2012 Society of Economic Geologists, Inc. Economic Geology, v. 107, pp.

81104

Controls on the Concentration of Zirconium, Niobium, and the Rare Earth Elements in the Thor Lake Rare Metal Deposit, Northwest Territories, Canada
EMMA R. SHEARD,1, ANTHONY E. WILLIAMS-JONES,1 MARTIN HEILIGMANN,1 CHRIS PEDERSON,2 AND DAVID L. TRUEMAN2
1 Earth

and Planetary Sciences, McGill University, 3450 University Street, Montreal, Quebec, Canada H3A 2A7 Rare Metals Inc., 130 Adelaide Street West, Suite 1901, Toronto, Ontario, Canada M5H 3P5

2 Avalon

Abstract
The Thor Lake rare metal (Zr, Nb, REE, Ta, Be, Ga) deposits in Canadas Northwest Territories represent one of the largest resources of zirconium, niobium, and the heavy rare earth elements (HREE) in the world. Much of the potentially economic mineralization was concentrated by magmatic processes. However, there is also evidence of autometasomatic processes and remobilization of Zr and REE by hydrothermal fluids. The deposits are situated at the southern edge of the Slave province of the Canadian Shield, within the 2094 to 2185 Ma alkaline to peralkaline Blachford Lake Intrusive Complex. A layered alkaline suite dominated by aegirine nepheline syenite occurs in the center of this suite of rocks and is considered to represent the youngest phase of the complex. Much of the rare metal mineralization occurs in two subhorizontal tabular layers, which form upper and lower zones of the Nechalacho deposit (formerly the Lake zone), and in which Zr is hosted primarily by zircon, Nb primarily by ferrocolumbite and fergusonite-(Y), and HREE by fergusonite-(Y) and zircon. The LREE are present mainly in monazite-(Ce), allanite-(Ce), bastnsite-(Ce), parisite-(Ce), and synchysite-(Ce). Much of the HREE mineralization in the lower mineralized zone occurs in secondary zircon, which forms small (1030 m) anhedral grains in pseudomorphs after probable eudialyte. In the upper zone, zircon is a magmatic cumulate mineral, which was replaced locally by secondary REE-bearing minerals. Element distribution maps of zircon crystals in the upper zone indicate that the HREE were mobilized from the cores and locally precipitated as fergusonite-(Y) along microfractures. The light rare earth elements (LREE) were also mobilized locally from both primary zircon and inferred primary eudialyte. The occurrence of zircon in fractures, wrapped around brecciated K-feldspar fragments, and as a secondary phase in pseudomorphs are evidence of its hydrothermal origin and/or of remobilization of primary zirconium. A model is proposed in which injection of separate pulses of miaskitic and agpaitic magma resulted in the crystallization of an upper zone rich in zircon and a lower zone rich in eudialyte. Primary eudialyte was later altered in situ to zircon-fergusonite-(Y)-bastnsite-(Ce)-parisite-(Ce)-synchysite-(Ce)-allanite-(Ce)-albitequartz-biotite-fluorite-kutnahorite-hematitebearing pseudomorphs by an inferred fluorine-enriched magmatic hydrothermal fluid. Zirconium, niobium, and REE in both the upper and lower zones were subsequently mobilized during multiple metasomatic events, which, for the most part, served to further enrich the primary layers in REE (albitization generally dispersed REE and high field strength elements (HFSE)) and created new secondary REE-bearing phases.

Introduction ZIRCONIUM is an incompatible trace element and occurs in most igneous rocks at parts per million concentrations as the accessory mineral, zircon. However, in ultra-alkaline complexes (e.g., Ilmaussaq: Gerasimovsky, 1969; Strange Lake: Miller, 1986; Thor Lake: Trueman et al., 1988; Lovozero: Kogarko, 1990), it is locally present in percentage level concentrations and may be accompanied by quantities of the heavy rare earth elements (HREE) sufficient to form a potentially exploitable resource. In most of these complexes, the zirconium occurs mainly as complex zirconosilicate minerals, such as elpidite (Na2ZrSi6O15 3H2O), catapleiite (Na2ZrSi3 O9.2H2O), wadeite (K2ZrSi3O9), eudialyte (Na15Ca6(Fe2+, Mn2+)3Zr3(Si25O73)(O,OH,H2O)3(OH,Cl)2), vlasovite (Na2Zr Si4O11), and gittinsite. (CaZrSi2O7), but at Thor Lake, the principal zirconium mineral is zircon. There is a broad consensus that ultra-alkaline igneous rocks are products of differentiation of partial melts from an undepleted, metasomatically enriched mantle (e.g., Marks et al., 2003; Halama et al., 2004). However, there is little agreement
Corresponding

author: e-mail, emma.rebecca.sheard@gmail.com

over why the rare earth elements (REE) concentrate in these intrusions, why HREE can be enriched relative to light rare earth elements (LREE), and whether the deposits are purely magmatic or partly the product of hydrothermal processes (Boily and Williams-Jones, 1994; Schmitt et al., 2002; Marks et al., 2003; Salvi and Williams-Jones, 2005). Although the reasons for the very high concentrations of Zr, Nb, and HREE in ultra-alkaline igneous systems are still poorly understood, experiments by Watson (1979) and Linnen and Keppler (2002) have shown that zircon solubility in magmas increases with increasing concentration of alkalis, and in peralkaline melts can exceed 3 wt % ZrO2. Studies of melt inclusions have yielded similar results, showing that agpaitic magmas can have concentrations of Zr, Nb, and REE that, in some cases, are orders of magnitude higher than those in other types of magma. For example, Kovalenko et al. (1995) reported concentrations of Zr, Nb, and REE from rare metal peralkaline granites of the Khadlzan-Buregtey Granitoid Complex of 2.65, 0.58, and 0.62 wt %, respectively. In several peralkaline complexes, fractional crystallization has served to further increase concentrations of the above elements over those originally present in the melt. For example, 81
Submitted: March 19, 2010 Accepted: July 5, 2011

0361-0128/12/4003/81-24

82

SHEARD ET AL.

at both Ilmaussaq and Lovozero, REE and high field strength elements (HFSE) were enriched locally by saturation of minerals like eudialyte and loparite ((LREE,Na, Ca)2(Ti,Nb)2O6) in the magma and their gravitational settling to form layers in which these minerals are dominant. There is also evidence that in some of these complexes autometasomatic processes have further concentrated these elements. For example, REE and the HFSE in the Tamazeght Complex, Morocco, are hosted in secondary phases such as calcic catapleiite ((Ca,Na)ZrSi13O9.2H2O) and rinkite ((Ca,LREE)4 Na(Na,Ca)2Ti(Si12O7)2F2(O,F)2), which replaced primary zircon and eudialyte (Salvi et al., 2000). In the most evolved lujavrites at Ilmaussaq (Srensen, 1997), there are hydrothermal veins of steenstrupine (Na14LREE6Mn++Mn+++Fe++2(Zr, Th)(Si6O18)2(PO4)7.3(H2O)) and at Strange Lake, Quebec/ Labrador, bulk-rock chemical analyses of fresh and altered rocks point to hydrothermal enrichment of the HFSE by as much as 25% (Salvi and Williams-Jones, 1996). The Thor Lake Nechalacho deposit is an ideal setting in which to investigate the relative importance of magmatic and hydrothermal processes involved in producing unusual enrichments of Zr, Nb, and REE. The bulk of the rare metal mineralization is hosted in zircon, which contains the highest concentrations of REE ever reported in the literature. There are cumulate textures involving both zircon and inferred eudialyte, there is extensive hydrothermal alteration, and there is strong evidence for the remobilization of REE, Zr, and Nb from primary zircon and inferred primary eudialyte. Exploration of the Thor Lake deposits began in 1970, and after years of intermittent exploration activity, five zones of rare metal mineralization were delineated, namely the R, S, T, Fluorite, and Lake zones (Trueman et al., 1988). By far the largest of these is the Lake zone, recently renamed the Nechalacho deposit, which drilling has demonstrated to be present in the subsurface over an area of at least 2 km2. The Nechalacho deposit has been the focus of recent exploration by Avalon Rare Metals Inc. (Avalon) for Zr, Nb, and REE mineralization and is the subject of the present study. This mineralization occurs in two zones, an upper zone with an indicated resource of 30.64 million metric tons (Mt) and a total REE concentration of 1.48 wt %, and a lower zone with an indicated resource of 57.49 Mt and a total REE concentration of 1.56 wt % (Table 1). Only a limited number of papers have been published on the Thor Lake deposits (Davidson, 1981; Cerny and Trueman, 1985; Trueman et al., 1988; Smith et al., 1991; Pinckston and Smith, 1995). However, an important conclusion of all of these studies is that Thor Lake differs from other REE deposits in that hydrothermal alteration obliterated most of the original igneous textures such that

even the nature of the host rocks could not be properly discerned. As a result of recent drilling by Avalon, we are now able to partly decipher the prealteration history of the deposit. The purpose of our study was to use the textural relationships and composition of zircon and other rare metal minerals in the Nechalacho deposit to investigate the role of primary magmatic, autometasomatic, and late hydrothermal processes in their crystallization, and determine the extent to which some or all of the REE and HFSE were remobilized. In doing so, this paper not only describes an important example of a newly recognized large REE- and HFSE-enriched layered alkaline complex but proposes a model that explains the genesis of the Nechalacho deposit and can be applied to the study of similar deposits elsewhere. Geologic Setting Regional geology The Thor Lake rare metal (Zr, Nb, REE, Ta, Be, and Ga) deposits are located approximately 100 km southeast of Yellowknife, Northwest Territories (Fig. 1) at the southern edge of the Slave province of the Canadian Shield in alkaline to peralkaline rocks of the Blachford Lake Intrusive Complex (Davidson, 1978; Trueman et al., 1988; Sinclair et al., 1992). According to Hoffman (1978), at ~ 2.1 Ga, the Slave Craton rested over hot spots at Great Slave and Coronation Gulf. A series of rifts developed, some in the Wopmay Orogen (ca. 1900 Ma) and the others along the eastern arm of Great Slave Lake (the Athapuscow Aulacogen), which coincides with the Great Slave Fault zone, a major strike-slip shear zone with a postulated displacement of 500 km (Davidson, 1978; Bowring et al., 1984). It is here, just prior to rifting, that a series of alkaline to peralkaline plutons were intruded to form the Blachford Lake Intrusive Complex. Davidson (1972, 1978) subdivided the Blachford Lake Intrusive Complex into six units representing five distinct intrusive events. These units are the Caribou Lake Gabbro, the Whiteman Lake Quartz Syenite, the Hearne Channel Granite, the Mad Lake Granite, the Grace Lake Granite, and the Thor Lake Syenite (Fig. 1). The youngest of the intrusive events produced the Grace Lake Granite and the Thor Lake Syenite, which have gradational contacts, and were therefore interpreted by Davidson (1982) to have been emplaced contemporaneously. A suite of igneous rocks, which we interpret to represent a layered alkaline complex (see below), was subsequently intersected by drilling in the core of the Thor Lake Syenite and intrudes the latter. This suite hosts the bulk of the rare metal mineralization at Thor Lake (the Nechalacho deposit). Several of the above units have been dated by U-Pb

TABLE 1. Provisional Concentrations of REE, Ta, Nb, Zr, Ga, and Hf Oxides for the Nechalacho Deposit (Avalon Rare Metals Inc. Resource Estimate, updated January 2011)1 Metric tons (millions) Lower zone (indicated) Upper zone (indicated) 57.49 30.64 TREO (%) 1.56 1.48 HREO (%) 0.33 0.15 ZrO2 (%) 2.99 2.1 Nb2O5 (%) 0.40 0.31 Ga2O3 (ppm) 133 173 Ta2O5 (ppm) 396 192

Abbreviations: HREO = high REE2O3, TREO = total rare earth oxides 1 Cutoff grade for TREO (%) is 1.6 0361-0128/98/000/000-00 $6.00

82

Zr, Nb, Y, & REE IN THE THOR LAKE RARE-METAL DEPOSIT, NWT, CANADA

83

N
Yellowknife

APHEBIAN Compton Intrusions

Thor Lake

Great Slave Supergroup BLACHFORD LAKE COMPLEX

Great Slave Lake

Fort Resolution

Thor Lake Syenite Grace Lake Granite Hearne Channel, Mad Lake Granites Whiteman Lake Quartz Syenite
100 km

