Niobium-Tantalum: IM-Mining.com

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A new guide to niobium and tantalum has been published by the British Geological Survey (BGS) on its website. These little-known metals have some unique properties which make them essential ingredients in a wide range of products, from mobile phones to artificial hips. As commodity prices rise and access to some raw materials becomes more difficult, a small group of so-called ‘critical metals’ is causing particular concern. Niobium and tantalum are two of the most widely used metals on this critical list. Because of their unique properties and their essential role in the manufacture of steel and electronic capacitors, they are hard to substitute.
Supply concerns surrounding these metals have been heightened because illegal mining of niobium-tantalum ore (sometimes known as ‘coltan’) has been linked to conflict in some parts of Africa.

The newly-published Niobium-Tantalum Commodity Profile from the BGS provides a concise, authoritative and easy to understand guide to the origins, production and trade of these important metals. Andrew Bloodworth, Head of Minerals and Waste at the BGS said: “Our profile on niobium and tantalum is the latest in a much-respected series from the BGS on critical metals, including rare earths, platinum and tungsten. Its publication is timely as it follows the recent release of the report of the House of Commons Science and Technology Committee inquiry into Strategically Important Metals which calls for more understanding of the role of these metals in our economy”.

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Niobium-Tantalum: IM-Mining.com

  1. 1. Niobium–tantalum April 2011 Definitions, mineralogy and Niobium (Nb) Tantalum (Ta) C en t re f o r su st ain ab le m in eral d evelo p m en t deposits Atomic number 41 73 Atomic weight 92.90638 180.9479 Definitions and characteristics MineralsUK Niobium (Nb) and tantalum (Ta) are transition metals with Density at 293 K 8.581 16.677 very similar physical and chemical properties, and are (g/cm3) thus commonly grouped together (Table 1). Niobium was Melting point °C 2468 2996 discovered in 1801 by Charles Hatchett, and was originally Boiling point °C 4930 5425 named ‘columbium’; it was subsequently also recog- Vickers hardness 1320 873 nised by a German chemist, Heinrich Rose, who named MPa it ‘niobium’. The names were used interchangeably for Electrical 152 at 0°C 131 at 20°C some time, before ‘niobium’ was finally accepted in 1949. resistivity (nano Tantalum was discovered in 1802 by a Swedish scientist, ohm-metres) Anders Ekeberg. Crystal structure Body centred Body centred Niobium is a shiny, ductile metal with a white lustre. Nat- cubic cubic urally-occurring niobium consists almost exclusively of the Table 1 Selected properties of niobium and tantalum. isotope 93Nb; natural tantalum is mainly 181Ta, with 0.012 per cent 180Ta. A number of other radioactive isotopes of The columbite-tantalite mineral group (Figure 1) is the both elements have been synthesised. most common group of tantalum- and niobium-bearing minerals. Wodginite is also an important source of The overall abundances of niobium and tantalum in the tantalum. The pyrochlore group (Figure 2) is of great average continental crust are relatively low, niobium economic importance, particularly for niobium. This group having an abundance of eight parts per million (ppm) and has a wide compositional range, including some species tantalum of 0.7 ppm (Rudnick and Gao, 2004). Compared to rich in both niobium and tantalum. Pyrochlore is typicallyMineral profile other metallic elements such as the light rare earths, nio- found as a primary mineral in alkaline igneous rocks. bium and tantalum are rather depleted in the continental crust. This can be attributed to the fact that much of the continental crust was formed at convergent margins above subduction zones, and that magmas formed in this setting are typically depleted in both niobium and tantalum. Mineralogy Niobium and tantalum do not occur naturally as free metals, but are essential components in a range of mineral species (Table 2). The majority of these are oxide minerals; silicates of niobium and tantalum do exist, but are relatively rare. Niobium and tantalum also substitute for major ions in a number of other minerals, in which they typically have low concentrations. The vast majority of the economically important species are oxides. Figure 1 Dark coloured tantalite with pale coloured albite1. Unless otherwise stated, copyright of materials contained in this report are vested in NERC. 1 Image taken by Rob Lavinsky. Permission to use given by a creative commons BGS © NERC 2011. All rights reserved. licence (accessed 25/03/2011 at www.commons.wikimedia.org). Attribution: Rob Lavinsky, iRocks.com (http://www.irocks.com/) – CC-BY-SA-3.0.
  2. 2. Mineral name Mineral group Formula Nb2O5 (%) Ta2O5 (%) Columbite Columbite-tantalite (Fe,Mn)(Nb,Ta)2O6 78.72 n.a. Tantalite Columbite-tantalite (Fe,Mn)(Ta,Nb)2O6 n.a. 86.17 Pyrochlore Pyrochlore (Na,Ca)2Nb2O6(O,OH,F) 75.12 n.a. Microlite Pyrochlore (Na,Ca)2Ta2O6(O,OH,F) n.a. 83.53 Tapiolite Tapiolite (Fe,Mn) (Ta,Nb)2O6 1.33 83.96 Ixiolite Ixiolite (Ta,Nb,Sn,Mn,Fe)4O8 8.30 68.96 Wodginite Wodginite (Ta,Nb,Sn,Mn,Fe)O2 8.37 69.58 Loparite Perovskite (Ce,La,Na,Ca,Sr)(Ti,Nb)O3 16.15 n.a. Lueshite Perovskite NaNbO3 81.09 n.a. Euxenite Euxenite (Y, Ca, Ce, U, Th)(Nb, Ti, Ta)2O6 47.43 22.53 Struverite Rutile (Ti,Ta,Fe)O2 11.32 37.65 Ilmenorutile Rutile Fex(Nb,Ta)2x4Ti1-xO2 27.9 n.a. Table 2 Selected niobium and tantalum minerals and indicative contents of Nb2O5 and Ta2O5. Deposits Niobium and tantalum mineral deposits are most com- monly associated with igneous rocks3, including granites, pegmatites4, syenites5 and carbonatites6. Some secondaryNiobium–tantalum deposits, where niobium- and tantalum-bearing minerals have been concentrated by weathering and sedimentary processes, are also known (see Table 3 and Figure 3 at the end of this section). In general, these secondary deposits occur in relatively close association with their primary sources, and so they are not considered separately in the descriptions below. Primary Niobium and Tantalum deposits can be divided into three main types, on the basis of the igneous rocks with which they are associated (Küster, 2009): 1. Carbonatites and associated rocks Figure 2 Pyrochlore. Source: Rob Lavinsky (iRocks.com) 2. 