Minerals xenotime

Of all the 17 rare-earths in the lanthanide series, terbium is number 14 in abundance. Terbium can be separated from the minerals xenotime (YPO ) and euxenite, a mixmre of the following (Y, Ca, Er, La, Ce, Y, Th)(Nb, Ta, Ti O ). It is obtained in commercial amount from monazite sand by the ion-exchange process. Monazite may contain as much as 50% rare-earth elements, and about 0.03% of this is terbium. 

Swedish chemist Carl Gustaf Mosander Found in the minerals xenotime and euxerite of which it is an impurity soft and malleable metal has few uses other than in inexpensive glass and jewelry. 

Dysprosium was discovered in 1866 by Boisbaudran. It occurs in the earth s crust associated with other rare earth metals. It is found in the minerals, xenotime YPO4, gadolinite, euxemite and monazite (Ce, La, Th)P04. The concentration of dysprosium in seawater is 0.9 ng/L and in the earth s crust 5.2 mg/kg. 

Terbium occurs in nature associated with other rare earths. It is found in minerals xenotime, a rare earth phosphate consisting of 1% terbia and in euxenite, a complex oxide containing about 1.3% terbia. It also is found in cerite, monazite, and gadolinite. Also, the element has been detected in stellar matter. Abundance of terbium in the earth s crust is estimated to be 1.2 mg/kg. 

Thulium was discovered in 1879 by Cleve and named after Thule, the earliest name for Scandinavia. Its oxide thulia was isolated by James in 1911. Thulium is one of the least abundant lanthanide elements and is found in very small amounts with other rare earths. It occurs in the yttrium-rich minerals xenotime, euxenite, samarskite, gadolinite, loparite, fergusonite, and yttroparisite. Also, it occurs in trace quantities in minerals monazite and... 

The mineral xenotime (YPO4) was the principal ore of yttrium and the other heavy rare earth elements. The ion-adsorption lateritic clays from Southern China replaced xenotime as the principal source of yttrium and the other heavy rare earth elements in the 1990s. These intensely weathered clays have rare earth ions adsorbed into the clay mineral structure. 

Intensive work with ytterbium was going on in Paris at the same time. Georges Ur-hain reported to the Paris Academy of Science on 4 " November 1907 (44 days before Auer s second report to the Vienna Academy) that he had performed a total of 800 fractionations of ytterbium nitrates, prepared from the mineral xenotime. Now he announced that he had divided ytterbium into two elements, for which he proposed the names neo-ytterbium Ny and lutecium Lu. The former was Marignac s element, now purified, the latter named after an old name for Paris, Lutetia Parisorum. 

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. 

A limited number of rare-earth minerals are mined for large-scale rare-earth production mona2ite, bastnaesite, loparite [12173-83-OJ, xenotime [13817-22-6]. In addition, siace the 1980s rare-earth-containing clays called ionic ore are mined ia China. Table 4 shows the rare-earth composition of typical mineral concentrates. 

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. 

Nearly all transition metals are oxidized readily, so most ores are compounds in which the metals have positive oxidation numbers. Examples include oxides (Ti02, mtile Fc2 O3, hematite C112 O, cuprite), sulfides (ZnS, sphalerite M0S2, molybdenite), phosphates (CeP04, monazite YPO4, xenotime both found mixed with other rare earth metal phosphates), and carbonates (FeC03, siderite). Other minerals contain oxoanions (MnW04, wolframite) and even more complex stmctures such as camotite, K2 (002)2 ( 4)2 2 O ... 

Rare Earths are produced primarily from three ores, monazite, xenotime, and bastnasite. Monazite is a phosphate mineral of essentially the cerium subgroup metals and thorium -(light rare Earths, Th) P04. The composition of monazite is reasonably constant throughout the world, with almost 50% of its rare Earth content as cerium and most of the remaining 50% as the other members of the cerium subgroup. Xenotime, like monazite, is a rare Earth orthophosphate but contains up to 63% yttrium oxide and also a markedly higher propor-... 

