Lanthanide mineral

Ytterby, a village in Sweden) Discovered by Mosander in 1843. Terbium is a member of the lanthanide or "rare earth" group of elements. It is found in cerite, gadolinite, and other minerals along with other rare earths. It is recovered commercially from monazite in which it is present to the extent of 0.03%, from xenotime, and from euxenite, a complex oxide containing 1% or more of terbia. 

The heavy mineral sand concentrates are scmbbed to remove any surface coatings, dried, and separated into magnetic and nonmagnetic fractions (see Separation, magnetic). Each of these fractions is further spHt into conducting and nonconducting fractions in an electrostatic separator to yield individual concentrates of ilmenite, leucoxene, monazite, mtile, xenotime, and zircon. Commercially pure zircon sand typically contains 64% zirconium oxide, 34% siUcon oxide, 1.2% hafnium oxide, and 0.8% other oxides including aluminum, iron, titanium, yttrium, lanthanides, uranium, thorium, phosphoms, scandium, and calcium. 

The lanthanides, distributed widely in low concentrations throughout the earth s cmst (2), are found as mixtures in many massive rock formations, eg, basalts, granites, gneisses, shales, and siUcate rocks, where they are present in quantities of 10—300 ppm. Lanthanides also occur in some 160 discrete minerals, most of them rare, but in which the rare-earth (RE) content, expressed as oxide, can be as high as 60% rare-earth oxide (REO). Lanthanides do not occur in nature in the elemental state and do not occur in minerals as individual elements, but as mixtures. 

Table 4. Lanthanide and Yttrium Distribution in Mineral Sources, wt %, ...

Absorption Spectra, of Aqueous Ions. The absorption spectra of Pu(III) [22541-70 ] Pu(IV) [22541 4-2] Pu(V) [22541-69-1] and Pu(VI) [22541-41-9] in mineral acids, ie, HCIO and HNO, have been measured (78—81). The Pu(VII) [39611-88-61] spectmm, which can be measured only in strong alkaU hydroxide solution, also has been reported (82). As for rare-earth ion spectra, the spectra of plutonium ions exhibit sharp lines, but have larger extinction coefficients than those of most lanthanide ions (see Lanthanides). The visible spectra in dilute acid solution are shown in Figure 4 and the spectmm of Pu(VII) in base is shown in Figure 5. The spectra of ions of plutonium have been interpreted in relation to all of the ions of the bf elements (83). 

There are a number of minerals in which thorium is found. Thus a number of basic process flow sheets exist for the recovery of thorium from ores (10). The extraction of mona ite from sands is accompHshed via the digestion of sand using hot base, which converts the oxide to the hydroxide form. The hydroxide is then dissolved in hydrochloric acid and the pH adjusted to between 5 and 6, affording the separation of thorium from the less acidic lanthanides. Thorium hydroxide is dissolved in nitric acid and extracted using methyl isobutyl ketone or tributyl phosphate in kerosene to yield Th(N02)4,... 

There are few principal lanthanide deposits, and there are no minerals that are sources for cerium alone. All the lighter lanthanides occur together in any potential deposit, and processes separating the lanthanides are necessary to obtain pure cerium products. 

Whereas certain rocks of igneous origin formed by melting and recrystallization can include minerals enriched in the lanthanides (4), cerium is usually present as a trace element rather than as an essential component. Only a few minerals in which cerium is an essential stmcture-defining component occur in economically significant deposits. Two minerals supply the world s cerium, bastnasite [68909-13-7] LnFCO., and monazite [1306-41 -8] (Ln,Th)PO. ... 

Bastnasite has been identified in various locations on several continents. The largest recognized deposit occurs mixed with monazite and iron ores in a complex mineralization at Baiyunebo in Inner MongoHa, China. The mineral is obtained as a by-product of the iron ore mining. The other commercially viable bastnasite source is the Mountain Pass, California deposit where the average Ln oxide content of the ore is ca 9%. This U.S. deposit is the only resource in the world that is minded solely for its content of cerium and other lanthanides. 

Phosphate rock, mined widely throughout the world for its fertilizer value (see Fertilizers), in certain regions contains a few percent of lanthanides. For example, the apatite deposits in the Kola peninsula on the Russian/Finnish border. The Ln content is recoverable from the various processing residues, and because other Ln-containing minerals, such as loparite [12173-83-0], are also found there, the location suppHes a significant part of the demand in Eastern Europe. 

