Zirconium elemental abundances

The refractory component comprises the elements with the highest condensation temperatures. There are two groups of refractory elements the refractory lithophile elements (RLEs)—aluminum, calcium, titanium, beryllium, scandium, vanadium, strontium, yttrium, zirconium, niobium, barium, REE, hafnium, tantalum, thorium, uranium, plutonium—and the refractory siderophile elements (RSEs)—molybdenum, ruthenium, rhodium, tungsten, rhenium, iridium, platinum, osmium. The refractory component accounts for —5% of the total condensible matter. Variations in refractory element abundances of bulk meteorites reflect the incorporation of variable fractions of a refractory aluminum, calcium-rich component. Ratios among refractory lithophile elements are constant in all types of chondritic meteorites, at least to within —5%. 

Titanium, which comprises 0.63% (i.e. 6320 ppm) of the earth s crustal rocks, is a very abundant element (ninth of all elements, second of the transition elements), and, of the transition elements, only Fe, Ti and Mn are more abundant than zirconium (0.016%, 162 ppm). Even hafnium (2.8 ppm) is as common as Cs and Br. 

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). 

Figure 4.18 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. Note the simultaneous occurrence of single ions (H", SR, 7.r ) and molecular ions (SiO, SiOH, ZrO, Zr02 ). 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 abundances. In addition to the peaks expected from zirconia on silica mounted on an indium foil, the spectrum of Fig. 4.18 also contains peaks from Na, K, and Ca. This is typical for SIMS Sensitivities vary over several orders of magnitude and elements such as the alkalis are detected when present in trace amounts. 

Zirconium can be a shiny grayish crystal-Uke hard metal that is strong, ductile, and malleable, or it can be produced as an undifferentiated powder. It is reactive in its pure form. Therefore, it is only found in compounds combined with other elements—mosdy oxygen. Zirconium-40 has many of the same properties and characteristics as does hafhium-72, which is located just below zirconium in group 4 of the periodic table. In fact, they are more similar than any other pairs of elements in that their ions have the same charge (+4) and are of the same general size. Because zirconium is more abundant and its chemistry is better known than hafnium s, scientists extrapolate zirconium s properties for information about hafnium. This also means that one twin contaminates the other, and this makes them difficult to separate. 

Zirconium is not a rare element. It is found over most of Earth s crust and is the 18th most abundant element, but it is not found as a free metal in nature. 

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.)... 

Hafnium had lain hidden for untold centuries, not because of its rarity but because of its dose similarity to zirconium (16), and when Professor von Hevesy examined some historic museum specimens of zirconium compounds which had been prepared by Julius Thomsen, C. F. Rammelsberg, A. E. Nordenskjold, J.-C. G. de Marignac, and other experts on the chemistry of zirconium, he found that they contained from 1 to 5 per cent of the new element (26, 27). The latter is far more abundant than silver or gold. Since the earlier chemists were unable to prepare zirconium compounds free from hafnium, the discovery of the new element necessitated a revision of the atomic weight of zirconium (24, 28). Some of the minerals were of nepheline syenitic and some of granitic origin (20). Hafnium and zirconium are so closely related chemically and so closely associated in the mineral realm that their separation is even more difficult than that of niobium (columbium) and tantalum (29). The ratio of hafnium to zirconium is not the same in all minerals. 

The abundances of the elements of the titanium group were compared to those of the zinc group in Table 13-1. It will be recalled that unlike the zinc group metals, which are rare but easily isolated, the titanium group metals are abundant, but purified with difficulty. Note from the (very rough) figures given that titanium is 50 times as abundant as zinc, zirconium is 3000 times as abundant as cadmium, and hafnium 30 times as abundant as mercury. 

Zirconium comprises 0.016% (162 ppm) of the Earth s crast and, as a transition element, is only less abundant than Fe, Ti, and Mu. Hafnium is much less abundant at 2.8 ppm, but is stUl comparable in quantity to Cs and Br. The most important minerals of zirconium are zircon (ZrSi04), which is mostly mined in Australia, South Africa, the USA, and Sri Lanka, and baddeleyite (Z1O2), found mostly in Brazil. The estimated reserves exceed a billion tonnes. Australia and South Africa account for about 80% of zircon mining. All zirconium minerals are contaminated by small quantities of hafnium (0.5-2% of Zr content), but in a few (such as alvite, MSi04 XH2O, M = Hf, Zr, Th) the content of Hf is comparable with that of Zr. The above-mentioned similarities in the chemical behavior of these metals explain their close association in Nature and the similarity of their isolation procedures. 

The constancy of refractory element ratios in the Earth s mantle, discussed before, is documented in the most primitive samples from the Earth s mantle. Figure 8 plots (modified from Jochum et ai, 1989) the PM-normalized abundances of 21 refractory elements from four fertile spinel Iherzolites. These four samples closely approach, in their bulk chemical composition, the primitive upper mantle as defined in the previous section. The patterns of most of the REEs (up to praseodymium) and of titanium, zirconium, and yttrium are essentially flat. The three... 

Zirconium is a fairly common element in Earth s crust. Its abundance is estimated to be 150 to 230 parts per million. That places it just below carbon and sulfur among elements occurring in Earth s crust. The two most common ores of zirconium are zircon, or zirconium silicate... 

Aluminum is the third most abundant element in the earth s crust (after oxygen and silicon), accounting for 8.2% of the total mass. It occurs most commonly in association with silicon in the aluminosilicates of feldspars and micas and in clays, the products of weathering of these rocks. The most important ore for aluminum production is bauxite, a hydrated aluminum oxide that contains 50% to 60% AI2O3 1% to 20% FeiOs 1% to 10% silica minor concentrations of titanium, zirconium, vanadium, and other transition-metal oxides and the balance (20% to 30%) water. Bauxite is purified via the Bayer process, which takes advantage of the fact that the amphoteric oxide alumina is soluble in strong bases but iron(III) oxide is not. Crude bauxite is dissolved in sodium hydroxide... 

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