Zirconium isotopes

Schonbachler M, Rehkamper M, Halliday AN, Lee D, Bourot-Denise M, Zanda B, Hattendorf B, Gunther D (2002) Niobium-zirconium chronometry and early solar system development. Science 295 1705-1708 Schonbachler M, Lee DC, Rehkamper M, Halliday A, Fehr AM, Hattendorf B, Gunther D (2003) Zirconium isotope evidence for incomplete admixing of r-process components in the solar nebula. Earth Planet Sci Lett accepted... 

Zirconium is the principal FP to arise in oxidation state (IV). Where Zircaloy clad fuel is involved, nonradioactive zirconium isotopes may also be present from fuel can residues. As with ruthenium, there may be a variety of nitrato complexes present in the solution including the aquated complexes Zr(N03)s where x = 1-6, and hydroxy nitrato complexes. However, species containing ZrO " " are not expected to be present since this ion is unstable in aqueous media and is rapidly hydrated to Zr(OH)2. The extraction chemistry is further complicated by the formation of inextractable polymeric species when the Zr" concentration exceeds ca. 10 M. An example of such oligomerization is afforded by the [Zr(0H)2(H20)4]4 ion which contains four Zr ions in a square arrangement linked by two /u-OH ligands on each square edge. Four water molecules complete the Zr coordination sphere in an approximately D2d dodecahedral geometry. 

Meyer, B. S. Clayton, D. D. The, L.-S. Molybdenum and Zirconium Isotopes from a Supernova Neutron Burst. Astrophys. J. Lett. 2000, 540,... 

FIG. 15.5. Auto-batch system for identification of short-lived zirconium isotopes. (From Trautmann et al.)... 

Compute the number of protons and neutrons for each zirconium isotope. 

Nudeosynthetic zirconium isotope anomalies in acid leachates of carbonaceous chondrites. Geochim. 

It is possible to increase the fuel efficiency by selecting the zirconium isotope which has the lowest neutron absorption cross section (0.08 bams see Table 7.2) for the fabrication of the zircaloy. Several attempts have been made since the high cost of an enrichment process is a major capital... 

Figure Bl.25.9(a) shows the positive SIMS spectrum of a silica-supported zirconium oxide catalyst precursor, freshly prepared by a condensation reaction between zirconium ethoxide and the hydroxyl groups of the support [17]. Note the simultaneous occurrence of single ions (Ff, Si, Zr and molecular ions (SiO, SiOFf, ZrO, ZrOFf, ZrtK. Also, the isotope pattern of zirconium is clearly visible. Isotopes are important in the identification of peaks, because all peak intensity ratios must agree with the natural abundance. In addition to the peaks expected from zirconia on silica mounted on an indium foil, the spectrum in figure Bl. 25.9(a)...

Zirconium [7440-67-7] is classified ia subgroup IVB of the periodic table with its sister metallic elements titanium and hafnium. Zirconium forms a very stable oxide. The principal valence state of zirconium is +4, its only stable valence in aqueous solutions. The naturally occurring isotopes are given in Table 1. Zirconium compounds commonly exhibit coordinations of 6, 7, and 8. The aqueous chemistry of zirconium is characterized by the high degree of hydrolysis, the formation of polymeric species, and the multitude of complex ions that can be formed. 

Table 21.1 summarizes a number of properties of these elements. The difficulties in attaining high purity has led to frequent revision of the estimates of several of these properties. Each element has a number of naturally occurring isotopes and, in the case of zirconium and hafnium, the least abundant of these is radioactive, though with a very long half-life ( Zr, 2.76%, 3.6 x 10 y Hf, 0.162%, 2.0 X 10 5 y). 

The best sealed-in minerals are zircons, zirconium silicate minerals which are formed when melted lava on the flanks of volcanoes solidifies. When the zircons crystallize out, they incorporate radioactive uranium (in particular 238U), which decays in several steps, leading Anally to the lead isotope 208Pb. The rate of decay is very low, as the half-life of uranium-238 is 4.5 x 109 years. Thus, the U-Pb-zircon method for age determination of Precambrian rock is very important. The fossils studied by Schopf were sandwiched between two lava layers (Schopf, 1999). The volcanic layers were dated to 3.458 0.0019 x 109 years and 3.471 0.005 x 109 years the age of the fossil layer (Apex chert) was thus determined to be about 3.465xlO9 years. 

This useful technique has made many contributions to radio- and nuclear chemistry, although primarily for investigational purposes rather than those of separation for its own ends. Thode and his co-workers have made many investigations into the inert gases produced in fission and it was by these means that the fine structure of fission was first discovered (79), (121). Since then several other elements, the rare-earths, strontium, caesium, zirconium, and molybdenum (35), (50), (132) have been investigated, and the isotopic ratios obtained provide relative values of fission-yields which are more accurate than can be obtained by standard radiochemical means. The latter technique, however, requires rather less heavily irradiated material than the former. 

