Transition elements abundances

None of the three elements is particularly abundant in the earth s crust though several minerals contain them as major constituents. As can be seen from Table 13.1, arsenic occurs about halfway down the elements in order of abundance, grouped with several others near 2 ppm. Antimony has only one-tenth of this abundance and Bi, down by a further factor of 20 or more, is about as unabundant as several of the commoner platinum metals and gold. In common with all the post-transition-element metals. As, Sb and Bi are chalcophiles, i.e. they occur in association with the chalcogens S, Se and Te rather than as oxides and silicates. 

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. 

Occurrence. In order of abundance in the earth s crustal rocks, it is the third within the transition elements (after Fe and Ti) and the 12th in the general order of all the elements. It occurs in several minerals such as primary deposits of silicates and as secondary deposits (commercially more important) of oxides and carbonates as pyrolusite, Mn02, hausmannite, Mn304, rhodochrosite, MnC03, etc. Large amounts of manganese are present in the deep sea nodules located over certain areas of the ocean floor. 

Partial covalency in essentially ionic bonds changes somewhat the distribution of electrons, detectable as electron delocalisation by the modem methods of nuclear magnetic and electron spin resonance (NMR and ESR). Although the interpretations of these measurements widely differ (see 292, 293, 320) they doubtless prove the existence of partial covalency (in the order of magnitude of 10%) even in the most ionic fluorides AMeFg. Little work seems to have been done one fluorides of the heavier transition elements (96), but there is an abundant literature on first transition series fluorides, of which an arbitrary selection is given below for further information. ... 

Manganese is the third most abundant transition element [1]. It is present in a number of industrial, hiological, and environmental systems, representative examples of which include manganese oxide batteries [2] the oxygen-evolving center of photosystem II (PSII) [3] manganese catalase, peroxidase, superoxide dismutase (SOD), and other enzymes [4, 5] chiral epoxidation catalysts [6] and deep ocean nodules [7]. Oxidation-reduction chemistry plays a central role in the function of most, if not all, of these examples. 

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... 

The metal ions of major biological significance are indicated in Figure 1, which shows part of the Periodic Table. Some information on the distribution and concentration levels of these metals in living systems is shown in Table 1. The transition metals and zinc are usually regarded as trace elements, as they are present in very small amounts. Of the transition elements, iron is the most abundant metal, and probably the most well studied. Iron is essential for all living systems with the exception of certain members of the lactic acid bacteria, which grow in environments notoriously low in iron, such as milk. Lactic acid bacteria are devoid of cytochromes, peroxidases... 

There are several approaches for obtaining spectral data for low-abundance transition metal ions, rare minerals and crystals of small dimensions. Data for a transition element in its chemical compounds, such as hydrates, aqueous solutions, molten salts or simple oxides, may be extrapolated to minerals containing the cation. Such data for synthetic transition metal-doped corundum and periclase phases used to describe principles of crystal field theory in chapter 2, appear in table 2.5, for example. There is a growing body of visible to near-infrared spectral data for transition metal-bearing minerals, however, and much of this information is reviewed in this chapter and the following one. These results form the data-base from which crystal field stabilization energies (CFSE s) of most of the transition metal ions in common oxide and silicate minerals may be estimated. 

Chapter 8 discusses aspects of the geochemistry of the first series transition elements, most of which are trace elements in the Earth s Crust (that is, their crustal abundances are below 1,000 ppm). 

Properties of the terrestrial planets that are central to this chapter are summarized in table 10.1 and information about element abundances is contained in Appendix 1. The crustal abundance data for the Earth indicate the presence of relatively high concentrations of Fe, and to a lesser extent Ti, compared to other first-series transition elements. However, the terrestrial abundance of Fe... 

Different evolutionary histories of other terrestrial planets have influenced the relative concentrations of the transition elements compared to their cosmic abundances, as suggested by geochemical data for surface rocks on the Moon, Mars and Venus (Appendix 1). Chemical analyses of lunar samples returned from the Apollo and Luna missions show that minerals and glasses occurring on the Moon contain high concentrations of Fe and Ti existing as oxidation states Fe(II), Ti(III) and Ti(IV). Some lunar minerals, notably olivine and opaque oxides, also contain significant amounts of Cr(H), Cr(III) and Mn(H). The lack of an atmosphere on the Moon simplifies interpretation of remote-sensed reflectance spectra of its surface. 

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