Rare Earth Elements Profile

MineralsUK Mineral profile Centre f or sust ainable mineral development 1 spanning atomic numbers 57 to 71 (Table 71 to 57 numbers atomic spanning elements are lanthanides The lanthanides. the and yttrium scandium, including elements, metallic similar chemically 17 of group a are metals) earth rare the as to referred (sometimes (REE) elements earth rare The Definitions andcharacteristics deposits Definitions, mineralogyand in the 18 the in chemists for challenge difficult a was REE individual the of Separation properties. physical and chemical similar have they as REE considered are yttrium and Scandium 2006). Hedrick, and (Castor isotopes stable or long-lived no has it as materials natural in quantities trace in occurs more stronglyconcentratedin thecontinentalcrustthan the lighterREEaremoreincompatibleandconsequently abundance thantheiroddnumberedneighbours.Secondly factors. REEwithevenatomicnumbershavegreater of theREEvariesconsiderablyandrelatestotwomain through tolutetium(Table 1). Therelativeabundance and theheavyrareearthelements(HREE)–gadolinium earth elements(LREE)–lanthanumthroughtoeuropium The lanthanidesarecommonlydividedinto:thelightrare 1985). McLennan, 0.3 of concentration a with lutetium to 33 at abundant most the cerium widely, from varies REE individual of abundance crustal The 2002). USGS, 2002; (Harben, lead and ppm) (50 copper to abundances crustal similar have REE abundant more the and silver than greater abundance crustal overall an having crust earth’s the in plentiful relatively are REEs contrast In from. isolated originally were they which minerals the of rarity the from arising misnomer a is earth rare term The difficult. metal pure to refinement making another one for substitute easily very can REE, the similarity chemical their of the 20 the occur in nature, although promethium although nature, in occur Promethium:isaradioactive element. BGS ©NERC2010. Allrightsreserved. contained inthisreportarevested inNERC. Unless otherwisestated,copyright ofmaterials th century that they were all identified. Because Because identified. all were they that century th and 19 and Rare Earth Elements th centuries, such that it was not until until not was it that such centuries, 1

, the rarest, only only rarest, the , ppm (Taylor ppm and

1). They all all They 1).

ppm ppm Photograph: FergusMacTaggart, BGS ©NERC. associated with albiteandquartz,Arran,Scotland. Elongate prismatic fergusoniteinanopencavity Gupta andKrishnamurthy(2005). Table 1 Promethium Neodymium Praseodymium Cerium Lanthanum Yttrium Scandium Element Lutetium Ytterbium Thulium Erbium Holmium Dysprosium Terbium Gadolinium Europium Samarium 1 Selected propertiesoftheREE.Compiledfrom Nd Pr Ce La Y Sc Symbol Lu Yb Tm Er Ho Dy Tb Gd Eu Sm Pm 60 59 58 57 39 21 number Atomic 71 70 69 68 67 66 65 64 63 62 61 144.24 140.90 140.11 138.90 88.90 44.95 weight Atomic 174.97 173.04 168.93 167.26 164.93 162.50 158.92 157.25 151.96 150.36 145.00 7.008 6.773 8.160 6.146 4.469 2.989 (gcm Density 9.841 6.966 9.321 9.066 8.795 8.551 8.230 7.901 5.244 7.520 7.264 -3 ) (°C) Point Melting 1021 931 798 918 1522 1541 1663 819 1545 1529 1474 1412 1356 1313 822 1074 1042 June 2010 kg/mm 10 kgload, hardness, Vicker’s 35 37 24 37 38 85 77 21 48 44 42 42 46 57 17 45 - 2 2 Rare Earth Elements available. element varies from the one shown, may exist. na: not one or more other chemical variants, in which the dominant specific chemical variant of the mineral identified. Note mineral name is followed by brackets the formula is for the exception of apatite (Caster and Hedrick 2006).Where the REO content based on Webmineral composition, with the formulae sourced from Clark (1993) and estimates of Table 2 in appearance. They are characteristically soft, malleable, As refined metals the REE are lustrous, iron grey to silvery earth’s crust(CastorandHedrick,2006). within asinglemineralandbroaddistributioninthe structures. ThisresultsintheoccurrenceofmultipleREE REE meanstheycansubstituteforoneanotherincrystal similar nature(ionicradiiandoxidationstates)ofthe the REEwithlargeratomicnumbers.Thechemically 3 2 magnetic field. Magnetic anisotropy:the dependenceofmaterialsmagneticproperties ondirection. Paramagnetic: atypeofmagnetismwhichonly occursinthepresenceofanexternal Huanghoite-(Ce) Samarskite-(Y) Cebaite-(Ce) Kainosite-(Y) Brannerite Aeschynite-(Ce) Mineral Loparite Knopite Yttrocerite Apatite Parisite-(Ce) Monazite-(Ce) Gadolinite-(Ce) Fergusonite-(Ce) Britholite-(Ce) Florencite-(Ce) Eudialyte Xenotime Synchysite-(Ce) Euxenite-(Y) Allanite-(Ce) Bastnäsite-(Ce)

A selection of REE-bearing minerals. Mineral BaCe(CO (Y,Ce,U,Fe Ba Ca (U,Ca,Y,Ce)(Ti,Fe) (Ce,Ca,Fe,Th)(Ti,Nb) Formula (Ce,La,Na,Ca,Sr)(Ti,Nb)O (CaTi,Ce (Ca,Ce,Y,La)F Ca Ca(Ce,La) (Ce,La,Nd,Th)PO (Ce,La,Nd,Y) (Ce,La,Nd)NbO (Ce,Ca) CeAl Na YPO ZrSi Ca(Ce,LA)(CO (Y.Ca.Ce,U,Th)(Nb,Ta,Ti) (Ce,Ca,Y) (Ce,La)(CO 3 2 5 4 (PO Ce (Y,Ce) (Ca,Ce) 8 4 O 3 . (PO 2 22 (CO 4 5 ) (OH,Cl) (SiO 3 2 (F,Cl,OH) 3 2 4 )O 2 2 ) Si ) (Al,Fe 3+ (CO 2 2 3 3 2 F. (OH) ) )F 3 ) (Fe 5 4 4 3 F O 2 ,PO (Nb,Ta,Ti) 3 Fe 3 2 .nH 3 12 ) . 2+ ) 2 2 4 3 6 CO F. 2+ (?). 3+ F ,Mn,Y) . 4 4 Be 2 ) 2 2 ) 3 . O 3 O. (OH,F) 3 (SiO .H 6 2 2 Si (O,OH) 2 O. 2 5 4 O O ) 2 3 O 3 10 16 OH. 6 . . 6 . 53 51 39 60 75 REO % Approximate 38 24 61 38 na 65 30 53 24 9 32 32 61 32 9 32 19 anisotropy Er, YbandHo(Harben,2002). Xenotime isdominated bytheheavierREEincluding Y, Dy, that monazitecontainstheradioactive elementthorium. La andmoreNdHREE.It is alsosignificanttonote Nd. Monazitehasadifferent balance asitcontainsless are theprimarysourceof LREE, mainlyCe,Laand others theoppositeiscase.Bastnäsiteandmonazite are particularlyenrichedrelativetotheHREE,whilstin monazite andxenotime.InsomeREEmineralstheLREE are associatedwithjustthreeminerals,bastnäsite, significant (Table 2). Thevastmajorityofresources relatively smallnumberareormaybecomecommercially Around 200mineralsareknowntocontainREE,althougha are requiredtoformtheirownminerals(Möller, 1986). substitute formajorions.HigherconcentrationsofREE are largelyhostedbyrock-formingmineralswherethey carbonates, oxidesandphosphates(Table 2). TheREE occur inawiderangeofmineraltypesincludinghalides, REE donotoccurnaturallyasmetallicelements. Mineralogy and Lu, are strongly paramagnetic metal production. The REE, with the exception of Sc, Y, La,point Yb has direct implications for the reduction process used in series, from 798 The melting points of REE generally increase across the gives them some unusual magnetic and optical properties. ductile and typically reactive. The electron structure of REE MacTaggart, BGS©NERC. open cavity, Arran,Scotland.Photograph:Fergus Allanite crystalassociatedwithalbiteandquartzinan 3 (Gupta and Krishnamurthy, 2005). ° C for cerium to 1663 www.MineralsUK.com 2 and have strong magnetic ° C for lutetium. Melting 3 Rare Earth Elements 18 Desilicified:arockin whichsilicahasbeenreleasedfromtheconstituent minerals. 17 Altered:hydrothermal orweatheringinducedchangestothechemical andmineralogicalcomposition ofarock. 16 Metasomatism:chemicalalterationofarock byfluids. 15 Peralkaline:igneousrockswhichhaveahigher molecularproportionofcombinedsodiumandpotassium thanaluminium. 14 Carbonatite:arockwhichcontainsmorethan 50percentcarbonateminerals,thoughttooriginatefrom carbondioxide-richandsilica-poormagmasfromtheuppermantle. 13 Pegmatite:averycoarse-grainedigneousrock. 12 Skarn:ametamorphicrockthatformsas result ofchemicalalterationbyhydrothermalandotherfluids. 11 Breccia:arockthathasbeenmechanically, hydraulicallyorpneumaticallybrokenintoangularfragments. 10 Ionicradius:halfthedistancebetween centres oftwoionsinanelement. 9 Geneticassociations–thegeologicalprocessesassociatedwithformationofamineral deposit. 8 Magmatic:relatedtomagma,moltenrockandfluidoriginatingdeepwithinorbelowthe Earth’s crust. 7 Hydrothermal–hotfluids. 6 Metamorphic:rockschangedbytemperatureandpressurewithintheEarth’s crust 5 Sedimentary:arockformedfromsedimentwhichmayoforganicorinorganicinorigin, 4 Igneous:rockswhichhaveacrystallinetextureandappeartoconsolidatedfrommolten rock. sedimentary in magmatic REE mineral deposits occur in a broad range of igneous Major depositclasses because oftheirlargeionicradius fluids fromtheuppermantleandinmeltsofcrustalorigin The REEarepreferentiallyenrichedinpartialmeltsor Primary deposits further subdivided depending on their genetic associations and weathering. Within these two groups REE deposits can be secondary deposits concentrated by sedimentary processes associated with igneous and hydrothermal processes and be broadly divided into two categories: primary deposits processes. Environments in which REE are enriched can and concentration through weathering and other surface phases and precipitation, and subsequent redistribution forming and hydrothermal distribution of REE in mineral deposits is influenced by rock- veins andbreccia may beassociatedwithquartz-andfluorite-bearing the magmaticandhydrothermalenvironmentREEminerals alkaline igneousrocksandcarbonatites. with magmaticprocessesandarefoundin,orrelatedto, commercially importantREEdepositsareassociated provided byOrrisandGrauch(2002)(Table 3). Themost comprehensive listingofREEdepositsandoccurrencesis deposits andminesisshowninFigure 3.Themost The globaldistributionofselectedREEoccurrences, surface weathering deposits, or a combination of these. crystallisation, others of vein/replacement types and residual/ into those directly associated with magmatic processes and example deposits associated with carbonatites can be divided or the involvement of multiple geological processes. For deposits is complicated by unclear genetic associations and/ mineralogy and form of occurrence. Classification of some it hasformed.Depositswhichhaveaspatialandgenetic by itsmineralogyandthegeologicalprocessesfromwhich economic potentialofaREEdepositisstronglyinfluenced 8 5 or hydrothermal fluids, separation into mineral and metamorphic 11 zones,skarns 7 processes including enrichment 6 rocks. The concentration and 12 10 andpegmatites (Möller, 1986).Within 13 . The 4 , 9 , metasomatically carbonatites arecommonlysurroundedbyazoneof 3–4 km indiameter(BirkettandSimandl,1999).Intrusive Pipe-like bodies,whichareacommonform,maybeupto that maynotbeassociatedwithotheralkalinerocks. isolated dykesandsills,smallplugsorirregularmasses forms includingintrusionswithinalkalicomplexes, and Kjarsgaard,2008).Carbonatitestakeavarietyof the KolaPeninsulainRussiaandsouthernBrazil(Woolley African Riftzones,easternCanada,northernScandinavia, worldwide, withthemainconcentrationsinEast More than500carbonatiteoccurrencesaredocumented of majorfaultingparticularlylarge-scaleriftstructures. cratonic regions,commonlyinassociationwithareas alkaline igneousprovincesandgenerallyoccurinstable upper mantle.Carbonatitesarefrequentlyassociatedwith from carbondioxide-richandsilica-poormagmasthe per centcarbonateminerals.Theyarethoughttooriginate Carbonatites areigneousrocksthatcontainmorethan50 Carbonatite-associated deposits igneous rocks(SamsonandWood, 2004). and relatedigneousrockstheotherwithperalkaline or potassium.Thesedesilicified 1996). magma orfromhydrothermalfluids(Wall andMariano, minerals wereprecipitateddirectlyfromthecarbonatite This frequentlymakesitdifficulttodeterminewhetherthe develop inthelatestagesofcarbonatiteemplacement. (Gupta andKrishnamurthy, 2005).REEmineralscommonly minerals suchasbastnäsite,allanite,apatiteandmonazite in carbonatitesarealmostentirelyLREEwhichoccur niobum, uraniumandthorium(Rankin,2004).TheREE including REE,barium,strontium,fluorine,phosphorous, addition tocarbondioxide,calcium,magnesiumandiron, are characteristicallyenrichedinarangeofelements produced fromthecarbonatiteintrusion.Carbonatites develop asaresultofreactionwithNa-K-richfluids into twocategories,oneassociatedwithcarbonatites association withalkalineigneousrockscanbedivided 16 altered 17 rock,enrichedinsodiumand/ www.MineralsUK.com 18 zones,knownasfenite, 14

15

4 Rare Earth Elements (c) Classifiedas‘carbonatites withresidualenrichment’byOrrisand Grauch (2002). (b) Fourteenplacersof‘uncertain origin’areexcluded. (a) Includesigneous-affiliated, metamorphic,otherfluoriteandlead depositsofOrrisandGrauch(2002). Notes: deposit types.Thegradesand tonnagesofdepositsvaryconsiderably within eachdepositclass. exception ofion-adsorptionclays (GrauchandMariano,2008),are indicative ofthedistributionknowndepositsacross than onemineraldepositclass*. Numberofdocumentedoccurrences, compiled fromOrrisandGrauch(2002),withthe Table 3 Ion-adsorption clays Lateritic deposits Paleoplacers Alluvial placers Marine placers igneous rocks) (unrelated toalkaline Hydrothermal deposits deposits) oxide-copper-gold Iron-REE deposits(iron alkaline igneousrocks Associated with associated Carbonatite- Primary deposits Secondary deposits Deposit type Key characteristicsandexamples ofthemajorREEdeposit types.Specific depositslistedmayfallintomore of REE-enrichedgranites formed fromtheweathering Residual claydeposits enriched igneousrocks chemical weatheringofREE- formed fromintense Residual surfacedeposits rocks consolidated, cemented typically forming Ancient placerdeposits channels heavy mineralsinriver Concentrations ofresistant, existing coastlines found alongorcloseto by coastalprocessesand heavy minerals,concentrated Accumulations ofresistant, pegmatites ofdiverseorigin polymetallic veinsand Typically quartz,fluorite, character andform in ironoxideanddiverse Copper-gold depositsrich and enrichmentinHFSE by abundantalkaliminerals igneous rockscharacterised Deposits associatedwith of majorfaulting igneous provincesandzones associated withalkaline carbonate-rich igneousrocks Deposits associatedwith Brief description >100 42(c) 13(b) 78(b) 264(b) 63(a) 4 122 107 documented *Number grade (0.03–0.35%REO) Most <10000tonnes,low- 9.7% REO(upto40%REO) Weld: 12.24milliontonnesat tonnes, 0.1–10%REOe.g.Mt to severalhundredmillion A few10sthousandsoftonnes REO million tonnes,typically(<0.1% 10s milliontonnesupto100 Grauch 2002) at 0.041%monazite(Orrisand Horse Creek:19milliontonnes typically <0.1%monazitee.g. 10s to<200milliontonnes, Grauch 2002) at 0.046%Monazite(Orrisand Jangardup 30milliontonnes generally <0.1%monazitee.g. to 1–3hundredmilliontonnes, commonly intheorderof10s Highly variabletonnage, Grauch 2002) tonnes at0.51%REO(Orrisand REO e.g.LemhiPass:39million 0.5–4.0%, rarelyupto12% grade variable,typically rarely upto50milliontonnes, Typically <1milliontonnes, and Grauch,2002) tonnes at0.3295%REO(Orris e.g. OlympicDam:2000million tonnes at1.96%REO REO e.g.ThorLake:64.2million grade variable,typically<5% (Lovozero >1000 million tonnes), Typically <100milliontonnes at 4.1%REO Bayan Obo:750milliontonnes tonnes, 0.1–10%REOe.g. to severalhundredmillion A few10sthousandsoftonnes Typical grades andtonnage www.MineralsUK.com Longnan, Xunwu,China Brazil; Kangankunde,Malawi Mount Weld, Australia;Araxá, Mountain, USA Elliot Lake,Canada;Bald Guangdong, China belt andHorseCreek,USA; India; Carolinamonazite Perak, Malaysia;Chavara, India; Bay, SouthAfrica;Chavara, Cove Springs,USA;Richards WIM 150,Australia;Green Eneabba, Jangardup,Capel, USA; HoidasLake,Canada Snowbird andBearLodge, Africa; LemhiPassand Steenkampskraal, South Naboomspruit and Karonge, Burundi; Ridge, USA Olympic Dam,Australia;Pea Mountain, USA Brockman, Australia;Pajarito Canada; Weishan, China; Thor LakeandStrangeLake, Khibina andLovozero,Russia; Ilimaussaq, Greenland; USA Itapirapuã, Brazil;IronHill, Amba Dongar, India;Barrado Obo, China;Okorusu,Namibia; Mountain Pass,USA;Bayan Major examples 5 Rare Earth Elements

