BriengPaper02/12

ProspectsforRareEarthElements FromMarineMinerals
JimHein|May2012
Rare earth elements (REEs) compose the lanthanide group of 15 elements in the periodic table, 14 of which occur in nature and one that does not occur in nature, promethium. Scandium and y rium are usually considered together with the REEs because of their similar geochemical characteris cs. Despite their name, REEsarerela velyabundantintheearth'scrust.However,becauseoftheirgeochemicalproper es,rareearth elementsaretypicallydispersedandnotcommonlyfoundinconcentratedandeconomicallyexploitableforms. Theirindustrialusesinemerginghighandgreentechnologyapplica onsgivethemanimmediatecri caland strategicimportance.
Table1:RareEarthElements

Chinacurrentlyproducesover Element 95percentoftheworld'sREE supplyandhasrecentlystarted Scandium torestrictexports,becausethe REEproduc onisbeingmore Y rium directedtodomes cuseandis beingconservedforfutureuse. TheusesofREEinmodern socie esareextensiveand includehybridandelectric cars,windturbines,weapons systems,motors,magnetsfor manyapplica ons,andahuge marketforphosphorsincolour televisionsandmonitors, amongmanyother applica ons.Theautomobile manufacturersworldwide cannotoperatewithoutthe availabilityofREEs.Withinthe groupofREEs,anumberof elementsarepar cularly cri calandpredictedtobein decitontheglobalmarketby 2014,forexampleneodymium, europium,terbiumand dysprosium(IMCOA,20111and othersources).
Cerium

Symbol Sc Y

Selected Applica ons Superalloys,lightaerospacecomponentsXraytubes, catalysts Ceramics,metalalloys,medicaluses,rechargeable ba eries,phosphorsforTVshightemperature superconductors Ba eries,op calglass,cameralenses,catalystsfor petroleumrening Catalysts,metalalloys,radia onshielding Magnets,lasers,pigments,cryogenicrefrigerant Highstrengthpermanentmagnets,lasers Nuclearba eries,guidedmissiles Hightemperaturemagnets,reactorcontrolrodsand neutronshielding,lasers Liquidcrystaldisplays,uorescentligh ng Magne cresonanceimagingcontrastagent,memory chips Greenphosphors,lasers,uorescentlamps,op cal computermemories Permanentrareearthsmagnets,lasers,catalysts, nuclearreactors Lasers,nuclearreactors,catalysts Lasers,vanadiumsteel,infraredabsorbingglasses PortableXraymachines Infraredlasers,chemicalreducingagent,rechargeable ba eries PETScandetectors,superconductors,highrefrac ve indexglass

Lanthanum

La Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu

Praseodymium Neodymium Promethium Samarium Europium Gadolinium Terbium Dysprosium Holmium Erbium Thulium Y erbium Lute um

This paper was prepared for the Interna onal Seabed Authority sensi za on seminar held in New York on 16 February 2012 on the work of the ISA and current issues rela ng to deep seabed mining. Dr. James Hein is a senior scien st with the United States Geological Survey (USGS) in California. He is also an Adjunct Professor of Ocean Sciences at the University of California at Santa Cruz. He has authored or coauthored more than 400 papers and abstracts. www.isa.org.jm

Upun lthe1990s,theUSAwas themainproducerofREEs,which camefromtheMountainPass mineinCalifornia(Figure1).This mineclosedin2002astheresult ofcompe onfromtheChinese BayanObomine,theworlds largestREEdeposit.Becauseof thereduc oninexportsfrom China,theMountainPassmine willreopenin2013andseveral newlydevelopingmineswill comeonlineduringthenext years,suchasinAustralia,South Africa,andelsewhere.Itmay takeun labout2016beforenew REEsourcesmakeupforthe reduc onsinChineseexports. Newconsidera onsforthe augmenta onofREEsupplies comefromtheREEsinthevery largetonnagedeepocean mineraldeposits,specically polymetallicnodulesandcobalt richcrusts.Bothdeposittypes haveasignicantpoten alto supplyREEstothemarketplace asabyproductoftheextrac on ofcopper,nickel,cobalt,and manganese.Eventhoughthe grades(concentra onofREEs)of themarinedepositsaregenerally lowerthanforthelandbased deposits,thetonnagesaremuch greaterthanthelandbased deposits.Thisistrueeven consideringthatthereareonly twoprimemineraldepositareas inthePacicOcean:TheClarion ClippertonnodulezoneintheNE Pacicintheinterna onal seabedarea,wherenine explora oncontractsare presentlyinforce(Figure 2);and theprimeequatorialPaciccrust zone,whichincludesboththe interna onalseabedareaand ExclusiveEconomicZonesof PacicIslandcountries(Figure 3).