2. Alkaline to peralkaline granites and syenites 3. Granites and pegmatites of the LCT family (enriched ˇ in lithium (Li), caesium (Cs), tantalum) (Cerný and Ercit, Other, less common oxides of niobium and tantalum 2005). include tapiolite, ixiolite, and minerals of the perovskite group. Niobium and tantalum also substitute for major Moderately high contents of niobium and tantalum may be ions in some common oxide groups such as cassiterite, found in some granites and pegmatites that do not fall into rutile, and ilmenite. Contents of niobium and tantalum in the categories given above, but economic examples are these minerals are rarely high enough to make them of not known. economic interest. Similarly, niobium and tantalum occur as substitutes in a range of silicate minerals, typically those found in alkaline igneous rocks such as eudialyte 3 Igneous rocks: rocks with a crystalline texture that crystallised from molten rock (magma). (Na4(Ca,Ce)2(Fe++,Mn,Y)ZrSi8O22(OH,Cl)2). 4 Pegmatites: very coarse-grained igneous rocks. 5 Syenites: coarse-grained igneous rocks that are composed largely of the 2 Image taken by Rob Lavinsky. Permission to use given by a creative commons potassium- and/or sodium-rich mineral alkali feldspar. 6 licence (accessed 25/03/2011 at www.commons.wikimedia.org). Attribution: Rob Carbonatites: igneous rocks consisting of more than 50 per cent primary Lavinsky, iRocks.com (http://www.irocks.com/) – CC-BY-SA-3.0. carbonate minerals. 2 www.MineralsUK.com
  3. 3. Carbonatites and associated rocks these minerals in the shallow subsurface. Late-stage veins Carbonatites are igneous rocks that consist of more than and areas of metasomatism, formed through carbohydro- 50 per cent primary carbonate minerals. They are almost thermal activity, are a third potential source of niobium exclusively found in areas of continental extension and mineralisation. rifting7, and their source magmas are thought to be derived directly from the mantle with very little crustal influence. Much of the world’s niobium supply comes from Bra- Carbonatites are most commonly found as dykes, sills and zil, where the main niobium deposits occur in alkaline small plugs (less than one kilometre in diameter), more ultramafic-carbonatite complexes of the Late Cretaceous17 rarely occurring as large plutons or as extrusive8 volcanic Alto Paranaiba igneous province, intruded into Neoprotero- sequences. They rarely occur in isolation, being more zoic18 metasedimentary rocks. The largest currently worked commonly associated with alkaline9 silicate rocks, either niobium deposit is at Araxá, and is owned and exploited nepheline syenite and other feldspathoid-bearing10 igneous by the Companhia Brasileira de Metalurgia e Mineraçao rocks, or mafic11 to ultramafic12 alkaline rocks (Woolley (CBMM). A second major niobium mine, at Catalão, is and Kjarsgaard, 2008). Many carbonatite bodies are sur- operated by Anglo American. These deposits are hosted rounded by a metasomatised13 or ‘fenitised’ zone, typically in rather unusual intrusions consisting of carbonatite- and rich in sodium (Na) and/or potassium (K), formed through phoscorite19-series rocks with no associated syenites. In alteration of the country rocks by fluids derived from the both deposits, pyrochlore is the main niobium ore mineral. carbonatite. Some carbonatite bodies are considered to be The Araxá deposit lies within the Barreiro Carbonatite carbohydrothermal14 — formed from carbon dioxide-rich Complex, a roughly circular intrusion approximately 4.5 kil- and water-rich fluids rather than magmas. ometre in diameter (Nasraoui and Waerenborgh, 2001), dominated by dolomite carbonatite with subordinate cal- Carbonatites are typically enriched in a range of elements, cite carbonatite, glimmerite20 and phoscorite. The central including the rare earth elements (REE), barium (Ba), part of the intrusion has been weathered under tropical strontium (Sr), fluorine (F), phosphorus (P), niobium (Nb), conditions to form a thick (>200 metres), lateritic21 cover inNiobium–tantalum zirconium (Zr), uranium (U) and thorium (Th). Niobium is which pyrochlore has become concentrated at a reported preferentially enriched over tantalum in carbon dioxide- mean grade of 2.5 per cent niobium oxide, and which is rich melts, and so carbonatites do not generally have exploited by open-pit mining. The country rocks to the high tantalum contents (Möller, 1989). Common niobium- carbonatite have been metasomatised in an aureole22 up bearing minerals found in carbonatites include members of to 2.5 kilometre wide (Nasraoui and Waerenborgh, 2001). the perovskite and pyrochlore mineral groups, as well as The main worked deposit at Catalão is in the Catalão I niobium-rich silicates such as titanite (Mitchell, 2005). alkaline-carbonatite complex, but a similar deposit occurs in the nearby Catalão II complex. Catalão I is a steep-sid- In general, bulk rock niobium contents for carbonatite ed, zoned intrusive body with a diameter of approximately bodies are moderately high (commonly 0.01–0.1 per cent, six kilometres at the surface. It is dominated by glimmerite rarely up to 1.0 per cent), but not ore-grade. However, (phlogopitite) at the margins of the complex, with sheets magmatic differentiation15 processes such as crystal set- and plugs of dolomite-carbonatite and phoscorite-series tling may concentrate niobium-bearing minerals such as rocks that become increasingly common towards the cen- pyrochlore. Weathering processes16 may also concentrate tre of the complex (Cordeiro et al., 2010). As at Araxá, the mined deposit is in the weathered lateritic zone above the 7 Continental rifting: the gradual break-up of a continent under extension, as is centre of the complex. occurring at the present day in East Africa. 8 Extrusive: extrusive volcanic rocks are formed by eruption of magma on to the Earth’s surface. 9 The largest active niobium mine outside Brazil is the Alkaline rocks: igneous rocks that are rich in sodium and potassium, and contain certain characteristic minerals. Niobec mine in Quebec, Canada, operated by the Iamgold 10 Feldspathoids: a group of light-coloured minerals that have relatively low silica contents. 11 17 Mafic rock: a rock containing abundant dark-coloured minerals that are rich in Late Cretaceous: a unit of geological time between 99 to 65 million years ago. 18 magnesium and/or iron. Neoproterozoic: a unit of geological time between 1000 to 542 million years 12 Ultramafic: a rock almost entirely made up of dark-coloured minerals that are ago. 19 rich in magnesium and/or iron. Phoscorite: A magnetite, olivine, apatite rock, usually associated with 13 Metasomatised: having undergone metasomatism, chemical alteration of a carbonatites. 20 rock by the action of fluids. Glimmerite: An ultramafic rock consisting almost entirely of mica, either 14 Carbohydrothermal: formed from hot carbon dioxide-rich and water-rich fluids. biotite or phlogopite. Can also be called biotitite or phlogopitite as appropriate. 15 21 Magmatic differentiation: processes by which certain elements or minerals Lateritic: relating to laterite, a residual deposit rich in iron and aluminium are concentrated either in the crystalline rock or in the residual molten magma. resulting from weathering under tropical conditions. 16 22 Weathering processes: processes by which rocks are altered at the earth’s Aureole: an area around a body of igneous rock in which the host rocks have surface. been altered by the effects of increased temperature, pressure or fluid flow. 3 www.MineralsUK.com