20

17 14

13 16 12 11 15 5 10 6 4 7 1 40 3 9 21 39 41 2 8 23 36 22 37 43 42

35 38

34

32 33 18 24 48 29 47 49 25 28 19 30 53 46 50 26 31 44 27 45 52 51

REE Other REE deposits/ mines occurences

Carbonatite-associated 1 Mountain Pass, USA 19 Barro do Itapirapua, Brazil 37 Orrisa, India 2 Pajarito Mountain, USA 20 Lovozero and Khibina complexes, Russia 38 Perak, Malaysis 3 Gallinas Mountains, USA 21 Tamazeght complex, Morocco 39 Maoniuping/Dalucao, China Alkaline igneous rock-associated 4 Iron Hill, USA 22 Bou Naga, Mauritania 40 Bayan Obo, China 5 Bald Mountain, USA 23 Nile Delta and Rosetta, Egypt 41 Weishan, China, Iron-REE deposits 6 Bear Lodge, USA 24 Etanero, Namibia 42 Xunwu/Longnan, China 7 Pea Ridge, USA 25 Okorusu, Namibia 43 Dong Pao, Vietnam 8 Green Cove Springs, USA 26 Steenkampskraal, South Africa 44 Eneabba, Australia Hydrothermal deposits exclusive 9 Carolina placers, USA 27 Zandkopsdrift, South Africa 45 Jangardup, Australia alkaline settings Primary deposits 10 Lemhi Pass, USA 28 Plinesberg Complex, South Africa 46 Mount Weld, Australia 11 Snowbird, USA 29 Naboomspruit, South Africa 47 Brockman, Australia Marine placers 12 Rock Canyon Creek, Canada 30 Palabora, South Africa 48 Nolans Bore, Australia www.MineralsUK.com 13 Hoidas Lake, Canada 31 Richards Bay, South Africa 49 Mary Kathleen, Australia 14 Thor Lake, Canada 32 Kangankunde, Malawi 50 Olympic Dam, Australia Alluvial placers 15 Elliot Lake, Canada 33 Congolone, Mozambique 51 WIM 150, Australia 16 Strange Lake, Canada 34 Karonge, Burundi 52 Dubbo Zirconia, Australia Paleoplacers 17 Ilimaussaq complex, Greenland 35 Chavara, India 53 Fraser Island, Australia 18 Araxa, Brazil 36 Amba Dongar, India Lateritic deposits

Ion-adsorption clays Secondary deposits

Figure 1 Map showing the global distribution of REE deposits. 6 Rare Earth Elements 26 25 24 23 22 21 20 19 deposits are stratabound east–west-trending zone, more than 18 main ore bodies (Main, East and West) lying along an mid-Proterozoic. The Bayan Obo deposit consists of three China craton, an extensional rifting environment in the deposit is located on the northern margin of the North Mongolia, China is the world’s largest REE deposit. The The Iron–REE–niobium deposit at Bayan Obo in Inner minerals (Wall and Mariano, 1996). may release REE which can potentially form secondary REE breakdown of primary minerals by lower temperature fluids earlier formed minerals. Subsequent alteration and cavity fillings or fine-grained disseminations overprinting REE mineralisation typically takes the form of fracture and including metamorphism and/or weathering. Hydrothermal date the intrusion, resulting from subsequent processes largely derived from the carbonatite or significantly post- carbonatites or the surrounding host rocks. The fluids can be late-stage vein and replacement mineralisation either within More commonly, REE deposits are also associated with (Evans, 1993; Castor and Hedrick, 2006; Castor, 2008a).minerals are rare in the ore, although galena is locallycent calcite common or dolomite and 20–25 per cent baryte.the Sulphide ore typically containing 10–15 per cent bastnäsite,rocks 65of pera similar age. The REE minerals occur in veins,carbonatites with are associated with potassium-rich igneous dipping, tabular Precambrian processes. The Mountain Pass carbonatite is a moderatelyUSA is an important example of a deposit formed by fluidsmagmatic (Möller, 1986). The Mountain Pass deposit suchin California, as bastnäsite and parisite as they crystallisesubsequently from the incorporated in monazite and other REEreplaced minerals by other minerals, releasing REE. These canapatite be and calcite. During later cooling, calcite crystallisescan be partially the majority of the REE are incorporatedprocesses into alone (Rankin, 2004). As a carbonatite bodyminerals can be concentrated by primary crystallisationAlthough rare, economic concentrations of REE-bearing rocks consisting of gneisses, granites and migmatites is thought to be largely Caledonian in age (420–555 within a dolomite marble (Wu, 2007). The mineralisation metasedimentary rocks of the Bayan Obo Group, largely Numerous carbonatite dykes are recognised in the district Cretaceous–ageological periodfromcirca145to65millionyearsago. Orogeny:amountainbuilding eventresultinginfoldingandfaultingof theEarth’s crust. Cenozoic:theperiodof geologicaltimefrom65millionyearsagotopresent. Stockwork:anetworkofmanycross-cuttingveins. Syenite:acoarse-grainedintrusiveigneousrock consistingpredominantlyofpotassiumfeldsparand littleornoquartz. Migmatite:averyhigh-grademetamorphicrock intermediatebetweenmetamorphicandigneous. Precambrian:theperiodoftimefromformation oftheEarth,about4500millionyearsagoto 590millionyearsago. Stratabound: anoredepositthatisconfinedto asinglesedimentarybedorhorizon. 21 and hosted by mid-Proterozoic 19 intrusion into metamorphic

km in length. The 20

Ma). . The stockwork systems consistingofpegmatites,carbonatitebreccias, deposit formedduringtheCenozoic calcite andbastnäsite(Houetal.2009).TheMaoniuping ores aredominatedbybaryte,fluorite,aegirine-augite, The LowerCretaceous averaging 2.89%rareearthoxide(REO)(Houetal.2009). deposit isestimatedtocontain1.2milliontonnesofore enriched byhydrothermalfluids(Wang etal.2008).The REE intheoriginalcarbonatitearethoughttohavebeen consists ofaveinsystemextendingforsome2.6 km. southern MalawiliesattheendofEast syenites is relatedtocarbonatitesillsanddykesassociated REE depositsandoccurrences.Themineralisation by Dulucaoandanumberofsmall-tomedium-sized Maoniuping, China’s second largest REE resource, followed long zone,measuring15 kmwide.Thelargestdepositis excess of3milliontonnesLREEandoccuralonga270 km south-west China.Thedepositscontaintotalreservesin carbonatite-alkaline complexesofwesternSichuan, identified inthe1990s,isassociatedwithHimalayan Less wellknownChineseREEmineralisation,only carbonatite magma, enriched in REE (Yang. et al. 2009). rocks metasomatised by fluids likely to be derived from a at Bayan Obo are derived from sedimentary carbonate published research concludes that carbonate minerals the result of carbonatite magmatism (Rankin, 2004). Recently proposing a sedimentary origin whilst others suggest it is dolomite hosting the deposit is disputed with some authors mineralisation have been proposed. The origin of the and hydrothermal iron oxide-copper-gold-(REE-uranium) Genetic models relating it to both carbonatite magmatism the Bayan Obo deposit is the subject of considerable debate. hematite and magnetite (Chao et al. 1997). The formation of being colombite. The most important iron minerals are niobium minerals are also common, the most widespread including huanghoite, parisite and cebaite. REE-bearing bastnäsite, although many other REE minerals are present and Chengyu, 2000). REE principally occur as monazite and evident and over 170 minerals have been identified (Smith and south of the ore bodies. Multiple mineralising stages are and several gabbros and alkali gabbros occur to the north 22 . Mineralisationishostedincomplexvein 23 zonesanddisseminatedmineralisation.The 26 ChilwaAlkalineProvinceof www.MineralsUK.com 24 orogeny 25 and 7 Rare Earth Elements A widezoneofbrecciationandfenitization fluids expelledbytheCretaceousOkorusucarbonatite. fluorite depositinnorthernNamibiadevelopedfrom of EnergyandMines,2009).TheREE-richOkorusu and extremelylowthoriumuraniumcontent(Ministry monazite atKungankundeisunusualforitshighCelevels containing monazite,strontianite,fluoriteandbaryte.The gneisses andfenite,surroundingacarbonatitecore approximately concentriczonesofagglomerate,breccia, the provinceandrichestinREE.Itconsistsof Kangankunde isoneofthelargestcarbonatitesin Chilwa Island,SongweandTundulu complexes. and alkalinecomplexes,includingtheKangankunde, African rift.Itcontainsnumerousmineralisedcarbonatitic aluminium. Importantlyperalkalinerocksarecommonly proportion ofcombinedsodiumandpotassiumthan classified asperalkalineiftheyhaveahighermolecular ultramafic Alkaline igneousrocksvarywidelyincomposition,from and amphiboles)notcommonlyfoundinotherrocktypes. bearing minerals(suchasfeldspathoids,alkalipyroxenes in alkalisthattheyprecipitatesodium-andpotassium- Alkaline igneousrocksformfrommagmassoenriched Deposits associatedwithalkalineigneousrocks mineralisation (Andradeetal.1999;Ruberti2008). LREE depletionandHREEenrichmentrelativetotheearlier and apatite.Asubsequenthydrothermalstageresultedin REE-mineralisation depositedfluorocarbonateswithquartz magmatic fluids.Theinitialstagerepresentingthepeak two stagesofhydrothermalactivity, probablyrelatedto and sulphideminerals.TheREEwereintroducedduring of quartz,apatite,fluorite,REEfluorocarbonates,barytes Hydrothermal alterationhasresultedintheintroduction from hydrothermaloverprintingoftheoriginalcarbonatite. Brazil areassociatedwithREEmineralisation,resulting Cretaceous BarradoItapirapuãcarbonatitesinsouthern mineralisation (Doroshkevichetal.2009).TheEarly enrichment ofthecarbonatitesandassociatedfluorite sandstones. HydrothermalactivityhasresultedinREE number ofsyeniteintrusions,hostedinlate-Cretaceous western Indiaconsistsofacarbonatiteringdykeand et al.2002).TheAmbaDongarCarbonatitecomplexin massive fluoriteveinsorreplacementdeposits(Buhn at theouteredgeofzonefenitizationaseither the Okorusucomplex.Thefluoritemineralisationoccurs 32 31 30 29 28 27 Peralkaline:igneousrocks withiftheyhaveahighermolecularproportion ofcombinedsodiumandpotassium thanaluminium. Cumulate:igneousrocks ormineral-richlayersformedbythesettling ofcrystalsinamagmachamber. Highfieldstrengthelement: elementswhicharenotreadilyincorporated intothestructuresofcommon rock-formingsilicatemineralsduringcrystallisation ofanigneousrock. Felsic:arockconsistingchieflyoffeldspars,feldspathoids, quartz,andotherlight-colouredminerals. Ultramafic:composedchieflyofferromagnesian (Fe-Mg)minerals,suchasolivineandpyroxene. Fenitization–alkalichemicalalterationofarock resultinginenrichmentsodiumand/orpotassium. 28 tofelsic 29 . Alkalinerockscanbefurther 27 surrounds several HFSE-enrichedperalkaline The StrangeLakeComplexineasternCanadaconsistsof cent REO (Salvi and Williams-Jones, 2004). 30 for about 50 years. Annual production is approximately loparite and apatite. Loparite has been mined periodically strontium, barium and phosphorus, which occur as eudialyte, Complex is rich in zirconium, niobium, REE, yttrium, enriched in yttrium amongst other elements. The Lovozero thought to have crystallised from a magma. The apatite is extensive nepheline syenite-associated apatite deposits igneous bodies in the world. The Khibina Complex hosts Peninsula, in Russia are some of the largest peralkaline cent REO. The Khibina and Lovozero complexes on the Kola total resource of about 2 million tonnes, grading 1.5 per separate eudialyte-rich layers have been defined, with a and niobium in eudialyte-rich cumulate layers. Twenty-nine contains potentially exploitable deposits of REE, zirconium The Ilimaussaq alkaline complex in southern Greenland minerals. substitute for calcium in fluorite or occur as associated REE in hydrothermal veins is a potential source of REE which Williams-Jones, 2004). Fluorspar which commonly occurs hydrothermal enrichment of around 25 times (Salvi and the deposit which grades 1.5–2.5 source of the mineralising fluids, is ~650 concentration in the quartz-syenite intrusion, the suggested the Gallinas Mountains in New Mexico, USA the total REE For example in the fluorspar associated REE deposits of dominant role, upgrading initial magmatic concentrations. In other examples hydrothermal processes have played the REE mineral-rich layers form part of a cumulate for the mineralisation, as is evident from deposits in which some instances magmatic processes are entirely responsible enrichment of HFSE results from magmatic processes. In poorly understood. It is generally agreed that the initial The formation of HFSE mineralisation in alkaline rocks is and HREE(CastorHedrick,2006). low-grade, although,theyaretypicallyenrichedinyttrium associated withperalkalinerocksaretypicallyrelatively titanium, yttrium,niobiumandREE.REEdeposits high-field strengthelements characterised byextremeenrichmentinalkalinemetals,

000 tonnes of loparite concentrate, containing 34 per 30 (HFSE)e.g.zirconium, www.MineralsUK.com

wt. per cent REE, requiring 32 plutons.Thedominant

ppm, compared to 31 sequence. 8 Rare Earth Elements the formofdisseminated and apatite)uraninitethorite. Depositstypicallytake (including bastnäsite,monazite,xenotime,allanite,parisite and othermineralsincludequartz,apatite,REE mineralisation. Coppersulphidesarecommonlypresent and hematite)formasignificantcomponentofthe rocks. Inthesedepositsironminerals(magnetite intrusive They arehostedbyavarietyofrocksrangingfrom these depositsastheyareabsentfrommanyexamples. REE concentrationsarenotadefiningcharacteristicof type oriron-oxide-copper-gold (IOCG)deposits. Notably these aretheiron-REEdeposits,alsotermedOlympicDam- to alkalineigneousrocks.Themostsignificantgroupof A diversegroupofREEdepositsarenotobviouslyrelated Deposits unrelatedtoalkalineigneousrocks with syeniteintrusions(CastorandHedrick,2006). consists ofbastnäsite-barite-carbonateveinsassociated The Weishan REEdepositinShangdongProvince,China Complex, SouthAfrica(SalviandWilliams-Jones,2004). the Tamazeght Complex,Morocco,andthePilanesberg of REEenrichmentassociatedwithalkalinerocksinclude REE, amongstotherelements.Othersignificantexamples contains 642milliontonnesoforegrading1.96.percent alkaline granite.Thelargeroftwodepositsdelineated Territories ofCanadaishostedinasyeniteandassociated and gadolinite.TheThorLakedepositintheNorthwest minerals includebastnäsite,monazite,kainosite,thorite REE-bearing mineralisgittinsite,butotherimportant 38 37 36 35 34 33 The AnchorHouse,Inc.2007. REE-bearing bastnäsite,ThorLake.©ClintCox, Diorite:an intrusive igneousrockdominated byplagioclase feldspar, hornblende, pyroxeneandlittleor noquartz. Granite:anintrusiveigneous rockdominatedbyquartzandfeldspar. Vein: mineralsdeposited infracturesarock. Massive:ahomogenous structure. Disseminated:small,fine-grainedparticlesof oremineraldispersedthrougharock. Intrusive:abodyofigneousrockemplacedinto pre-existingrocks. 33 igneoustovolcanicandavarietyofsedimentary 34 tomassive 35 replacement

