Calcium isotope analysis

Of all of the machines used for microanalysis LAMMA seems to be the most problematic. A laser beam is used to disintegrate a spot in the sample, and the material emitted is then analyzed in a mass spectrometer. It has similar lateral resolution to PIXE, and like SIMS can be used to distinguish between isotopes of the same element. It has, however, proved very difficult to quantify, and is destructive to the specimen. One recent investigation (13) ofthe distribution of stable isotopes of calcium, magnesium, and potassium in Norway spruce used three microprobes EDAX at 0.3 pm lateral resolution isotope specific point analysis, using LAMMA at 1.5 pm lateral resolution and isotope specific imaging using SIMS at 1-3 pm lateral resolution. 

Laser ablation combined with LA-MC-ICPMS provides a new dimension to the analysis of Mg isotopes in calcium aluminum-rich inclusions from primitive meteorites. Dispersion in 26Mg - Al/ Mg evolution lines can be correlated with mass-dependent variahons in 5 Mg that distinguish open-system from closed-system processes. The ultimate product of such studies will be a better understanding of the chronological significance of variations in Mg in these objects. 

Ireland TR, Fahey AJ, Zinner EK (1991) Hibonite-bearing microspherules a new type of refractory inclusions with large isotopic anomalies. Geochim Cosmochim Acta 55 367-379 Johnson CM, Beard BL (1999) Correction of instrumentally produced mass fractionation during isotopic analysis of Fe by thermal ionization mass spectrometry. Int J Mass Spect 193 87-99 Jungck MHA, Shimamura T, Lugmair GW (1984) Calcium isotope variations in Allende. Geochim Cosmochim Acta 48 2651-2658... 

Singh and Wrenn (1988) describe a method for uranium isotopic analysis of air filters. Air filters are ashed, redissolved, and co-precipitated with iron hydroxide and calcium oxalate. The uranium is further purified by solvent extraction and electrodeposition. An alpha spectroscopy detection level of 0.02 dpm/L for in solution was reported (Singh and Wrenn 1988). 

Thermal ionization mass spectrometry has been used extensively in the geological nuclear and analytical sciences for stable isotope measurements A new technique resonance ionization mass spectrometry offers a comprehensive approach to sensitive and selective elemental and isotopic analysis Recent developments in thermal and resonance ionization mass spectrometry are reviewed) and specific applications of the technology to zinc and calcium metabolism studies and to trace element analysis of foodstuffs are summarized ... 

Ml. MacIntyre, I., The flame-spectrophotometric determination of calcium in bio-bgical fluids and an isotopic analysis of the errors in the Kramer-Tisdall procedure. Biochem. J. 67, 164-172 (1957). 

A., and Chiba, M. (2008) Isotopic analysis of calcium in blood plasma and bone from mouse samples by multiple collector-ICP-mass spectrometry. Anal. Sci., 24, 1501-1507. 

Figure 1. Schematic representation of the calcium mass spectrum in (a) natural materials, (b) a Ca- Ca tracer solution used for separating natural mass dependent isotopic fractionation from mass discrimination caused by thermal ionization, and (c) a typical mixture of natiwal calcium and tocer calcium used for analysis. The tracer solution has roughly equal amounts of Ca and Ca. In (c) the relative isotopic abundances are shown with an expanded scale. Note that in the mixed sample, masses 42 and 48 are predominantly from the tracer solution, and masses 40 and 44 are almost entirely from natural calcium. This situation enables the instrumental fractionation to be gauged from the Ca/ Ca ratio, and the natural fractionation to be gauged from the sample Ca/ Ca ratio.

Ca = 0.000031, and Ca = 0.001824. The high relative abundance of °Ca (a result of its mass number A, which is a multiple of 4 and thus exceptionally stable cf section 11.3) is one of the two main problems encountered in this sort of dating (in Ca-rich samples, the relative enrichment in °Ca resulting from °K decay is low with respect to bulk abundance). The other problem is isotopic fractionation of calcium during petrogenesis (and also during analysis see for this purpose Russell et al., 1978). These two problems prevent extensive application of the K-Ca method, which requires extreme analytical precision. The isochron equation involves normalization to the Ca abundance... 