Hay River

Caribou Lake Gabbro Leucoferrodiorite ARCHEAN Two-mica Granite Yellowknife Supergroup: Burwash Formation

THOR LAKE PROPERTY T-ZONE

NECHALACHO DEPOSIT

Hea rn
5 km

e Cha

nnel

FIG. 1. Geologic map of the Blachford Lake Intrusive Complex, showing the location of the Nechalacho deposit and T zone within the Thor Lake rare metal deposit (modified after Davidson, 1982).

geochronology. Bowring et al. (1984) obtained a zircon age for the Hearne Channel Granite of 2175 7 Ma and reported an unpublished zircon age (supplied by A. Davidson) for the Whiteman Lake Quartz Syenite of 2185 5 Ma. These authors also reported a zircon age of 2094 10 Ma for a drill core sample interpreted to represent the Thor Lake Syenite. Sinclair et al. (1994) subsequently dated the Grace Lake Granite using zircon and monazite, at 2176.2 1.3 Ma, which is essentially the same as the age obtained for the Hearne Channel Granite. They also reinterpreted the origin of the sample of supposed Thor Lake syenite dated by Bowring et al. (1984) and, based on its description as a magnetic rock containing 10 to 20% zircon euhedra and xenomorphic grains, concluded that the sample was from the rock unit that we now refer to as the Nechalacho Layered Alkaline Suite. We concur with this reinterpretation and believe that this sample is from the upper mineralized zone (see below). The age of 2094 10 Ma previously attributed to the Thor Lake Syenite is thus considered to represent the age of the Nechalacho Layered Alkaline Suite and/or the rare metal mineralization contained therein.
0361-0128/98/000/000-00 $6.00

All of the above rock units were intruded into Archean mica schists of the Yellowknife Supergroup, which surrounds the Blachford Lake Intrusive Complex. To the south are graywackes, shales, and carbonates of the Great Slave Supergroup (Trueman et al., 1988), which are separated from the Blachford Lake Intrusive Complex by a postulated faulted contact along the Hearne Channel of Great Slave Lake. The Nechalacho Layered Alkaline Suite The Nechalacho Layered Alkaline Suite consists of a sequence of silica-undersaturated intrusive rocks that increase in alkalinity with depth. The suite is only exposed at surface locally in a small area between Long Lake and Thor Lake (Fig. 2), but based on drill intersections, it is postulated to dip beneath the Thor Lake Syenite in all directions, forming a dome-shaped body that at the current depth of drilling (~300 m) has a diameter of >1.5 km; its depth extent is unknown. In cross section, the suite progresses downward from a roof zone of sodalite cumulates, through coarse-grained to pegmatitic aegirine (arfvedsonite) syenite and layers of cumulate zircon, 83

84

SHEARD ET AL.

Sub-outcrop map (based on drill-hole data)

Cross section based on drill holes L09-154 and L09-139

L09-154 L09-139

6,888,000m

LEGEND
Location of cross section
6,887,000m

Nechalacho Layered Alkaline Suite Sodalite roof cumulate Albitized aegirine nepheline syenite Biotitized and iron-oxide altered (plus minor quartz) aegirine nepheline syenite

6,886,000m

Upper mineralized zone Lower mineralized zone

500m
415,000m 416,000m 417,000m

Blachford Lake Complex Thor Lake Syenite (undifferentiated) Grace Lake Granite

199.95m

230.45m

FIG. 2. Suboutcrop geology map (based on drill hole data) and north-south geologic cross section through the Nechalacho Layered Alkaline Suite, showing the distribution of the various geologic units. The cross section through drill holes L09154 and L09-139 illustrates the relationship of the mineralized zones to the host rocks.

to foyaitic aegirine nepheline syenite with laterally continuous layers of zircon-bearing pseudomorphs inferred to represent eudialyte cumulates (see below). Pervasive metasomatic fluids have strongly altered the rocks in this upper sequence, largely replacing the original mineralogy. However, below the inferred eudialyte cumulates the primary mineralogy and textures are increasingly preserved and relatively unaltered aegirine- and nepheline-bearing syenites and sodalite foyaites are observed. The roof sodalite cumulates are strongly altered, mediumto coarse-grained rocks that display intrusive contacts with the overlying Thor Lake Syenite. Hexagonal, primary sodalite phenocrysts have been completely altered to fine-grained muscovite, illite, and/or chlorite in most samples examined. Sodalite crystals display a distinctive orange fluorescence under UV illumination (Fig. 3A), which allows them to be easily identified in drill core despite their extensive alteration and replacement. In less altered samples, crystals of altered sodalite are enclosed in coarse anhedra of orthoclase and an unknown altered dark green mineral, which could have been aegirine or arfvedsonite. Orthoclase and albite are the interstitial minerals and are commonly intergrown and display a perthitic exsolution texture. A sharp contact, commonly obscured by the alteration overprint, is observed between the roof sodalite cumulates and strongly altered aegirine (arfvedsonite) syenite below them. This medium- to coarse-grained rock unit is highly heterogeneous in texture and is variably porphyritic and foyaitic with common pegmatitic lenses. A ~15 to 30 m thick upper rare metal mineralized zone, comprising fine wavy laminations and/or ribbons of zircon crystals (Fig. 3B, C) and
0361-0128/98/000/000-00 $6.00

macroscopically visible brick red bastnsite-(Ce) with locally intense biotite + magnetite and fluorite + albite alteration occurs within this unit. Zircon is also present in veins where it is wrapped around brecciated K-feldspar fragments. Both the upper and lower boundaries to this zone are gradational. The underlying foyaitic aegirine nepheline syenites are characterized by trachytic flow textures (Fig. 3D) imparting a pronounced subhorizontal alignment of the phenocryst phases (aegirine and/or K-feldspar and/or nepheline). The foyaites are highly heterogeneous, both mineralogically and texturally, displaying numerous cyclical changes in the dominant phenocryst phase and local interlayering of microsyenites and coarser grained porphyritic syenites. This unit hosts the ~15 to 60 m thick lower mineralized zone, which is composed of densely packed pseudomorphs (Fig. 3E) inferred to represent eudialyte cumulates (see below), and generally has a gradational upper boundary and sharp lower contact (Fig. 3F). In some drill holes, the two mineralized zones are separated by unmineralized rocks, whereas, in other holes, the upper zone grades directly into the lower zone. Plots of REE abundance with depth (Fig. 4) indicate that the heavy REE are concentrated in the lower mineralized zone, that intermediate REE (e.g., Gd, Dy) have no apparent preference for upper or lower mineralized zones, and that the light REE are concentrated in the upper mineralized zone. The ore mineralogy in each zone is broadly similar. Zirconium is hosted mainly by zircon, niobium by ferrocolumbite and fergusonite-(Y) ((Ce,La,Nd,Y)NbO4), the HREE by fergusonite(Y) and zircon, and the LREE by monazite-(Ce) ((Ce,La,Th, Nd,Y)PO4), allanite-(Ce), bastnsite-(Ce) ((Ce,La,Y)F(CO3)), parisite-(Ce) (Ca(Ce,La)2(CO3)3F2) and synchysite-(Ce) (Ca 84

Zr, Nb, Y, & REE IN THE THOR LAKE RARE-METAL DEPOSIT, NWT, CANADA

85

A
sdl chl

bt or zrn

1 cm C
aln zrn bt or mag bt mnz chl

1 cm D
zrn

200 m E F

1 cm

1 cm G
or ab ne

1 cm H
aeg

zrn

1cm

1 cm

FIG. 3. A. Photograph of roof sodalite (sdl) cumulate in drill core under UV illumination showing a distinctive orange fluorescence. B. Drill core from typical upper mineralized zone rocks showing wavy laminations and/or ribbons of tan-colored zircon (zrn) perpendicular to core axis (vertical hole). C. SEM-BSE image of type 1a zircon (zrn) in undulating laminations wrapping around pseudomorphs of precursor aegirine (aeg) now filled by magnetite (mag) and biotite (bt). Within the laminations, zircon crystals are broken and locally replaced by allanite-(Ce) (darker gray; aln) and monazite-(Ce) (white; mnz). Biotite and magnetite are the darker gray and/or black phases surrounding zircon-rich layers. D. Drill core showing a trachytic flow texture defined by K-feldspar and pseudomorphs after eudialyte in a dark matrix of chlorite and sericite. E. Drill core containing densely packed tan-colored pseudomorphs after primary eudialyte. F. Drill core showing the boundary between a microlayer of hematized zircon (pseudomorphs after eudialyte?) below and a foyaitic cumulate layer above. G. Drill core displaying a cumulate zone with fine subhorizontal internal magmatic layering. H. Photograph of aegirine nepheline syenite in drill core with aegirine (aeg) and nepheline (ne) as phenocrysts in a groundmass of orthoclase (or). 0361-0128/98/000/000-00 $6.00

85

86
40000 80000

SHEARD ET AL.

4000

30000

60000

3000

20000

40000

Sm2O3
0 50 100 150

La2O3

Ce2O3

2000

10000

20000

1000

0 0 50 100 150

0 0 50 100 150

3000

1500

600

2000

1000

400

Gd2O3

Dy2O3

1000

500

Yb2O3
0 50 100 150

200

0 0 50 100 150

0 0 50 100 150

Upper mineralized zone Lower mineralized zone

FIG. 4. Plots of REE abundance (ppm) with depth (m) illustrating differences in the distribution of the REE content in the upper and lower mineralized zones in drill hole L07-55, located within the North Tardiff zone (see Fig. 2).

(Y,Ce,La,Nd,Gd)[F(CO3)2]). Table 2 lists the names and compositions of ore minerals identified in the deposit. In the lower zone, zircon and REE-bearing minerals are secondary phases in pseudomorphs formed after the in situ dissolution of inferred primary eudialyte (see below). Beneath the lower mineralized zone is a series of heterogeneous, magmatically layered aegirine nepheline sodalite syenites. These rocks are variably fine grained to pegmatitic and contain interlayers of microsyenite (Fig. 3G), foyaitic syenite, porphyritic aegirine nepheline syenite, and sodalite-rich syenite. In the dominant unit, the aegirine nepheline syenite, aegirine and nepheline form phenocrysts in a groundmass consisting dominantly of orthoclase with minor accessory phases and secondary alteration minerals (Fig. 3H). The nepheline phenocrysts form subhedral oikocrysts, up to 1 cm in diameter, and typically display a poikilitic texture produced by lath-shaped poikalites of aegirine and albite, and anhedral poikalites of chlorite and zircon. Aegirine phenocrysts display a range of shapes and sizes. They vary in length from <1 up to 8 mm and can be both unzoned and rimmed by inclusion-free overgrowths. Most aegirine crystals are fractured along cleavage planes with the fractures filled by biotite, albite, magnetite/hematite, and minor fluorite. The aegirine also hosts inclusions of allanite(Ce) ((LREE,Ca,Y)2(Al, Fe3+)3(SiO4)3(OH)), zircon, and a CaZr silicate (possibly gittinsite or vlasovite). Interstitial, bladed albite is common in the groundmass between nepheline and aegirine crystals and locally replaces both. Sporadic, irregularly shaped patches of rare metal mineralization occur
0361-0128/98/000/000-00 $6.00

throughout, and are dominated by zircon, but also contain minor britholite-(Ce) (Ca2 [(Y,Ce)Ca]3[(OH,F)(SiO4,PO4)3]), allanite-(Ce), and thorite. Many of these patches, particularly in the lower mineralized zone, have regular geometric shapes with planar elements reminiscent of crystal faces, suggesting that they represent pseudomorphs of an earlier mineral, inferred to be eudialyte. This interpretation is supported by the occurrence of unaltered eudialyte intergrown with analcime (NaAl(Si2O6). (H2O)) and oneillite (Na15Ca3Mn3Fe2+3Zr3Nb (Si25O73)(O,OH,H2O)3(OH,Cl)2) in core from drill hole 85-L6 at a depth of 349 m. Hydrothermal Alteration The rocks in the upper part of the layered alkaline suite have been intensely altered by hydrothermal fluids, leaving only relicts of their primary mineralogy. Hydrothermal alteration is pervasive and is not conformable to igneous layering. The principal alteration minerals are magnetite, hematite, biotite, chlorite, illite, muscovite, calcite, quartz, fluorite, and bladed albite (cleavelandite). Minor alteration minerals are ankerite, siderite, kutnahorite (Ca(Mn,Mg,Fe)(CO3)2), scapolite, pyrite, and sphalerite. Magnetite and biotite are the dominant alteration minerals in the upper mineralized zone and were temporally and spatially associated with the formation of fergusonite-(Y), ferrocolumbite, allanite-(Ce), monazite-(Ce), and bastnsite-(Ce). These minerals replaced earlier minerals, such as aegirine and zircon, and filled fractures in primary K-feldspar. Locally, biotite replaced magnetite. 86