Canada is hosted by granitic and apatite. The Hoidas Lake REE deposit in Saskatchewan, in quartz, biotite and feldspar with hematite, monazite, thorite Pass area along the Idaho-Montana border. The veins are rich sedimentary rock-hosted veins and breccia zones in the Lemhi quartz and carbonate. REE-thorium mineralisation occurs in and baryte, REE minerals (synchysite and parisite dominate), and breccia-hosted mineralisation associated with fluorite Creek mineralisation varies from finely disseminated to vein the Snowbird deposit in Montana, USA. At Rock Canyon at Rock Canyon Creek in British Colombia, Canada and at associated REE mineralisation in sedimentary rocks occurs rocks of the Rocky Mountains in North America. Fluorite include the REE mineralisation hosted in sedimentary associated with alkaline or carbonatite intrusions. Examples characteristics of the iron-REE deposits and are not obviously There are a number of REE deposits which do not display 2000). cent Fe)(SamsonandWood, 2004; SmithandChengyu, abundant ironoxides(1.5billiontonnescontaining35per deposit, ChinaintheOlympicDamclassbecauseof researchers includethehugeBayanOboiron-REE-niobium to beenrichedinREE(CastorandHedrick,2006).Some and hematitedepositsatKiruna,Swedenarereported significant HREEenrichment.Theextensivemagnetite xenotime, andisdominatedbyLREE,butalsocontains to agraniticbody. Thedepositcontainsmonaziteand REE mineralisationisassociatedwithbrecciapipesrelated At thePeaRidgeirondepositinMissouri,USAhigh-grade at around0.5percentREO. containing upto90percenthematite.Theoreislow-grade in SouthAustraliaconsistslargelyofabreccia-typeore massive OlympicDamcopper-uranium-silver-gold deposit monazite andxenotime(SamsonWood, 2004).The baryte. OtherREE-bearingmineralsincludeflorencite, in associationwithhematite,quartz-sericite,borniteand Dam depositthismineralisingstageconsistsofbastnäsite considerably moreimportant.InthecaseofOlympic has alowREEcontent.However, thesecondstageis the generallylowabundanceofapatite,whichtypically this stageofmineralisationislesssignificantbecause magnetite mineralisation.Fromaneconomicperspective deposit formationtheREEoccurinapatiteassociatedwith with twostagesofmineralisation.Intheearlystage class theintroductionofREEiscommonlyassociated bodies, veins 36 andbrecciazones.Indepositsofthis 37 to dioritic www.MineralsUK.com 38 , high-grade 9 Rare Earth Elements high-grade metasedimentary lenses and veins of massive allanite and apatite, hosted in Kathleen uranium-REE skarn deposit consists of numerous nearly 500 the Australian coastline. Rutile-zircon-ilmenite deposits Extensive heavy mineral sand placer deposits occur along can contain 1–2 per cent monazite (Möller, 1986). to 1 per cent monazite and Indian ilmenite placer deposits However, Australian deposits have local concentrations up economic because of the production of the other minerals. and, as a result, REE production from placers was only than 0.1 per cent) among the other heavy mineral phases forms a minor constituent of these deposits (typically less radioactivity (Castor and Hedrick, 2006). Monazite typically typically high thorium content and associated high levels of derived from monazite-bearing placers, owing to their historically important very little REE production is currently were one of the most important sources of REE. Although produced from titania-zircon beach placers in Australian zirconium content. During the 1980s monazite and xenotime deposits are largely exploited for their titanium and by wave action, tides and currents. These heavy mineral shorelines. The minerals in these deposits are concentrated origin, developed along or in close proximity to current 1986). The most important placer deposits are of marine samarskite, allanite, knopite, pyrochlore and loparite (Möller, minor quantities of xenotime, fergusonite, euxenite, REE-bearing mineral in placer deposits is monazite, with than 360 placer deposits world-wide. The most important and Hedrick, 2006). Orris and Grauch (2002) identify more known as paleoplacers are found in a few countries (Castor Quaternary in age. However, deposits as old as Precambrian, significant quantities of REE minerals are Tertiary or and REE. The most important placer deposits containing frequently include minerals rich in titanium, zirconium can originate from a diverse range of primary sources and by rivers and/or coastal processes. These detrital minerals minerals transported and deposited with sand and gravel Placer deposits are concentrations of resistant, heavy Placer deposits Secondary deposits forming a 60 allanite. The veins are controlled by north-east-trending faults of a pyroxene- and apatite-rich vein system, containing lies close to a major fault zone. The mineralisation consists metamorphic rocks. The deposit is structurally controlled and 39 intrusion (Samson and Wood, 2004). Metasedimentary:sedimentary rockthatshowsevidenceofhavingbeen subjectedtometamorphism.

metres (Harvey et al. 2002). In Australia, the Mary

metre wide mineralised zone, extending for 39 rocks close to an alkali granite 2008b). have subsequently enriched the heavy minerals (Castor, brannerite. Metamorphism and hydrothermal activity may conglomerate containing REE in monazite, uraninite and uranium, consists of a metamorphosed early Proterozoic Ontario, Canada. The deposit, formerly mined chiefly for minerals of possible placer origin occurs at Elliot Lake in A considerably older deposit containing REE-bearing and Krishnamurthy, 2005;CastorandHedrick,2006). Idaho wheremonaziteandeuxenitewereproduced.(Gupta occurrences aretheCarolinamonazitebeltanddepositsin ilmenite, zircon,magnetiteandotherminerals.Notable placer deposits.Inthesemonazitetypicallyoccurswith USA. TheUSAhassomehistoricallyimportantnon-marine Pleistocene marinesandsatGreenCoveSpringsinFlorida, in additiontootherheavymineralswasproducedfrom dominated yttriumproductionfromxenotime.Monazite monazite andxenotimeMalaysiahistorically Alluvial tindepositsinMalaysiacontainsignificant occur inplacerdepositsworkedfortin,zirconandtitania. tonnes ofREO.Insouth-eastAsia,monaziteandxenotime present coastlineandareestimatedtocontain2.7million minerals. Themajorityofthedepositsoccuralong deposits containingmonaziteinadditiontootherheavy number ofothercountries.Indiahasextensivebeachsand Monazite hasbeenproducedfromplacerdepositsina and Hedrick, 2006; Whitehouse et al. 2000). tonnes of monazite and 170 mineral sand body. Estimated reserves exceed 580 000 Miocene, 14 of Victoria. Here the WIM 150 deposit consists of a mid- resource, is located inland in the southern Murray Basin placer deposit in Australia, containing a large REE mineral minor historical monazite production. Another important production is largely confined to rutile and zircon, with sand dunes also occur along Australia’s east coast. Current found in south-west Australia. Quaternary beach placers and monazite-bearing placers of Pleistocene to Recent age are reworked to form the placer deposits. Ilmenite-zircon, incorporated in Mesozoic sedimentary rocks before being be derived from Achaean metamorphic rocks which were above current sea level. The heavy minerals are thought to Tertiary to early Pleistocene and are now located about 30 between 0.5–7 per cent. These deposits formed in the late at Eneabba is about 6 per cent, with a monazite content tonnes of monazite. The heavy mineral content of the sands Historically these deposits annually produced about 2500 occur at Eneabba on the west coast, north of Perth.

metre thick sheet-like titanium and zirconium

000 tonnes of xenotime (Castor www.MineralsUK.com

m 10 Rare Earth Elements (Grauch andMariano,2008). with lowgradesbetween0.03–0.35 percenttotalREO are smalldeposits,intherange of3000–12 000tonnes, and Hedrick,2006;Kanazawa andKamitani,2006).These zone withthesamemineralsasoriginalrock(Castor weathered layer(3–5 metres);andaweakly weathered zoneenrichedinREE(5–10 metres),asemi- an upperlayerdominatedbysoil(0–2 metres);astrongly and canbedividedintofourlayersbasedonmineralogy: REE-rich zonestypicallyrangefrom3to10 metresthick and otherclaymineralssuchashalloysite.Theweathered, the breakdownofprimarymineralsareabsorbedbykaolin REE releasedduringtheweatheringofgranitesand Guangdong, HunanandFujian(GrauchMariano,2008). southern China,particularlyintheprovincesofJiangxi, weathered REE-enrichedgranitesoccurthroughout ion-adsorption clays.Thesedepositsassociatedwith are residualdepositsofREE-bearingclays,termed A relativelynewlyrecognisedclassofREEdeposits minerals (Pirajno, 2009; Castor and Hedrick, 2006). and niobium. The REE largely occur in secondary phosphate weathering has created a laterite rich in phosphorus, REE is a ring complex about 4.5 lateritic zones. The Cretaceous Araxá carbonatite in Brazil enrichment of various mineral commodities associated with A number of Brazilian carbonatites display supergene period (Lottermoser, 1990; Castor and Hedrick, 2006). and redeposition of REE by groundwater over a sustained the extreme enrichment is thought to result from leaching unweathered carbonatite contains 0.1–0.2 per cent REO and per cent occurring mainly in REE phosphate minerals. The The deposit has exceptionally high REO contents of up to 40 a thick laterite, above a Proterozoic deposit at Mount Weld, Western Australia is developed in high-grade, containing 10–25 per cent REO. The major REE phosphates including monazite. The deposits are typically be incorporated in new supergene dolomite and apatite. REE released from these minerals can weathering of carbonatites causes dissolution of calcite, may be enriched to form an economic deposit. Chemical parent rock is enriched in REE, such as in carbonatites, REE and aluminium). Under certain conditions and where the residual enrichment of less mobile elements (e.g. iron of certain elements (e.g. calcium and magnesium) and breakdown of many rock-forming minerals, leaching prolonged tropical weathering which leads to the Laterites are in situ residual deposits derived from Residual weatheringdeposits 41 40 Proterozoic:theperiod ofgeologicaltimeextendingfrom2500–542million yearsago. Supergene:near-surface processes ofleachingandtransportationmetals followedbyre-precipitation. kilometres in diameter. Deep 40 41 minerals, commonly carbonatite intrusion. (Jackson and Christiansen, 1993). When placer deposits deposits placer When 1993). Christiansen, and (Jackson precipitates calcareous or ferruginous by cemented been has sand the where areas limited in except required generally not is blasting and Drilling 2010). (Iluka, bodies ore discontinuous of series a in occur or rock of bands hard contain shallow, are deposits where suitable is mining Dry plant. processing the to ore consolidated poorly typically the transport and collect to loaders and bulldozers scrapers, use operations mining Dry land. on or water in submerged are they whether on dependent are deposits placer for methods Mining and Kamitani,2006). required considerablyreducingextractioncosts(Kanazawa using open-pitmethods.Nodrilling,blastingormillingis surface, unconsolidatednature.Thedepositsaremined is simplerthanforothertypesofdepositduetotheirnear- China, arerelativelylowgradebutminingandprocessing Ion adsorptiondeposits,suchasthosefoundinsouthern fluorescence (CastorandHedrick,2006). at 3–4 metrespacingandassayedforREOusingX-ray pit, whichwas150 metresdeep.Blastholesweredrilled Pass depositinCaliforniawasalsominedasanopen approach (JacksonandChristiansen,1993).TheMountain from twolargeopenpitsusingastandardopen-pitmining For example,theBayanObodepositinChinaismined extracted usingeitheropenpitorundergroundmethods. rock depositssuchasthosecontainingbastnäsiteare to accessshallowanddeeperpartsofanorebody. Hard single mine,andmaytakeplacesimultaneouslyinorder and undergroundminingaresometimescombinedata belt forstockpilingpriortofurtherprocessing.Surface explosives, thenremovingtheorebytruckorconveyor removing theoverburden,diggingoreorblastingwith or massiveorebodies.Thismethodtypicallyinvolves <100 metres, whicharelower-grade, steeplydipping most appropriatefornear-surface deposits,typically operate thanundergroundmines.Open-pitminingis Surface minesaregenerallycheaperandsaferto Surface mining Extraction methods the typeofminingused. will frequentlydictatetheeconomicsofoperationand frequently exploitedasby-productsofothermetals,these techniques usedintheirexploitation.BecauseREEare considerable variationintheminingandprocessing The diversityofREE-bearingdepositsresultsin Extraction methodsandprocessing www.MineralsUK.com 11 Rare Earth Elements Placer deposit mining © image courtesy of Iluka Resources a by-product of iron ore extraction. Loparite production in in production Loparite extraction. ore iron of by-product a as China in Obo Bayan from extracted originally were REE REE. of recovery the for exclusively operated has which mine only the is California in Pass Mountain mine. a of product primary or only the as mined rarely very are REE By-product production pit methods (Castor and Hedrick, 2006). complex in Russia is mined using both underground and open uranium production (Harben, 2002). Loparite from the Lovozero in Canada where REE were extracted as a by-product of room and pillar methods were used at the Elliot Lake, mine worked, as well as providing more roof support. Underground forcing air to travel through only those areas that are being be backfilled with waste material to improve ventilation by the shaft using an underground rail system. Old workings may support. Ore is blasted using explosives then transported to stopes or rooms leaving pillars of solid material for roof progresses in a near horizontal direction by opening multiple and pillar is an underground mining method where mining introduce more mechanisation into the workplace. Room blasting techniques, though attempts are being made to Typically, these operations use labour-intensive drillingmethods and depending on the characteristics of the ore body. Underground extraction uses a variety of standard mining Underground mining 2010). (Iluka, concentrator floating a to form slurry in ore pumping ponds, artificial in used also are Dredgers column. water the of base the from material recover to device suction a or buckets of series a use either which vessels floating are Dredgers dredger. a uses typically extraction table, water high a by affected are or water in submerged are bond andtoahydroxyl group, OH,byasinglebond). 46 45 44 43 42 Dicarboxylicacid:organic compoundsthataresubstitutedwithtwocarboxyl functionalgroups(acarboxyl functionalgroupconsistsofacarbonatom joinedtoanoxygenatombyadouble Hydroxamate:ahydroxylamine (areactivechemicalwithformulaNH Reagent:asubstanceor compoundthatisaddedtoasysteminorder tobringaboutachemicalreaction. Suspension:amixtureinwhichfineparticles aresuspendedinafluidwheretheysupportedby buoyancy. Frothflotation:aprocessforselectivelyseparating hydrophobic(lackingaffinityforwater)materials fromhydrophilic(havingastrongaffinityforwater). 2 OH) compoundcontaining aCONOHgroup. to produceasuspension Following grinding,waterisaddedtothepowderedore minerals usingwater, chemicalsandcompressed air. Froth flotation by flotationtoproduceabastnäsiteconcentrate(Figure 2). containing 30–35 per cent solids. The slurry was processed reagents beingaddedateachstagetoproduceaslurry to sixconditioningtreatmentswithsteamanddifferent approximately 0.1 mm.Thematerialthenunderwentup to aballmillwheretheparticlesizewasreduced subsequently senttothemill’s fineorebinandconveyed an averageofsevenpercentREEoxide.Thismaterialwas was depositedinlayerstoformblendingpilescontaining At theMountainPassdepositinCaliforniacrushedore Following miningbastnäsiteoreiscrushedandscreened. Hard rockdeposits Physical beneficiation physical andchemicalprocesses. separating REEandgangueminerals,usingarangeof close to,theminesiteandinvolvescrushingore REE content.Concentrationisnormallyundertakenat,or After miningtheoresareprocessedtoincreasetheir Processing and dicarboxylic for monaziteflotationincludefattyacids,hydroxamates a frothatthesurfaceandareremoved.Reagents to theirsurfaces.Consequently, thesemineralscollectin minerals waterrepellentandcauseairbubblestostick the tanks.Chemicalsareaddedwhichmakespecific Krishnamurthy, 2005). Krishnamurthy, and (Gupta content REE their for purely exploited be to potential the have Australia in Weld Mount as such Deposits REE. the than rather content thorium the for principally However,was this monazite. for exclusively worked been has deposit sand mineral a where country only the is Brazil extraction. tin or zircon titanium, of by-products generally are deposits sand mineral in REE niobium. and zirconium to addition in REE produce will Australia in operation Zirconia Dubbo The Canada. in operations mining uranium from recovered been have REE and extraction titanium of by-product a was Russia Krishnamurthy, 2005). and calcite,havesimilarflotation properties(Guptaand minerals associatedwithbastnäsite,suchasbaryte with flotationseparationassomeofthecommongangue 42 isaselectiveprocessforseparating 46 acids.However, thereareproblems 43 . Airisblownupwardsthrough www.MineralsUK.com 44 used 45

