Elemental abundances refractory lithophile elements

The actinides (U, Th, Pu), alkaline earths (Be, Mg, Ca, Sr, Ba), lanthanides (elements La - Lu), Al, and the elements in groups 3b (Sc, Y), 4b (Ti, Zr, Hf), and 5b (V, Nb, Ta) of the periodic table are refractory lithophile elements. The refractory lithophiles are 5% of the total mass of the rock in solar composition material. Aluminum Al, calcium Ca, and titanium Ti are the three most abundant refractory lithophiles, and they form minerals that are the host phases for most of the less abundant refractory lithophile elements such as the actinides, lanthanides, and transition elements in group 5b of the periodic table. Some of the less abundant refractory lithophiles - the group 4b elements Zr, Hf, and the group 3b elements Y and Sc - condense as oxides before any Ca, Al, Ti-bearing minerals form [9], But the rest condense into the more abundant host phases. 

Updated solar photospheric abundances are compared with meteoritic abundances. It is shown that only one group of chondritic meteorites, the Cl chondrites, matches solar abundances in refractory lithophile, siderophile, and volatile elements. All other chondritic meteorites differ from Cl chondrites. The agreement between solar and Cl abundances for all elements heavier than oxygen and excluding rare gases has constantly improved since Goldschmidt (1938) published his first comprehensive table of cosmic abundances. 

Elemental abundance patterns for ordinary, Rumuruti-like (R), and Kakangari-like (K) chondrites are fairly flat and enriched relative to Cl for lithophile and refractory lithophile elements. Enstatite chondrites have the lowest abundance of refractory lithophile elements. 

Figure 3 Mean abundances of lithophile elements normalized to Cl chondrites and silicon arranged in order of increasing volatility in seven chondrite groups (Wasson and Kallemeyn, 1988). Refractories (elements condensing above V) are uniformly enriched in CO, CM, and CV chondrites and depleted in H, L,and EH chondrites. Moderately volatile elements, which condense below magnesium and silicon, are all depleted relative to Cl chondrites. These fractionations are related in poorly understood ways to the formation of CAIs and chondrules (reproduced by permission of The Royal Society from Phil. Trans. Roy. Soc. London, 1988, A325, p. 539).

Trace elements concentrations have been measured in 10 AOAs from Allende (Grossman et al, 1979). Most AOAs have unfractionated abundances of refractory lithophile and side-rophile elements (2-20 X Cl) two AOAs analyzed have group II REE patterns. 

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%. 

The two elements calcium and aluminum are RLEs. The assumption is usually made that aU RLEs are present in the primitive mantle of the Earth in chondritic proportions. Chondritic (undifferentiated) meteorites show significant variations in the absolute abundances of refractory elements but have, with few exceptions discussed below, the same relative abundances of lithophile and siderophile refractory elements. By analogy, the Earth s mantle abundances of refractory lithophile elements are assumed to occur in chondritic relative proportions in the primitive mantle, which is thus characterized by a single RLE/Mg ratio. This ratio is often normalized to the Cl-chondrite ratio and the resulting ratio, written as (RLE/Mg)N, is a measure of the concentration level of the refractory component in the Earth. A single factor of (RLE/Mg) valid for all RLEs is a basic assumption in this procedure and will be calculated from mass balance considerations. 

Figure 7 shows the abundances of the four refractory lithophile elements—aluminum, calcium, scandium, and vanadium—in several groups of undilferentiated meteorites, the Earth s upper mantle and the Sun. The RLE abundances are divided by magnesium and this ratio is then normalized to the same ratio in Cl-chondrites. These (RLE/Mg)N ratios are plotted in Figure 7 (see also Figure 1). The level of refractory element abundances in bulk chondritic meteorites varies by less than a factor of 2. Carbonaceous chondrites have either Cl-chondritic or higher Al/Mg ratios (and other RLE/Mg ratios), while rumurutiites (highly oxidized chondritic meteorites), ordinary chondrites, acapulcoites, and enstatite chondrites are depleted in refractory elements. The (RLE/Mg)N ratio in the mantle of the Earth is within the range of carbonaceous chondrites.

The Lu- Hf isotopic system (half-life —37 Gyr) is, in many ways, chemically similar to Sm- Nd. In both isotopic schemes the parent and daughter elements are refractory lithophile elements, such that their relative abundances in the Earth were probably not modified during accretion, nor did they participate in core formation. Thus, as for the Sm-Nd system, the compositions of chondritic meteorites can, in principle, be used to establish bulk silicate Earth isotopic compositions and Lu/Hf ratios directly. The potential, therefore, exists for establishing a precise isotopic baseline to use for recognizing fine-scale deviations in isotopic compositions, which can then be used to reveal... 