Zr, Nb, Y, & REE IN THE THOR LAKE RARE-METAL DEPOSIT, NWT, CANADA TABLE 2. A List of Minerals (and their compositions) Found in the Nechalacho Deposit Name Silicates Aegirine Aenigmatite Albite Allanite Analcime Annite Barkevikite Biotite Britholite Catapleiite Cerianite Chamosite Chlorite Eudialyte Ferro-bustamite Synchysite Ferroricherite Gittinsite Lepidolite Mesolite Natrolite Oneillite Orthoclase Pectolite Quartz Scapolite Sericite Sodalite Thorite Topaz Uranothorite Willemite Wollastonite Zinnwaldite Zircon Sulfides Barite Chalcopyrite Molybdenite Pyrite Pyrrhotite Sphalerite BaSO4 CuFeS2 MoS2 FeS2 Fe7S8 ZnS NaFe3+(Si2O6) Na2Fe2+5TiSi6O20 Na(AlSi3O8) Ca(La,Y,Ce)(Al2Fe2+)Si3O12 NaAl(Si2O6).(H2O) KFe2+3AlSi3O10(OH)1.5F0.5 Ca2(Fe,Mg,Al)-5(Si,Al)8O22(OH)2 K2(Mg,Fe2+)6-4(Fe3+,Al,Ti)0-2[Si6-5Al2-3O20](OH,F)4 Ca2[(Y,Ce)Ca]3[(OH,F)(SiO4,PO4)3] Na2Zr(Si3O9).2H2O (Ce4+,Th)O2 (Fe2+,Mg)5Al[(OH)8AlSi3O10] (Mg,Fe2+,Fe3+,Mn,Al)12[(Si,Al)8O20](OH)16 Na15Ca6(Fe2+,Mn2+)3Zr3(Si25O73)(O,OH,H2O)3(OH,Cl)2 Ca(Fe2+,Ca,Mn2+)Si2O6 Ca(Y,Ce,La,Nd,Gd)[F(CO3)2] Na[Ca,Na][Fe2+5][(OH)2Si8O22] CaZrSi2O7 K(Li,Al)3(Si,Al)4O10(OH,F)2 Na2Ca2(Al2Si2O10)3.8H2O Na2(Al2Si3O10).2H2O Na15Ca3Mn3Fe2+3Zr3Nb(Si25O73)(O,OH,H2O)3(OH,Cl)2 K(AlSi3O8) NaCa2(HSi3O9) SiO2 Na4[Cl(AlSi3O8)3] Ca4[CO3(Al2Si2O8)3] K2Al4(Si6Al2O20)(OH,F)4 Na8(Al6Si6O24)Cl2 (Th,U)SiO4 Al2SiO4(OH,F)2 (Th,U)SiO4 ZnSiO4 CaSiO3 K(Li,Fe,Al)3(Si,Al)4O10(OH)F ZrSiO4 ZrSiO4 Formula Name Halides Fluorite Phosphates Apatite Monazite Carbonates Ankerite Bastnsite Calcite Dolomite Kutnahorite Lanthanite Parisite Siderite Oxides Aeschynite Ashanite Betafite Cassiterite Ceriopyrochlore Columbite Columbo-tantalite Fergusonite Ferrocolumbite Hematite Ilmenite Ixiolite Limonite Magnetite Nioboaeschynite Polycrase Samarskite Specularite Titanomagnetite Uraninite Yttrocolumbite CaF2 Ca5(PO4)3(OH,F,Cl) (Ce,La,Th)PO4 Ca(Mg,Fe2+,Mn)(CO3)2 (Ce,La,Y)F(CO3) CaCO3 CaMg(CO3)2 Ca(Mn,Mg,Fe)(CO3)2 (Ce,La,Nd)2(CO3)38H2O Ca(Ce,La)2(CO3)3F2 FeCO3 Formula

87

(Ce,Nd,Y,Ca,Fe,Th)(Ti,Nb)2(O,OH)6 (Nb,Ta,U,Fe,Mn)4O8 (Ca,U)2(Ti,Nb)2O6(OH) SnO2 (Ce,Ca,Y)2(Nb,Ta)2O6(OH,F) (Fe,Mn)(Nb,Ta)2O6 (Fe,Mn)(Nb,Ta)2O6 (Ce,La,Nd,Y)NbO4 Fe++Nb2O6 Fe2O3 Fe2+TiO3 (Ta,Nb,Sn,Fe,Mn)4O8 FeO.OH.nH2O Fe2+Fe23+O4 (Y,Ca,Ce,Nd,Th)(Nb,Ta,Ta)2(O,OH)6 (Y,Ca,Ce,U,Th)(Ti,Nb,Ta)2O6 (Y,Ce,U,Fe,Nb)(Nb,Ta,Ti)O4 Fe2O3 Fe(Fe,Ti)2O4 UO2 (Y,U,Fe++)(Nb,Ta)O4

Magnetite is also the dominant alteration mineral in the lower mineralized zone and biotite is much less abundant than in the upper mineralized zone. Magnetite replaced the secondary minerals in pseudomorphs after inferred eudialyte and is the dominant mineral in the fine-grained groundmass surrounding the pseudomorphs, where it is accompanied by minor biotite and albite. Below the lower mineralized zone, magnetite decreases sharply in abundance and hematite, becomes prevalent, forming rims around feldspar phenocrysts and locally magnetite, commonly replacing these minerals completely. In the layered aegirine nepheline sodalite syenites at depth, sodalite is typically replaced by fine-grained muscovite, and aegirine by magnetite or hematite. Albitization is widespread but is most pervasive in the upper 50 m of the complex where a pegmatitic unit was replaced almost entirely by blades of albite (cleavelandite),
0361-0128/98/000/000-00 $6.00

displaying intense red cathodoluminescence (triggered by Fe3+ activators). Albite having these characteristics is a common product of alkali-metasomatism (Rae and Chambers, 1988; McLemore and Modreski, 1990). Pegmatitic syenites lower down in the complex have also been albitized and, where the albitization is less intense, remnant, partially altered K-feldspar megacrysts are observed. Vugs are common in all the albitized pegmatites, suggesting that this alteration was accompanied by a significant loss of volume; the vugs have been variably filled by late carbonates, clays, fluorite, and minor pyrite. In addition to affecting the pegmatites, albitization also locally overprinted magnetite- and biotite-altered aegirine arfvedsonite syenite and where these rocks were mineralized, destroyed zircon and the associated REEbearing minerals. Late-stage silicification (quartz), illitization, and carbonatization also affected the deposit. These alteration types, which 87

88

SHEARD ET AL.

overprint all the earlier alteration types including albitization, were only developed locally and except, for carbonatization, do not appear to have been accompanied by any redistribution of HREE. However, carbonatization (calcite, ankerite, siderite) may have been associated with REE fluoro-carbonate crystallization, as calcite, fluorite, and bastnsite-(Ce) commonly occur together. This has been suggested by Coulson and Chambers (1996) for the rocks of the North Qroq Centre in Greenland. Distribution and Paragenesis of Rare Metal Minerals HREE-bearing minerals Zircon and fergusonite-(Y) are the two main hosts to heavy rare earth elements in the deposit; minor amounts of HREE are also present in ferrocolumbite. Three varieties of zircon are distinguishable microscopically. Type 1 zircon is a tan-colored variety that occurs almost exclusively in the upper mineralized zone and consists predominantly of euhedral, bipyramidal, zoned crystals (typically, 3060 m and locally 100 m in diameter), which have distinct cores and rims and are locally brecciated. In most crystals, the cores are a dark brown color due to alteration by very fine grained chlorite, quartz, samarskite-(Y), monazite(Ce), and uranothorite. The cores are also the focus for fractures, which radiate outward and transect the translucent rims. Type 1 zircon occurs either as isolated crystals or is concentrated in subhorizontal undulating laminations, which wrap around pseudomorphs (now filled mainly by magnetite and biotite), interpreted to represent aegirine phenocrysts (Fig. 3B). The laminations are parallel to the igneous layering and locally form zones up to 30 cm thick, containing >30 vol % zircon. Petrographically and particularly in backscattered electron imagery, the zircon in these laminations is observed to have been extensively replaced by allanite-(Ce) and to a much lesser extent by monazite-(Ce) and ferrocolumbite (Fig. 3C). A second tan-colored variety of zircon, which like type 1 zircon is also restricted to the upper mineralized zone, forms clots and irregular streaks, and occurs in veinlets (Fig. 5) that wrap around brecciated feldspar crystals. Its crystals are typically broken and form fragments in a matrix of biotite and magnetite. For this reason and its chemical similarity to type 1 zircon (discussed later), this second type is interpreted to represent mechanically remobilized type 1 zircon. In order to distinguish this zircon from that described in the previous paragraph, it will be referred to henceforth as type 1b zircon and that of the previous paragraph as type 1a zircon. Type 2 zircon comprises the bulk of the zircon in the lower mineralized zone, forming small (1030 m) anhedral grains that occur within pseudomorphs, which are present in layers varying from tens of centimeters to several meters in thickness, and are interpreted to represent igneous cumulates. The pseudomorphs have two distinctive morphologies, range from submillimeter to centimeter size, and contain no relicts of their precursor mineral(s). However, one of these pseudomorph types (the overwhelmingly predominant type) has a tabular habit very similar to that of eudialyte. These pseudomorphs typically have subrounded shapes and contain the following mineral assemblage: zircon + fergusonite-(Y) +
0361-0128/98/000/000-00 $6.00

FIG. 5. Photomicrograph in plane-polarized light of broken type 1b zircon (zrn) crystals in a biotite (bt)-cemented vein through brecciated albite (ab).

bastnsite-(Ce) + parisite-(Ce) + synchysite-(Ce) + allanite(Ce) + albite + quartz + biotite + fluorite + kutnahorite minor hematite and rare sphalerite (Fig. 6A). The zircon within these pseudomorphs forms anhedral grains or larger clusters of grains (Fig. 6B), some of which are rimmed by an overgrowth of younger zircon. Pseudomorph cores are commonly replaced entirely by hematite and more rarely magnetite, leaving a rim of zircon inside the original outline of the pseudomorph. Over several meters both above and below the lower mineralized zone, the pseudomorphs have been partially to completely replaced by magnetite and/or hematite, indicating that the mineralized zone may have extended much farther prior to alteration. Some pseudomorphs contain spherical patches of quartz with radiating vermicular zircon, which are reminiscent of symplectic intergrowths (Fig. 6C). These pseudomorphs contain the same mineral assemblage as that shown in Figure 6A and are considered a variant of the original alteration of eudialyte. The second variety of pseudomorph, which is far less common, has the shape of a doubly terminated prism and has been replaced predominantly by zircon (Fig. 6D). This shape is similar to that of elpidite, a common primary magmatic mineral in the Strange Lake Complex, Quebec/Labrador (Birkett et al., 1992; Salvi and Williams-Jones, 1995). The proportion of zircon in these pseudomorphs is approximately 80 vol %, which is much higher than would be expected for elpidite, suggesting that, if our interpretation of their precursors is correct, Na, silica, and H2O were removed during alteration. Type 3 zircon is relatively uncommon, occurs in irregular patches and in zones of brecciation mainly in the upper mineralized zone, and is locally replaced by secondary albite. The rims on this zircon are narrow and characterized by unusually high birefringence, oscillatory zoning, and colloform textures (Fig. 7A). The rims and irregular patches within the cores can be further distinguished by their response to UV illumination. Whereas type 1 and 2 zircons do not fluoresce or luminesce, type 3 zircon exhibits a blue to greenish-yellow fluorescence. Cathodoluminescence images reveal bright greenish-yellow luminescing patches within crystals of this zircon and paler 88