12 Rare Earth Elements methods varygreatly. Inmanycases gravityseparationis mineralogy and chemicalcompositionthebeneficiation Since placerdepositsshowconsiderable variationin Placer deposits 2006). Hedrick, and (Castor concentrate loparite cent per 95 a produce to methods electrostatic and gravity of combination a uses Russia in loparite of beneficiation Physical 1994). (McKetta, produced are concentrate -monazite bastnäsite mixed a and concentrate bastnäsite a and flotation by separated is ore iron The 2006). Hedrick, and (Castor requirement this by influenced is process beneficiation the so recovered also are oxide niobium and fluorite hematite, magnetite, deposit Obo Bayan the at example For greatly. vary methods beneficiation the accordingly and minerals other of by-product a as REE produce generally operations Other mine. the from product only the are REE that in unusual is Pass Mountain 2005). recovery of65to70percent(GuptaandKrishnamurthy, final concentrateof60percentREEoxidewithanoverall a fourstagecleaningmethodwasdevisedproducing Following flotationtheoreiscleaned.AtMountainPass Figure 2 R efining surface/underground Generalised bastnäsitebeneficiationflowdiagram,based upontheMountainPassoperation. Mining by methods REO 60% concentrate Bastnäsite filtering, drying) further gravity methods asitismoderatelysusceptible to is thenseparated fromthezirconbyelectromagnetics or and isseparated,withzircon, byelectrostaticmethods.It heavy mineralsfoundinplacer deposits,isnon-conductive Monazite, incontrasttoilmenite, rutileandmanyother of gravity, magnetic andelectrostaticmethods(Figure3). ene, zircon and monazite are produced using a combination essed inadrymill.Concentratesofilmenite,rutile,leucox The concentrateproducedbygravityconcentrationisproc Krishnamurthy, 2005). do notrequirethispre-concentratingstage(Guptaand sands inIndiacontain70–80percentheavymineralsand grade depositssuchastheChavraandManavalakurichi into previouslyminedareas(McKetta,1994).Higher during miningandunwantedtailingsaredischargedback the initialgravityseparationiscompletedondredge separation (CastorandHedrick,2006).Inplacerdeposits cone concentratorsandshakingtablesareusedingravity are alsoremoved.Equipmentincludingjigs,spiraland The higherdensitymineralsofeconomicvaluesinkand a lowerdensity, tendtofloatandareremovedaswaste. fed intoasuspension,andthegangueparticles,having with significantdifferencesindensities.Thesedimentis used asitisparticularlyeffectiveforseparatingminerals (thic Cleaning grinding Crushing k ening, & Ground ore concentrate Bastnäsite steam conditioning www.MineralsUK.com Chemical and flotation Impurities F roth (30-35% solids) Ore slurry Chemicals added - - 13 Rare Earth Elements as theyhaveverysimilardensityandmagneticproper separated frommonaziteusingprecisegravitymethods magnetism andhasahigherdensity. Xenotime isusually mineral concentrateisbakedwithsulphuricacidat (Jackson andChristiansen,1993).AtBayanObothe carbon dioxideleavingan85–90%REOconcentrate carbonates. Calcinationwasthenusedtoremovethe hydrochloric acidtoremovestrontiumandcalcium was upgradedtoabout70percentbyleachingwith (about 60%REO)obtainedfromphysicalbeneficiation At theMountainPassdepositbastnäsiteconcentrate Hard rockdeposits Kingsnorth, 2002). and theeconomicsofoperation(Chegwidden processing routeselecteddependsonthetypeofminerals developed considerablyoverthelast20yearsand the REE(Figure4).Theprocessesusedforthishavenot concentrate subsequentprocessingisrequiredtoextract Following physicalbeneficiationtoproduceaREEmineral Chemical beneficiation 2005). method soflotationisused(GuptaandKrishnamurthy, 15 and100microns)gravityseparationisnotanefficient ties (McKetta,1994).Forfinergraineddeposits(between Figure 3 CONCEN XENO TIME TRA Generalised flow diagramforextractionof monazite and xenotimefromplacerdeposits. TE or airtable W dredging orscraping et table CONCEN MONAZITE Mining by TRA magnetics Induced TE separation magnetic Induced Zircon Non-conductors Non-conducti S - creening Electrostatic Leuco separation ve xene Conducti Conductors use as it does not yield a pure product (Gupta and and (Gupta product pure a yield not does it as use in longer no is it but past the in basis commercial a on used been has method acid sulphuric The 2006). Hedrick, and (Castor sulphates double as REE and thorium deposits precipitation selective of process a whereby follows stage dilution A content. phosphate the remove to water with leaching then digestion acid sulphuric hot uses treatment Acid treatment). (acid solutions acidic or method) soda (caustic alkaline concentrated hot in minerals the of dissolution involves xenotime and monazite from extraction REE Unconsolidated deposits thorium (CastorandHedrick,2006). and sodiumcarbonateisusedtoprecipitatetheREE ammonium sulphate.Water isaddedtodilutethesolution cake isthendissolvedinsulphuricacidthepresenceof and otherelementswhichremainasafusioncake.This niobium andtantalumareseparatedfromREEchlorides temperatures inthepresenceofreducingagents.Titanium, in Russiaisprocessedusinggaseouschlorinationathigh with hydrochloricacidforpurification.Lopariteconcentrate double sulphates,convertedtohydroxidesandleached (liquid-solid separation).TheREEarethenprecipitatedas into solutionandprecipitatingotherelementsaswaste 300–600°C andleachedwithwater, takingtheREE ve Sized ore Non-magnetics Magnetic separation Magnetic added W Ilmenite ater Non-magnetic Magnetics Dry concentrate Sized oreslur www.MineralsUK.com ry Gravity separation spiral separation Multiple stages dewatering, Washing, drying Concentrate 14 Rare Earth Elements the phosphate is lost (Gupta and Krishnamurthy, 2005). Krishnamurthy, and (Gupta lost is phosphate the treatment acid with whereas by-product, marketable a as recovered be can phosphate the as treatment chemical for process preferred the is This 2002). Latifah, and Yusoff (Meor 1994 in closure its until plant (ARE) Earth Rare Asian the at Malaysia in used was and Ltd Earths Rare Indian by India in used is method soda caustic The 2005). Krishnamurthy, and (Gupta waste cake thorium forms and filtered is material undissolved the whilst acid hydrochloric concentrated in dissolved are REE which in dissolution partial using thorium from separated are REE phosphate. trisodium as recovered and water in dissolving by separated is compound phosphate The hydroxides. to thorium and REE the converting 140–150°C, at hydroxide, sodium of solution concentrated a in minerals the of dissolution involves method soda caustic 2005).The Krishnamurthy, HCl, hydrochloricacid(adaptedfromChegwiddenandKingsnorth, 2002). Figure 4 Calcination (650ºC) REE purification Mountain P 85-90% REO concentrate HCI leac Examples ofchemicalprocessingroutesforthemajor REE-bearing minerals.H h ass concentrate Bastnäesit L e REE purification P Con recipitate REE Liquid-solid W H h Bayan Obo separation 30 as double sulphates HCI leac ydro 2 ater leac SO ver 0-60 4 sion to xides bak 0°C h e h S ORE T YPE L due totheirsimilar chemicalproperties(Morais and individual REE from concentratesisaverydifficult process separation intohighpuritycompounds. Separating The highvalueofREEdepends ontheireffective Separation ofindividualREE enrichment in HREE and yttrium. low contents of cerium and radioactive minerals, and their (Grauch and Mariano, 2008). Additional benefits include their despite their relatively low grades (0.03 to 0.35% total REO) means these types of deposits can be economically exploited can be precipitated (Molycorp, 1993). This simple procedure produces a solution containing REE from which a concentrate characterise hard rock deposits. A simple leaching process do not require the processing of complex minerals that forward compared with other types of REE deposit as they Processing of ion adsorption clays is relatively straight REE purification REE h P Con recipitate REE Liquid-solid W separation Acid route Hot H as double sulphates HCI leac digestion ater leac ver ydro sion to 2 SO xides h 4 h concentrate Monazite/ S x enotime Th w aste 2 SO L S www.MineralsUK.com REE purification 4 , sulphuricacid; Alk to h Liquid-solid Liquid-solid Con separation separation aline route ydro leac HCI ver h sion xides S L w aste 15 Rare Earth Elements precipitation display divalency the trivalent state and samarium, europium and terbium characteristically trivalent useful in the separation process. In general REE are Selective oxidation or reduction of certain REE can be (Zhongde, 2009). per centpureREEandJapanesesources99.9 purity, whilstFrenchcompaniestypicallyproduce 99.99 China, whichcansupplyREEproductsat99.9999percent Ciminelli, 2004).REEprocessingismostadvancedin preferred route(Molycorp,1993). For largescaleproductionsolventextractionisthe purified commerciallyonasmallscaleusingionexchange. it isatimeconsumingprocessandonlyfewHREEare produces highlypureREEinsmallquantities.However, for thevariousREE(EPA, 2008).Theionexchange method using acomplexingagentwhichhasdifferentaffinities deposited ontheresin.IndividualREEarethenseparated containing theexchangedcations,withamixtureofREE on theresinsurface.Thisproducesanaqueouswaste and terbium can occur in the tetravalent can be separated using fractional crystallisation generally separated by selective oxidation whilst other REE (Gupta and Krishnamurthy, 2005). Cerium and europium are can be exploited in the separation of individual elements in basicity methods. These methods are based on the small differences the ionexchangeresin.TheREEdisplacecations solid. ThesolutioncontainingtheREEisthenpassedover between asolutionandaninsoluble(usuallyresinous) Ion exchangeisaprocessinwhichionsareexchanged this method (Moore, 2000). LREE, with the HREE being more difficult to extract using extraction method is most appropriate for separating the extraction (Gupta and Krishnamurthy, 2005). The solvent more effective techniques like ion exchange and solvent and inefficient and have consequently been superseded by separating REE. These processes, however, are laborious crystallisation were the only techniques available for Until the early 1950s fractional precipitation and fractional from lanthanum to lutetium (Morais and Ciminelli, 2004). component crystallisesout. 54 53 52 51 50 49 48 47 Immiscible:one(ormore) liquidsthatareunmixableorinsolublewith eachother. Cation:apositivelycharged ion. Basicity:Thedegreetowhichasubstanceisbasic oralkali. Fractionalprecipitation:removalofsomeions fromsolutionbyprecipitationwhileleavingotherions withsimilarpropertiesinsolution. Fractionalcrystallisation:theprocessofseparating thecomponentsofasolutiononbasistheir differentsolubilities,bymeansofevaporatingthesolutionuntil least soluble Divalency:Havingavalanceoftwo(valencyis ameasureofthenumberchemicalbondsformedby theatomsofagivenelement). Tetravalent: Havingavalenceoffour. Trivalent: Havingavalanceofthree. 52 , resulting from decreasing size in ionic radius 51 , solvent extraction and ion exchange 49 . These differences in chemical behaviour 47 but cerium, praseodymium 48 state as well as 50 , fractional 53