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Figure1:Historyofrareearthelementproduction(fromUSGS)

Figure2:PolymetallicnodulesexplorationlicensesandreservedareasinClarion ClippertonFractureZone(MapISA)

richcrustsintheAtlan candIndian Oceansareexpectedtobeasrichin REEcontentasinthePacic,butdata andknowledgeforthoseareas remainpoortodate.

Polymetallicnodulesaresmallgolf ballsizedconcre onsthatsitonthe sedimentsurfaceondeepwater (4,5006,500meters)abyssalplainsof theglobalocean(Figure 4).Theyare composedpredominantlyof Crusts,onaverage,exhibitabout manganeseandironoxideswith three meshigherREE muchlesseramountsofcopper, concentra onsthannodulesand nickel,cobalt,REEs,lithium,and someofthedepositshavesimilar molybdenum.Themainmetalsare concentra onstothelandbased derivedfromcoldambientseawater oresinSouthernChina.Itis andfromporewatersinthe worthwhileno ngthatcobalt
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sediment.Theminormetalsare adsorbedontothemajorironand manganesephases.Crustsform pavementsonhardrocksubstrates onsubmarineseamountsandridges throughouttheglobalocean(Figure 5).Thoseofeconomicinterestoccur atwaterdepthsofabout1,0002,500 meters.Theyarecomposed predominantlyofmanganeseand ironoxides,cobalt,nickel,REEs, tellurium,molybdenum,zirconium, tanium,bismuth,niobium,pla num, andtungsten.Themetalsofinterest arederivedfromcoldambient seawaterandareadsorbedontothe majorironandmanganesephases.

ProspectsforRateEarthElementsfromMarineMinerals

Thereareseveralpossible advantagestominingthe marinedepositsinorderto augmenttheproduc on fromlandbaseddeposits. Themainmessageisthatthe economical,geologicaland environmentalfactorsfor landbasedandmarine depositsneedtobe evaluatedonequalfoo ng. Economically,therela ve contentofthepar cularly interes ngheavyREEs (HREEs)ishigherinseabed depositsthaninthelargest landbasedREEmines,for examplethelargestREE mine,BayanObo(China)and thesecondlargest,Mountain Pass(USA).Bothlandbased depositsmen onedabove containlessthan1%HREEs
Figure 3:Map of most permissive area for cobaltrich crusts in the global ocean, located in the western equatorial Pacic (from Hein et al., 2009) 2

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(percentageoftotalREEcontent), whereastheCCZnoduleshavea rela vecontentof10%HREEsand Paciccrustsaveragemorethan6.3% HREEs.ThesmallerlandbasedREE deposits,forexampletheion adsorp onclaysinSouthernChina, havesimilarHREEconcentra onsas foundinthemarinedeposits.

ComparingtheCCZnodulesandPacic primecrustswiththesetwolargest exis nglandbasedREEmines,theland baseddepositsaregenerallyhigherin gradebutlowerintonnageofore. Howeverthecontainedmetal(REEs)in thecrustsandnodulesiscomparableto thoseintheBayanOboandMountain Passdeposits,respec vely.

Figure4:(Left)Polymetallicnodules(fromHeinandKoschinsky,2012)3;Figure 5: (Right) Photo of seabed at 2,000m water depth showing crust pavement (below) and crusts recovered in the Marshall Islands area (from Hein and Koschinsky, 2012)3

Anaddi onaladvantageofthemarinedepositsisthat itissaidtotake1,000stepstoprocessalandbased oretoisolateoneoftheHREEs.Incontrast,because theREEsareadsorbedontothemainironand manganesephases,theycanbedissolvedfromseabed oresusingrela velysimpleprocedures(diluteacid leach)inamorecostecientway. Athirdadvantagerelatestoseveralenvironmental considera ons.Themajorlandbaseddepositshave highconcentra onsoftoxicwasteproducts(thorium) thatneedtobecarefullymanaged.Apossible advantageofseabeddepositsistheabsenceofsuch radioac vecomponentsinthedepositsthat signicantlyincreasethetechnologicalcomplexityand costsofREEprocessingonland.Amoveablemining