Zr, Nb, Y, & REE IN THE THOR LAKE RARE-METAL DEPOSIT, NWT, CANADA

89

50m

or chl zrn

mag

200m

1mm

FIG. 6. A. Photomicrograph in plane-polarized light of a single pseudomorph replaced by zircon (zrn) + fergusonite-(Y) (ferg) + allanite-(Ce) (aln) + parisite-(Ce)/synchysite-(Ce) + albite (ab) + quartz (qtz) + biotite (bt) + fluorite + calcite (cal). B. SEM-BSE image of anhedral to subrounded grains of zircon within a pseudomorph (white is fergusonite-(Y)). C. SEMBSE image illustrating several pseudomorphs containing radially distributed vermicelli of zircon (pale gray) and interstitial quartz (black). D. Photomicrograph of a zircon pseudomorph after probable elpidite.

blue zoned rims (Fig. 7B). This zoning is also evident in backscattered electron imagery. The greenish-yellow emission is attributed to Sm3+ or Dy3+ activation, as these REE are known to produce a green emission. Similar luminescence has been reported in zircon from the Khaldzan Buregte and Tsakhir Nb-Zr-REE deposits in the Mongolian Altai (Kempe et al., 1999), where it was clearly demonstrated that the emission was caused by Dy3+ activation. Fergusonite-(Y) is present in both the upper and lower mineralized zones but is much more abundant in the latter where it typically comprises 1 to 5 vol % of the rock and is the dominant HREE-bearing mineral along with zircon. In the upper mineralized zone, fergusonite-(Y) occurs as small (<1 mm) anhedral grains adjacent to primary zircon. In the lower mineralized zone, however, it forms small (<1 mm) anhedral grains and more densely packed aggregates within the pseudomorphs after eudialyte where it is intimately associated with zircon, which it also locally replaced (Fig. 8A). Fergusonite-(Y) also occurs outside the pseudomorphs as a replacement product of columbite-(Mn). Ferrocolumbite occurs as pinwheels with rounded black centers and radiating spines up to 0.1 mm in diameter (Fig. 8B).
0361-0128/98/000/000-00 $6.00

It also locally replaced zircon and fergusonite-(Y), in both the upper and lower mineralized zones. Columbite-(Mn) forms small, isolated anhedral crystals and larger clusters of these crystals (up to 50 m in diameter) adjacent to type 1 zircon and inferred eudialyte pseudomorphs (it also occurs within some pseudomorphs) and occurs as inclusions within biotite, chlorite, magnetite, and albite. These crystals commonly have been replaced by both fergusonite-(Y) (Fig. 8C) and bastnsite(Ce). The relationship of columbite-(Mn) to ferrocolumbite is unclear as these minerals are not observed together. However, the fact that fergusonite-(Y) replaced columbite-(Mn) and was in turn replaced by ferrocolumbite indicates that formation of ferrocolumbite postdated that of columbite-(Mn). Lastly, samarskite-(Y) is present as anhedral inclusions in the cores of zircon crystals in the upper mineralized zone and also as larger grains (up to 30 m diam) in biotite. LREE-bearing minerals REE fluoro-carbonate minerals, predominantly bastnsite(Ce), synchysite-(Ce), and minor parisite-(Ce), are most common several tens of meters above the intervals containing the highest concentrations of HREE in the upper mineralized 89

90

SHEARD ET AL.

In the lower mineralized zone, the LREE occur predominantly in bastnsite group minerals and allanite-(Ce) and are found both within and beyond the confines of the pseudomorphs after probable eudialyte. There are a number of intimate intergrowths of these minerals and other HREE-bearing minerals within the pseudomorphs, namely between bastnsite-(Ce)-parisite-(Ce)-synchysite-(Ce)-allanite(Ce) and fergusonite-(Y)-bastnsite-(Ce)-gittinsite. The textures suggest that these minerals most likely formed coevally. Fluorite, sulfides, thorite, and apatite Dark purple fluorite is common throughout the deposit and occurs in many forms: infilling vugs in albitized pegmatites, together with bastnsite-(Ce) and other LREE-rich minerals; as a local replacement of magnetite and biotite; in fractures in primary K-feldspar; intergrown with illite in massive patches from tens of centimeters to several meters in thickness; and intergrown with zircon and other REE-bearing minerals in zones of brecciation. Pyrite, chalcopyrite, sphalerite, and molybdenite are locally abundant in the upper parts of the deposit. In particular, pyrite occurs in calcite veins and commonly as disseminations in magnetite-rich horizons where it locally replaced magnetite. Thorite and other minor accessory minerals occur as small (13 m) anhedral grains in the cores of type 1 zircon crystals. Minor apatite, surrounded by albite, is associated with monazite-(Ce). Summary In summary, all the REE minerals described above locally replaced zircon, an observation that is significant and will be discussed further. The simplified paragenesis of rare metal minerals and major alteration minerals in the upper mineralized zone is represented by the sequence: zircon magnetite-biotite-zircon-REE minerals albite fluorite-calcite-quartz-chlorite-hematite. A more detailed paragenesis is given in Figure 9. In the lower zone, all the REE minerals formed synchronously by replacement of inferred eudialyte to create pseudomorphs. Mineral Chemistry The compositions of the REE-bearing minerals were determined using wavelength-dispersive spectrometers on a JEOL JXA-8900L electron microprobe at McGill University with a focused beam and an acceleration voltage of 20 kV, a 30 nA beam current, a beam diameter of 3 m for zircon, fergusonite-(Y), ferrocolumbite, and eudialyte; and a 10 m beam diameter for allanite-(Ce), monazite-(Ce), and bastnsite(Ce). Data reduction was performed using the ZAF correction method. Counting times and standards used for each element analyzed are reported in Table 3 and detection limits are presented in Tables 4 and 5 with the relevant analytical data. Element X-ray maps were obtained using the same instrument with the probe beam moving over a 900 900 point grid; counting intervals for X-rays at each spot were 60 msec. Brighter zones in the element maps reflect higher count rates. Many of the analyses of zircon crystals, particularly of the cores, reported low totals (e.g., type 1b core: 94.91 wt %). This is most likely due to the presence of H2O in the zircon structure. Phosphorous contents are below detection and are not reported. 90

FIG. 7. A. Photomicrograph in plane-polarized light of type 3 zircon (zrn) with colloform zoned rims, locally replaced by albite (ab) and biotite (bt). B. Cathodoluminescence image of the same zircon showing oscillatory zoning (blue fluorescence) and bright green-yellow fluorescent patches.

zone, where they are associated with fluorite and calcite and are important hosts of the LREE. Macroscopically, bastnsite(Ce) is brown-red to brick-red in color, reflecting alteration to hematite. It occurs with the other fluoro-carbonate minerals as fine-grained disseminations interstitial to biotite, magnetite, and zircon, and more rarely forms rims around zircon crystals and replaced allanite-(Ce), occurring as streaks and irregular patches within this mineral (Fig. 8D). Synchysite(Ce) and parisite-(Ce) are intimately intergrown with both bastnsite-(Ce) and allanite-(Ce) (Fig. 8E). Allanite-(Ce) forms anhedral grains up to 1.5 mm in diameter and more massive clusters, which are commonly interstitial to zircon, and pseudomorphs after probable eudialyte. It occurs in both the upper and lower mineralized zones but is much more abundant in the upper zone. Typically red in color, it displays a fiery orange luminescence under cathodoluminescence excitation (Fig. 8F). Monazite-(Ce), which is found mainly in the upper zone proximal to zones of HREE mineralization, occurs as elongate needles and/or rods or as tiny crystals in zircon, K-feldspar, quartz, and biotite, having replaced the interiors of these minerals. Locally, monazite(Ce) also replaced both bastnsite-(Ce) and allanite-(Ce).
0361-0128/98/000/000-00 $6.00

Zr, Nb, Y, & REE IN THE THOR LAKE RARE-METAL DEPOSIT, NWT, CANADA

91

FIG. 8. A. SEM-BSE image illustrating fergusonite-(Y) (white; ferg) that locally replaced zircon (zrn). B. Photomicrograph in plane-polarized light of zircon, monazite-(Ce) (mnz), and ferrocolumbite (pinwheels with black rounded centers and radiating spines) surrounded by quartz (qtz). Ferrocolumbite (fc) that replaced zircon can be seen on the right-hand side of the photograph. C. SEM-BSE image showing columbite-(Mn) (col) that was replaced by fergusonite-(Y) and bastnsite-(Ce) (bast). D. SEM-BSE image of bastnsite-(Ce) (bast) after allanite-(Ce) (aln). E. SEM-BSE image of allanite-(Ce) intergrown with parisite-(Ce) (par) on the rim of a pseudomorph after probable eudialyte in the lower mineralized zone. F. Cathodoluminescence image of fiery orange allanite-(Ce) between zircon crystals.

0361-0128/98/000/000-00 $6.00

91

92
REE-BEARING MINERALS Upper zone: Zircon Fergusonite-(Y) Columbite-(Mn) Ferrocolumbite Allanite-(Ce) Monazite-(Ce) Parisite-(Ce) Synchysite-(Ce) Bastnaesite-(Ce) Lower zone: Eudialyte Zircon Fergusonite-(Y) Allanite-(Ce) Parisite-(Ce) Synchysite-(Ce) Bastnaesite-(Ce) MAJOR ALTERATION MINERALS Magnetite Biotite Hematite Chlorite Quartz Albite Fluorite Calcite

SHEARD ET AL.

Magmatic

Hydrothermal

? ? ?

FIG. 9. Paragenetic sequence for the major REE-bearing and alteration minerals in the Nechalacho deposit. Line widths indicate relative abundances of phases. Uncertainty in the precise placement of a mineral within the paragenesis due to a lack of textural evidence is indicated by ?.

REE mineral chemistry The REE are present in significant concentrations in zircon, fergusonite-(Y), allanite-(Ce), monazite-(Ce), and bastnsite-(Ce). The concentration of total REO (as REE2O3) in type 1 zircon crystals is highly variable, ranging from <1 to 6.45 wt %, and the distribution varies from rim to core with significant zoning apparent in backscattered electron images. Electron microprobe X-ray element maps were produced in order to observe the chemical nature of the zonation and changes in the distribution of Zr, Nb, Y, Ce, Nd, Gd, Hf, Th, Si, Fe, Mg, K, and Ca within the structure of the four types of zircon and within the pseudomorphs. The images were acquired by scanning the beam across the sample in a grid. The signals collected at each point in the grid were plotted with pixel brightness as a function of signal intensity (i.e., higher intensities were plotted as brighter colors). The above elements were selected as they are the major elements in zircon, markers for the light, middle, and heavy REE or help identify alteration minerals present in the altered cores. Most of the type 1a and b zircon crystals that were mapped display a central Y (up to ~3 wt % Y2O3) and Gd-rich, Nd and
0361-0128/98/000/000-00 $6.00

Hf-poor core and an outer Y-poor, Nd- and Hf-rich rim, with sharp boundaries between the core and rim. This suggests that the rims were overgrown on the cores. LREE, represented by La2O3 and Ce2O3, occur in concentrations up to 0.05 and 0.50 wt % in the rims but only 0.02 and 0.35 wt % in the cores, respectively. The corresponding concentrations of middle REE (MREE), represented by Sm2O3, Gd2O3, and Dy2O3, are up to 0.98, 0.88, and 0.55 wt % in the rims and 1.18, 1.14, and 1.04 wt % in the cores, respectively. HREE, represented by Yb2O3, occur in concentrations up to 0.43 wt % in the rims and 0.72 wt % in the cores. In general, it is the MREE, namely Sm, Gd, and Dy, which are most enriched in type 1 zircon relative to the other REE. An important feature of these crystals is that the cores have been preferentially altered and yttrium was mobilized along radiating fractures to the rims and beyond (Figs. 10, 11). This alteration likely represents an atoll texture, in which the core of the crystal was less stable than the rim and therefore more susceptible to alteration. The occurrence of rare crystals of monazite-(Ce), samarskite-(Y), and thorite in some zircon cores can be explained by calling upon the radiating fractures to act as pathways for hydrothermal fluids into the grains. Transects from 92