The production of cerium derivatives begins with ore beneficiation and production of a mineral concentrate. Attack on that concentrate to create a suitable mixed lanthanide precursor for later separation processes follows. Then, depending on the relative market demand for different products, there is either direct production of a cerium-rich material, or separation of the mixed lanthanide precursor into individual pure lanthanide compounds including compounds of pure cerium, or both. The starting mineral determines how the suitable mixed lanthanide precursor is formed. In contrast the separation... 

Mischmetal. Mischmetal [62379-61-7] contains, in metallic form, the mixed light lanthanides in the same or slightly modified ratio as occurs in the resource minerals. It is produced by the electrolysis of fused mixed lanthanide chloride prepared from either bastnasite or mona2ite. Although the precise composition of the resulting metal depends on the composition of chloride used, the cerium content of most grades is always close to 50 wt %. 

Several instmmental methods are available for quantitative estimation of from moderate to trace amounts of cerium in other materials. X-ray fluorescence is widely available, versatile, and suitable for deterrninations of Ce, and any other Ln, at percent levels and lower in minerals and purer materials. The uv-excited visible luminescence of cerium is characteristic and can be used to estimate Ce content, at ppm levels, in a nonluminescing host. X-ray excited optical luminescence (15), a technique especially appropriate for Ln elements including cerium, rehes on emissions in the visible, and also measures ppm values. Atomic emission spectrometry is appHcable to most lanthanides, including Ce (16). The precise lines used for quantitative measurement must be chosen with care, but once set-up the technique is suitable for routine analyses. 

Historically the use of mona2ite, a thorium-containing mineral, as the principal lanthanide resource led to confusion regarding the relation between radioactivity and the lanthanides. Inadequate separations produced Th-contaminated Ln products. Modem processing technology results in products that meet all regulatory requirements. 

Scandium is very widely but thinly distributed and its only rich mineral is the rare thortveitite, Sc2Si20v (p. 348), found in Norway, but since scandium has only small-scale commercial use, and can be obtained as a byproduct in the extraction of other materials, this is not a critical problem. Yttrium and lanthanum are invariably associated with lanthanide elements, the former (Y) with the heavier or Yttrium group lanthanides in minerals such as xenotime, M "P04 and gadolinite, M M SijOio (M = Fe, Be), and the latter (La) with the lighter or cerium group lanthanides in minerals such as monazite, M P04 and bastnaesite, M C03F. This association of similar metals is a reflection of their ionic radii. While La is similar in size to the early lanthanides which immediately follow it in the periodic table, Y , because of the steady fall in ionic radius along the lanthanide series (p. 1234), is more akin to the later lanthanides. 

Yttrium and lanthanum are both obtained from lanthanide minerals and the method of extraction depends on the particular mineral involved. Digestions with hydrochloric acid, sulfuric acid, or caustic soda are all used to extract the mixture of metal salts. Prior to the Second World War the separation of these mixtures was effected by fractional crystallizations, sometimes numbered in their thousands. However, during the period 1940-45 the main interest in separating these elements was in order to purify and characterize them more fully. The realization that they are also major constituents of the products of nuclear fission effected a dramatic sharpening of interest in the USA. As a result, ion-exchange techniques were developed and, together with selective complexation and solvent extraction, these have now completely supplanted the older methods of separation (p. 1228). In cases where the free metals are required, reduction of the trifluorides with metallic calcium can be used. 

In 1751 the Swedish mineralogist, A. F. Cronstedt, discovered a heavy mineral from which in 1803 M. H. Klaproth in Germany and, independently, i. i. Berzelius and W. Hisinger in Sweden, isolated what was thought to be a new oxide (or earth ) which was named ceria after the recently discovered asteroid, Ceres. Between 1839 and 1843 this earth, and the previously isolated yttria (p. 944), were shown by the Swedish surgeon C. G. Mosander to be mixtures from which, by 1907, the oxides of Sc, Y, La and the thirteen lanthanides other than Pm were to be isolated. The small village of Ytterby near Stockholm is celebrated in the names of no less than four of these elements (Table 30.1). 

The minerals on which the work was performed during the nineteenth century were indeed rare, and the materials isolated were of no interest outside the laboratory. By 1891, however, the Austrian chemist C. A. von Welsbach had perfected the thoria gas mantle to improve the low luminosity of the coal-gas flames then used for lighting. Woven cotton or artificial silk of the required shape was soaked in an aqueous solution of the nitrates of appropriate metals and the fibre then burned off and the nitrates converted to oxides. A mixture of 99% ThOz and 1% CeOz was used and has not since been bettered. CeOz catalyses the combustion of the gas and apparently, because of the poor thermal conductivity of the ThOz, particles of CeOz become hotter and so brighter than would otherwise be possible. The commercial success of the gas mantle was immense and produced a worldwide search for thorium. Its major ore is monazite, which rarely contains more than 12% ThOz but about 45% LnzOz. Not only did the search reveal that thorium, and hence the lanthanides, are more plentiful than had previously been thought, but the extraction of the thorium produced large amounts of lanthanides for which there was at first little use. 

