Analytical techniques, concentration isotopic abundances

The low concentrations of Pb found in Greenland and Antarctic snow and ice makes reliable concentration and isotopic composition measurements difficult to determine. Contamination with anthropogenic Pb during sample collection or drilling must be minimised, then extreme precautions must be taken to access a contamination-free sample (12, 28). Sensitive analytical methods which can analyse pg quantities of Pb are also required. A number of different methods meet this requirement however, discussion in this chapter will be limited to Thermal Ionisation Mass Spectrometry (TIMS) because this is the only technique, to date, to be successfully used to measure isotope abundances in polar ice. IDMS is an integral part of the technique used to measure the isotopic composition of the samples. 

Quantitative mass spectrometry, also used for pharmaceutical appHcations, involves the use of isotopicaHy labeled internal standards for method calibration and the calculation of percent recoveries (9). Maximum sensitivity is obtained when the mass spectrometer is set to monitor only a few ions, which are characteristic of the target compounds to be quantified, a procedure known as the selected ion monitoring mode (sim). When chlorinated species are to be detected, then two ions from the isotopic envelope can be monitored, and confirmation of the target compound can be based not only on the gc retention time and the mass, but on the ratio of the two ion abundances being close to the theoretically expected value. The spectrometer cycles through the ions in the shortest possible time. This avoids compromising the chromatographic resolution of the gc, because even after extraction the sample contains many compounds in addition to the analyte. To increase sensitivity, some methods use sample concentration techniques. 

The contribution of MS to identification of compounds and quantification of their concentration is complementary to other detection techniques and, despite being very practical and versatile, it remains fundamentally replaceable. However, knowledge of molecular weight is a prerequisite for techniques that rely on the synergies with stable isotopic tracers. In fact, powerful analytical methods exist to obtain important insights on cell dynamics from the ratiometric measurement of marked and not-marked species (or atoms). We cite, for example, (1) relative abundances of virtually all metabolites or proteins in two separate cultures are quantified based on the isotope dilution theory [43 5] (2) information on the mechanisms and kinetics of nonlinear chemical processes can be extracted from response tracer experiments [46 7] and (3) the labeling patterns in metabolic intermediates are used to resolve the relative rate in convergent reactions in vivo [48,49]. 

Since the 1950s, when the elemental abundance distribution depicted in Figure 1 became available, significant improvements have occurred in the accuracy with which the Solar System abundances are known. In part this is owing to the realization that Type I carbonaceous chondrites - made up of low-temperature condensates that escaped the many alteration processes which affected other classes of meteorites - closely approximate the condensable fraction of primordial Solar System material, and so represent our best opportunity of obtaining an abundance distribution which approximates reality. Isotope dilution mass spectrometry (IDMS) is an effective analytical method for determining trace element concentrations, because of the excellent sensitivity, accuracy and precision of the technique, and because a quantitative recovery of the element concerned is not required. The abundance of the... 

Qualitative analysis is the process of the determination of the presence (or absence) of a particular element or group of elements in a sample. The ability to perform a comprehensive qualitative analysis is directly related to the sensitivity of the analysis method and hence the detection capability. Ideally, it is desirable to determine major, minor, trace, and ultratrace concentration level elements simultaneously on the same sample aliquot, which requires an instrument and technique that exhibits a wide dynamic range of measurement of the ion currents for the various element isotopes. However, in practice, it is often difficult to determine the high intensity of major elements on the same sample dilution as that required for ultratrace concentration element determination (usually measured on undiluted sample). This problem is often accommodated by the use of very low abundance isotopes of the major concentration analyte, reducing the analysis sensitivity. Where no low abundance isotope is available, instrumentation with dual detectors (electron multiplier for low concentration analytes and Faraday analog detectors for high concentration elements) can be used effectively. 

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