Zr, Nb, Y, & REE IN THE THOR LAKE RARE-METAL DEPOSIT, NWT, CANADA TABLE 3. Counting Times and Standards Used in Electron Microprobe Analyses Element La Y Nb Eu Ce F Hf Dy Er Si U Ca Gd Fe Al Pr Th Sm Nd Zr Yb Na Tb Ti Mg Mn P K Ta Counting time (sec) 150 50 100 150 60 100 40 60 60 20 100 20 60 20 20 60 100 60 60 20 70 20 60 20 20 20 20 20 60 Standard MAC-La MAC-Y Na2Nb2O6 MAC-Eu MAC-Ce CaF2 Zircon MAC-Dy MAC-Er Zircon UO2 Diopside MAC-Gd gar1 gar1 MAC-Pr ThO2 MAC-Sm MAC-Nd Zircon MAC-Yb Na2Nb2O6 MAC-Tb TiO2 Spinel Spessartine Ba-Feld Orthoclase MAC-Nd

93

rim to rim across individual crystals show that concentrations of thorium are elevated in the altered cores (Fig. 12), suggesting that metamictization may have played an important role in promoting core alteration. Electron microprobe element maps of the pseudomorphs after inferred eudialyte (Fig. 13) show that Zr, Y, and Nb are confined within the crystal boundaries, suggesting that these elements were only remobilized on a scale of tens of microns. By contrast, Ca and LREE such as Ce are observed beyond the crystal boundaries and were thus remobilized on a larger scale. Table 4 reports the compositions of the different zircon types. Overall, the compositions of type 1a and b zircon crystals are fairly similar (Fig. 14A, B). The rims, in particular, have very similar compositions, but their cores differ somewhat in that the cores of type 1b zircon are slightly more enriched in HREE than those of type 1a. Type 2 zircon has a distinctive chondrite-normalized REE profile characterized by a strong depletion in the LREE and enrichment in the HREE (Fig. 14C) relative to type 1 zircon. For example, the average concentration of Y2O3 in type 2 zircon is 2.71 wt %, two to three times the concentration in type 1 zircon. Concentrations of Yb2O3 and Er2O3 are distributed similarly to those of Y2O3. Type 3 zircon is enriched in HREE in the narrow oscillatory zoned rims and is depleted in all REE in the cores (Fig. 14D). The compositions of the rims are similar to those of type 1a and b zircon. Table 5 reports the compositions of the other major REEbearing mineral phases in the Nechalacho deposit. Fergusonite-(Y) is preferentially enriched in the middle and heavy

TABLE 4. Average Compositions (wt %) of Rims and Cores of the Different Zircon Types Analyzed Using the Electron Microprobe (the figures report the standard deviations for each set of analyses) Type 1a core (n = 18) ZrO2 SiO2 HfO2 FeO Al2O3 UO2 ThO2 CaO F Na2O Y2O3 Nb2O5 La2O3 Ce2O3 Pr2O3 Nd2O3 Sm2O3 Eu2O3 Gd2O3 Dy2O3 Er2O3 Tb2O3 Yb2O3 Total 60.48 1.27 29.46 1.13 1.38 0.50 1.01 0.44 0.25 0.10 b.d. 0.05 0.05 0.32 0.29 0.66 0.37 0.20 0.09 0.81 0.43 1.16 0.71 b.d. 0.21 0.13 b.d. 0.53 0.39 0.44 0.32 0.11 0.07 0.56 0.42 0.28 0.18 0.07 0.02 b.d. b.d. 98.01 Type 1a rim (n = 18) 60.69 0.55 29.25 0.42 1.09 0.18 0.57 0.29 0.08 0.03 b.d. 0.19 0.10 0.13 0.05 0.70 0.20 0.08 0.04 0.66 0.27 2.62 0.49 b.d. 0.28 0.10 0.16 0.06 1.17 0.26 0.52 0.18 0.10 0.04 0.41 0.17 0.19 0.07 0.09 0.04 b.d. 0.10 0.09 99.07 Type 1b core (n = 24) 59.01 1.61 27.11 1.12 1.16 0.42 0.72 0.51 0.16 0.13 b.d. 0.10 0.09 0.21 0.14 0.67 0.40 0.06 0.01 1.70 0.06 1.32 0.66 b.d. 0.15 0.14 b.d. 0.44 0.40 0.46 0.35 0.10 0.09 0.84 0.67 0.46 0.37 0.15 0.13 b.d. 0.11 0.09 94.91 Type 1b rim (n = 36) 60.60 1.47 28.36 0.82 1.21 0.19 0.33 0.17 0.10 0.05 b.d. 0.07 0.06 0.25 0.06 0.62 0.29 b.d. 0.36 0.22 3.31 1.28 b.d. 0.37 0.09 0.15 0.09 1.18 0.30 0.52 0.23 b.d. 0.36 0.23 0.11 0.07 b.d. b.d. b.d. 97.81 Type 2 core (n = 49) 55.15 4.70 32.07 5.87 1.22 0.19 1.90 1.20 0.36 0.26 0.04 0.03 0.17 0.13 0.19 0.12 0.15 0.12 0.21 0.13 2.71 1.22 0.71 0.57 b.d. 0.06 0.04 b.d. 0.11 0.04 b.d. b.d. 0.27 0.14 0.35 0.19 0.28 0.12 b.d. 0.23 0.07 96.17 Type 2 rim (n = 9) 57.98 1.72 28.01 0.43 1.06 0.11 0.61 0.26 0.15 0.05 b.d. 0.20 0.08 0.14 0.04 0.99 0.18 0.19 0.06 3.63 2.31 2.07 0.70 b.d. 0.12 0.06 b.d. 0.42 0.34 0.31 0.24 b.d. 0.70 0.15 0.79 0.46 0.30 0.22 b.d. 0.15 0.10 97.82 Type 3 core (n = 7) 64.76 23.71 30.90 10.99 1.56 0.56 0.42 0.34 0.10 0.09 b.d. b.d. 0.28 0.23 0.16 0.08 0.06 0.05 b.d. 0.44 0.34 b.d. b.d. b.d. b.d. b.d. b.d. b.d. b.d. b.d. b.d. b.d. 98.88 Type 3 rim (n = 7) 60.81 22.61 29.00 10.85 1.29 0.47 0.52 0.20 0.21 0.09 b.d. 0.05 0.04 0.25 0.13 0.69 0.23 0.31 0.13 0.63 0.54 1.75 0.61 b.d. 0.30 0.13 b.d. 0.92 0.32 0.29 0.11 b.d. 0.29 0.24 0.29 0.19 0.08 0.08 b.d. b.d. 97.67

Notes: b.d. = below detection limit, which are as follows for oxides (wt %): Zr, 0.11; Si, 0.03; Hf, 0.10; Fe, 0.12; Al, 0.02; U, 0.04; Th, 0.04; Ca, 0.03; F, 0.11; Na, 0.05; Y, 0.05; Nb, 0.06; La, 0.09; Ce, 0.04; Pr, 0.15; Nd, 0.11; Sm, 0.09; Eu, 0.09; Gd, 0.09; Dy, 0.11; Er, 0.05; Tb, 0.04, Yb, 0.06 0361-0128/98/000/000-00 $6.00

93

94

SHEARD ET AL. TABLE 5. Average Compositions (wt %) of Fergusonite-(Y), Ferrocolumbite, Eudialyte, Monazite-(Ce), Allanite-(Ce), and Bastnsite-(Ce) Analyzed Using the Electron Microprobe (the figures report the standard deviations for each set of analyses) Fergusonite-(Y) (n = 42) Ferrocolumbite (n = 12) 1.96 0.83 19.01 0.87 0.22 0.06 2.65 1.00 0.05 0.02 b.d. 0.06 0.04 0.30 0.19 70.64 3.11 4.23 3.44 0.18 0.10 b.d. b.d. 99.30 Eudialyte (n = 21) 10.73 0.18 46.68 0.64 0.31 0.05 b.d. 6.42 0.22 9.16 0.20 0.21 0.04 10.99 0.38 0.46 0.03 2.18 0.50 3.87 0.24 1.34 0.18 1.86 0.41 0.20 0.04 0.75 0.20 0.15 0.05 0.40 0.05 0.37 0.09 0.20 0.05 0.12 0.04 96.40 Monazite-(Ce) (n = 47) 0.09 0.07 29.80 0.40 1.51 0.73 0.23 0.17 0.48 0.07 0.66 0.59 14.42 1.49 31.99 2.47 3.99 0.40 14.26 1.87 1.62 0.57 0.17 0.13 0.95 0.48 0.18 0.15 100.35 Allanite-(Ce) (n = 33) 31.73 0.58 13.89 1.46 16.40 1.86 0.37 0.19 0.63 0.25 9.01 0.78 0.13 0.10 6.53 0.92 12.68 1.23 1.48 0.18 4.50 0.50 0.34 0.16 0.16 0.09 0.25 0.14 98.10 Bastnsite-(Ce) (n = 26) b.d. 0.14 0.12 7.76 1.56 0.31 0.24 16.67 2.02 35.31 2.20 4.22 0.48 15.24 2.63 1.38 0.50 0.33 0.24 0.87 0.53 0.10 0.12 20.74* 2.04 103.07

ZrO2 SiO2 HfO2 TiO2 FeO Al2O3 MgO MnO P2O5 UO2 ThO2 CaO F Na2O K2O Y2O3 Nb2O5 Ta2O5 SnO2 La2O3 Ce2O3 Pr2O3 Nd2O3 Sm2O3 Eu2O3 Gd2O3 Dy2O3 Er2O3 Yb2O3 CO2 Total

0.20 0.14 0.56 0.36 0.44 0.39 0.28 0.16 24.53 2.13 45.88 1.61 2.57 1.02 0.47 0.24 0.21 0.19 2.56 1.04 2.80 1.06 0.88 0.31 6.76 1.11 5.91 1.16 2.06 0.53 0.76 0.31 96.87

Notes: b.d. = below detection limit, which are as follows for oxides (wt %): Zr, 0.11; Si, 0.03; Hf, 0.10; Ti, 0.07; Fe, 0.04; Al, 0.02; Mg, 0.02; Mn, 0.03; P, 0.08; U, 0.04; Th, 0.05; Ca, 0.02; F, 0.04; Na, 0.03; K, 0.03; Y, 0.03; Nb, 0.06; Ta, 0.14; Sn, 0.05; La, 0.10; Ce, 0.04; Pr, 0.05; Nd, 0.11; Sm, 0.07; Eu, 0.03; Gd, 0.09; Dy, 0.09; Er, 0.05; Yb, 0.06 * calculated by stoichiometry, - = not analyzed

REE, up to 7.5 wt % Dy2O3 and Gd2O3 (Fig. 14E), and is the main host of yttrium in the deposit (it contains ~25 wt % Y2O3). It also hosts significant concentrations of Ta2O5 (up to 6 wt %; avg ~2.7 wt %), which has its highest bulk rock concentration in the lower part of the lower mineralized zone (up to 0.12 wt %; avg ~0.06 wt %); this is where fergusonite-(Y) is most abundant. The average stoichiometry of fergusonite-(Y) is (Y0.51Gd0.10Dy0.08Nd0.04Sm0.04Ta0.04)Nb1.00O4. Ferrocolumbite has an average composition of (Fe2+ 0.92 Mn0.14)Ta0.11Nb1.80O6 and an Nb/Ta ratio very similar to that of fergusonite-(Y) (16.4 vs. 25), consistent with the observation that ferrocolumbite replaced fergusonite-(Y). Ferrocolumbite hosts up to 7.95 wt % Ta2O5, 0.68 wt % Y2O3, and an average of ~68.5 wt % Nb2O5. Columbite-(Mn) is similar in composition to ferrocolumbite but has higher concentrations of Ta2O5 and MnO (up to 21.85 and 6.04 wt %, respectively) and lower concentrations of Nb2O5 and FeO (36.54 and 9.11 wt %, respectively). The unaltered eudialyte in drill core from hole 85-L6 has an average composition of (Na11.96Ca1.32K0.33)(Ca4.19REE1.08 2+ Y0.65Mn0.08)6(Mn2+ 2.98Fe0.02)3Zr2.94Nb0.98(Si26.09O72) (O,OH,H2O)3
0361-0128/98/000/000-00 $6.00