EmUiani C (1966) Paleotemperature analysis of Caribbean core P6304-8 and P6304-9 and a generalized temperature curve for the past 425000 years. J Geol 74 109-126 Emiich K, Ehhalt DH, Vogel JC (1970) Carbon isotope fractionation during the precipitation of calcium carbonate. Earth Planet Sci Lett 8 363-371 Engel MH, Macko SA, SUfer JA (1990) Carbon isotope composition of individual amino acids in the Murchison meteorite. Nature 348 47-49... 

The investigation of body fluids with respect to nutrient (essential) elements and toxic elements -which are challenging topics for analytical chemistry - include the determination of concentrations at the trace and ultratrace level. However, isotope variation and isotope effects (especially of lighter elements such as hydrogen, carbon, nitrogen, oxygen but also of iron and calcium) have also been studied.22 23 The most frequently applied mass spectrometric technique for the analysis of body fluids today, which fulfils all requirements and also results in accurate and precise data, is ICP-MS. 

The presence of radium in biological materials or environmental samples is generally determined by virtue of its radioactivity. Except in the laboratory where radium compounds have been isolated and determined for a certain purpose, determination of radium compounds in biological and environmental samples is relatively rare. As a Group IIA alkaline earth element, radium is similar in its chemical behavior to other members of that group, especially its nearest neighbor, barium. For example, radium tends to precipitate as the sulfate, which is the basis for its isolation for chemical analysis by coprecipitation with barium sulfate. Furthermore, radium associates with calcium in living systems and accumulates in bone. The determination of radium compounds or specific isotopes is usually accomplished by a separation procedure, followed by quantitative analysis of total radium based on its radioactivity. 

Among the commonly observed spectral overlap problems due to molecular oxide and molecular hydroxide ions are those due to TiO+ (with 5 isotopes of Ti from mass 46 to 50) that result in overlaps with a minor isotope of nickel, 62Ni+ both isotopes of copper, 63Cu+ and 65Cu + and the two major isotopes of zinc, MZn+ and 66Zn+. Calcium oxide and hydroxide ions overlap with all five isotopes of nickel, both isotopes of zinc, and three of the four isotopes of iron. The analysis of rare earth elements is particularly complicated by molecular oxide and hydroxide ion spectral overlaps [141,142]. 

Calcium-aluminum-rich inclusions The CAIs reveal a lot of isotopic action in calcium. But 4°Ca itself is taken as a reference for other isotopes because it is the most abundant. What is measured is the ratio of the other Ca isotope abundances to that of 4°Ca therefore attribution of an anomalous isotopic ratio to an anomaly in 4°Ca abundance is seldom made. Because of systematic linear variations with isotopic mass of the measured isotopic abundances, moreover, it is common to remove that effect by defining the ratio 44Ca/4°Ca as normal, a doubtful procedure, but common. Anomalies in other Ca isotopes thus appear as deviations from the linear slope set by the 44Ca/4°Ca ratio. All this is to say that a self-consistent analysis of the entire Ca suite is required. 

Thermal ionization has been used to determine isotopic abundance of virtually all the elements We have recently extnded our own capability in this direction by adapting the silica gel/phosphoric acid filament coating technique (5) to our system Five 1 of a fine silica gel suspension is placed on a filament Five l of the analyte ion solution is coated, dried then coated with 2 pi of a 0 7N phosphoric acid solution and heated until dry again The analysis is performed in a similar manner as before, except that the signal is more transient and somewhat less intense than the calcium analysis With this approach, however, we have made natural abundance isotope ratio measurements on zinc, copper, and magnesium Table II shows our measurements compared to the accepted values, shown in parenthesis, for these elements The isotope used as reference... 

The SAAM (Simulation, Analysis And Modeling) computer program developed by Berman and Weiss (8) was used to analyze the isotope dilution and balance data. The observed time dependent dilution of both calcium tracers in plasma, as reflected in urine at longer times, coupled with their cumulative appearance in urine and feces is used to calculate kinetic parameters of the model. The balance data are then used to calculate the steady state... 

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