with exploiting these deposits due chiefly to their their to chiefly due deposits these exploiting with associated are issues environmental significant However, 2006). Kamitani, and (Kanazawa content element radioactive low their is China southern in deposits clay adsorption ion the of advantage major A (Curtis, 2009). Australia, China and Europe due to environmental concerns of beach sands containing monazite has been banned in were closed (Meor Yusoff and Latifah, 2002). Processing that the Malaysian processing industry failed and the plants 2% uranium and 0.7% thorium. This was the main reason xenotime in Malaysian placer deposits typically contains relates to the radioactivity of some ores. For example REE are mined and processed. One of the most significant environmental regulations and controls in the areas where REE production. These commonly result from insufficient There are many environmental issues associated with Environmental implications method (CastorandHedrick,2006). of morethan99.99percentcanbeproducedusingthis then ground(Rhodia,2009).REEcompoundswithapurity separated, driedorcalcinedathightemperaturesand obtained fromthesolventextractionprocess.Thisis oxides. Aninsolublesaltisprecipitatedfromthesolution The endproductsofSXareusuallysolid-rareearthsaltsor et al.,2000). successfully separatedfromtheothers(Rhodia,2009;Uda when theprocessisrepeatedmanytimeseachREE only incrementalvariationwithatomicnumber. However, the chemicalpropertiesofREEionsinsolutionshow process. Initiallytheprocessisrelativelyineffectiveas repetitive fractionationduringacontinuouslyflowing a groupofmixersettlers,calledbatteries.Thisallows On anindustrialscaletheSXprocessiscarriedoutin phases used. differences intherelativesolubilitiesofREEliquid water andanorganicsolvent.Thisprocessrelieson relative solubilitiesintwoimmiscible method usedtoseparatecompoundsonthebasisoftheir Solvent extraction(SX),orliquid-liquidextraction,isa www.MineralsUK.com 54 liquids,typically 16 Rare Earth Elements 56 55 to increased energy efficiency (Turner et al., 2007). refrigeration significantly reduce carbon dioxide emissionsin duefluorescent lamps and gadolinium and thulium in magnetic not contain cadmium or lead (Haxel et al., 2002). Use of REEas, unlike most other types of rechargeable batteries, theyof donickel-cadmium, results in fewer environmental problems example, using lanthanum in rechargeable batteries instead energy efficiency and can reduce carbon dioxide emissions.environmental For applications as they offer improvements in Conversely REE products are increasingly used in production. this mayprovetobeasignificantfactorinfluencingREE concerns aboutclimatechangeandcarbonemissions is suppliedbycoal-firedpowerstations.Withincreasing considerable amount of energy, and in China most of which As withallextractiveoperations,REEproductionusesa 2010). Daily, (China damaging environmentally less and efficient more technology refining make to aiming projects seven undertaking is industry, the for institute research largest world’s the Earths, Rare of Institute Batou the addition In 2009). (Williams, supplies global on impact to likely is which performance, environmental and efficiency improve attempt an in facilities production REE eighty closed has It production. REE of impacts environmental the of aware increasingly becoming is China that indications are there However, market. the of dominance its to contributing producers, to costs reduced in resulted has industry REE China’s on controls regulatory limited the that suggested is It 2010). Daily, (China waste radioactive of tonnes 1.4 and water acidic oxide can potentially produce 60 000 m 000 60 produce potentially can oxide REE of tonne one refining that reported been has It 2009). (Hilsum, farmland of destruction and pollution water residents, local of poisoning occupational and disease for responsible been have process refining the in used chemicals the that indicate Reports processing. in used chemicals the of because hazards significant pose still Batou, in deposits bastnäsite working mines the as well as China, southern in mines regulated the even However, regulation. environmental to adherence of lack and status illegal they were first exploited. Over the last 40 years the form REE have been traded in a wide variety of forms since Specifications and uses containing sulphuric and hydrofluoric acid, 200 m 200 acid, hydrofluoric and sulphuric containing Fluidcrackingcatalyst: catalystusedinthetransformationofheavymolecules intolightercompounds. Catalyst:asubstancethat initiatesoracceleratesachemicalreaction withoutitselfbeingaffected. 3 of waste gas gas waste of 3 of of Catalysts Catalysts molecular filterinthisapplication (Lynas, 2010). and chemistryofthehighsurface areazeolitesusedasa Lanthanum andceriumareused tostabilisethestructure up petrolandotherfuelssuchasgas,jetfueldiesel. the heavymoleculesintolightercompoundsthatmake are usedintheprocessofrefiningcrudeoil,transforming REE arealsoimportantinfluidcrackingcatalysts (Lynas, 2010). and other precious metals required, thereby decreasing costs increase the effectiveness and reduce the amount of platinum and also enable it to run at high temperatures. They also critical role in the chemical reactions within the autocatalyst catalyst system (Castor and Hedrick, 2006). The REE play a substrate and as a component of the converter’s oxidising Cerium carbonate and cerium oxide are used in the catalyst pollutants in engine exhaust gases into non-toxic compounds. automotive catalytic converters, which transform the primary total market value (Kingsnorth, 2009). REE are essential in market by volume (19 per cent), but only five per cent of the critical inarapidlygrowinganddevelopingworld. efficiency andenablingdigitaltechnology, makingthem a vitalroleinenvironmentalprotection,improvingenergy applications (Figures5–7).IntheseREEplay indispensable inelectronic,optical,magneticandcatalytic any groupofelements(CastorandHedrick,2006).REEare REE areusedinthewidestrangeofconsumerproducts penalty (CastorandHedrick,2006). by higher-grade ceriumproductswithlittleornoprice oxide productusedintheglassindustryhasbeenreplaced specification products,forexamplea90percentcerium processing techniqueshaveremovedthemarketsforlower and metalsvarydependingontheirend-use.Advancesin Specifications forREEmineralconcentrates,compounds and liquid crystal displays (LCDs) (Kingsnorth, 2008a). REE such as magnets, computer hard drives, electric motors considerable trade in components and products containing phosphors and polishing powders. In the 2000s there is end of the decade trade was dominated by REE magnets, REE oxides and metals were in greater demand, but by the as carbonates and chlorides. By the early 1990s separated in the 1980s to predominantly mixed REE chemicals such 1970s exports were largely mineral concentrates, changing of Chinese REE exports has changed considerably. In the 55 accounts for a significant share of the REE www.MineralsUK.com 56 which 17 Rare Earth Elements drives. The voice coil motor which controls the arm that reads Permanent magnets are also used in hard disk- and DVD- in smaller, lighter devices with improved performance. numerous other high performance speakers. This results for consumer devices such as MP3 players, as well as in neodymium magnets are used in the speakers in earphones size which has lead to many miniaturised applications. Tiny alternatives, they provide improved performance for a smaller Because neodymium magnets are more powerful than by valueand21percentvolume. account forapproximately38percentoftheREEmarket (Gupta andKrishnamurthy, 2005).Permanentmagnets is significantlycheaperandmoreabundantthancobalt the principalconstituentisiron(84.4percent)which greater thanthesamarium-cobaltversions.Inaddition magnets possesamagneticenergyofupto2.5times (Castor andHedrick,2006).Neodymium–iron–boron cobalt magnets,exceptinhightemperatureapplications developed andhavenowlargelyreplacedsamarium– the mid1980sneodymium–iron–boronmagnetshadbeen 1960s whensamariumalloyedwithcobaltwasused.By magnets. Thisapplicationwasfirstdevelopedinthe An increasinglyimportantuseofREEisinpermanent Magnets Figure 5 -Industrial P -Chemical processing -Diesel additi -Catalytic con -P La, Ce(P CA -F -Pigments Ce, -W -Defence (Nd,Pr -Nuclear (Eu,Gd,Ce, O THER er etroleum refining ater treatment TALY tiliser Applications ofrareearths.ImagescourtesyJohnson MattheyPlc,Mercedes-BenzandIngreyPublishing. STS r, Nd) s ollution S ves ver Y , Dy ter , Tb, Eu, Y, Sm,Er) crubber Y, La,Lu,S -Decolouriser -P Ce, La,Pr GLA -X-ray imaging -UV resistantglass olishing componds SS c, Sm) AND POLISHING , Nd,Gd,Er s/colouriser RARE EAR , Ho -R -S -Colourants -S -Capacitor Eu, Gd,Lu,Dy La, Ce,Pr CERAMICS efractories cintillator ensor s s requiring onekilogram ofneodymium(Lifton, 2009b). any individualproductwitheach electricmotorinaPrius suggested thatthePriusis largestconsumerofREE during breaking(Avalon RareMetals,2010).Ithasbeen powered electricmotorsand brakes thatcaptureenergy consumption bycombiningapetrol engine,battery- such astheToyota Prius.Hybrid carsreducefossilfuel Neodymium magnetsareessentialforhybridcars alternators (Reuk,2007). so strongneodymiummagnetsmakeconsiderablybetter stronger themagnets,highercurrentgenerated, generated isthestrengthofmagnetsused.The One factorwhichdeterminestheamountofelectricity generated inanalternatorwhenmagnetspasswirecoils. 2010; Lifton,2009a).Inwindturbineselectricityis approximately 30percentisREE(Avalon RareMetals, of neodymiummagnetspermegawatt,which that windturbinesuseintherangeof0.6 ‘green’, carbonreducingtechnologies.Itisestimated Neodymium–iron–boron magnetsareimportantinmany and more data storage (Lynas, 2010). magnet which gives improved control allowing thinner tracks and writes information onto the disk uses a neodymium-based , Nd, s THS s -Fibre optics -Laser -Medical imaging -Fluroscent lighting Eu, PHOSPHOR -Display phosphor Y Y, Tb, Nd,Er s S , Gd(Ce,Pr) s CR T, LPD,LCD -Magnetic refrigeration rs -Microphones andspeake -P -MRI -Disc dri -Motor Nd, Pr (Tb,Dy) MA ower generation www.MineralsUK.com -Aluminium/Magnesium -Super alloys -Lighter flints -Steel -F -NimH batteries La, Ce,Pr METALLURGICAL GNETS uel cells s ves , Nd, –1.0 tonne Y ALLO YS 18 Rare Earth Elements 57 In 2008 this use accounted for 18 per cent of global global of cent per 18 for accounted use this 2008 In alloys. metallurgical in applications major have REE Metallurgical alloys high temperatures(Venter, 2009). of dysprosiumorterbiumpreventsthisfromhappeningat to losetheirmagnetismastheyheatup,buttheaddition and terbiumarealsousedinmagnets.Manymagnetstend the samelevelofperformance(London,2009).Dysprosium power consumptionbyupto50percentwhilstretaining of REEmagnetsinairconditioningsystemscanreduce energy efficiencyofmanyappliances.Forexampleuse The useofREEmagnetshasthepotentialtoincrease Figure 7 Figure 6 Magnets Phosphors Pyrophoric:amaterial which canspontaneouslyigniteinair. 38% Magnets 7% 21% Ceramics 6% REE consumptionbyvalue(Kingsnorth,2009). REE consumptionbyvolume(Kingsnorth,2009). Other 7% Other 3% Catalysts 19% Metal alloys Phosphors 13% 32% Metal Metal alloys 18% Polishing Glass 10% 4% Glass Ceramics Catalysts Polishing 2% 12% 5% 3% in certainnickelandcobaltsuperalloy compositions. component butlanthanumand ceriumarealsoused (where Misiron,nickelorcobalt), yttriumistheactive resistance. InM–chromium–aluminium–yttrium alloys generators. AddingREEenhancesthealloy’s oxidation environments suchasingasturbineenginesandelectric applications involvingintense,high-temperatureoxidising Superalloys areaclassofheatresistantalloysusedin 2009). Wilson, and (Lundin cracking promote to likely less are which particles rounded more form to inclusions sulphide the with combines cerium The steels. and irons cast in inclusions controlling for additives alloying minor as used commonly are cerium and Mischmetal 2009). (Venter, soft too is alone alloy REE the since oxide magnesium and oxide iron with blended is it purpose this for although torches, and lighters many of device ignition flint the in is alloy this of use common most The praseodymium. and neodymium of amounts small with lanthanum cent per 25 and cerium percent 50 about is composition Typical 2005). Krishnamurthy, and (Gupta concentrates bastnäsite the in occur naturally they as proportions same the in present are REE individual a pyrophoric a mischmetal, in is alloy an as REE of uses oldest the of One 2008a). (Kingsnorth, volume by consumption Wind turbine©BGSNERC. 57 alloy containing only REE metals. The The metals. REE only containing alloy www.MineralsUK.com 19 Rare Earth Elements Inc. 2010. vehicle © Molycorp a hybridelectric applications in Figure 8 of hydrogenisbetterthanstorageascryogenic of hydrogenatroomtemperature.Solidstatestorage M isiron,cobaltornickel)couldabsorbalargeamount intermetallics identified in1969whenitwasdiscoveredthatthe The useofREEasamethodstoringhydrogenwas Krishnamurthy, 2005). can dramaticallyimproveitsperformance(Guptaand Less thanonepercentofREEmetalinasuperalloy REE arecommonlyusedinphosphors Phosphors Prius batteryuses10to15kgoflanthanum(Lifton,2009b). Prius (Figure8).IthasbeencalculatedthateachToyota particularly importantforhybridcarssuchastheToyota in additiontomanyotherREE-bearingcomponents,are battery (AustralianRareEarths,2010).Thesebatteries weight. LanthanumisthemainREEusedinNiMH battery, representingabout26percentofthebattery’s rare earthmetalalloyisusedastheanodeinNiMH batteries thatpowermanyelectronicproducts.Amixed REE areusedinnickelmetalhydride(NiMH)rechargeable 2005). pressure andenergysavings(GuptaKrishnamurthy, compressed gasintermsofsafety, volume,weight, computer screensandanyothervisualdisplaydevicesthat (Kingsnorth, 2009).Phosphorsareimportantintelevisions, value in2008,althoughonlysevenpercentbyvolume accounted for32percentofglobalconsumptionby 64 63 62 61 60 59 58 Phosphor: a substance that exhibits the phenomenon of phosphorescence (sustained glowing after exposure to energized particles such as electrons or ultraviolet photons). Epidermis: the thin,outermostlayer ofskin. Ablate:elimination oftissuefrom the body. Photon:discretebundle (orquantum)ofelectromagneticlight)energy. Luminescence:anyprocess inwhichenergyisemittedfromamaterial atadifferentwavelengthfrom thatatwhichitisabsorbed. Cryogenicgas:agasthathasbeenliquefied by loweringthetemperature,usuallytoatemperature underabout-100°C. Intermetallic:solidstatephasesinvolvingmetals. REE 58 REM5(whereREistherareearthand 60 . Thisapplication 59 and lasers areusedincosmetictreatmentstoablate This isoneofthemajorapplicationsforerbium.Erbium increasingly usedformedicalanddentistryapplications. (Jackson andChristiansen,1993).REElasersarebeing over exceptionallylargedistanceswithoutboosterstations activator. GlassfibrescontainingREEcan transmit data lasers. InlasersREE,typicallyneodymium,areusedasan REE areusedinthemanufactureoffibreopticsand compact fluorescentbulbs(Avalon RareMetals,2010). incandescent lighting,and40percentmoreefficientthan for whiteLEDs.LEDsare80percentmoreefficientthan (Lynas, 2010).MorerecentlyREEphosphorsarebeingused amount oflightasthestandardincandescentbulb only aquarterofthepowerneededtoproducesame phosphors. Thecompactfluorescentlamp(CFL)uses Energy efficientlightingisamajorapplicationofREE longer thanpreviousbluephosphors(Lynas, 2010). based bluephosphorwhichretainsbrightnesstentimes screens weredevelopedwiththeaidofaneweuropium- cavity preparationinadditiontomanysoft-tissueand safe andeffectivefortheremovaloftoothdecay underlying skin.Indentistry, theerbiumlasershaveproven epidermis by photons These phosphorsemitluminescence for greenandcerium–strontium–sulphideblue. yttrium compoundsforred,terbium–fluoride–zincsulphide seen onthedisplaycomefromuseofeuropium– display paneltechnologies(GWMG,2010).Thecolours requires cathoderaytube,liquidcrystaldisplayorplasma 64 62 revealingthesmootherandyoungerlooking (JacksonandChristiansen,1993).Plasma www.MineralsUK.com 61 whenactivated 63 the 20 Rare Earth Elements LED bulb.Ingreypublishing. praseodymium to provide UV protection. Lanthanum is an Sunglasses contain cerium as well as neodymium and product and prevent browning of the glass due to radiation. ultraviolet light. Cerium is used in glass bottles to protectREE the are important in glass due to their ability to absorb elements (GuptaandKrishnamurthy, 2005). melts. OthercoloursareobtainedbymixingREEwithother colour glasspinkanditistheonlytrulystablein praseodymium greenandholmiumblue.Erbiumisusedto and largerquantitiesbrown.Neodymiumcoloursglassred, decolourise glassbutaboutonepercentwillturnityellow used asdyesinglass.Smallamountsofceriumwill the iron(JacksonandChristiansen,1993).REEarealso causing ayellow–greencolour. Addingceriumoxidises as ironoxideisalwayspresentanimpurityinglass decolourising agentinglass.Decolourisingisnecessary use ofceriumwasin1896whenitfirstusedasa cent byvalue(Kingsnorth,2009).Theearliestcommercial REE consumptionbyvolumein2008,althoughonlysixper polishing applicationsaccountedfor22percentoftotal REE arecommonlyusedintheglassindustry. Glassand Glass andpolishing hard-tissue surgicalprocedures(Margolis,2006). 70 69 68 67 66 65 Capacitor: an electric device consisting of two electrical conductors isolated from one other by a dielectric material, capable of storing electrical energy for release at some predetermined time. Piezoelectric:asubstance thatproducesanelectricchargewhenamechanical stressisapplied. Dielectric:non-conductingorinsulatingmaterial. Sintering:amethodformakingobjectsfrompowder, byheatingthematerialinasinteringfurnace. Dispersion:thephenomenoninwhichphase velocityofawavedependsonitsfrequency. Refractiveindex:ameasureofhowmuchthe speed ofawaveisreducedinsidethatmediumcompared tothespeedofwaveinareferencemedium. dispersion Rare earthoxidesareusedinceramiccapacitors three percentbyvalue(Kingsnorth,2009). for sixpercentofglobalconsumptionREEin2008and (Guanming etal.,2007).Ceramicapplicationsaccounted as stabilisersandsintering adding REO(yttriumoxideandceriuminparticular) and toughnessofstructuralceramicsisimprovedby REE oxidesareessentialinceramics.Boththestrength Ceramics using ceriumoxide(Haxeletal.,2002). television faceplatesandcathoderaytubesarefinished majority ofpolishedglassproducts,forexamplemirrors, efficient thanotheragentssuchassilicaandzirconia.The dissolution andmechanicalabrasionmakingitmore as apolishingagentitremovesglassbybothchemical used topolishglasssurfaces.Ceriumisespeciallysuitable Substantial amountsofceriumconcentratesandoxideare for selective light absorption (Jackson and Christiansen, 1993).coatings on lenses and as a constituent of tinted glass filtersKrishnamurthy, 2005). Praseodymium is used for anti-reflectionfor magneto-optical and electro-optical systems (Gupta and temperatures andarecommonlyusedtomakecrucibles. Refractories arematerialsthatretaintheirstrengthathigh 2005). Krishnamurthy, and (Gupta processes firing double and single in used be can so temperatures high at stable are pigments These purple. light a neodymium and colour orange an gives yttrium pigment, yellow a makes silica and zirconia to added praseodymium example, For ceramics. in colourants as used are oxides earth rare of amounts Small the capacitoralongerlifespan(Roskill,1986). neodymium results in a stable dielectric constant and gives dielectrics. Addinglanthanum,cerium,praseodymiumand properties ofthevariousbariumtitaniteceramic the temperature-compensating,dielectricandpermeability microwave dielectric in functionalceramicssuchassemiconductorsensors, temperature andproductioncosts.REOarealsoimportant lanthanum oxide has a high refractive index integral part of camera lenses as low silica glass containing 66 . Optical lenses containing gadolinium are used 68 andpiezoelectric 67 aidstoreducesintering www.MineralsUK.com 69 ceramics 65 and low 70 toalter 21 Rare Earth Elements earth phosphatefertiliser(REPF) containingbetween0.04 production ofcalciumsuperphosphatetocreatearare in China.REEsolutionsorcompoundsareaddedduring REE havebeenusedinagricultureasafertiliser, mainly claustrophobic forthepatient(Avalon RareMetals,2010). coils. ThisenablestheMRImachinestobewiderandless systems toreducetheelectricalresistanceinwire systems ofsupercoolingwirecoilsinliquidhelium magnets arebeingusedtoreplaceexpensivetraditional Magnetic ResonanceImaging(MRI)equipment.Permanent magnets areimportantformedicalapplications,suchas gadolinium providesbetterimagingoftumours.AlsoRE There aremanymedicalapplicationsofREE,forexample materials (Molycorp,2009). communications, guidanceandcontrol,lasersaircraft sonar transducers dependent inREEareoptics,surveillanceandprotection, defence applications.Examplesoftechnologies The rare-earthelements(REE)haveawidevarietyof surface primerforpaints(Hedrick,2001). coating toprovidecorrosionresistanceandalead-free (Gupta andKrishnamurthy, 2005).Yttriumisusedasa to makethemmoredurableandresistantsunlight Cerous acetateisusedtotreattitaniumdioxidepigments them moreresistanttofadingduelightexposure. compounds areusedtocoatleadchromepaintsmake REE arewidelyusedinpigmentsandpaints.Cerium Krishnamurthy, 2005). operation asitisagoodneutronabsorber(Guptaand Europium isusedforcontrolrodstoregulatereactor oxide fuelisusedup(World NuclearAssociation,2009). the progressivebuildupofotherabsorbersasuranium which decaysunderneutronexposure,compensatingfor reactor overtime.Gadoliniumoxideisaneutronabsorber boiling waterreactors,toevenouttheperformanceof Gadolinium isusedasa‘burnablepoison’,especiallyin high temperatures(JacksonandChristiansen,1993). to theirabilityabsorbneutronsandremainstableat REE havearangeofapplicationsinnuclearenergydue Other applications material, usuallyzirconia(Roskill,1986). used incruciblestoprotecttheprincipalrefractory Yttrium oxide,andtoalesserextentceriumare 74 73 72 71 Energystate:definite stable energythataphysicalsystemcanhave; usedespeciallyofthestate electrons inatomsormolecules. Electron:asubatomicparticlethatcarriesnegative electriccharge. Superconductor:amaterialthroughwhichelectricity flowswithzeroresistance. Sonartransducer:adeviceusedunderwater to convertelectricalenergysoundand toelectricalenergy. 71 , microwavecommunication,powerand issues to be resolved before the first commercial unitscurrently can used (Kennedy, 2010). There are still arefrigeration number of while eliminating harmful chemical compoundsglobal fossil fuel consumption associated with coolingmagnets and will make it possible to reduce up to 15 perinvolved cent of (Brück et al., 2007). It has been calculatedIn additionthat REE no ozone-depleting or hazardous chemicalsenergy are efficiency results in less carbon dioxide beingfriendly released. on account of its higher cooling efficiency.methods This are higher considerable. It is also more environmentallyadvantages offered by magnetic refrigeration over Givenconventional the reliance of modern society on refrigeration, the boron magnets(GschneidnerandPecharsky, 2007). household andtransportapplicationsisneodymium–iron– the magneticfieldsourcemostpracticaloptioninboth and hasbeensuggestedasthemagneticrefrigerant.For Gadolinium hasbeenfoundtoexhibitthiseffectstrongly causing thetemperaturetofall(Dieckmannetal.,2007). increase quality(Xiangshengetal.,2006). can improvecropyields,decreasediseasedplantratesand and 0.16percentREE.ResearchhasshownthatthisREPF lowered theelectrons application ofamagneticfield.Whenthefieldis (MCE) whichistheresponseofamagneticsolidto refrigeration isbasedonthemagnetocaloriceffect efficient thanstandardrefrigerationmethods.Magnetic on REEwhichismoreenvironmentallyfriendlyand Magnetic refrigerationisanewtechnologydependent Magnetic refrigeration and advancedsuperconductors processors, advancedsatellitecommunicationsystems technologies, forexample,sub-light-speedcomputer There areseveralapplicationsforREEinnewelectronic and efficiencyenvironmentalprotection. discovered, especiallyintheareasofenergyconservation more applicationsforREEarebeingdevelopedand As researchandtechnologycontinuestoadvancemany New technologies technologies (Kennedy, 2010). further applicationsforREE,includinginnano-particle made inmaterialsscienceitislikelytherewillbe energy state 74 , absorbingheatfromthematerialand 73 withinthematerialspininahigher www.MineralsUK.com 72 . Asadvancesare 22 Rare Earth Elements earths La,Ce,PrandNd. 77 76 75 shown that electrolytes due to the high cost of the performance. Recent research has conventional SOFCs face challenges in commercialisation of the most promising fuel cell technologies. However, generate electricity at high efficiencies. The SOFC is one are a clean, low-pollution technology to electrochemically REE are essential in solid oxide fuel cells (SOFC). These Fuel Cells (Gschneider and Pecharsky, 2007). technology could have a significant impact on REE demandbe released into the market. However, if commercialised, this known duetothequalityand availability ofdata.USGS An accuratefigureforglobalrareearthresourcesisnot Resources World resources and production the waste volume (Molycorp, 2009). sequestration methods and would produce only one-third of of the volume of raw materials required by conventional is suggested that the process would consume just a fraction extremely stable compound for easy filtering and disposal. It to remove arsenic by converting it to a concentrated and technology for use in the mining and smelting industries by selective adsorption. They have also developed this States army, have invented a portable device to purify water in water treatment. Molycorp, together with the United New technologies are being developed which will use REE Water Treatment transportation use(FrenetteandForthoffer, 2009). been foundthatwillproducesufficientenergydensity is promising,currentlynolowercostcatalystmaterialhas catalyst (HuandNoréus,2003).Althoughresearchtodate AB5-type hydrogenstoragealloy factor. Researchhasexaminedtheuseof REE-based the highcostoffuelcellshasalwaysbeenalimiting such asplatinumorpalladiumareusedacatalyst, for zeroemissionelectricvehicles.Asnoblemetals recent yearstodevelopfuelcellsaspowergenerators A considerableamountofworkhasbeenundertakenin potentially important future use of REE (Zhu et al., 2008). temperature making them more cost effective. SOFC’s are a are able to achieve excellent fuel cell performance at low lanthanum, cerium and praseodymium (LCP) carbonates Energydensity:theamount ofenergystoredinagivensystemorregion ofspaceperunitvolume,or per unitmass. AB5alloys:commercialalloysusuallyofthetype Mm(nickel,cobalt,aluminium,manganese)5,containing typically10wt%Co.MmdenotesMischmetal,acost-effective mixture oftherare Electrolyte:asolutionthatconductselectricity. 75 made using industrial grade mixed 76 asanoblemetal-free 77 for Another importantresourcein theUSisatBearLodge to contain4.3milliontonnesofREO(Kingsnorth,2008a). production by2012(Hedrick,2009).Thedepositisreported 2002 andwhichMolycorpplanstobringitbackinto Mountain PassinCaliforniawhichwasexploiteduntil of REEat13milliontonnes.Thelargestdepositis The UnitedStateshoststheworld’s thirdlargestreserves USA associated withuraniumminetailings. Kazakhstan haspotentiallysignificantREEresources REE estimatedat51500tonnes(Bogdetskyetal.,2005). (Hedrick, 2010).Kyrgyzstanhassignificantreservesof reserves oftheCISareestimatedat19milliontonnes during theprocessingoftheseores(Naumov, 2008).Total Peninsula butREEarenotcurrentlybeingextracted REE resourcesintheapatite-nephelineoresofKola deposits (Kosynkinetal.1993).Russiahassignificant The REEresourcesoftheCISaredominatedbyloparite Commonwealth ofIndependentStates Weishan deposit,inShandong Province. Island andassociatedwithalkalinerocks,forexamplethe largely in the coastal areas of west Guangdong and Hainan China’s additionalreservesoccurasplacerdeposits, per centoftheworld’s resourcesofHREE(Vulcan, 2008). HREE andthesedepositsarethoughttocontainabout80 Importantly thesedepositsarerichinthelesscommon resources iscontainedinionadsorptiondeposits. Kamitani, 2006).AsignificantproportionofChina’s at least48milliontonnes6%REO(Kanazawaand deposit intheworldandcontainsreportedreservesof deposits. TheBayanObobastnäsitedepositisthelargest possessing hardrock,placerandionadsorptionclay China hasthemostabundantREEresourcesinworld, China and Indonesia(Table 4andFigure9;Hedrick,2010). Namibia, Mauritania,Burundi,Malawi,Vietnam, Thailand, Canada, Malaysia,Brazil,India,Greenland,SouthAfrica, remaining 22percentofreservesisdividedbetween with 13percentandAustralia6cent.The Independent Stateswith19percent,theUnited 37 percent.ChinaisfollowedbytheCommonwealthof 99 milliontonnes.Chinadominatesworldreserveswith estimates totalworldreservesofrareearthoxidestobe www.MineralsUK.com 23 Rare Earth Elements (Ucore Uranium,2010)Ahistoricresourceestimate elements associatedwiththeuraniummineralisation significant concentrationsoflightandheavyrareearth Mountain uraniumprojectinAlaskaindicatespotentially Rare ElementResourcesLtd.ExplorationattheBokan project inWyomingwhichiscurrentlybeingexploredby include onlyrecoverablematerials(Hedrick,2010). extraction facilitiesareinplaceandoperative.Reserves of determination.Thetermreservesneednotsignifythat could beeconomicallyextractedorproducedatthetime defined byUSGSasthatpartofthereservebasewhich Table 4 reserves (Hedrick,2010). distribution ofREE Figure 9 World Total Other Countries Malaysia Brazil India Australia United States Independent States Commonwealth of China Country Estimated worldREEreserves(reservesare Global 99 000 22 000 30 000 48 000 3 100000 5 400000 13 000 19 000 36 000 Reserves (tonnes) Independent States Independent Commonwealth of of Commonwealth 19% India Other Other Countries 3% 22% Hoidas Lakeproject(ownedbyGreatWestern Minerals Canada hassubstantialundevelopedREEresources.The Canada Resources) and WIM 150 (owned by Australian Zircon). Arafura Resources), Cummins Range (owned by Navigator project (owned by Alkane Resources), Nolans Bore (owned Australian resources of note include the Dubbo Zirconia due to radioactivity issues (Lambert et al., 2008). Other sands containing monazite, but these are not worked significant REE reserves (3.4 million tonnes) in heavy mineral grade (0.5% REO) to be currently exploited. Australian has million tonnes of REO. However, the material is of too low Dam deposit in South Australia is estimated to contain 45 tonnes at a grade of 9.7% REO. The polymetallic Olympic of the mineralisation, has a total resource of 12.24 million deposit in Western Australia, notable for the high grade distributed across a range of deposit types. The Mount Weld Australia has the fourth largest reserves of REE in the world, Australia Montana andMissouri(Hedrick,2008). Group Ltd,2010).REEresourcesarealsopresentinIdaho, in therangeof0.14–0.80%REO(GreatWestern Metals REE mineralisation.Surfacesamplinghasreturnedgrades sands depositinUtahhasrevealedpotentiallyextensive Western MetalsGroupontheDeepSandsheavymineral at BokanMountain(Hiyate,2010).ExplorationbyGreat produced bytheUSGSindicates374millionlbsofREO www.MineralsUK.com United United States 13% China 37% Australia 6% 24 Rare Earth Elements Utah. ©GreatWestern Minerals GroupLtd. Rare earthelementbearingsands,DeepSands, tonnes REO(Lynas Corp,2007).AlsoinMalawi the is estimatedto containaninferredresource of 107000 Kangankunde deposit(owned byLynas Corp)inMalawi Frontier Minerals’Zandkopsdrift carbonatitedeposit.The Ltd, 2009).Afurthernotableresource inSouthAfricais a reserveof29400tonnesREO (historicfigures,GWMG monazite deposit,withanaveragegradeof17%REOand grade REEdepositintheworld,Steenkampskraal South Africahaswhatisclaimedtobethehighest Africa more than43000tonnesREO(Batten,2010). suggesting thattheminewillhaveanannualoutputof completed aninterimreportfromthefeasibilitystudy million tonnesREO.GreenlandMineralsandEnergyhave in theIlimaussaqintrusionisestimatedtocontainof4.91 of globaldemand(Lewis,2009a).TheKvanefjelddeposit resources whichcouldpotentiallymeetabout25percent It hasbeensuggestedthatGreenlandcontainsREE Greenland stage projectsarebeingevaluatedinCanada. Rare Metals,2009).Anumberofother, relatively early Resources of64.2milliontonnesat1.96%REO(Avalon Rare Metals).ThedepositcontainstotalInferredMineral significant resourceoccursatThorLake(ownedby Avalon tonnes at2.43%REO(Billingsley, 2010).Afurther Group) isthemostadvanced,withreservesof2.6million