  4. 4. Corporation. This mine lies in the southern part of the well-studied examples from Lueshe (Democratic Republic Neoproterozoic-age Saint-Honoré carbonatite complex, of Congo), Oka (Quebec, Canada), and Sökli (Finland). The which has an elliptical shape and is approximately four Lueshe syenite-carbonatite complex, which is Cambrian27 kilometres across at the surface. It consists of a series in age, has a central core of syenite some 800 metres in di- of crescentic lenses of carbonatite, younging inwards ameter, bordered by a ring dyke of calcite carbonatite and from calcite carbonatite through dolomite carbonatite to dolomite carbonatite (Nasraoui and Bilal, 2000). Intense ferrocarbonatite (Belzile, 2009). The carbonatite body is weathering of the carbonatites has formed a laterite hori- surrounded by a ring of syenites and diorites, and is almost zon which is enriched in pyrochlore, and has been mined entirely covered by Palaeozoic23 limestones. Pyrochlore for niobium. The Cretaceous28 Oka carbonatite complex is is the main niobium mineral in the Saint-Honoré com- an elongate pluton, about seven kilometres long, compris- plex. It is disseminated throughout the carbonatite, but ing carbonatites and feldspathoid-bearing silicate rocks. is particularly abundant in mineralised lenses that are It includes three separate niobium-mineralised deposits 50–150 metres wide and up to approximately 750 metres containing minerals of the perovskite and pyrochlore long, with grades of 0.44–0.51 per cent niobium oxide groups (Zurevinski and Mitchell, 2004). The Sökli carbon- (Belzile, 2009). These mineralised zones occur at depths of atite-phoscorite complex is Devonian29 in age, with an area over 100 metres beneath the surface, and the Niobec mine of about 20 square kilometres, and comprises metasoma- is the only underground niobium mine in the world. On the tised ultramafic rocks, carbonatites and phoscorites, with same structural lineament, the nearby Crevier syenite- abundant pyrochlore in the younger units of the complex carbonatite complex contains a niobium-tantalum deposit (Lee et al., 2006). The major Bayan Obo rare earth element which is currently being evaluated. deposit in China, which is also enriched in niobium, is as- sociated with carbonatite magmatism and may have been Numerous other carbonatite-hosted niobium deposits formed by the interaction of carbonatite-derived fluids and are known across the world, but are not currently being sedimentary host rocks (Yang et al., 2009). exploited. The most significant of these are the TomtorNiobium–tantalum deposit in Siberia, Russia and the Morro dos Seis Lagos Alkaline to peralkaline granites and syenites deposit in Brazil (Pollard, 1995). The Neoproterozoic- The alkaline igneous rocks are classified, on the basis of age Tomtor alkaline complex comprises an outer ring of mineralogy, as those rocks containing certain sodium- or nepheline-syenites, with a central stock24 of carbonatite, potassium-rich minerals (feldspathoids, alkali amphi- having a surface area of approximately 12 square kilome- boles, or alkali pyroxenes). Peralkaline rocks are a subset tres (Kravchenko and Pokrovsky, 1995). Pyrochlore is dis- in which the molecular amount of Na2O + K2O exceeds seminated throughout the carbonatite, but is particularly Al2O330. Alkaline rocks are most commonly found in intra- concentrated in two ore horizons. The lower ore horizon, plate settings such as zones of continental rifting, but they which is up to 300 metres thick, represents the weath- may also be formed in post-collisional31 to post-orogenic32 ered and altered top to the carbonatite body, whilst the environments. The most evolved alkaline igneous rocks, upper ore horizon is a buried placer deposit25 formed in an such as alkali granites and syenites, are characterised ancient lake, associated with Permian26 sedimentary rocks. by high contents of iron (Fe), fluorine, niobium, zirconium, The upper ore horizon contains more than 12 per cent rubidium (Rb), uranium, thorium and rare earth elements niobium (Kravchenko and Pokrovsky, 1995). The Morro dos but low niobium and tantalum (Pollard, 1989, Küster, 2009). Seis Lagos deposit is poorly known, to the extent that even Mineral deposits in alkaline igneous rocks typically contain its age is uncertain (Berger et al., 2009), but it is thought to high contents of zirconium, yttrium (Y), niobium and the represent the largest single niobium deposit in the world rare earth elements, but are less commonly enriched in with 2897 million tonnes niobium (Pollard, 1995). tantalum. A total of 58 carbonatite bodies containing niobium and Several factors contribute to the enrichment of High Field rare earth element mineral deposits have been recorded in Strength Elements33 (HFSE), such as niobium and zirco- published work (Berger et al., 2009) and other such depos- its may remain to be found. The smaller deposits include 27 28 Cambrian: a unit of geological time between 542 and 488 million years ago. Cretaceous: a unit of geological time between 145 and 65 million years ago. 29 Devonian: a unit of geological time between 416 and 359 million years ago. 23 30 Palaeozoic: a unit of geological time between 542 and 251 million years ago. Na2O, K2O and Al2O3: sodium oxide, potassium oxide and aluminium oxide. 24 31 Stock: a small body of igneous rock, emplaced beneath the Earth’s surface, Post-collisional: post-dating the peak of continental collision. 32 usually cylindrical with steep margins. Post-orogenic: post-dating all tectonic processes associated with a continen- 25 Placer deposit: a concentration of heavy minerals transported and deposited tal collision event (orogeny). 33 by rivers and/or coastal processes. High field strength elements: Elements of high valency (able to combine with 26 Permian: a unit of geological time between 299 and 251 million years ago. many other elements to form compounds) that are incompatible (see footnote 34). 4 www.MineralsUK.com