(OH,Cl0.38F0.45)2, calculated using the method of Johnsen et al. (2003). This is close to the composition of the end member, kentbrooksite, in terms of Mn-REE-Nb-F, but in terms of Ca-Fe-Si-Cl is intermediate between kentbrooksite and eudialyte. In view of this, the mineral is referred to as eudialyte in this paper. This phase hosts up to 4.08 wt % Nb2O5, 2.97 wt % Y2O3, and 5.97 wt % other REE oxides. Monazite-(Ce), allanite-(Ce), and bastnsite-(Ce) all display similar chondrite-normalized REE profiles, being preferentially enriched in the LREE with a concave trend from La to Sm (Fig. 14F). The average compositions of these minerals are (Ce0.47Nd0.22La0.19Pr0.06)P0.99O4, (Ca0.89Ce0.45La0.22 Nd0.15Pr0.05)(Al1.78Fe1.12)Si2.93O12 and (Ce0.38Nd0.19La0.17Pr0.05) F0.66C0.87O3, respectively. The HREE concentrations are generally below the limit of detection of the electron microprobe. Monazite-(Ce) contains the highest concentrations of Ce2O3 (35 wt %) and Nd2O3 (15 wt %) of any of the REE-bearing minerals and rare zoned crystals have rims that are preferentially enriched in MREE and thorium. By contrast, allanite(Ce) contains, on average, 7 wt % La2O3, 13 wt % Ce2O3, and 4.5 wt % Nd2O3. 94

Zr, Nb, Y, & REE IN THE THOR LAKE RARE-METAL DEPOSIT, NWT, CANADA

95

BSE IMAGE

NEODYMIUM

BSE IMAGE

NEODYMIUM

ZIRCONIUM

YTTRIUM

ZIRCONIUM

YTTRIUM

HAFNIUM HAFNIUM

GADOLINIUM GADOLINIUM

100m 100m FIG. 10. Electron microprobe element maps of type 1a zircon crystals, showing the distribution of Nd, Zr, Y, Hf, and Gd. The key features to note are the preferential enrichment of Nd, Zr, Hf, and Gd in the rims and Y in the cores. Yttrium is also observed along fractures penetrating the rims.
Discussion Origin of the zircon Although zirconium is widely believed to be immobile during fluid-rock interaction and zircon is regarded by many as a strictly igneous mineral, there have been a number of reports in the literature of textures involving zircon consistent with its formation by hydrothermal processes (e.g., Rubin et al., 1993; Schaltegger,
0361-0128/98/000/000-00 $6.00

2007; Anderson et al., 2008; Lichtervelde et al., 2009). For example, Rubin et al. (1989) reported Hf-enriched hydrothermal overgrowths on magmatic zircon from the Sierra Blanca Peaks, Texas, and similar overgrowths have since been reported for the Boggy Plain zoned pluton, Australia (Hoskin, 2005), and the Mole Granite, Australia (Pettke et al., 2005). Kerrich and King (1993) also documented hydrothermal zircon with a spongy texture containing abundant inclusions of Au and fluid. 95

96

SHEARD ET AL.

YTTRIUM

0.6 0.4 0.2

zrn

0.0 THORIUM 8.0 6.0 4.0

ferg 40m
FIG. 11. Electron microprobe map for yttrium illustrating fractures along which yttrium moved from zircon (zrn) cores to form adjacent fergusonite(Y) (ferg).

2.0 0.0 YTTRIUM 1.5 1.0

In the Nechalacho deposit, there is evidence for the occurrence of both magmatic and hydrothermal zircon. Based on the nature of its distribution in wavy laminations and/or ribbons, which parallel igneous layering and lithologic contacts, type 1 zircon (the main variety of zircon in the upper mineralized zone) is interpreted to be a magmatic cumulate mineral. It is, however, likely that the rims of type 1 zircon crystals represent overgrowths on primary cores which acted as nuclei for crystallization of later zircon and, it is thus possible that this later zircon deposited from a hydrothermal fluid. It is also possible that the overgrowths simply represent a second stage of magmatic crystallization. Irrespective of which interpretation is correct, an important finding of our study is that the zircon of the upper mineralized zone is dominantly of magmatic origin and therefore substantial proportions of the REE (particularly the HREE) were concentrated magmatically as a result of crystallization of zircon; the cores of type 1 zircon are elevated with respect to the middle to heavy REE. In contrast to type 1 zircon, type 2 zircon (the main variety of zircon in the lower mineralized zone) is clearly hydrothermal in origin. It formed in pseudomorphs of a mineral that we interpret to be eudialyte and we consider it likely that this zircon obtained its zirconium from the residues of the dissolution of the eudialyte. There are several lines of evidence that support this interpretation. First, the relative volume proportions of each of the secondary minerals (zircon + fergusonite(Y) + bastnsite-(Ce) + parisite-(Ce) + synchysite-(Ce) + allanite-(Ce) + albite + quartz + biotite + fluorite + kutnahorite minor hematite) are roughly consistent from one pseudomorph to another, suggesting that one or more elements (e.g., Zr, Y, Nb, Ce, Mn, Fe) were conserved. Second, the homogeneous distribution of zircon in the pseudomorphs (Fig. 13) suggests strongly that Zr was conserved, and third, the volume proportion of zircon (~15%) is consistent with the proportion of Zr that would have been made available by dissolution of eudialyte (eudialyte contains ~11 mol % zirconium silicate). Finally, we note that the ratio, TREE2O3/ZrO2 in eudyalite from drill hole 85-L6 is fairly similar to that for the bulk rock in the lower mineralized zone (0.71 vs. 0.55; Tables 1, 5), and that
0361-0128/98/000/000-00 $6.00

0.5 0.0 GADOLINIUM 1.5 1.0 0.5 0.0 HAFNIUM 1 2 3 4 5 6 7 8

FIG. 12. Transects from rim to rim across a single zircon crystal, illustrating differences in the distribution of Th, Y, Gd, and Hf between the core (35) and rims (12 and 68). The Y axis is in wt %.

the slightly lower ratio for the latter is consistent with the greater mobility of the REE relative to Zr. Coulson (1997) reported a similar process of complete in situ breakdown and replacement of primary eudialyte by new pseudomorphing phases in lujavrites from the North Qroq Centre. The colloform nature of type 3 zircon (Fig. 7A) provides strong evidence that this variety of zircon is also hydrothermal in origin, but that in contrast to type 2 zircon, both Zr and Si were supplied by the hydrothermal fluid. If this interpretation is correct, then it follows that the rims of type 1 zircon are also hydrothermal in origin as the distribution of the REE in them is very similar to that of type 3 zircon. In summary, our observations of the Nechalacho deposit suggest that zircon in the upper mineralized zone was dominantly magmatic and that zircon in the lower mineralized zone formed by an in situ replacement of eudialyte, without hydrothermal mobilization of Zr on a scale of more than microns. However, there was more substantial mobilization of Zr in the upper mineralized zone and this produced colloform hydrothermal type 3 zircon and overgrowths on type 1 zircon. 96

Zr, Nb, Y, & REE IN THE THOR LAKE RARE-METAL DEPOSIT, NWT, CANADA

97

BSE IMAGE

YTTRIUM

ZIRCONIUM

NIOBIUM

CALCIUM

CERIUM

100m

150 m
FIG. 13. Electron microprobe element maps of a pseudomorph of inferred eudialyte illustrating the intensities of Y, Zr, Nb, Ce, and Ca. The relative proportions of each of these elements within the outline of the original crystal are approximately equal to those of the primary eudialyte.

Magmatic concentration of Zr, Nb, and REE Zr, Nb, and REE mineralization in the Nechalacho deposit is confined to cumulate layers of zircon in the upper zone, with associated columbite-(Mn), and to layers of pseudomorphs after cumulate eudialyte in the lower zone. The layers in both zones typically contain > 6 wt % ZrO2, up to 0.8 wt % Nb2O5, and >3 wt % total rare earth oxides (TREO), achieved
0361-0128/98/000/000-00 $6.00

by a combination of crystal settling and compaction of discrete zircon and eudialyte crystals and later alteration, remobilization, and concentration by magmatic hydrothermal fluids. Most researchers agree that peralkaline melts are products of low degrees of partial melting in an undepleted, metasomatically enriched mantle (Marks et al., 2003; Halama et al., 2004) and that silica-undersaturated rocks originate from differentiation of these magmas under relatively dry and variable 97

98

SHEARD ET AL.

Type 1a zircon - core Type 1a zircon - rim

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

Type 1b zircon - core Type 1b zircon - rim

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

Type 2 zircon - core Type 2 zircon - rim

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

Type 3 zircon - rim

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

E
100000

10000

1000

Fergusonite-(Y)
100

Monazite-(Ce) Bastnsite-(Ce) Allanite-(Ce)

La Ce Pr Nd Pm Sm Eu Gd Tb Dy

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

FIG. 14. Chondrite-normalized REE profiles (Boynton, 1984) for zircon, fergusonite-(Y), monazite-(Ce), bastnsite-(Ce), and allanite-(Ce). The Y-axis in all graphs represents sample/REE chondrite (McDonough and Sun, 1995).

fO2 conditions. A key characteristic of such magmas is their ability to evolve to high Cl and F contents before exsolving an aqueous fluid phase (Kogarko, 1974; Markl et al., 2001), allowing for extreme fractionation to low temperature. It is known that elevated concentrations of alkalis and F in these magmas increase the solubility of the REE and HFSE by promoting formation of alkali-silicate or alkali-fluoride complexes with them (Keppler, 1993; Peiffert et al., 1996; Linnen, 1998; Marr et al., 1998; Baker et al., 2002), thereby providing a mechanism for transporting these elements. Keppler (1993)
0361-0128/98/000/000-00 $6.00

examined the effect of fluorine on zircon solubility in felsic melts and demonstrated a strong positive correlation between solubility and fluorine content in melts containing 0 to 6 wt % F. Concentrations of Zr, Nb, and REE can reach several thousands of parts per million in natural systems. For example, Olivo and Williams-Jones (1999) reported concentrations of Zr, Nb, and REE in nepheline syenite from the Pilanesberg Complex, South Africa of 1.81, 0.21, and 0.71 wt %, respectively. In many cases, the REE and HFSE are further concentrated by saturation of the magma with minerals like eudialyte 98

Zr, Nb, Y, & REE IN THE THOR LAKE RARE-METAL DEPOSIT, NWT, CANADA

99

and their settling under gravity to form cumulate layers in which these minerals are dominant (Srensen et al., 2006). However, to our knowledge, there have been no reports in the literature of cumulate zircon. The presence of both simple and complex zirconosilicates, namely primary zircon and eudialyte in the same system, is rare but has been reported, for example, from the Tamazeght Complex, Morocco (Salvi et al., 2000; Marks et al., 2008). In this complex, eudialyte is the principal Zr-bearing mineral in agpaitic nepheline syentites and forms cumulates, whereas zircon is the main Zr-bearing mineral in miaskitic nepheline syenites but is a comparatively minor phase and does not form cumulates. Another example of the same phenomenon is provided by the McGerrigle Mountains, Quebec, where zircon is concentrated in miaskitic rocks (2.2 modal % in one sample) and eudialyte is restricted to agpaitic rocks (Wallace et al., 1990). The primary zirconium mineralogy is a function of the alkalinity of the rocks, where zircon is dominant in miaskitic rocks, eudialyte in agpaitic rocks, and both zircon and eudialyte occur in rocks of intermediate composition. Indeed, the term agpaitic, which was originally introduced to refer to syenites with atomic (Na + K)/Al ratio > 1.2 (alkalinity index; Ussing, 1912), now has the added restriction that Zr and Ti minerals should be in the form of complex minerals, such as eudialyte and rinkite rather than zircon or ilmenite (Srensen, 1997). The term miaskitic is reserved for nepheline syenites in which Zr is in the form of zircon and for which the alkalinity index is generally, but not exclusively, less than unity. We propose that the upper mineralized zone of the Nechalacho deposit at Thor Lake, which contains zircon cumulates, represents less evolved miaskitic rocks, and that the eudialyte cumulate-bearing lower mineralized zone represents more evolved agpaitic rocks. This interpretation is supported by large numbers of bulk rock analyses of 1 to 2 m long intervals of drill core from a representative selection of drill holes (Fig. 15), which show that rocks from the upper mineralized zone
60 50 40 30 20 10 0
<0.80 0.81-0.85 0.86-0.90 0.91-0.95 0.96-1.00