by Australia (Naumov, 2008). During the 1980s China the principal producer (largely from Mountain Pass) followed deposits started to be exploited and the United States was Between the 1960s and 1980s bastnäsite carbonatite began production primarily of monazite from placer deposits. deposits until the 1940s when Australia and Malaysia Brazil were the world’s main sources of REE from these they were identified (Castor and Hedrick, 2006). India and pegmatites, the first geological environment in which REE were initially produced in minor quantities from granite Historical production Production Important REE resources also occur in Argentina and Uruguay. of laterite averaging 13.5% REO (Castor and Hedrick, 2006). carbonatite complex is reported to contain 800 000 tonnes rock deposits (Jackson and Christiansen, 1993). The Araxá (Hedrick, 2010). These reserves include placer and hard Brazilian REE reserves are estimated at 48 000 tonnes South America (Gupta andKrishnamurthy, 2005). area alsopresentinThailand,IndonesiaandMalaysia currently unavailable.HeavymineralsandREEreserves in theDongPaoarea.However, reliableresource datais Vietnam isknowntohaverare earth deposits,forexample 2008). Yearbook, Minerals (Indian deposits placer inland and beach in monazite of tonnes million 10.21 had India 2005 in that indicate Energy Atomic of Department the by reported figures Official 2010). (Hedrick, reserves of tonnes million 3.1 has country the that estimates USGS the and deposits placer and rock hard both contains India South andeastAsia and Krishnamurthy, 2005). Nile DeltaandRosettaplacermonaziteinEgypt(Gupta Congolone heavymineralsandsinMozambique;andthe hard rockmonaziteBouNagadepositinMauritania;the the KarongehardrockbastnäsitedepositsinBurundi; million tonnesofREO.OtherresourcesinAfricainclude: at EtanenoinNamibiaandisestimatedtocontain20 cent REO.Amajorcarbonatite-associateddepositoccurs to containsixmilliontonnesofmaterialwithaboutfiveper overlying acarbonatiteatMrimaHillinKenyaisreported REO (IndustrialMinerals,2009a).Amonazite-richlaterite, to contain14.4milliontonnesofmaterialgrading1.52% 2009). TheTantalus projectinMadagascarisestimated very earlyexplorationstages(GlobeMetalsandMining, acquired byGlobeMetalsandMiningbutisstillinthe Machinga REEproject,richinHREE,hasrecentlybeen www.MineralsUK.com 25 Rare Earth Elements with over134000tonnes. the last15years(Figure10).Peakproductionwasin2006 000 tonnes).World productionhas morethandoubledin tonnes, afourpercentincreasecomparedto2007(121 reported worldproductionofREOin2008was126000 reliable estimatesofquantitiesaredifficulttoobtain. Total Kyrgyzstan, Mozambique,Nigeria,RussiaandVietnam but Kazakhstan, DemocraticP.R ofKorea,Republic REE mineralsarebelievedtobeproducedinIndonesia, disclosed inofficialfigures(Hedrick,2009).Inaddition using stockpiledmaterial,althoughthisproductionisnot mining REEorebuthasbeenproducingproducts Mountain Passminein2002,theUSAhasnotbeen China, India,BrazilandMalaysia.Sincetheclosureof The onlycountriesknowntobeactivelyminingREEare Current production situation of virtually no REE mines outside China. deposits have since been developed, resulting in the current REE prices at this time were relatively low and no new until 2002 when environmental issues resulted in its closure. the Mountain Pass mine in California which remained active compete with low priced Chinese exports. The exception was 2009). Producers in other countries were generally unable to for 96.8 per cent of supply (Chinese rare earth industry report, China now dominates world production of REE, accounting producer by 1988 (Gupta and Krishnamurthy, 2005). overtaking the United States to become the world’s largest began to produce REE, mainly from the Bayan Obo deposit, Figure 10 Tonnes REO 100000 120000 140000 160000 20000 40000 60000 80000 0 Annual reported worldproductionofREObetween 1992–2008 (World MineralsStatistics Database,BGS). 1992 1993 1994 1995 1996 1997 1998 1999 (Industrial Minerals,2009b). Technologies Inc.(NMT)andJapan’s MitsubishiCorp mine inajointventurebetweenCanada’s NeoMaterial to produceREEasaby-productfromtheTaboca Pitingatin been graduallyincreasingsince2004.Therearealsoplans Brazil producesREEfrommonaziteandproductionhas (Naumov, 2008). Ltd whichextractsmonazitefromheavymineralsands produces yttriumoxideandKeralaMineralsMetals Rare earthcompaniesincludeIndianEarthLtdwhich of rareearthschloride(IndianBureauMines,2008). fluorides, ceriumoxideandhydratefromconversion earths wereproducedrespectively, mainlyrare earth unavailable in2006and20074535tonnesofrare placer deposits.Althoughrecentproductiondatais India isthoughttobeproducingREEfrombeachsands Group (Naumov, 2008). Group, GansuRareEarthCorpandSichuan China are the Batou Iron and Steel Group, Batou Rare Earth annually) (London,2009).ThemajorproducersofREEin ion adsorptionclaysinSouthernChina(7000tonnesREO Sichuan andMianning(31000tonnesREOannually) mining, butalsofrombastnäsite-bearingcarbonatitesin (46 000 tonnesREOannually)asaby-productofironore (Figure 11). ProductionisprimarilyfromBayanObo for inexcessof95percentglobalproduction 125 000tonnesofREOwereproducedin2008,accounting Chinese productionofREEhasbeenincreasingand 2000 2001 2002 2003 2004 www.MineralsUK.com 2005 2006 2007 2008