There are over 100 minerals known to contain lanthanides but the only two of commercial importance are monazite, a mixed La, Th, Ln phosphate, and bastnaesite, an La, Ln fluorocarbonate (M C03F). Monazite is widely but sparsely distributed in many rocks but, because of its high density and inertness, it is concentrated by weathering into sands on beaches and river beds, often in the presence of other... 

The most important minerals of the lanthanide elements are monazite (phosphates of La, Ce, Pr, Nd and Sm, as well as thorium oxide) plus cerite and gadolinite (silicates of these elements). Separation is difficult because of the chemical similarity of the lanthanides. Fractional crystallization, complex formation, and selective adsorption and elution using an ion exchange resin (chromatography) are the most successful methods. 

Actinium is similarly easy to find a proxy for. It forms large trivalent cations with an ionic radius of 1.12 A in Vl-fold coordination. This is somewhat larger than La (1.032 A), which we will adopt as a proxy. The partitioning behavior of the lanthanides (denoted collectively Ln) is sufficiently well understood to make this a prudent choice. In some minerals, however, the larger size of Ac, may place it onto a larger lattice site than the lanthanides. This possibility should be considered for minerals with very large cation sites, such as amphiboles and micas. 

Many U-series elements occur in nature at much lower concentrations than the more commonly used trace elements, such as the lanthanides. This fact, coupled with the highly incompatible nature of many U-series elements, means that in some cases factors other than lattice strain may influence the uptake of cations into a mineral, and so affect the partition coefficient. 

The overall distribution of lanthanides in bone may be influenced by the reactions between trivalent cations and bone surfaces. Bone surfaces accumulate many poorly utilized or excreted cations present in the circulation. The mechanisms of accumulation in bone may include reactions with bone mineral such as adsorption, ion exchange, and ionic bond formation (Neuman and Neuman, 1958) as well as the formation of complexes with proteins or other organic bone constituents (Taylor, 1972). The uptake of lanthanides and actinides by bone mineral appears to be independent of the ionic radius. Taylor et al. (1971) have shown that the in vitro uptakes on powdered bone ash of 241Am(III) (ionic radius 0.98 A) and of 239Pu(IV) (ionic radius 0.90 A) were 0.97 0.016 and 0.98 0.007, respectively. In vitro experiments by Foreman (1962) suggested that Pu(IV) accumulated on powdered bone or bone ash by adsorption, a relatively nonspecific reaction. On the other hand, reactions with organic bone constituents appear to depend on ionic radius. The complexes of the smaller Pu(IV) ion and any of the organic bone constituents tested thus far were more stable (as determined by gel filtration) than the complexes with Am(III) or Cm(III) (Taylor, 1972). 

Pigments, minerals, gemstones, glasses, and many related materials are colored by impurity defects that absorb some of the incident white light, leaving a depleted spec-hum to color the solid. Colors in these materials are thus characterized by the absorption spectrum of the solid. Common inorganic colorants are the transition-metal and lanthanide metal ions. The colors ate characteristic of the ions themselves and are due... 

Mineral sources, lanthanide and yttrium distribution in, 14 6311 Mineral spirits, solvent for cosmetics, 7 832 Minerals processing, history of, 16 596t. 

The basis for the claim of discovery of an element has varied over the centuries. The method of discovery of the chemical elements in the late eightenth and the early nineteenth centuries used the properties of the new sustances, their separability, the colors of their compounds, the shapes of their crystals and their reactivity to determine the existence of new elements. In those early days, atomic weight values were not available, and there was no spectral analysis that would later be supplied by arc, spark, absorption, phosphorescent or x-ray spectra. Also in those days, there were many claims, e.g., the discovery of certain rare earth elements of the lanthanide series, which involved the discovery of a mineral ore, from which an element was later extracted. The honor of discovery has often been accorded not to the person who first isolated the element but to the person who discovered the original mineral itself, even when the ore was impure and that ore actually contained many elements. The reason for this is that in the case of these rare earth elements, the earth now refers to oxides of a metal not to the metal itself This fact was not realized at the time of their discovery, until the English chemist Humphry Davy showed that earths were compounds of oxygen and metals in 1808. 

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