generally have alkalinity indices <1 (mean of 169 samples = 0.89), whereas those from the lower mineralized zone generally have alkalinity indices >1 (mean of 38 samples = 1.20). However, it must be emphasized that both zones were intensely altered and it is therefore likely that there was considerable mobilization of the alkalis. The factors determining whether a magma crystallizes zircon or more complex zirconosilicates are not well understood. Clearly and not surprisingly the formation of complex zirconosilicate minerals is favored by high alkalinity as shown by field observations that zircon occurrence seems to be restricted to miaskitic rocks. However, silica activity may also play a role as suggested by the results of experiments by Marr et al. (1998) with peralkaline melts, which showed that zircon was the melt-saturated phase for SiO2 contents above 55 wt %, whereas for lower SiO2 contents wadeite, a potassium zirconosilicate, was the melt-saturated phase. In the Nechalacho deposit, it may therefore not be a coincidence that rocks in the zircon-rich upper mineralized zone have a higher content of SiO2 than in the lower zone, where Zr is interpreted to have been present dominantly as eudialyte (Fig. 16). Finally, there is evidence from field studies that temperature may play a role. For example, at Strange Lake, zircon was the earliest mineral to crystallize, followed by the sodium zirconosilicates, vlasovite, and elpidite (Birkett et al., 1992). Another important HREE-bearing mineral interpreted to be magmatic is columbite-(Mn), which, because of its relatively high density, accumulated with zircon in the upper mineralized zone, where it is most abundant, and with eudialyte in the lower mineralized zone. This interpretation is based on its close spatial association with primary zircon and eudialyte, textural evidence of selective replacement of columbite-(Mn) by fergusonite-(Y), and the occurrence of columbite-(Mn) as inclusions in alteration minerals such as biotite, chlorite, magnetite, and albite. However, columbite-(Mn) can also be secondary as indicated by its presence in some pseudomorphs after eudialyte.
16 14 12 10 8 6 4 2 0
1.00-1.10 1.11-1.20 1.21-1.30 1.31-1.40 >1.41

(Na + K) / Al

(Na + K) / Al

FIG. 15. Histograms of bulk-rock alkalinity indices ((Na + K) / Al) of 1 to 2 m long intervals of drill core taken from a representative selection of drill holes throughout the deposit: A. Upper mineralized zone. B. Lower mineralized zone. These histograms show that rocks from the upper mineralized zone generally have alkalinity indices <1, whereas those from the lower mineralized zone generally have alkalinity indices >1. 0361-0128/98/000/000-00 $6.00

99

100
80 70 60 SiO2 (wt. %) 50 40 30 20 10 0 0 50 100 150 200 (m)

SHEARD ET AL.

FIG. 16. Bulk-rock silica content (wt %) as a function of depth in drill hole L09-162. Samples represent 1 to 2 m long intervals of drill core.

Hydrothermal Zr, Nb, and REE mobilization In most igneous systems, Zr, Nb, and REE are immobile during fluid-rock interaction, and for this reason are widely used as petrogenetic indicators (Pupin, 1980; Hoskin and Schaltegger, 2003; Schaltegger et al., 2005). However, there is increasing evidence in the literature that these elements can be transported by hydrothermal fluids under the restrictive sets of conditions that commonly prevail in alkaline igneous settings. It has also been shown that the hydrothermal durability of many minerals enriched in HFSE is compromised by alpha-decay-induced damage (Pidgeon et al., 1966; Sinha et al., 1992; Geisler et al., 2001; Lumpkin, 2001). Our study has provided evidence of metamictization, which resulted in preferential alteration of the cores of type 1 zircon crystals and mobilization of HREE from these crystals to form minerals such as fergusonite-(Y), which only occurs adjacent to zircon. Similar alteration has been documented by Anderson et al. (2008) for zircon from the Georgeville Granite, Nova Scotia. In this latter study, Anderson et al. (2008) showed that REE in metamict zircon were redistributed during alteration by diffusion and dissolution and reprecipitation along microfractures on a scale of tens of micrometers. The current study has provided evidence of some remobilization of Zr and HREE by hydrothermal fluids. In the upper mineralized zone, minor zircon (type 3) forms colloform lamellae and overgrowths, and the HREE were mobilized out of the cores of type 1 zircon to form crystals of fergusonite-(Y) by replacement of nearby grains of primary magmatic columbite-(Mn). The latter is also true to a lesser extent in the lower mineralized zone, where columbite-(Mn) adjacent to eudialyte pseudomorphs was replaced by fergusonite-(Y). In contrast to this limited mobility of Zr and the HREE, the LREE appear to have been mobilized on scales ranging from micrometers to meters. They are concentrated in the minerals, allanite-(Ce) and monazite-(Ce), which typically occur interstitially to magmatic zircon and eudialyte, and as bastnsite-(Ce), parisite-(Ce), and synchysite-(Ce), which commonly show no spatial association with primary zircon and eudialyte pseudomorphs; in the upper mineralized zone these minerals are most abundant meters above the intervals containing the highest concentrations of HREE.
0361-0128/98/000/000-00 $6.00

As a result of recent experimental studies, we now have some insights into the behavior of Zr in hydrothermal fluids (Migdisov and Williams-Jones, 2009) and a relatively good understanding of the behavior of the REE in these fluids (Migdisov and Williams-Jones, 2002, 2007; Migdisov et al., 2009). The study of Zr shows that this element forms its strongest complexes with fluoride and that fluids with HF concentrations on the order of 0.1 m can dissolve 10s ppm of zircon at 200C. Significantly higher concentrations of REE can be dissolved by fluids with such HF concentrations. Furthermore, the LREE form considerably stronger complexes with fluoride than the HREE and are therefore more easily mobilized. The REE also form relatively strong complexes with chloride and, as for fluoride, the strongest complexes are with the LREE. These studies satisfactorily explain the relatively limited mobility of Zr and the HREE, and the much greater mobility of the LREE in the Nechalacho deposit. In light of the above discussion and the abundance of fluorite in the deposit, it seems plausible that the REE were leached from primary minerals, namely zircon and eudialyte, by forming fluoride complexes, and then redeposited as fergusonite-(Y), allanite-(Ce), monazite-(Ce), bastnsite-(Ce), parisite-(Ce), and synchysite-(Ce). In the case of fergusonite(Y), allanite-(Ce), and monazite-(Ce), the mobilization, for the most part, was on the scale of millimeters, and for fergusonite-(Y) was controlled by the occurrence of proximal columbite-(Mn). However, as noted above, the REE concentrated in bastnsite-(Ce), parisite-(Ce), and synchysite-(Ce) of the upper mineralized zone were mobilized on a scale of meters. By analogy with the model proposed for the deposition of these minerals in the Strange Lake Pluton, QubecLabrador (Salvi and Williams-Jones, 1990), and noting their association with fluorite and calcite, we propose that the LREE were transported as fluoride complexes in magmatic hydrothermal fluids, which subsequently mixed with calciumand carbonate-bearing fluids near the top of the layered complex. These latter fluids were likely external and their mixing with the magmatic hydrothermal fluids caused immediate deposition of fluorite, which is relatively insoluble in the presence of Ca. This destabilized the REE-fluoride complexes, making the REE available for deposition as fluorocarbonate minerals. Genetic model The proposed geologic model for the Zr, Nb, and REE mineralization in the Nechalacho deposit involves intrusion of an alkaline, volatile-rich, aegirine nepheline syenite into the Thor Lake Syenite, at the center of the Blachford Lake Intrusive Complex. The alkaline nature of the rocks and their high concentration of incompatible elements suggest a small degree of partial melting of upwelled mantle, possibly at depths of 60 to 100 km (Srensen, 1997; Martin, 2006). Repeated injections of magma, fractional crystallization, and convective overturn produced a layered igneous body. As the convecting magma went through cycles of saturation and undersaturation in a phase (i.e., aegirine, nepheline, K-feldspar, sodalite, zircon, or eudialyte), because of convective overturn and mixing of different pulses of magma, layers were formed (Fig. 17). The mixing likely caused monomineralic crystallization of zircon or eudialyte by displacing the liquidus from a cotectic to a

100

Zr, Nb, Y, & REE IN THE THOR LAKE RARE-METAL DEPOSIT, NWT, CANADA

101

FIG. 17. Cartoon illustrating the intrusion of aegirine nepheline syenite into the Thor Lake Syenite. Repeated injections of magma, bottom upward crystallization due to gravity accumulation and convective overturn due to decreasing temperature, produce a layered igneous body. Hydrothermal alteration of the upper and lower mineralized zones leads to remobilization of a variety of elements, including the LREE.

field in which only a zirconosilicate mineral was stable. The result was a lower mineralized zone comprising multiple eudialyte cumulate layers and an upper zone comprising multiple zircon cumulate layers. We propose that the difference between these two zones was the result of the alkali content of the magmas that formed them, i.e., miaskitic or less alkaline in the case of the upper mineralized zone and agpaitic or more alkaline in the case of the lower mineralized zone. Fluids of probable magmatic origin exsolved from aegirine nepheline syenite at depth were responsible for alteration of the primary eudialyte and zircon (autometasomatism). These metasomatic fluids also caused biotitization, K-feldspathization, and replacement of primary minerals (mainly aegirine)
0361-0128/98/000/000-00 $6.00

by magnetite or hematite as the fluids evolved compositionally with evolution of the aegirine nepheline syenite magma. The eudialyte crystals were dissolved and completely replaced by secondary phases within the original crystal boundaries. Some elements, e.g., Zr, Nb, and the HREE, were only remobilized on a scale of microns or tens of microns, i.e., they remained largely within the boundaries of the pseudomorphs, whereas other elements, e.g., Na, Ca, Cl, H2O, and LREE, were removed by the fluids exsolved from the lower, more peralkaline part of the intrusion. Zirconium and REE were mobilized from type 1a and b metamict zircon cores in the upper mineralized zone along fractures to form secondary zircon, fergusonite-(Y), allanite-(Ce), and monazite-(Ce). The

101

102

SHEARD ET AL.

LREE were mobilized from both eudialyte and zircon as fluoride complexes by magmatic hydrothermal fluids and deposited distal to their hosts. In the upper parts of the complex, this occurred as a result of mixing with Ca-bearing fluids of probable external origin, which caused precipitation of fluorite, destablizing the REE-fluoride complexes. Later Narich fluids overprinted and locally replaced the bulk of the primary mineralogy, including zircon and eudialyte, with albite (cleavelandite), mainly, but not exclusively, in the upper parts of the deposit. Comparison to other deposits A small number of HREE-enriched deposits occur in other parts of the world. The Ilmaussaq layered alkaline complex in the Gardar province of southern Greenland (Marks et al., 2004) is similar in many respects to the Nechalacho deposit, in geologic setting, size, and the preferential enrichment of the HREE. At Ilmaussaq, the HREE are concentrated in lujavrites, which comprise cumulates of aegirine, arfvedsonite, and eudialyte (Larsen and Srensen, 1987), whereas in the Nechalacho deposit there are also cumulates of zircon, and eudialyte is pseudomorphous after a zircon-bearing mineral assemblage. To our knowledge, Nechalacho is the only HREE deposit in which zircon cumulates have been recognized. However, both zircon and eudialyte occur in the Tamazeght alkaline complex in Morocco (Salvi et al., 2000) and, although zircon is not a cumulate mineral and is present in relatively small proportions, it is hosted by miaskitic rocks as has been proposed for the Nechalacho deposit. The Motzfeldt intrusive suite, also located in the Gardar province of southern Greenland (Schoenenberger and Markl, 2008), formed by successively intruding melt batches of varying composition from a common magma source at depth as is proposed for the Nechalacho deposit. Five units crystallized a miaskitic mineral assemblage and a final magmatic batch an agpaitic assemblage. This complex is a type example of the transition from miaskitic to agpaitic mineral assemblages. Hydrothermal alteration is less significant in these other complexes than in the Nechalacho deposit, however, it is locally important. For example, at Tamazeght, primary zircon and eudialyte have been partly or completely replaced by secondary phases that are richer in F and Ca, such as cancrinite, calcic catapleiite, and rinkite, and primary eudialyte has been partially replaced by secondary eudialyte enriched in REE and HFSE (Schilling et al., 2009). In the Gardar province of southern Greenland, the transition from an oxidized to a reduced fluid was shown to be correlated with a change from a more reduced, Fe2+-bearing miaskitic mineral assemblage to a more oxidized, Fe3+-bearing agpaitic assemblage (Schoenenberger and Markl, 2008). Although many similarities can be drawn between Ilmaussaq, Motzfeldt, Tamazeght, and the Nechalacho deposit, the Nechalacho deposit is unusual in its REE mineralogy and in hosting a potentially economic resource of the HREE. Conclusions The Nechalacho deposit at Thor Lake contains extraordinarily high concentrations of Zr, Nb, and REE as zircon, fergusonite-(Y) and ferrocolumbite, bastnsite-(Ce), allanite(Ce), and monazite-(Ce). Upper and lower mineralized zones
0361-0128/98/000/000-00 $6.00