26 Rare Earth Elements Figure 11 technologies, hasresultedinconsiderableexploration with thegrowingdemandforREE,particularly‘green’ in concernsoversecurityofsupply. This,inconjunction China’s dominanceoftheglobalREEindustryhasresulted Projects underdevelopment (Bogdetsky etal.,2005). although thecountryisstillproducingREEfrominventories and Germany. TheREEminesarenolongeroperational USSR’s REEinadditiontoexportingJapan,SouthKorea the 1980sprovidingasignificantproportionofformer 2001). KyrgyzstanwasasignificantproducerofREEin but since2001virtuallynonehasbeenproduced(Polyakov, Russia wasoneoftheworld’s largestproducersofREE Production dataisnotavailablefortheCIS.In1990s 2009). (Hedrick, products refined and intermediates REE and concentrates, bastnäsite produce to material stockpiled using 2007 since operation in been has site the at plant separation the Pass Mountain at mined being currently not is ore Although 000 REOtonnesperyearby2011(Curtis,2009). its processingplantinMalaysia,withplanstoproduce11 the MountWeld depositinAustralia,hasdecidedtobuild tonnes ofmonazite.Lynas Corp,thecompanydeveloping Production fluctuateseachyearandin2008wasonly233 of tinextractionandhasproducedxenotimeinthepast. Malaysia currentlyproducesmonaziteasaby-product Tonnes REO 100000 120000 140000 160000 20000 40000 60000 80000 Chinese andworld productionofREObetween 1992–2008 (World MineralsStatisticsDatabase, BGS). 0 primary sourceofREE(IndustrialMinerals,2010a). as welltheKutessayIImine,onceSovietUnion’s licence fortheREE-bearingAktyuzOreFieldinKyrgyzstan, Stans EnergyCorp,hasrecentlyacquiredanexploration 2009). (Hampton, market REO global current the of cent per 14 about to equivalent be would This tonnes. 000 22 about to increase later will which tonnes 000 11 of rate annual an at 2011 in start to expected is Production 2009). (Miezitis, Australia from REO of production recorded no currently is there and Malaysia in construction under is plant concentration A 2009b). (Curtis, ore of tonnes 000 773 about stockpiled has and 2007 in deposit bastnäsite Weld Mount the mining began Ltd. Corporation Lynas 2010). (O’Driscoll, 2012 by tonnes 000 20 to increasing 2010–2011, for forecast is REO of tonnes 3000 of Production mine. the from produced previously been had as oxides, just than rather produced be will metals and (NdFeB) alloys oxides, RE processing. REE rejuvenate and mine the reopen to planning 2008, in operation Pass Mountain the bought Minerals Molycorp (O’Driscoll, 2010;Table 5). resource evaluationandmetallurgicaltestingstages for theirREEpotentialandseveralhavereachedthe Canada, SouthAfricaandtheUSAarebeinginvestigated interest inrecentyears.Over100depositsAustralia, www.MineralsUK.com China World 27 Rare Earth Elements Table 5 Kyrgyzstan Kutessay II, Eco Ridge,Canada Greenland Kvanefjeld, Deposit Archie Lake, Canada Canada Hoidas Lake, USA Mountain Pass, Deep Sands,USA (Bear Lodge),USA Bull HillSouthwest Malawi Kangankunde Hill, Australia Mount Weld, Lofdal, Namibia Canada Lake –Zone), Nechalacho (Thor Australia Cummins Range, Australia Nolans Bore, Australia Yangibana, South Africa Steenkampskraal, Australia Dubbo Zirconia, Machinga, Malawi Canada Strange Lake, The sizeandstatus ofselectedREEprojects. *Historicaldata. Stans EnergyCorp. Resources Pele Mountain and EnergyLtd. Greenland Minerals Company Development Corp. Quantum RareEarth Minerals GroupLtd. Great Western Molycorp Minerals Minerals GroupLtd. Great Western Resources Ltd. Rare Element Lynas CorporationLtd. Lynas CorporationLtd. Inc. Etruscan Resources Inc. Avalon RareMetals Ltd. Navigator Resources Arafura Resources Ltd. Artemis Resources Group Ltd. Western Minerals Co. Ltd.&Great Rare EarthExtraction Alkane ResourcesLtd Mining Globe Metalsand Quest Uranium 0.06* have beenidentified concentrations ofREO project butsignificant Predominantly auranium 4.91 (million tonnes) REO reserves REE+Y Early explorationstage,recentchipsamplinghasreturnedanaverage gradeof3.8% 0.07 4.3 0.8% REO Early explorationstage,surfacesamplinghasreturnedgradesinthe rangeof0.14%to 0.12 1.18 Early explorationstage,surfacesamplinghasreturnedanaveragegrade of0.7%REE+Y 0.07 0.85 Early explorationstage,rockchipsamplinghasreturnedanaverage grade of2.84%REO 0.03* Early exploration stage, rock chip sampling has returned a maximum value of 2.64% REO 457 tonnes) (million Ore reserves 2.6 9.8 50 2.53 64.2 12.24 4.17 30.3 35.7 0.25* 52* 0.41* 1.07 (% REO) Grade cut-off) 2.43 (1.5% cut-off) 4.1 (1.5% cut-off) 8-9 (5% cut-off) 4.24 (3.5% 1.96 cut-off) 9.7 (2.5% cut-off) 1.72 (1% cut-off) 2.8 (1% Y REO, 0.14% 0.745% 17* 0.66 Y 1.3 REO, 2 O 3 2 O 3 * www.MineralsUK.com Advanced exploration Advanced exploration anticipated forlate2011 Feasibility study, production Feasibility study 2015 to begin 2013, production by Pre-feasibility. Construction Project status Pre-feasibility Advanced exploration anticipated for2010-2011 Feasibility study, production Advanced exploration Pre-feasibility for 2011 2007, production anticipated Construction. Mining began in Advanced exploration anticipated for2012 Feasibility study, production Closed, duediligence 28 Rare Earth Elements Mt Weld openpit. ©ClintCox,TheAnchorHouse, Inc.2010. cheap andeasytoprocess(Cox,2009). mining andtheionadsorptionclaydepositsarerelatively significant proportionisderivedasby-productofiron production islikelytoremainmorecompetitiveasa of competitors(Kennedy, 2010).FurthermoreChinese China couldeasilycontrolREEpricingtothedetriment it hasbeensuggestedthatwiththecurrentmonopoly development anexpensiveandtimeconsumingprocess, may struggletocompetewithChina.Notonlyismine in theworlditispossiblethatalternativesources Despite therebeingplentifulREEresourceselsewhere cent ofJapan’s currentdemand(Lewis,2009b). about 3000tonnesofREEayear, supplyingabout10per uranium oreresidue.Thissourceisexpectedtoproduce Sumitomo CorpandKazatompromtoproduceREEfrom mines. However, anarrangementhasbeenmadebetween Kazakhstan doesnotcurrentlyhaveanyoperatingREE (Cox, 2009). have ledtoincreaseddemandfordysprosiumandterbium demand forthiselement.Recenttechnologicalinnovations magnets becamewidelyusedresultinginconsiderable of samarium-cobaltmagnets.Inthe1980sneodymium the dominant REE being used by industry for the production increased sharply. However, bythe1960ssamariumwas the colourtelevisionwasintroduceddemandforeuropium fluctuated markedlyinrecentdecades.Forexamplewhen dramatic changes.DemandfortheindividualREEhas developments. Themarkethasahistoryofabruptand fluctuates overtime,largelyasaresultoftechnological and theirbroadrangeofapplicationsforwhichdemand many othersbecauseofthelargenumberelements minerals. TheREEmarketismorecomplicatedthan billion (2008),relativelysmallcomparedwithmanyother The currentvalueoftheREEmarketisaboutUS$1.25 World trade metals at 6300 tonnes. Japan is followed by China Hong Kong Figure 12). Japan is also by far the largest importer of REE tonnes, France (10 000 tonnes) and Austria (7000 tonnes; two countries were followed by Germany importing 11 000 2007 nearly 24 000 tonnes of imports were reported. These 28 000 tonnes. 2008 data is not available for the USA but in importer of REE compounds in 2008 was Japan at just over Japan, USA, Germany, Austria and France. The largest Imports of REE compounds and metals are dominated by Imports andexports become reliantonillicitlyimportedmetals(Lewis,2009b). Japanese industry, theworld’s largestimporterofREE,has Ministry ofEconomy, Trade andIndustrysuggestedthat recovering theREE(Bradsher, 2009).Anofficial atthe detect. Theprocessisreversedintheimportingcountry, steel, exportedassteelcomposites,makingthemhardto Illicit exportsaretypicallyintheformofREEmixedwith from Chinain2008wassmuggled(O’Driscoll,2009). that aboutathirdofthe39000tonnesREEexported reliance onillegalsupplyfromChina.Statisticsindicate Supply constraintshaverecentlyledtoconsiderable 2009). cent and15–20perrespectively(Table 6;Kingsnorth, which havepredictedannualgrowthratesof10–15per consumption, particularlyformagnetsandmetalalloys Significant growthisforecastinmostsectorsofREE tonnes by2014(O’Driscoll,2009). Total demandispredictedtoreach170000190 was only85000tonnes(Avalon RareMetalsInc.,2009). increase of45percentcomparedto2003whendemand 2007). Total REOdemandin2008was124000tonnes,an a positionofoversupplytodemandshortages(Roskill, last threeyearsthemarkethaschangedsubstantiallyfrom rare earthmarkethasbeenfairlystable.However, inthe Historically thebalanceofdemandandsupplyinworld www.MineralsUK.com 29 Rare Earth Elements 78 recent yearsithasbeenreducing exportquotasforREO Although China’s REEproductionhasbeenincreasingin 2010). Figure 13allexportedlessthan300tonnes(UNcomtrade, and Belgium(303tonnes).Theothercountriesshownin followed bytheUSA(1200tonnes),Austria(370tonnes) of REEmetals,withatotalnearly7000tonnes.Itwas Kingdom (Figure13).Chinawasalsothelargestexporter Estonia, France,SriLanka,KazakhstanandtheUnited exporters ofREEcompoundsin2008weretheUSA, followed byRussiawith6000tonnes.Othersignificant 2008. The third largest exporter was Japan at 9000 tonnes, exported justover11000tonnesofREEcompoundsin cerium compoundsandsolutions(Hedrick,2002).Austria alloys, individualREEmetals,mischmetalandfifteen REE, ferrocerium/lighterflintalloys,hydrogenstorage diverse rangeofREEproducts,includingoxidesallthe The Austrian-basedcompanyTreibacher AGexportsa exporter, Austria,whichisnotaprimaryproducerofREE. 2008, greaterthanfourtimesasmuchthenextlargest China exported48000tonnesofREEcompoundsin importing about 500 tonnes of metal (UN comtrade, 2010). SAR (Kingsnorth, 2009). Table 6 SAR:SpecialAdministrative Region,aprovincial-leveladministrative divisioninthePeople’s RepublicofChina. Total/range Other Ceramics and pigments Phosphors Magnets Metal alloys Polishing Glass Application Catalysts 78 with 1000 tonnes, USA, Austria, Brazil and France, all Global demandforREEin2008and2014 124 000 8500 7000 9000 26 500 22 500 15 000 12 500 2008 (tonnes) Consumption REO 23 000 170–190 000 10–12 000 8–10 000 11–13 000 39–43 000 43–47 000 19–21 000 12-13 000 28–30 000 (forecast) 2014 8–11 7–9 7–9 7–10 10–15 15–20 6–8 Negligible 6–8 rate % growth Annual

europium oxideissoldforUS$525 perkilogram.HREEare Cerium oxidetradesatabout US$5 perkilogramwhereas different REEmetalsandoxides (Table 8andFigure14). There iscurrentlysignificant variation inthepriceof confidential contractsandpricesaresetbyproducers. (Vulcan, 2008).REOaretypicallysuppliedonlong term oxides aresoldbyspecialistREE-tradingcompanies which REEmetalsaretraded.Boththeandtheir As withmanyminormetals,therearenoexchangeson Prices (Table 7; IMCOA, 2009). 2009). IMCOA, 7; (Table 2014 by surplus in be to predicted all are praseodymium and cerium Lanthanum, neodymium. is demand meet to not predicted LREE only The 2014. by europium and dysprosium terbium, for supply outpace will demand that estimated been has it but varies REE individual for demand Predicted 2009c). Minerals, (Industrial deposits these from levels recovery in reduction significant a been has there resources, these of mining inefficient the of result a As China. southern of deposits clay adsorption ion are which of source main the HREE, the of supply the over concern greater is there However, demand. global meet to sufficient remain will LREE the of supply that appears It 7). (Table REE heavy and light the between and elements individual for considerably vary to likely is balance supply-demand the reality In 2010). (Hedrick, demand expected to relative large very be to thought are resources undiscovered that indicates which USGS the by supported is view This 2009a). (Lifton, shortfall Chinese domestic any supply ultimately to but supplies, REE China’s in reduction for compensate only not to world the in elsewhere reserves sufficient are there suggest commentators Industry as discussedabove. many additionalsourcesoutsideChinaarebeingevaluated concern aboutthesecurityoffuturesuppliesREEand than theREO(Hong,2006).Accordinglythereisgrowing value finishedgoodscontainingREEbeingexportedrather manufacturing enterprisestoChinaresultingin,higher to Chineseexportscouldforceconsumersmove Chinese supplies.Ithasbeensuggestedthatrestrictions due toenvironmentalconcernshasfurtherimpactedon increased to 16 per cent in 2008. Closure of REE operations 2007 a10percentexporttariffwasimposed,which increasing thetariffsonrareearthmetalsandoxides.In due toincreasingdomesticdemand.Chinahasalsobeen www.MineralsUK.com 30 Rare Earth Elements by 2014(IMCOA, 2009). (±15%) Thoseshowninboldare predictedtobeindeficit Table 7Forecastsupply/demandbyelementin2014 Database (UNComtrade)Nationswith*indicates2007figures. Figure 12 Demand Lanthanum Cerium Praseodymium Neodymium Samarium Europium Gadolinium Terbium Dysprosium Erbium Yttrium Ho, Tm,Yb,Lu Total Major importersofREEcompoundsandmetalsin2008. SourceUnitedNationsCommodityTrade Statistics tonnes REO 51050 65750 7950 34900 1390 815 2300 565 2040 940 12100 200 180000 % 28.4 36.5 4.4 19.4 0.8 0.5 1.3 0.3 1.1 0.5 6.7 0.1 100 Supply tonnes REO 54092 79156 9909 33665 4596 659 3575 512 1830 1181 12735 1592 203502 % 26.5 38.9 4.9 16.5 2.3 0.3 1.8 0.2 0.9 0.6 6.3 0.8 100 deficit Surplus/ 3042 13406 1959 -1235 3206 -156 1275 -53 -210 241 635 1392 legislation) which use less REE resulted in decreased decreased in resulted REE less use which legislation) environmental to (due catalysts cracking fluid to industry petroleum the in change a 1985 by However, 1980s. early the during stable were Prices prices. in increase an to leading costs energy rising and inflation to due increased had costs operating 1970s late the By pace. kept demand and 1970s the in increase to continued Supplies applications. commercial in metals and compounds REE of use widespread and California in Mine Pass Mountain the of opening the of result a as largely decreased prices 1971 and 1958 Between inflation andenergycosts(Hedrick1997). to environmentallegislationandeconomicfactorssuchas largely asaresultofthesupply/demandbalance,related REE priceshavefluctuatedsignificantlysincethe1950s, value-added propertiesattracthigherprices(Lynas, 2009). specific end-userrequirements.Higherpuritiesandother by thepuritylevelofproductwhichisdictated which varywithtime.FurthermoreREEpricesareaffected individual elementsisalsoaffectedbydemandpatterns another factorwhichinfluencestheprice.Thepriceof and associatedexpenseinextractingeachelementis lower abundanceinmostdeposits.Therelativedifficulty typically moreexpensivethanlighterLREEduetotheir www.MineralsUK.com REE compounds REE metals 31 Rare Earth Elements Database (UNComtrade)Nationswith*indicates2007figures. Figure 13 Table 8 2010). US$ perkilogramonanFOBChina basis(metal-pages, shown areforaminimum99% purityandarequotedin REE Cerium Dysprosium Europium Gadolinium Lanthanum Neodymium Praseodymium Samarium Terbium Yttrium REO andmetalpricesinApril 2010.Prices Major exportersofREEcompoundsandmetalsin2008. SourceUnitedNationsCommodityTrade Statistics Metal Price ($perkg) 8.50–9 240–260 770–800 18.5–19.5 10.5–11 41–43 41–42 20.5–21 610–650 35–45 Oxide 4.7–5.2 188–198 515-535 7.4–7.9 6.2–6.5 30.5–31 30–30.5 4.25–4.75 560–600 10.5–11.5