  5. 5. nium, in alkaline igneous rocks such as alkaline granites In Russia’s Kola Peninsula, the Devonian-age Lovozero and syenites. Alkaline magmas are most commonly syenite massif contains layered syenites with layers that considered to be derived from the enriched sub-continental are rich in eudialyte, loparite and apatite. Loparite has lithospheric34 mantle, and are enriched in the HFSE from been mined on and off for many years, and the loparite their formation. The HFSE are incompatible35 and thus concentrates have average grades of eight weight per they become enriched in the most evolved, granitic and cent niobium oxide and 0.7 weight per cent tantalum oxide syenitic magmas; in some localities, ore minerals are (Salvi and Williams-Jones, 2005). The Mesoproterozoic- found disseminated throughout highly evolved granites age Pilanesberg Complex of South Africa is another large and syenites. Further concentration can occur because the (> 500 square kilometres) alkaline complex with eudialyte- HFSE typically form relatively dense minerals, which may rich syenites that are enriched in zirconium, niobium and be accumulated through crystal settling into layers. The the REE. most famous example of a niobium deposit formed in this way is in the Ilímaussaq Complex of south-west Green- In eastern Canada, the Strange Lake peralkaline granite land. However, many mineralised deposits within alkaline pluton, which is Mesoproterozoic in age, outcrops over an rocks, such as the Motzfeldt deposit in Greenland, have area of about 36 square kilometres. It has a central ore undergone further concentration of elements such as the zone where the granite has undergone extensive haema- HFSE and REE through hydrothermal36 processes (Salvi and tisation38 and calcium metasomatism, producing a range Williams-Jones, 2005). The HFSE and REE appear to be of secondary HFSE-bearing minerals, including gittinsite39 highly mobile in fluids associated with peralkaline magmas and pyrochlore. Ore from this zone has an average grade that are enriched in fluorine, chlorine (Cl) and/or carbon of 0.56 weight per cent niobium oxide (Salvi and Williams- dioxide (Goodenough et al., 2000, Salvi and Williams- Jones, 2005, Salvi and Williams-Jones, 2006). In Canada’s Jones, 2005). Northwest Territories, the Palaeoproterozoic Blatchford Lake igneous complex comprises syenites and peralkaline At the time of writing, there are few niobium or tantalum granites with a number of hydrothermally altered miner-Niobium–tantalum mines operating in alkaline granite and syenite complexes, alised zones, known as the Thor Lake deposits. These de- although exploration is under way in some areas. One posits are enriched in beryllium (Be), yttrium, REE, niobium, major area of interest lies in the Mesoproterozoic37 Gardar tantalum and zirconium, with columbite-tantalite minerals Igneous Province in south-west Greenland, including the hosting the majority of the niobium and tantalum, and Ilímaussaq and Motzfeldt complexes. The Ilímaussaq average grades up to 0.4 weight per cent niobium (Salvi Complex is elliptical, 8 x 17 kilometres at the surface, and and Williams-Jones, 2005). The Thor Lake deposits are comprises a range of mineralogically unique syenites and currently owned by Avalon Rare Metals Inc, which intends alkaline granites which are spectacularly layered in places to develop them for REE, niobium and tantalum. (Larsen and Sorensen, 1987). The main mineral deposits occur in a unit of layered syenites known as kakortokites, In Mongolia, the Devonian-age Khaldzan-Buregtey which contains twenty-nine separate layers that are rich zirconium-niobium-REE deposit is formed by the hydrother- in eudialyte, with high contents of zirconium, yttrium, mally altered late phase intrusions of a peralkaline granite niobium and the REE. The average grade of niobium in massif (Kovalenko et al., 1995). Pyrochlore is the main these layers is 0.1 weight per cent niobium oxide (Salvi niobium ore mineral. In Malawi, exploration is ongoing at and Williams-Jones, 2005). In the Kvanefjeld area of the the Kanyika niobium-tantalum deposit, which comprises Ilímaussaq Complex, hydrothermal veins in the syenites an elongate body of nepheline syenite over 3.5 kilome- and their country rocks contain significant uranium-niobium tres long with numerous mineralised, pyrochlore-bearing mineralisation. Zones of hydrothermally altered syenite veins (BGS, 2009). In Saudi Arabia, the Ghurayyah alkaline also host the niobium-tantalum-REE pyrochlore mineralisa- granite stock is about 800 metres in surface diameter and tion in the Motzfeldt intrusion (Steenfelt, 1991) which is contains disseminated tantalum and niobium ore minerals, the subject of an ongoing exploration programme. chiefly columbite-tantalite and pyrochlore. The distribu- tion of these ore minerals appears to be remarkably consistent throughout the granite (Küster, 2009). In Brazil, 34 Lithospheric: the lithosphere is the outer, rigid layer of the Earth, including niobium and tantalum are extracted along with tin from both the Earth’s crust and the uppermost part of the mantle. a Palaeoproterozoic-age albite-rich peralkaline granite at 35 Incompatible elements: are those that are concentrated into molten magmas, rather than into early-forming crystals of solid minerals. 36 38 Hydrothermal: formed from hot water-rich fluids. Haematisation: alteration associated with the formation of the iron oxide 37 Mesoproterozoic: a unit of geological time between 1600 and 1000 million mineral, haematite. 39 years ago. Gittinsite: A calcium-zirconium-bearing silicate mineral. 5 www.MineralsUK.com