The Moon also has an unusually low iron content. Typical inner solar system objects contain about 30% iron - Cl chondrites, for example contain about 36% iron by mass -whereas the Moon contains only 13 wt%. Some of this iron is probably located in the lunar core, although this will only account for a small amount of iron, since the lunar core is small (3-4% of its mass) compared to that of the Earth. In contrast the more refractory lithophile elements such as Al are more abundant on the Moon given the thick aluminous lunar crust (Taylor, 1987). 

The HfrW ratio of a bulk planetary mantle must be inferred by comparing the W concentrations with another element that behaves similarly during silicate melting (i.e., has a similar incompatibility), tends to stay in the mantle and whose abundance relative to Hf is known. The latter two conditions are met by refractory lithophile elements (RLE) because their relative abundances in bulk planetary mantles are chondritic (see above). This is because they are neither fractionated by core formation (because they are lithophile) nor by volatile element depletion (because they are refractory). The Hf/W ratio of a bulk planetary mantle can thus be calculated as follows ... 

Figure 12.17a shows lithophile element abundances, and Figure 12.17b shows sid-erophile and chalcophile element abundances in CM chondrites, normalized to Cl chondrites. Illustrated for comparison are the abundances in CO chondrites, which are the anhydrous carbonaceous chondrite group most closely allied to CM chondrites. As in other chondrites, the greatest differences are in volatile elements. The volatile and moderately volatile elements in CM chondrites are present at 50-60% of the abundances of the refractory elements. The volatile elements are primarily located in the matrix, and the matrix comprises 50-60% of CM chondrites. This implies that the matrix has essentially Cl abundances of all elements, while the chondrules and refractory inclusions have Cl relative abundances of refractory elements but are highly depleted in the volatile elements. The sloping transition in the region of moderately volatile elements indicates... 

Figure 23 Bulk concentrations of lithophile elements normalized to Cl chondrites and silicon in skeletal-olivine and cryptocrystalline chondmles including cryptocrystalline inclusions in metallic Fe,Ni in two CBb chondrites (HH 237 and QUE 94411). Shaded regions show compositional range of chondmles in other carbonaceous chondrites, excluding the CH group chondmles that are closely related to CB chondmles. The wide range of refractory abundances in CBb chondmles ((0.02-3) X Cl levels) appears to reflect fractional condensation with skeletal-ohvine chondmles condensing at higher temperatures than cryptocrystalline chondmles. Both types are more depleted in moderately volatile elements than other carbonaceous chondrites (after Krot et ah, 2002a).

Few comprehensive bulk compositional analyses are available for silicate inclusions from HE irons, and many of them are of small samples. Netschaevo silicates have magnesium-normalized abundances of refractory, moderately volatile, and volatile lithophile elements within the ranges of ordinary chondrites. The nickel-normalized abundances of refractory and moderately volatile siderophile elements are also similar to those of ordinary chondrites. The silicates have siderophi-le/Mg ratios of (1.9-2.2)xCI chondrites, however. The silicate inclusion in Watson has Cl-normalized element/Mg ratios of —0.86 for most refractory and moderately volatile lithophile elements (Figure 2). Siderophile elements are depleted, and show increasing abundance with increasing volatility (Olsen et al., 1994) Os/Mg = 0.028 X Cl and Sb/Mg = 0.066 X Cl. 

In addition to making comparisons with chondrites, the bulk composition of the Earth also has been defined in terms of a model mixture of highly reduced, refractory material combined with a much smaller proportion of a more oxidized volatile-rich component (Wanke, 1981). These models follow on from the ideas behind earlier heterogeneous accretion models. According to these models, the Earth was formed from two components. Component A was highly reduced and free of all elements with equal or higher volatility than sodium. All other elements were in Cl relative abundance. The iron and siderophile elements were in metallic form, as was part of the silicon. Component B was oxidized and contained all elements, including those more volatile than sodium in Cl relative abundance. Iron and all siderophile and lithophile elements were mainly in the form of oxides. 

Abundances of nonrefractory incompatible lithophile elements (potassium, rubidium, caesium, etc.) or partly siderophile/chalcophile elements (tungsten, antimony, tin, etc.) are calculated from correlations with RLE of similar compatibility. This approach was first used by Wanke et al. (1973) to estimate abundances of volatile and siderophile elements such as potassium or tungsten in the moon. The potassium abundance was used to calculate the depletion of volatile elements in the bulk moon, whereas the conditions of core formation and the size of the lunar core may be estimated from the tungsten abundance, as described by Rammensee and Wanke (1977). This powerful method has been subsequently applied to Earth, Mars, Vesta, and the parent body of HED meteorites. The procedure is, however, only applicable if an incompatible refractory element and a volatile or siderophile element have the same degree of incompatibility, i.e., do not fractionate from each other during igneous processes. In other words, a good correlation of the two elements over a wide... 

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