continuing to exceed demand (Naumov, 2008). computers during the first half of 2001 resulting in supplies decrease in demand for telecommunication equipment and China decreased production. However, this failed due to a prices. In an attempt to combat this and help prices recover this led to over production of other REE and a decrease in metals and oxides. Because REE cannot be selectively mined and China responded by increasing production of both increased dramatically due to their use in Nd-Fe-B magnets By 2000 demand for neodymium and dysprosium had 2008). (Naumov, year following the reduce to prices causing production, increasing by reacted China prices. on pressure upward placing and supply over concern causing considerably, increased had REE for demand 1995 By demand. exceeded supply that rapidly so growing industry REE Chinese the of result as a 1990s the since low artificially been have prices REE 1997). (Hedrick year following the prices in rises a to leading response, in decreased production Mine demand. www.MineralsUK.com REE compounds REE metals 32 Rare Earth Elements Table 9 Figure 14 REO (purity99%min) 2001 2002 2003 2004 2005 2006 2007 2008 2009 April 2010 %increase 2002–2008 %increase 2008–2009 REO pricetrends2002–2010(Lynas Corp,2009;metal-pages,2010). REO andmetalpricesinApril 2010(metal-pages,2010). La 7 2.3 1.5 1.6 1.5 2.2 2.8 8.8 5.9 6.4 284 -33 Ce 4 2.3 1.7 1.6 1.4 1.7 2.6 4.4 3.8 5.0 95 -13 Nd 11 4.4 4.4 5.8 6.1 11.1 31.2 32.9 14.5 30.8 656 -56 Price ($perkg) Pr 6.2 3.9 4.2 8 7.6 10.7 30.4 32.6 14.5 30.3 728 -56 Sm 9 3 2.7 2.7 2.6 2.4 3.1 4.8 4.8 4.5 61 -1 Dy 35 20 14.6 30.3 36.4 70.4 88.3 120.8 112 193 504 -7 Eu 310 240 235.4 310.5 286.2 240 311 491 495 525 105 1 www.MineralsUK.com Tb 135 170 170 398 300 434 575 740 360 580 335 -51 REE oxide REE metal 33 Rare Earth Elements Figure 16 Figure 15 Price trendsforselectedLREOfrom2001to2009(Lynas Corp,2010). Price trendsforselectedHREOfrom2001to2009(Lynas Corp,2010). www.MineralsUK.com 34 Rare Earth Elements Figure 17 (Figure 17). Prices for praseodymium and neodymium began of 2009 as demand has increased and supplies tightened REE prices have been recovering since the final quarter 16). (Figure 2009 of most for level that at stabilising before 2008 of half second the in dramatically fell both also prices neodymium and Praseodymium 15). (Figure 2008 in kilogram per US$740 of peak its from cent per 50 than more of decrease a kilogram, per US$360 to fell terbium example for significantly; decrease to prices REE caused This costs. lower to inventories existing use to began industries many 2008 of half second the During 2009d). Minerals, (Industrial recession the by affected deeply been has industry REE the sectors resource-based many with As 2008. and 2002 between respectively cent per 300 and 500 by increasing oxide terbium and oxide dysprosium of prices the with 2000s the during industry in important increasingly became rarer, HREE being the to addition In 2008. and 2002 between cent per 700 approximately by price in increasing both rises, largest the showed neodymium and praseodymium oxides LREE the Of 2008. of half first the in peaking accelerated, subsequently increase of rate (Table The 2006 9). until increasing gradually before 2003 and 2002 between low a reached REO most for Prices Price trendsforselectedREOfromJanuary2008toApril 2010(IndustrialMinerals,2010b). they arecommonly anotherREEoramoreexpensive performance (Haxeletal.,2002). Wheresubstitutesexist and substitutesareeitherunknown orprovideinferior Many oftheapplicationsREE arehighlyspecific Substitutes recycling could reduce pressure on primary production. concerns about security of supply, secondary sources and technologies and substitutes. However, with rising prices and a result there has been little incentive to investigate recyclingIn recent years the REE market has been in over-supply and as Recycling andsubstitution constant at US$2.25 per pound for at least the last 2 years. 2010. The price for bastnäsite concentrate has stayed and reached a high of US$188-198 per kilogram in April Dysprosium prices have been rising since the end of 2009 high purity glass for digital camera lenses (Russell, 2010). are rising partly due to an improvement in the market for praseodymium and neodymium. Lanthanum oxide prices have also started to rise, but not at the same rate as for applications. Prices for cerium and lanthanum oxide escalating demand from key markets such as magnetic respectively. By April 2010 these increases are due to US$14.5 per kilogram to US$30 and US$30.5 per kilogram to increase rapidly in October 2009 and had risen from www.MineralsUK.com 35 Rare Earth Elements 2005). Krishnamurthy, and (Gupta x-rays of intensifiers as and pigments glass, decolouring and colouring components, glass optical and magnets phosphors, catalysts, applications, polishing in required be will REE that assumed is it future foreseeable the for Consequently, (Table likely 10). less is substitution properties magnetic special certain and chemical optical, specific on based applications However, those in involved. are properties magnetic and metallurgical where possible be may earths rare than other materials by REE of Substitution relatively low abundance, high demand and no substitute. cathode ray tube and LCD no success (Smith, 2009b). Europium, used in the colour- find alternatives for the neodymium-iron-boron magnet with For approximately 20 years scientists have been trying to autocatalysts inplaceofREE(BonelandChapman,2005). for examplecanbeusedinpetroleumcrackingand material suchasplatinum-groupelements.These disposed of containing functional magnets (Trout, example,2007). discs drives only last a few years and are generallymagnet is longer than that of the device in which it isis used.another For option. In many applications the lifetime ofAlthough the recycling of magnets is problematic, reusing magnets conditions (Saitoetal.,2006). to improvetherecoveryratebyoptimisingprocessing containing borontrioxidebutfurtherresearchisneeded Neodymium wassuccessfullyremovedfromneodymium recovering REEfromopticallensesandpolishingsludges. 2006). Studieshavealsobeenundertakentoinvestigate carbon andoxygeninrecycledmagnets(Itakuraetal., issue resultsfromcontaminationbyimpurities,largely as thosepreparedfromprimaryrawmaterials.Thisquality from recycledmaterialsdonothavethesameperformance have notbeendevelopedcommerciallyasmagnetsmade have beenproposedforrecyclingREEmagnetsbutthey several elements(Takeda etal.,2006).Severalprocesses very difficultasitformsextremelystablecompoundswith beneficial. Howeverrecyclingneodymiumfromscrapis means ofrecyclingNdfromthissourcewouldbehighly generates asignificantamountofscrapsoaneffective neodymium-iron-boron magnetsincreasesannuallyand recycling difficultandexpensive.Manufactureof REE arecommonlyusedincompoundformmaking Only smallquantitiesofREE-bearingscraparerecycled. Recycling 79 LCD:liquidcrystaldisplay. 79 in computer monitors, has a 2009c). (Lifton, products end-of-life and waste of recovery and recycling to through materials raw to access from product, a of cycle life complete the in interested increasingly becoming are manufacturers product how illustrates This Vietnam. in developed being mine REE a in interest an with company a owns also Toyota 2009). (Burns, expectancies life long having batteries the as decade next the into well until substantially increase not will returned being batteries end-of-life of volume the However, life. its of end the at returned is it when $200 receives customer the and tagged is battery Every batteries. Nickel-metal-hydride of quantities significant use which vehicles hybrid their of introduction the alongside programmes refining and return effective developed have Toyota and Honda another. of manufacture the in used is product or process one from by-product or waste the where system production a is This products. their in essential are that REE of use and control maintain to order in technologies new of introduction the accompany to programmes recycling loop closed established have manufacturers Some (Gupta andKrishnamurthy, 2005). Table 10 Application Nodular iron Metallurgy Steel Control rod energy Nuclear Polishing Glass storage Hydrogen tiles Glazed ceramic Ceramics Alternatives toREEinsomeapplications. Material REE metal Misch REE silicide Europium oxide Cerium nickel alloy Lanthanum Cerium www.MineralsUK.com Alternative Magnesium Calcium Hafnium process Plate glass(Pilkington) Iron titaniumalloy Tin, zirconium 36 Rare Earth Elements more than40percentof theterrigenousmaterialissilt. continental separationandlithosphericattenuation duringtheearlystagesofopeningNorth Atlantic. 84 83 82 81 80 2009e). could solve the potential REE shortage (Industrial Minerals, the process could be expanded to a commercial scale it oxides could be recovered. It has been suggested that if significant amounts of neodymium, cerium and lanthanum efficiency in TiO dangerous waste from processing and to improve energy ▪ ▪ ▪ occur inanumberofgeologicalsettings: of REEresourcesinBritain.Howeverareknownto There hasbeennosystematic,comprehensiveevaluation Focus onBritain (TiO method of recovering REE from recycling titanium dioxide Research at the University of Leeds has identified a in certainhorizonswithintheVariscan sedimentary rocksoftheWelsh Basinandalsooccur Monazite nodulesarepresentintheLowerPalaeozoic Nodular monazite collected fromcatchmentsdrainingOrdovicianandSilurian high ceriumlevelsisinsouth-centralWales, fromsamples of nodularmonazite.Themostextensiveareacontaining anomalies resultfromthepresenceofadistinctiveform concentrates fromWales andsouth-westEngland.These of REE(>5000ppmcerium)inpannedstreamsediment geochemical drainagesurveyswhichshowedhighlevels These monaziteoccurrenceswereidentifiedbyBGS succession ofsouth-westEngland. Ce reportedinalluvialareas. Wales iswidelydistributedwith highcontentsofLaand economic potential,althoughthenodularmonazitein Most ofthesearesmalloccurrenceswithnodemonstrated ▪ ▪ ▪ ▪ ▪ Turbidite: type of sedimentary rock composed of layered particles that grade upward from coarser to finer sizes and are thought to have originated from ancient turbidity currents in the oceans. Pyroxenite:ultramafic igneous rockconsistingessentiallyofminerals ofthepyroxenegroup. Hemipelagicsediment:deep-sea,muddysediment formedclosetocontinentalmarginsbythesettling offineparticles,inwhichbiogenicmaterialcomprises5–75%the totalvolumeand Variscan: orogenycausedbyLatePalaeozoiccontinental collisionbetweenEuramerica(Laurussia)and GondwanatoformthesupercontinentofPangaea. BritishTertiary IgneousProvince:Areaofthenorth-west BritishIsleswhereintenseigneousactivity occurredduringthePalaeoceneandearlyEocene(about63to52Ma)asa resultof Igneous Province Various REEbearingmineralsfromtheBritish Tertiary intrusive complexesofnorth-westScotland REE-bearing mineralsassociatedwiththealkaline rocks ofsouth-centralWales andExmoor Nodular monaziteinLowerPalaeozoicsedimentary the NorthPennines(Figure19). lead-zinc-barytes mineralisationintheAlstonBlockof Synchysite andotherREEmineralsassociatedwith 2 ) waste. The purpose of this study was to eliminate 2 extraction. However, it was discovered that 80

81 sedimentary allanite, ancylite REE mineralsidentifiedintheBenLoyalareainclude 1993). Gunn, and (Shaw respectively complexes Loyal Ben and Ailsh Loch the from reported were La+Ce cent per 2.5 and 0.7 apatite. cent per 2 to up with associated Y ppm 986 and Ce ppm 1764 Ce, ppm 739 to up values REE contain to found were region, Assynt the of corner south-west apatites of the Loch Borralan pyroxenite Borralan Loch the of apatites The Scotland. of Highlands north-west the of intrusions igneous alkaline Caledonian the of potential REE the evaluate to undertaken been have studies Limited Alkaline igneousrocks nordmarkite organic-rich hemipelagic concentrations (Smithetal.,1994). be requiredtoassessthetruepotentialofplacer sufficient monazitetobeeconomicandfurtherworkwould deposits, whicharethesourceofREE,donotcontain placer deposits.Thestudyconcludedthatthebedrock of themorevaluableHREE,arehigherthanaveragefor with workingthem.Inadditionlevelsofeuropium,one potential asitreducestheradioactivehazardassociated nodules arelowinthoriumwhichincreasestheireconomic economic potentialoftheWelsh nodularmonazites.The An assessmentwasundertakenin1994toinvestigatethe (Milodowski andZalaciewicz1991). and grewduringdiagenesiscompactionaldewatering has beenrecordedinmiaroliticcavitites Gunn, 1993).Inadditionahydratedspeciesofmonazite migration ofREEupwardsfromturbidite al., 1987).Itisthoughtthatthenodulesformedby between thecoreandrimofsinglegrains(Readet of lightandheavyREEastrongdifferentiation host rock(Cooperetal.,1983).Thenodulesshowzonation inclusion fabricwhichisindistinguishablefromthatofthe flattened, ellipsoidal,0.05to2mmindiameterwithan derived fromgraniticsources.Thenodulesaregrey, different fromnormaldetritalmonazite,whichislargely The physicalappearanceofthistypemonaziteisvery 1983). sedimentary rocksoftheWelsh Basin(CooperandRead, 89 intrusion.Themodeofoccurrencesuggests 85 , betafite 83 layerswheretheynucleated 86 andrhabdophane www.MineralsUK.com 88 82 84 withina mudsintothe , located in the the in located , 87 (Shawand 37 Rare Earth Elements Fergus MacTaggart, BGS©NERC. Northern Arrangranite,Strathclyde,ScotlandPhotograph: Prismatic gadolinite-(Y)inamiaroliticcavitywithinthe and yttrium and the gadolinite by yttrium. The gadolinite acicular crystals up to 2 mm long, is dominated by neodymium and orthoclase. The fergusonite, which occurs as prismatic gadolinite are found associated with, and growing on, albite Arran granite (Hyslop et al., 1999). The fergusonite and have been identified within miarolitic cavities of the northern REE element-bearing minerals including allanite and zircon al., 1999). Fergusonite and gadolinite associated with other and Skye granites making up the northern sector (Hyslop et the southern sector of the province with the lower silica Mull Eocene. The Mourne Mountains and Arran granites represent igneous activity occurred during the Palaeocene and early Province, an area of the north-west British Isles where intense identified within the granites of the British Tertiary IgneousSeveral minor occurrences of REE-bearing minerals have been Tertiary granites fluid phase(vonKnorringandDearnly, 1959). that themineralwasdepositedfromalatestageaqueous 92 91 90 89 88 87 86 85 Nordmarkite: A quartz-bearing alkalic syenite that has microperthite as its main component with smaller amounts of oligocase, quartz, and biotite and is characterized by granitic or trachytoid texture. Chevkinite:cerium–titanium–ironsilicate.Formula: Ce Miaroliticcavity:crystallinedirregularcavity or vugmostcommonlyfoundingraniticpegmatites,but alsofoundinavarietyofigneousrocks. Rhabdophane:hydratedneodymium-dominant phosphate.Formula:(Nd,Ce,La)PO Sphene:calcium–titanium silicate.Formula:CaTiSiO Zirkelite:titanium–zirconium–iron–yttrium–calcium oxide.Formula:(Ca,Th,Ce)Zr(Zr, Ti) Betafite:CalciumSodiumUranium Titanium Niobium Tantalum Oxide.Formula:(Ca,Na,U) Ancylite:hydratedstrontium–cerium–carbonate hydroxide.Formula:SrCe(CO 5 . 4 (Ti, Fe 2+ , Fe 3+ ) 5 O 8 (Si 2 O 7 ) 3 2 ) . 2 (OH) 4 • • H H 2 O. 2 2 O. O 7 . 2 (Ti, Nb,Ta)2O Photograph: FergusMacTaggart, BGS©NERC. Euhedral crystalofzircononanalbitesurface Skye (Green and McCallum, 2005). McCallum, and (Green Skye on granites the within cavities miarolitic in identified been also have kainosite and Gadolinite 1980). (Exley, respectively REO cent per weight 46 and 25 of average an returning analyses with enriched LREE particularly are identified in the granites of Skye. Allanites and sphenes and Allanites Skye. of granites the in identified been have minerals accessory REE-enriched Various 1982). al., et (Harding rock host the of cent per one than less up make minerals REE the However, REE. total cent per 41 to up contain can and common most the is Hebrides, allanite, chevkinite allanite, Hebrides, Outer the in Kilda, St of granites the in identified been have content REE significant with minerals Three 2005). al., et Green 1999, al., et (Hyslop Ireland Northern of granite Mountains Mourne the in vugs in occur to reported been has monazite, of type coloured honey-brown unusual an to addition in Gadolinite 2.5 mm long (Hyslop et al., 1999). occurs as dark green, vitreous, turbid, prismatic crystals up to 6 (OH, F). 90 90 www.MineralsUK.com and zirkelite and 91 . Chevkinite Chevkinite . 92

38 Rare Earth Elements Figure 19 REE mineraloccurrencesinBritain(MountainHighMap frontiers™©1998DigitalWisdom). St Kilda Mountains Mourne Skye Arran Borralan Loch Loch Hill Preseli s Ben Loyal Ails h Exmoor Harlech Dome Garrigill Wa Central Dome Berwyn les Shap Pennines Northern Zn-Pb-Ba mineralisation-relate Nodular monazite Alkaline intrusion-relate Tertiary granite-relate www.MineralsUK.com d d d 39 Rare Earth Elements Block (Ixer and Stanley, 1987). earliest, highest temperature mineralisation of the Alston with an assemblage which is believed to be part of the Tynebottom Mine, near Garrigill. The synchysite is associated et al., 1996). Synchysite has also been identified at the xenotime and adularia, intergrown with bismuthinite (Ixer Rookhope contain synchysite, and more rarely monazite, Block. Bismuthinite-bearing quartz veins near Stanhope and mineralisation in the Northern Pennine Orefield of the Alston been identified associated with lead-zinc-fluorite-barite Small quantities of synchysite and other REE minerals have Lead-zinc-fluorite-barite mineralisation www.MineralsUK.com 40 Rare Earth Elements Geology, 186,75–98. from theOkorusufluoritedeposit,Namibia.Chemical precipitating REE,Sr-rich fluorite:fluid-inclusion evidence The natureoforthomagmatic,carbonatiticfluids www.australianrareearths.com Elements —'Specialty Metals'ForAGreenerWorld. (invited). Magnetocaloric refrigeration near roomtemperature In: associated deposits:magmatic,replacementandresidual. A A A references Further readingandselected B B B B B B B B A (C, O). Behaviour Of Selected Trace Elements And Stable Isotopes In The Barra Do Itapirapua Carbonatite, Southern Brazil: 1999. Ni_43-101/ Estimate. http://avalonraremetals.com/projects/thor_lake/ Economy. www.avalonraremetals.com Earths 10,RareEarthElementsAndTheGreenEnergy MineralDepositProfiles. and Mines.www.empr.gov.bc.ca/Mining/Geoscience/ Industrial Minerals,BritishColombiaMinistryofEnergy British ColumbiaMineralDepositProfiles, Volume 3, News. 2February, 2010.www.miningnews.net March, 2010. Ltd, SpecialityandMinorMetalsInvestmentSummit,18 Mine toMarketStrategy, GreatWestern MineralsGroup destructively. Management forMiningandNaturalResources. Capacity inGovernanceandRevenuesStreams Kyrgyzstan, PIUofWorld BankIDFGrantforBuilding Mining IndustryasaSourceofEconomicGrowthin BGS, MetalBulletin,Im. Minerals Review2005includinglateststatisticsanddata, Vol. 310,p2793–2799. rück radsher onel ogdetsky uhn irkett illingsley a ndr valon valon ustralin tten S imandl a , B,R , KA, , ET

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and The China Carbonatite 2000. and Solid oxide Geochimica Geological W , W L illiams , uo , , This commodity profile was produced by the British Geological Survey (2010).

It was compiled by Abigail Walters and Paul Lusty with the assistance of Claire Chetwyn and Amanda Hill.

This report is one of a series of Commodity Profiles available to download free-of-charge from www.MineralsUK.com.

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