  6. 6. the Pitinga mine (Bastos-Neto et al., 2009). Alkaline to between 2008 and 2011. Both mines are owned by Global peralkaline intrusions with the potential for niobium and/or Advanced Metals (previously Talison). The Greenbushes tantalum deposits occur in many other countries, including mine in south-western Australia is hosted in a giant Morocco, Nigeria, and Namibia. (greater than three kilometre long) syn-tectonic44, zoned, complex-type pegmatite body of Archaean45 age, which Granites and pegmatites of the LCT family (enriched contains large resources of both tantalum and lithium, as- in lithium, caesium, tantalum) sociated with tin mineralisation. This pegmatite does not Granites and pegmatites of the LCT family are typically appear to be genetically associated with a larger granitic peraluminous40 and enriched in lithium, rubidium, caesium, body (Partington et al., 1995). Three phases of tantalum beryllium, tin (Sn), tantalum and niobium (tantalum greater mineralisation are recorded within this pegmatite: early- ˇ than niobium) (Cerný and Ercit, 2005). These magmas are formed minerals such as wodginite and ixiolite, which formed by melting of pre-existing crustal rocks, and were form inclusions in cassiterite and tourmaline; tantalites most commonly emplaced as post-orogenic plutons in and tapiolites in fractures within early silicate phases; zones of continental collision. Granites and pegmatites of and later hydrothermal mineralisation, where microlite is this type are the main hosts for tantalum deposits across the main tantalum mineral (Partington et al., 1995). The the world. These intrusions typically take the form of a Greenbushes pegmatite has been exploited by both open large peraluminous leucogranitic41 pluton surrounded by a pit and underground mining. In north-western Australia, halo of pegmatites, with the most mineralised pegmatites a large number of pegmatite swarms occur within the ˇ at the greatest distance from the granite (Cerný, 1989), Archaean rocks of the Pilbara Craton, and many of these although in some areas swarms of pegmatites are not as- include some tantalum-mineralised examples. The most sociated with exposed granitic plutons. important area here is the Wodgina pegmatite district, which includes the Wodgina Main Lode and Mount Cassit- The granite bodies contain minerals such as biotite, erite tantalum-mineralised pegmatites. The Wodgina Main muscovite, topaz and tourmaline, and are typically rather Lode is a dyke-like pegmatite about one kilometre long,Niobium–tantalum heterogeneous, showing extensive albitisation42 and of albite-type, with manganese-rich tantalite as the main alteration by late-stage fluids. These granites may contain tantalum mineral, together with some manganese-rich disseminated tantalum ore minerals, particularly concen- columbite and wodginite. At Mount Cassiterite the deposit trated in the uppermost parts of the granitic body (Linnen is formed by a series of pegmatite sheets of albite-spo- and Cuney, 2005). dumene type, and wodginite is the main tantalum mineral (Sweetapple and Collins, 2002). Tantalum from these Many of the largest tantalum deposits occur in pegmatite pegmatites is extracted by open pit mining. swarms. LCT pegmatites can be divided into five types: the beryl type; the complex (spodumene-petalite-amblygonite) An Archaean pegmatite body also forms the host for the type; the complex lepidolite type; the albite-spodumene tantalum mineralisation at Tanco, in Manitoba, Canada, ˇ type; and the albite type (Cerný, 1989). Many of the owned by Cabot Corporation. It is part of the rare-metal pegmatites falling into the first three types are zoned. All bearing Bernic Lake pegmatite group, which intrudes types can contain a range of tantalum minerals, of which metavolcanic46 Archaean rocks. The Tanco pegmatite the most important are generally columbite-tantalite, forms a shallowly dipping sheet, up to about 100 metres microlite, ixiolite and wodginite. Tantalum-rich cassiterite thick and 1600 metres along strike, which is exploited in (tin oxide) is also an important ore mineral in some bodies. a room-and-pillar underground mine. It is of the complex Many of the pegmatites have been highly affected by late- pegmatite type, and is strongly zoned; tantalum ore miner- stage alteration, such as kaolinisation43. als are found throughout, though concentrated at higher grade in certain zones. A wide range of tantalum minerals In recent years, much of the world’s production of tantalum occur (14 in all) and they are generally fine-grained, mean- has come from the Greenbushes and Wodgina mines in ˇ ing that processing of Tanco ore is rather difficult (Cerný, Australia, although production from these mines ceased 1989). Caesium and lithium are also produced from the Tanco pegmatite. In addition, numerous other tantalum- 40 Peraluminous: a chemical term used for rocks in which the total molecu- mineralised pegmatites are known from the Superior lar (calcium oxide + sodium oxide + potassium oxide) is less than molecular aluminium oxide. 41 44 Leucogranitic: a light-coloured, silica-rich type of granite. Syn-tectonic: formed during an episode of tectonic activity and deformation of 42 Albitisation: alteration by fluids to produce the sodium-rich mineral, albite, a the Earth’s crust, usually an episode of continental collision. 45 type of feldspar. Archaean: a unit of geological time between 3800 and 2500 million years ago. 43 46 Kaolinisation: alteration of rocks to produce kaolin, also known as china clay. Metavolcanic: metamorphosed volcanic rocks. 6 www.MineralsUK.com
  7. 7. Province of Ontario and Manitoba (Selway et al., 2005). In North Africa, intruded into the Neoproterozoic rocks of Brazil, a large (about one kilometre long), zoned, Protero- the Arabian-Nubian Shield (Küster, 2009). These include zoic47 pegmatite body of albite-spodumene type is mined the Kenticha pegmatite field in Ethiopia, the Majahayan for tantalum, niobium and lithium at the Volta Grande mine pegmatites of Somalia, and the Abu Dabbab and Nuweibi at Nazareno, in the Minas Gerais district (Lagache and granites in Egypt. At Kenticha, the pegmatite field as a Quemeneur, 1997). whole has an area of approximately 2500 square kilome- tres, but tantalum mining is focused on the Main Kenticha In Mozambique, the Alto Ligonha Pegmatite Province Pegmatite, a Cambrian-age dyke-like zoned pegmatite of contains numerous mineralised pegmatites which have complex-spodumene type which is mined for columbite- been mined since 1926, with tantalum mining and explora- tantalite minerals (Küster, 2009). In Egypt, the Abu Dabbab tion currently focused in the zoned Marropino and Morrua and Nuweibi prospects are currently being developed pegmatites, owned by Noventa Ltd. These pegmatites are towards production. These deposits are unusual in that intruded into the Proterozoic rocks of the Nampula Sub- the mineralisation is found in stock-like granite intrusions, province, and they are considered to be Ordovician48 in age rather than in pegmatites. Columbite-tantalite minerals are (Graupner et al., 2010). Numerous examples of tantalum- disseminated throughout these intrusions, and although mineralised granites and pegmatites are also found in the granites show significant evidence of later metaso- matic alteration, the tantalum minerals are considered to 47 Proterozoic: a unit of geological time between 2500 and 542 million years ago. be magmatic in origin (Küster, 2009). 