Meyer BS (1994) The r-, s-,and p-processes in nucleosynthesis. Annu Rev Astronom Astrophys 32 153-190 Mostefaoui S, Lugmair GW, Hoppe P, El Goresy A (2003) Evidence for live iron-60 in Semarkona and Chervony Kut a nanosims study. Lunar Planet Sci XXXIV 1585 Murthy VR, Sandoval P (1965) Chromium isotopes in meteorites. J Geophys Res 70 4379-4382 Nicolussi GK, Davis AM, Pellin MJ, Lewis RS, Clayton RN, Amari S (1997) s-Process zirconium in presolar silicon carbide grains. Science 277 1281-1283... 

Nicolussi GK, Pellin MJ, Lewis RS, Davis AM, Clayton RN, Amari S (1998b) Strontium isotopic composition in individual silicon carbide grains a record of s-process nucleosynthesis. Phys Rev Lett 81 3583-3586 Nicolussi GK, Pellin MJ, Lewis RS, Davis AM, Clayton RN, Amari S (1998c) Zirconium and molybdenum in individual circumstellar graphite grains new data on the nucleosynthesis of the heavy elements. Astrophys J 504 492-499... 

Example The high-resolution spectrum in the molecular ion range of a zirconium complex is typified by the isotopic pattern of zirconium and chlorine (Fig. 3.22). Zr represents the most abundant isotope of zirconium which is accompanied by Zr, r, Zr and Zr, all of them having considerable abun-... 

ISOTOPES Zirconium has 37 isotopes, ranging from Zr-79 to Zr-110. Four of them are stable, and one is a naturally radioactive isotope, with a very long half-life. All five contribute to the element s natural existence on Earth. The stable isotopes are the following Zr-90 = 1.45%, Zr-91 = 11.22%, Zr-92 = 17.15%, and Zr-94 = 17.38%. The one natural radioactive isotope is considered stable Zr-96, with a half-life of 2.2 x 10+ years, contributes 2.80% to zirconium s total existence on Earth. All of the other isotopes are artificially radioactive and are produced in nuclear reactors or particle accelerators. They have half-lives ranging from 150 nanoseconds to 1.53 x 10+ years. 

Zirconium-95 is the most important of the artificial radioactive isotopes of zirconium. It is placed in pipelines to trace the flow of oil and other fluids as they flow through the pipes. It is also used as a catalyst in petroleum-cracking plants that produce petroleum products from crude oil. 

Fig. 5.5. Decomposition of Solar System abundances into r and s processes. Once an isotopic abundance table has been established for the Solar System, the nuclei are then very carefully separated into two groups those produced by the r process and those produced by the s process. Isotope by isotope, the nuclei are sorted into their respective categories. In order to determine the relative contributions of the two processes to solar abundances, the s component is first extracted, being the more easily identified. Indeed, the product of the neutron capture cross-section with the abundance is approximately constant for aU the elements in this class. The figure shows that europium, iridium and thorium come essentially from the r process, unlike strontium, zirconium, lanthanum and cerium, which originate mainly from the s process. Other elements have more mixed origins. (From Sneden 2001.)... 

Resonance-ionization mass-spectrometry is still in the development stage in terms of its application to cosmochemistry. The Charisma instrument, which is operated by Argonne National Laboratories, uses multiple lasers to resonantly ionize only the elements of interest, which are then analyzed with a time-of-flight mass spectrometer. The Charisma instrument has made isotopic measurements of molybdenum, zirconium, strontium, ruthenium, barium and other elements in presolar grains. These measurements are made possible by the high ionization efficiency of the RIMS technique and its ability to completely eliminate isobaric interferences. Work is now underway to build a RIMS instrument that can be operated by an individual investigator in a university laboratory. If this succeeds, RIMS will play an increasing role in analysis of extraterrestrial materials. 

The group IV B elements titanium, zirconium, and hafnium exhibit the normal isotope effect. Most of the data for the titanium-hydrogen system have been obtained at elevated temperatures. However, extrapolation of the available data (II, 13,31) to room temperature indicates a normal effect for hydrogen and deuterium. The group VB metals vanadium, niobium, and tantalum, on the other hand, exhibit inverse isotope effects indeed, these are the only pure metals that exhibit the inverse effect near room temperature. Extensive data have been reported for these systems. The P-C-T data obtained by Wiswall and Reilly (32) for vanadium hydrogen and deuterium clearly show a greater stability for... 

Physical Properties. Hafnium is a hard, heavy, somewhat ductile metal having an appearance slightly darker than that of stainless steel. The color of hafnium sponge metal is a dull powder gray. Physical properties of hafnium are summarized in Table 1. These data are for commercially pure hafnium which may contain from 0.2 to 3% zirconium. Although a number of radioactive isotopes have been artificially produced, naturally occurring hafnium consists of six stable isotopes (Table 2). Hafnium crystallizes in a body-centered cubic system which transforms to a hexagonal close-packed system below 2033 K. 

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