pla ormformarinedepositsallowfortheminingof justthehighgrade,hightonnagedepositsthereby impac ngtheleastamountofseabednecessarywithin acrustornodulezone.Deepoceananimalpopula on densi esarealsogenerallylow. Anotherenvironmentaladvantageisthatlandbased minesleaveasubstan alfootprintintermsof infrastructureattheminesite,whereasmarine depositsdonothaveseabedinfrastructureandonly theseabedminerimpactstheseabed.Landbased minescommonlyrequiretheremovalofsignicant amountsofbarrenoverburdenrock,24 mesmore thanthesizeoftheorebodyitself.Incontrast,marine depositssitattheseabedwithnooverburdento remove.
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ISATechnicalStudy Deepocean deposits may oer a par al solu on to projected shortages of REEs. In 2011 the Authority commenced work on a technical study designed to address the ques on of whether sea oor deposits have the poten al to become an alterna ve source of REEs. During the rst phase of the project, the geochemical proper es of REEs and their geographic varia on are being examined in detail. Ini ally, a global geochemical database of trace metal grades with approximately 2,000 analysed samples, thereof about 700 REE samples has been compiled from various sources, covering the major geographic areas of interest for cobaltrich crusts and the major polymetallic nodule provinces, including the Central Pacic, the Central Indian Ocean, the Peru Basin, the Penrhyn Basin, the Manihiki Plateau, the Rio Grande Seamounts and other areas of poten al interest. The geochemical analyses of metal contents carried out to date in the context of the project are promising, not considering metallurgical factors and processing costs in detail at this stage. Generally, the extrac on of REEs from tailings and interim products may represent a costecient way to produce REEs compared to landbased produc on, without a nega ve eect on the produc on of the main metals because iron is not a target metal; REE by product opera ons could turn such residues into prots. An important working hypothesis is that REEs might be par cularly enriched in ironhydroxide bearing tailings and the grades in these tailings may exceed the grades of the REE deposits mined in China. Relevant nodule processing owsheets with interim products can be found in Halbach et al. (1988)4 and in Mukhopadhyay et al. (2008)5.

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Endnotes
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IndustrialMineralsCompanyofAustralia.(2011).In:Smith,M. Rare earth minerals: The indispensable resource for clean energy technologies. Hein,J.R.,T.A.Conrad,andR.E.Dunham.(2009).Seamountcharacteris csandminesitemodelappliedtoexplora onandmining leaseblockselec onforcobaltrichferromanganesecrusts. Marine Georesources and Geotechnology, 27 (2), 160176. Hein,J.R.andA.Koschinsky.(2012).Deepoceanferromanganesecrustsandnodules.InSco ,S.,(ed.)The Trea se on Geochemistry,v.12.Elsevier(inpress). Halbach,P.,G.FriedrichandU.vonStackelberg(1988).The Manganese Nodule Belt of the Pacic Ocean.Stu gart:FerdinantEnke. Mukhopadhyay,R.,A.K.GoshandS.D.Iyer.(2008).The Indian Ocean Nodule Field: Geology and Resource Poten al.London: Elsevier.

The Interna onal Seabed Authority is an autonomous interna onal organiza on established under the 1982 United Na ons Conven on on the Law of the Sea and the 1994 Agreement rela ng to the Implementa on of Part XI of the United Na ons Conven on on the Law of the Sea. The Authority is the organiza on through which States Par es to the Conven on shall, in accordance with the regime for the seabed and ocean oor and subsoil thereof beyond the limits of na onal jurisdic on (the Area) established in Part XI and the Agreement, organize and control ac vi es in the Area, par cularly with a view to adminis tering the resources of the Area. As part of its mandate to conduct resource assessments of prospec ve mineral deposits in the Area, the Authority, together with its contractors and scien sts, joined forces with a group of technical experts to establish and develop a Geological Model of polymetallic nodule deposits in the ClarionClipperton Fracture Zone. The publica on (A Geological Model of Polymetallic Nodule Deposits in the ClarionClipperton Fracture Zone: ISA Technical Study No. 6) is available online on www.isa.org.jm/les/ documents/EN/Pubs/GeoModweb.pdf. The Geological Model consists of a set of digital and hard copy maps and tables describing the predicted metal content abun dance of deposits in the CCZ, along with associated error es mates. The Prospectors Guide examines all poten al proxy data variables iden ed as important indicators of metal content and abundance, and outlines specic data sets that qualify for use in the Geological Model. The area of interest for this study is 110o160o W longitude and 0o20o North la tude

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