48 Ordovician: a unit of geological time between 488 and 443 million years ago. Deposit type Brief description Typical grades and tonnage Major examples Carbonatite-hosted Niobium deposits found Niobec, proven & probable Niobec, Canada; Oka, primary deposits within carbonatitic igneous reserves: 23.5 million tonnes CanadaNiobium–tantalum rocks in alkaline igneous at 0.59% Nb2O5 provinces Carbonatite-sourced Zones of intense weather- < 1000 million tonnes at up to Araxá and Catala Brazil; ˘o, secondary deposits ing or sedimentary succes- 3% Nb2O5 in lateritic deposits. Tomtor, Russia; Lueshe, sions above carbonatite Up to 12% Nb2O5 in placer Democratic Republic of intrusions in which niobium deposit at Tomtor, tonnage not Congo ore minerals are concen- known trated Alkaline granite and Niobium and lesser tanta- Generally < 100 million tonnes, Motzfeldt and Ilímaussaq, syenite lum deposits associated at grades of 0.1 to 1% Nb2O5 Greenland; Lovozero, Rus- with silicic alkaline igneous and < 0.1% Ta2O5 sia; Thor Lake and Strange rocks. Ore minerals may be Lake, Canada; Pitinga, concentrated by magmatic Brazil; Ghurayyah, Saudi or hydrothermal processes Arabia; Kanyika, Malawi LCT-type granite Tantalum and lesser Generally < 100 million tonnes, Abu Dabbab and Nuweibi, niobium deposits associ- at grades of < 0.05% Ta2O5 Egypt; Yichun, China ated with peraluminous leucogranitic plutons, which are often hydrothermally altered LCT-type pegmatite Tantalum and lesser nio- Generally < 100 million tonnes, Greenbushes and Wodgina, bium deposits associated at grades of < 0.05% Ta2O5 Australia; Tanco, Canada; with pegmatites of LCT Volta Grande, Brazil; Ken- (Li-Cs-Ta-enriched) type ticha, Ethiopia; Morrua & Marropino, Mozambique Table 3 Key characteristics and examples of the major types of niobium and tantalum deposits (grades and tonnages are very variable between deposits and figures given are indicative only). 7 www.MineralsUK.com
  8. 8. 8 Niobium–tantalum Figure 3 Map showing the global distribution of niobium and tantalum mines, deposits and major occurrences.www.MineralsUK.com
  9. 9. In Central Africa, a zone of Neoproterozoic-age tantalum- blasting where materials have become cemented. For mineralised pegmatites cuts the Mesoproterozoic Kibaran example, tin-tantalum placers in Malaysia are mined using belt which extends through Burundi, Rwanda, Uganda and simple stripping methods, whilst hard-rock surface opera- the Democratic Republic of Congo (Romer and Lehmann, tions, such as Wodgina Mine, are mined using drilling and 1995). Columbite-tantalite minerals are mined both from blasting techniques. deeply weathered pegmatites and from secondary placer deposits derived from the pegmatites. Capital and operating costs for open-pit techniques are far less than those for underground operations. Several regions of China have tantalum-mineralised gran- ites and pegmatites. The most well known is the Yichun Underground mining deposit, which is hosted in a small (less than 10 square Underground mining methods are usually employed when kilometres) granitic batholith of Jurassic age. The upper- surface methods are, or become prohibitively expensive, for most part of this batholith is a highly fractionated topaz- example if the deposit becomes too deep. Another major lepidolite granite, which contains tantalum mineralisation factor in the decision to use underground methods is the in the form of disseminated columbite-tantalite, tantalum- waste to ore ratio, or strip ratio. Once the ratio becomes rich cassiterite, and minor microlite (Yin et al., 1995). large, open-pit mining methods become uneconomic. Elsewhere in China, the Altai pegmatites (north-western China) and the Nanping pegmatites (south-eastern China) Underground operations commonly require extensive mine have been mined for columbite-tantalite in the past. In development including shaft sinking, de-watering, ventila- Malaysia and south-western Thailand, tin is produced from tion, geo-technical support and ore handling. Room and weathered tin-mineralised granites and pegmatites, and pillar is an underground mining technique where mining from secondary placer deposits. The tin slags are being progresses in a horizontal direction by developing numer- reprocessed to produce tantalum. ous stopes49, or rooms, leaving pillars of material for roof support. Ore is blasted and then transported by rail,Niobium–tantalum Extraction methods and processing conveyor or dump truck to the processing plant. Room and pillar mining methods were used at the Tanco pegmatite in Extraction Manitoba, Canada. The mine is located under Bernic Lake The mining methods employed to extract niobium and and is accessed via a 60-metre shaft and via a 20-degree tantalum are similar to other metals of comparable occur- decline50 from the surface (Cabot, 2001). rence. Factors that dictate the selection of mining methods include: the physical and chemical properties of the ore By-product production mineral; the tonnage and grade; and the shape, geometry Niobium and tantalum can also be extracted as a by-product and depth of the orebody. The most common methods of of tin smelter waste. Niobium produced in this way accounts extraction are surface (or open-pit) and sub-surface (or for less than two per cent of total global niobium production. underground) mining, or a combination of both. Significant However, the percentage is much higher for tantalum at amounts of niobium and tantalum are also extracted by around 14 per cent. Tantalum is extracted from cassiterite51 artisanal and small scale mining (ASM). placer middlings52 using shaking tables, and magnetic53 and electrostatic54 separation methods. Tin smelter waste Surface mining typically contains eight to 10 per cent tantalum oxide, Massive, or steeply-dipping, low-grade near-surface although exceptionally this may rise to 30 per cent. Low- ore bodies are amenable to open-pit mining techniques. grade smelter wastes can be upgraded by electrothermic Open-pit methods commonly involve removing overburden, reduction55 yielding a synthetic concentrate with up to 50 digging or blasting the ore, followed by removal of the ore per cent tantalum and niobium oxides (Roethe, 1989). by truck or conveyor belt for stockpiling prior to processing. Open-pit mining may reach depths of several hundred me- 49 Stope: the void created by extracting the ore. tres but seldom exceeds 100 metres. Heavily weathered 50 Decline: a mine entrance which is neither horizontal nor vertical; often it takes ore bodies, such as the Araxá carbonatite deposit in Brazil, the form of a spiral ramp. 51 are also mined using open-pit methods. Cassiterite: tin oxide ore mineral, SnO2. 52 Middlings: particles of intermediate grade and size. 53 Magnetic separation: the selective sorting of magnetically susceptible ore Land-based placer deposits are amenable to strip mining minerals using magnetic force. 54 Electrostatic separation: the selective sorting of ore minerals using an electric involving scrapers, bulldozers and loaders. Placer deposits field. can be poorly consolidated, and only require drilling and 55 Electrothermic reduction: a reduction reaction performed in an electric arc furnace, utilising calcium oxide, iron oxide and carbon as reducing agents. 9 www.MineralsUK.com
