this postwar technique depends typically upon the separation of components, most commonly volatile ones, in a moving gas stream. 

Quite generally, each sensitive spectiometric approach today requires instruments of rapidly escalating cost, and these have to be centralised for numerous users, with resident experts on tap. The experts, however, often prefer to devote themselves to improving the instruments and the methods of interpretation so there is a permanent tension between those who want answers from the instruments and those who have it in their power to deliver those answers. 

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Valentin J J 1985 Coherent anti-Stokes spectroscopy Spectrometric Techniques vol 4, ed G A Vanasse (New York Academic) pp 1-62... 

The alkah metals are commonly separated from all other elements except chlorine before gravimetric determination. In the absence of other alkaUes, sodium maybe weighed as the chloride or converted to the sulfate and weighed. WeU-known gravimetric procedures employ precipitation as the uranyl acetate of sodium—2inc or sodium—magnesium. Quantitative determination of sodium without separation is frequently possible by emission or atomic-absorption spectrometric techniques. 

Benzene profile in a fuel-rich propene flame (C/O = 0.77), measured independently with three different mass spectrometric techniques X(. mole fraction, h height above burner. 

Sim PG, Boyd RK, Gershey RM, Gueveemont R, Jamieson WD, Qdilliam MA, and Geegely RJ (1987) A comparison of chromatographic and chromatographic/mass spectrometric techniques for the determination of polycyclic aromatic hydrocarbons in marine sediments. Biomed Environ Mass Spectrosc 14 375-381. 

TABLE 5.2. Representative BDEs for closed-shell organic molecules measured by using mass spectrometric techniques. ... 

Recently, Zewail and co-workers have combined the approaches of photodetachment and ultrafast spectroscopy to investigate the reaction dynamics of planar COT.iii They used a femtosecond photon pulse to carry out ionization of the COT ring-inversion transition state, generated by photodetachment as shown in Figure 5.4. From the photoionization efficiency, they were able to investigate the time-resolved dynamics of the transition state reaction, and observe the ring-inversion reaction of the planar COT to the tub-like D2d geometry on the femtosecond time scale. Thus, with the advent of new mass spectrometric techniques, it is now possible to examine detailed reaction dynamics in addition to traditional state properties." ... 

In this chapter we discuss improvements documented in the literature over the past decade in these areas and others. Chemical procedures, decay-counting spectroscopy, and mass spectrometric techniques published prior to 1992 were previously discussed by Lally (1992), Ivanovich and Murray (1992), and Chen et al. (1992). Because ICPMS methods were not discussed in preceding reviews and have become more commonly used in the past decade, we also include some theoretical discussion of ICPMS techniques and their variants. We also primarily focus our discussion of analytical developments on the longer-lived isotopes of uranium, thorium, protactinium, and radium in the uranium and thorium decay series, as these have been more widely applied in geochemistry and geochronology. 

In addition to instrumental improvements, various approaches have been used to improve the purity or geometry of sources of natural samples for gamma spectrometric measurement. For example, improvements in source preparation for " Th measurement in water and sediment samples by gamma spectrometry are discussed in Cochran and Masque (2003). It should be emphasized that one of the main advantages of gamma spectrometry is ease of use, since in many cases samples may be analyzed directly or with significantly reduced sample preparation compared to alpha, beta, or mass spectrometric techniques. 

Measurement of U-series disequilibria in MORB presents a considerable analytical challenge. Typical concentrations of normal MORB (NMORB) are variable but are generally in the 50-150 ppb U range and 100-400 ppb Th range. Some depleted MORB have concentrations as low as 8-20 ppb U and Th. The concentrations of °Th, Pa, and Ra in secular equilibrium with these U contents are exceedingly low. For instance, the atomic ratio of U to Ra in secular equilibrium is 2.5 x 10 with a quick rule of thumb being that 50 ng of U corresponds to 20 fg of Ra and 15 fg of Pa. Thus, dissolution of a gram of MORB still requires measurement of fg quantities of these nuclides by any mass spectrometric techniques. 

Mass spectrometric techniques for analysis of Th- U disequilibria were first developed to date corals for paleoclimate research (Edwards et al. 1987). Soon thereafter, workers at Los Alamos National Laboratory (LANE) developed methods for silicate analysis by TIMS (Goldstein et al. 1989). Typical TIMS analysis of MORE requires 0.5 to 1 gram of material in order have an analyzable load of 100 ng of Th. TIMS analyses of U and Th last 2-3 hrs and produce a precision of 0.5-2% (2a). SIMS techniques for measuring Th isotopes have also been developed (England et al. 1992 Layne and Sims 2000). Analysis of Ra and Pa isotopes by TIMS was developed in the early 1990 s significantly increasing the sensitivity over decay counting analysis (Volpe et al. 1993 Cohen and Onions 1993 Pickett et al. 1994 Chabaux et al. 1994). 

Of note are the values for °Th and as the revised values postdate the development of mass spectrometric techniques for measurement of U and Th in natural materials. Data published prior to Cheng et al. (2000b) does use not use the revised values whereas data published subsequently may or may not use the new values. The revised half-lives do have a small, but significant effect on calculated °Th ages, particularly ages older than about 100 ka. Furthermore, the new value for the half-life changes values as these are calculated from measured atomic ratios using... 

L234 are about 3 per mil lower than those calculated with commonly used X234 values, hence the revised modem sea water of 145.8 1.7 per mil (Cheng et al. 2000b), compared to earlier values about 3 per mil higher. In general half-lives are now known precisely enough so that their contribution to error in age is comparable to or smaller than typical errors in isotope ratios (determined with mass spectrometric techniques). 

As discussed above, mass spectrometric techniques are the methods of choice for measurement of nuclides pertinent to this study. They supercede earlier decay-counting techniques because of their ability to detect a much larger fraction of the nuclides of... 

Figure 15. Error in age vs. age, both on log scales (after Edwards et al. 1997). Each data point represents data from a particular sample analyzed by thermal ionization mass spectrometric techniques. Solid circles represent Pa ages. Contours of aniytical error in Pa/ U pertain to the Pa data points. Shaded squares represent °Th ages. See text for discussion.

Speleothem frequency distributions have provided a useful tool for broad comparisons, but they suffer from the problem of biased sampling strategies and low resolution at times of known abrupt change. The increased precision afforded by mass-spectrometric techniques will result in fewer studies using this approach to assess of growth frequency and, more often, records of continuous deposition and growth rate studies will be graphically illustrated. 

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