Euxenite is a titanotantalum/niobium-containing mineral and has a complex formula (Table 24.1) with variable chemical composition. It is usually found in sand deposits together with monazite, xenotime, zircon, beryl, columbite and other minerals. 

Several minerals have been identified in polished thin sections of various rock types including massive sulphide, gossan, intermediate crystal-lapilli tuff, and felsic ash tuff (Fig. 2). These minerals include apatite, monazite, zircon, allanite, titanite, xenotime, magnetite, cassiterite, cobaltite-gersdorffite, rutile, ilmenite, goethite, sphalerite, galena, arsenopyrite, chalcopyrite, pyrite, and pyrrhotite. These minerals range in size from 20 pm to 250 pm and represent potential Indicator minerals. 

Fig. 2. SEM-BSE images of phosphate minerals in massive sulfides, (a) detrital monazite grain with a metamorphic rim, (b) detrital zircon grain with a xenotime rim, (o) complex zonation of a xenotime mass, and (d) apatite mass with a syntaxial overgrowth...

Contents of REE in massive sulfides from the BMC are strongly controlled by the abundance of and REE concentrations in phosphate minerals, specifically apatite, xenotime and monazite. Strong positive Eu anomalies in apatite, account for the anomalous Eu signatures of exhalative sulfides whereas REE in monazite masses are largely reflective of detrital sources and may mask hydrothermal signatures. Limited release of mobile trace elements (LREE and Eu) during green-schist facies metamorphism has partly modified REE profiles for VMS deposits of the BMC. 

Biotite and magnetite are also usually present and visible in hand specimen, muscovite may be present, and more rarely other oxides may be seen. Field estimates of modes ranged from 20-35 vol.% quartz, 15-35 vol.% plagioclase, 30-50 vol.% potassium feldspar, and 1-10 vol.% biotite. Accessory minerals include magnetite, muscovite, monazite, xenotime, zircon, apatite, epidote, ilmenite, titanite, allanite, molybdenite, and galena. The major U and Th minerals are uraninite and uranothorite. 

Lutetium occurs in nature in small amounts in yttrium-containing minerals. It is found in xenotime, precambrian granites, and North American shales. It also exists at 0.001% in monazite, from which the metal is produced commercially. Lutetium has very httle commercial apphcation. The metal emits beta particles after thermal neutron activation, and is used to catalyze organic reactions. 

Samarium occurs in nature widely distributed but in trace quantities, always associated with other rare earth metals. The two most important minerals are (i) monazite, which is an orthophosphate of thorium and the rare earths and (ii) bastanasite, which is a rare earth fluocarbonate. The samarium content of these ores is about 2%, as oxide. It also is found in precambri-an granite rocks, shales, and certain minerals, such as xenotime and basalt. Its abundance in the earth s crust is estimated to be 7.05 mg/kg. 

Terbium is recovered from the minerals, monazite, xenotime, and euxenite. The recovery processes are quite similar to those of other lanthanide elements (See individual lanthanide elements). The metal is separated from other rare... 

Ytterbium occurs in minerals euxenite, a complex titanium niobotantalate gadolinite, a rare earth iron beryUium sdicate monazite, a thorium-rare earth phosphate and xenotime, also a rare earth-thorium phosphate. Abundance of ytterbium in the earth s crust is estimated to be 3.2 mg/kg. 

Yttrium oxide is produced as an intermediate in recovery of yttrium from xenotime and monazite (See Yttrium, Recovery). The oxide is produced after separation of rare earth sulfates obtained from digesting the mineral with sulfuric acid on a cation exchange bed, precipitating yttrium fraction as oxalate, and igniting the oxalate at 750°C. 

Phosphates. The two major phosphate bearing ores are monazite and xenotime, the former being a source of light lanthanides and the latter a source of the heavy rare earths, see Table IV. Deposits in the form of heavy mineral sands are the major source of monazite. They are usually exploited as a byproduct of rutile, ilmenite, and zircon mining operations. 

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