  10. 10. 10 Niobium–tantalum ORE TYPE Pyrochlore Tantalite e.g. Niobec Mine e.g. Greenbushes Mine Crushing, milling and Undersize material screening stages to tailings Coarse desliming Fine desliming Coarse and fine gravity separation using shaking Coarse carbonate Fine carbonate tables, jigs and spirals flotation flotation Concentrate de-watering using cyclones and filter bed Desliming Slimes Concentrate drying Low intensity Magnetite magnetic separation Concentrate (4-6% Ta2O5) Diamine collector Pyrochlore flotation Tailings High intensity magnetic Non-magnetic separation fraction to tailings Xanthates Sulphide flotation Sulphides Magnetic fraction roasted Antimony and Hydrochloric Concentrate leaching minor sulphides to Acid tailings Concentrate (54% Nb2O5) Concentrate (20-30% Ta2O5) Figure 4 Generalised beneficiation flow diagrams, based upon the Niobec and Greenbushes operations.www.MineralsUK.com
  11. 11. Processing At the Greenbushes mine in Australia tin-tantalum ores After mining the ores are processed to increase their are processed using a circuit of shaking tables, spirals niobium and tantalum contents. Initial concentration is nor- and jigs63. The rough concentrate is de-watered and dried mally undertaken at, or close to, the mine site and involves producing a tantalum concentrate containing about four crushing the ore followed by separation of niobium and to six per cent tantalum oxide. High intensity magnetic tantalum ore from gangue56 material, using a combination separation is used to separate the paramagnetic64 tanta- of physical and chemical methods. Although niobium and lum grains from the non-magnetic tin-tantalum grains; the tantalum are geochemically similar each requires a differ- paramagnetic fraction is further concentrated to around ent processing route. 30 per cent tantalum oxide by roasting. The non-magnetic fraction is further processed using a combination of froth Ore beneficiation flotation and roasting to remove sulphides, and smelting to Niobium ore is first crushed in jaw, cone or impact crushers separate tantalum from tin (Figure 4) (Fetherston, 2004). and milled in rod or ball mills operating in closed circuits with vibrating screens and screw classifiers57 to liberate niobium Conversion to metal mineral particles. The slurry containing niobium and waste Tantalum and niobium metal can be produced from three rock is further concentrated to around 54 per cent niobium different compounds — fluorides, oxides and chlorides oxide using a number of methods in multiple stages: grav- (Albrecht, 1989). The tantalum and niobium compounds are ity separation58, froth flotation59, magnetic and electrostatic reduced to form pure metals and metal powders by two separation, and acid leaching60 may be used, depending on main methods. the physical and chemical characteristics of the ore. A mixed niobium-tantalum concentrate is digested using a At the Niobec operation in Canada niobium ore is screened mixture of hydrofluoric and sulphuric acids. The niobium- and classified, after which the resultant slurry is sent for tantalum-bearing acid solution is then treated using liquid- desliming61. Carbonate material is removed by two stages liquid separation methods, involving solvent extraction orNiobium–tantalum of froth flotation, followed by an additional desliming ion exchange, to separate niobium from tantalum. Niobium stage. Magnetite is removed from the slurry, by low and tantalum can be extracted from the hydrofluoric- intensity magnetic separation, and sent to waste. The sulphuric acid mixture by using organic solvents, such as sought-after pyrochlore is collected from the slurry by cyclohexanone, tributyl phosphate (TBP) or methyl isobutyl froth flotation using diamine collectors62. A final stage of ketone (MIBK), whilst leaving behind impurities such as froth flotation is used to remove sulphides, such as pyrite. iron, manganese, tin and titanium (Figure 5). Ion exchange Residual impurities are leached by hydrochloric acid, leav- is used to produce high-purity solutions of niobium and ing a final concentrate that contains around 54 per cent tantalum and is usually performed using an amine extract- niobium oxide (Figure 4) (Iamgold, 2009). ant in kerosene. Tantalum ores are initially treated in a similar manner to Niobium and tantalum are precipitated as hydroxides from niobium ores; they are crushed, milled and screened to the mixed organic solvent solution by the addition of am- liberate tantalum mineral particles. The slurry containing monia (NH3). The resultant hydroxides are calcined65 in a tantalum and waste material is concentrated to around furnace to form niobium and tantalum oxides. The process 30 per cent tantalum oxide using predominantly gravity of sintering66 the oxide products, with carbon, at high and magnetic separation techniques, again depending temperature is used to produce niobium and tantalum car- upon the characteristics of the ore. bides. Niobium oxide is also the starting point for niobium metal production. The addition of potassium fluoride to the 56 Gangue: waste material associated with ore minerals. mixed organic solvent solution results in the crystallisation 57 Screw classifiers: a wet gravity separation method in which dense particles of potassium tantalum fluoride (K2TaF7), the pre-requisite are removed from a slurry by a series of rotating rakes (similar to an Archimedes for tantalum metal production (Figure 5). Screw) 58 Gravity separation: the selective sorting of ore minerals by exploiting natural variations in mineral density. 59 63 Froth flotation: the selective separation of hydrophobic (water-repelling) ore Shaking tables, spirals and jigs: water and gravity based separation devices. 64 minerals from hydrophilic (water-attracting) ore minerals. Paramagnetic: a form of magnetism that only occurs in the presence of an 60 Acid leaching: the process of extracting metal from a concentrate using externally applied magnetic field. 65 mineral acids. Calcined: a thermal process applied to ores in order to bring about decomposi- 61 Desliming: the removal of particles in the micron size range prior to process- tion, phase transitions or the removal of volatile matter (e.g. carbon dioxide and ing. water). 62 66 Diamine collectors: a positively charged cationic collector used to float rare- Sintering: a process of forming a coherent bonded mass by heating metal metal oxides. powders without melting. 11 www.MineralsUK.com
  12. 12. Mixed Nb-Ta concentrate Chemical decomposition with hydrofluoric and sulphuric acid Filtration Residue to waste or recycle Methyl Isobutyl Ketone Nb and Ta are extracted from Iron and titanium-bearing (MIBK) or Tributyl Phosphate the acid solution using solvent raffinate to waste (TBP) organic solvents extraction added Ammonia (NH3) is added to Ammonia (NH3) is added to precipitate niobium as Nb-Ta mixed solution precipitate tantalum as Nb-hydroxide Ta-hydroxide Sintering oxide powders Tantalum hydroxide is Niobium hydroxide is Potassium-tantalum-fluoride with carbon at high calcined to form tantalum calcined to form (K2TaF7) is directly crystallised by temperature produces oxide (Ta2O5) niobium oxide (Nb2O5) adding potassium fluoride to the Nb-and Ta-carbides extract solution Nb2O5 is reduced by aluminothermic reaction Ta2O5 is reduced by reaction to form niobium metal with molten sodium to form tantalum metalNiobium–tantalum Figure 5 Chemical processing of niobium and tantalum concentrates. Two slightly different production routes are available for the Artisanal mining of coltan production of niobium metal: one is used to produce pure niobium metal and the other is used to produce ferro-niobi- um. High-purity niobium metal is produced by aluminother- mic reduction67 of high-purity niobium oxide with aluminium, lime and fluorspar. Electron beam melting is commonly used to increase the purity of niobium. To produce ferro-niobium, containing about 60 per cent niobium, iron oxide powder is added to the mixture prior to reduction (Albrecht, 1989). The reduction of potassium tantalum fluoride by reaction with sodium is the most common method of producing tan- talum metal. Potassium tantalum fluoride is blended with liquid sodium and inert salts to form a paste. The paste is Figure 6 Coltan (columbite-tantalite). Source: Sasha then roasted in a continuous furnace to produce tantalum Lezhnev (© Enough Project) 69. metal powder, potassium fluoride and sodium fluoride. To ensure a high degree of purity, as required by the electron- ics industry, the conversion process is performed using Although niobium and tantalum are extracted and pro- tantalum vessels under low-oxygen conditions. Further cessed conventionally, significant amounts are also purification is achieved by vacuum arc furnace or electron extracted by artisanal and small scale mining (ASM). beam melting68 of tantalum powder (Albrecht, 1989). Artisanal and small scale mining (ASM) is believed to 67 Aluminothermic reduction: an exothermic reaction involving aluminium oxide provide a livelihood for over 100 million people worldwide and iron oxide as reducing agents. 68 Electron beam melting: a high-temperature (700-1000°C) vacuum furnace, 69 utilising high-energy electron beams as a heat source. Image taken by Sasha Lezhnev. © Enough Project. Used with Permission. 12 www.MineralsUK.com
  13. 13. and is defined as mining activities that are labour-intensive but capital-, mechanisation- and technology-poor. ASM is Small scale mining of coltan in Democratic characterised by: Republic of Congo ▪ Poor occupational safety ore ▪ Poorly qualified and trained personnel ▪ Inefficiency in extraction and processing Ore is transported ▪ Low salaries to neighbouring ▪ Insufficient consideration of environmental issues Rwanda, Uganda or Burundi Additionally, ASM is often unregulated with many activi- ties falling outside the host countries’ legal framework ore (Hentschel et al., 2003). Certain minerals, such as gold, tin, tungsten and colum- Ore shipped to bite-tantalite (coltan) (Figure 6), which are produced in Asia for smelting and significant quantities by ASM, can sometimes be mined in conversion to metal conditions of armed conflict and human rights violations. The mining of these minerals under such conditions has processed material given rise to the term ‘conflict minerals’. Their illicit mining is often organised by armed groups who use the profits Processed material from the sale of the conflict minerals to further their own shipped to the western ends and to finance further fighting. world to produce electrical componentsNiobium–tantalum Coltan is found in significant quantities in parts of central such as capacitors Africa, in particular the Democratic Republic of Congo (DRC). It is estimated that in 2009 over 50 per cent of electrical components global tantalum production was from Africa. In the DRC small scale mining of coltan, from either alluvial or Components shipped pegmatite sources, is labour intensive and unregulated. to Asia to manufacture Consequently it is difficult to accurately calculate the circuit boards and quantity of coltan mined and exported. It is believed that consumer electronics the majority of coltan mined in the DRC ends up in neigh- bouring countries such as Rwanda, Burundi and Uganda. consumer goods It is estimated that rebel groups in the DRC made in excess of $1 billion in 2009 through conflict mineral trad- ing (Bunting, 2010). Mobile phones, MP3 players, laptops and cameras are sold in Illegally traded coltan ore may end up in consumer elec- Europe and the USA tronic products throughout the world. Ore from Rwanda, Burundi or Uganda may be shipped to Asia for processing and smelting. Once processed it is impossible to determine Figure 7 An example of a conflict mineral supply the source of the original ore. The processed material may chain. Source: (Enough Project, 2011). then be shipped to the western world for use in electrical components such as capacitors. Finally these components may be exported to Asia for inclusion in consumer elec- refusing to use conflict mineral-bearing components in tronic goods such as mobile phones (Figure 7). their products. However, it is likely to prove difficult to completely avoid the use of these components for the Many non-governmental organisations (NGOs) and reasons explained above. The success of these schemes charities have initiated schemes aimed at alleviating also relies on the ability of countries like the DRC to the problems of ASM and conflict mineral trading. In monitor exports, control its army and combat rebel forces addition some large electronics companies are now (Bunting, 2010). 13 www.MineralsUK.com

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