have been defined, with the former representing discontinuous, heterogeneous zircon-rich cumulate layers and the latter multiple cumulate eudialyte layers. Primary eudialyte has been completely replaced by secondary phases, namely zircon, fergusonite-(Y), bastnsite-(Ce), parisite-(Ce), synchysite(Ce), allanite-(Ce), albite, quartz, biotite, fluorite, kutnahorite, and minor hematite, which are pseudomorphous after the precursor eudialyte, and primary zircon has been leached of REEs. The model proposed to explain the origin of the mineralization in the Nechalacho deposit calls on both magmatic and hydrothermal processes. The eudialyte and zircon cumulate layers can be explained by the intrusion, fractional crystallization, and mixing of evolving alkaline to peralkaline magmas. Magmatically derived hydrothermal fluids altered the distribution of REE within the upper and lower mineralized zones, locally enriching and depleting them, and created a set of secondary minerals, which will be the main target of future exploitation. Acknowledgments E. Sheard gratefully acknowledges the support of a Natural Sciences and Engineering Research Council (NSERC) Alexander Graham Bell postgraduate scholarship, a GEOTOP (Quebec interuniversity network for advanced studies and research in geoscience) postgraduate scholarship, and a McGill Principals Graduate Fellowship. Financial support for the research was provided by a grant from Avalon Rare Metals Inc. and a matching grant from the NSERC-CRD program to AEW-J. Avalon Rare Metals Inc. also provided access to the field area, drill core, geochemical data, and internal reports. The research benefited from helpful discussions with V.J. van Hinsberg, J.R. Clark, A. Migdisov, K. MacWilliam, and W. Mercer. L. Shi provided valuable analytical assistance and V. Moeller provided several drill core photographs. The manuscript was improved by the reviews of I. Coulson, D. Sinclair, and R. Taylor.
REFERENCES
Anderson, A.J., 2008, The alteration of metamict zircon and its role in the remobilization of high-field-strength elements in the Georgeville Granite, Nova Scotia: Canadian Mineralogist, v. 46, p. 118. Baker, D.R., Conte, A.M., Freda, C., and Ottolini, L., 2002, The effect of halogens on Zr diffusion and zircon dissolution in hydrous metaluminous granitic melts: Contributions to Mineralogy and Petrology, v. 142, p. 666678. Birkett, T.C., Miller, R.R., Roberts, A.C., and Mariano, A.N., 1992, Zirconium-bearing minerals of the Strange Lake Intrusive Complex, QubecLabrador: Canadian Mineralogist, v. 30, p. 191205. Boily, M., and Williams-Jones, A.E., 1994, The role of magmatic and hydrothermal processes in the chemical evolution of the Strange Lake plutonic complex, Qubec-Labrador: Contributions to Mineralogy and Petrology, v. 118, p. 3347. Bowring, S.A., Van Schmus, W.R., and Hoffman, P.F., 1984, U-Pb zircon ages from Athapuscow aulacogen, East Arm of Great Slave Lake, N.W.T., Canada: Canadian Journal of Earth Sciences, v. 21, p. 13151324. Boynton, W.V., 1984, Geochemistry of the rare-earth elements: Meteorite studies, in Henderson, Rare earth element geochemistry: Amsterdam, Elsevier, p. 63114. Cerny, P., and Trueman, D.L., 1985, Polylithionite from the rare-metal deposits of the Blachford Lake alkaline complex, N.W.T., Canada: American Mineralogist, v. 70, p. 11271134. Coulson, I.M., 1997, Post-magmatic alteration in eudialyte from the North Qroq Centre, South Greenland: Mineralogical Magazine, v. 61, p. 99109. Coulson, I.M., and Chambers, A.D., 1996, Patterns of zonation in rare-earthbearing minerals in nepheline syenites of the North Qroq Centre, South Greenland: Canadian Mineralogist, v. 34, p. 11631178.

102

Zr, Nb, Y, & REE IN THE THOR LAKE RARE-METAL DEPOSIT, NWT, CANADA Davidson, A., 1972, Granite studies in the Slave Province: Geological Survey of Canada Paper 72-1A, p. 109115. 1978, The Blachford Lake Intrusive Complex: An Aphebian Alkaline Plutonic Complex in the Slave Province, Northwest Territories: Geological Survey of Canada Paper 78-1A, p. 119127. 1981, Petrochemistry of the Blatchford Lake Complex, District of Mackenzie: Geological Survey of Canada Open File 764. 1982, Petrochemistry of the Blachford Lake Complex near Yellowknife, Northwest Territories: Geological Survey of Canada Paper 81-23, p.7179. Geisler, T., Ulonska, M., Schleicher, H., Pidgeon, R.T., and van Bronswijk, W., 2001, Leaching and differential recrystallization of metamict zircon under experimental hydrothermal conditions: Contributions to Mineralogy and Petrology, v. 141, p. 5365. Gerasimovsky, V.I., 1969, Geochemistry of the Ilmaussaq Alkaline Massif (South-West Greenland), 174 p. Nauka Moskow (in Russian) (not seen; extracted from Lithos, v. 26, p. 167, 1990). Hamala, R., Marks, M., Bruegmann, G., Siebel, W., Wenzel, T., and Markl, G., 2004, Crustal contamination of mafic magmas: Evidence from a petrological, geochemical and Sr-Nd-Os-O isotopic study of the Proterozoic Isortoq dike swarm, South Greenland: Lithos, v. 74, p. 199232. Hoffman, P.F., 1978, Tectonic history of Athapuscow Aulacogen (middle Precambrian), Great Slave Lake, Northwest Territories: American Association of Petroleum Geologists Bulletin, v. 62, p. 522523. Hoskin, P.W.O., 2005, Trace-element composition of hydrothermal zircon and the alteration of Hadean zircon from the Jack Hills, Australia: Geochimica et Cosmochimica Acta, v. 69, p. 637648. Hoskin, P.W.O., and Schaltegger, U., 2003, The composition of zircon and igneous and metamorphic petrogenesis: Reviews in Mineralogy and Geochemistry, v. 53, p. 2755. Johnsen, O., Ferraris, G., Gault, R.A., Grice, J.D., Kampf, A.R., and Pekov, I.V., 2003, The nomenclature of eudialyte-group minerals: Canadian Mineralogist, v. 41, p. 785794. Kempe, U., Gotze, J., Dandar, S., and Habermann, D., 1999, Magmatic and metasomatic processes during formation of the Nb-Zr-REE deposits Khaldzan Buregte and Tsakhir (Mongolian Altai): Indications from a combined CL-SEM study: Mineralogical Magazine, v. 63, p. 165177. Keppler, H., 1993, Influence of fluorine on the enrichment of high field strength trace elements in granitic rocks: Contributions to Mineralogy and Petrology, v. 114, p. 479488. Kerrich, R., and King, R., 1993, Hydrothermal zircon and baddeleyite in Val dOr Archean meothermal gold deposits: Characteristics, compositions, and fluid-inclusion properties, with implications for timing of primary gold mineralization: Canadian Journal of Earth Sciences, v. 30, p. 23342352. Kogarko, L.N., 1974, Role of volatiles, in Srensen, H., ed., The alkaline rocks: London, John Wiley and Sons, p. 474487. 1990, Ore-forming potential of alkaline magmas: Lithos, v. 26, p. 167175. Kovalenko, V.I., Tsaryeva, G.M., Goreglyad, A.V., Yarmolyuk, V.V., Troitsky, V.A., Hervig, R.L., and Farmer, G.L., 1995, The peralkaline granite-related Khaldzan-Buregtey rare metal (Zr, Nb, REE) deposit, western Mongolia: ECONOMIC GEOLOGY, v. 90, p. 530547. Larsen, L.M., and Srensen, H., 1987, The Ilmaussaq intrusion: Progressive crystallization and formation of layering in an agpaitic magma: Geological Society Special Publication 30, p. 473488. Lichtervelde, M., Melcher, F., and Wirth, R., 2009, Magmatic vs. hydrothermal origins for zircon associated with tantalum mineralization in the Tanco pegmatite, Manitoba, Canada: American Mineralogist, v. 94, p. 439450. Linnen, R.L., 1998, The solubility of Nb-Ta-Zr-Hf-W in granitic melts with Li and Li + F: Constraints for mineralization in rare metal granites and pegmatites: ECONOMIC GEOLOGY, v. 93, p. 10131025. Linnen, R.L., and Keppler, H., 2002, Melt composition control of Zr/Hf fractionation in magmatic processes: Geochimica et Cosmochimica Acta, v. 66, p. 32933301. Lumpkin, G.R., 2001, Alpha-decay and aqueous durability of actinide host phases in natural systems: Journal of Nuclear Materials, v. 298, p. 136166. Markl, G., Marks, M., Schwinn, G., and Sommer, H., 2001, Phase equilibrium constraints on intensive crystallization parameters of the Ilmaussaq Complex, South Greenland: Journal of Petrology, v. 42, p. 22312258. Marks, M., Vennemann, T., Siebel, W., and Markl, G., 2003, Quantification of magmatic and hydrothermal processes in peralkaline syenite-alkali granite complex based on textures, phase equilibria, and stable and radiogenic isotopes: Journal of Petrology, v. 44, p. 12471280. 0361-0128/98/000/000-00 $6.00

103

2004, Nd-, O- and H-isotopic evidence for complex, closed-system fluid evolution of the peralkaline Ilmaussaq intrusion, South Greenland: Geochimica et Cosmochimica Acta, v. 68, p. 33793395. Marks, M., Schilling, J., Coulson, I.M., Wenzel, T., and Markl, G., 2008, The alkaline-peralkaline Tamazeght Complex, High Atlas Mountains, Morocco: Mineral chemistry and petrological constraints for derivation from a compositionally heterogeneous mantle source: Journal of Petrology, v. 49, p. 10971131. Marr, R.A., Baker, D.R., and Williams-Jones, A.E., 1998, Chemical controls on the solubility of Zr-bearing phases in simplified peralkaline melts and application to the Strange Lake intrusion, Qubec-Labrador: Canadian Mineralogist, v. 36, p. 10011008. Martin, R.F., 2006, A-type granites of crustal origin ultimately result from open-system fenitization-type reactions in an extensional environment: Lithos, v. 91, p. 125136. McDonough, W.F., and Sun, S.S., 1995, The composition of the Earth: Chemical Geology, v. 120, p. 223253. McLemore, V.T., and Modreski, P.J., 1990, Mineralogy and geochemistry of altered rocks associated with Lemitar carbonatites, central New Mexico, U.S.A.: Lithos, v. 26, p. 99113. Migdisov, A.A., and Williams-Jones, A.E., 2002, A spectrophotometric study of neodymium (III) complexation in chloride solutions: Geochimica et Cosmochimica Acta, v. 66, p. 43114323. 2007, An experimental study of the solubility and speciation of neodymium (III) fluoride in F-bearing aqueous solutions: Geochimica et Cosmochimica Acta, v. 71, p. 30563069. 2009, The stability of Zr in F-bearing hydrothermal solutions: Geochimica et Cosmochimica Acta, v. 73, p. A879. Migdisov, A.A., Williams-Jones, A.E., and Wagner, T., 2009, An experimental study of the solubility and speciation of the rare earth elements (III) in fluoride- and chloride-bearing aqueous solutions at temperatures up to 300C: Geochimica et Cosmochimica Acta, v. 73, p. 70877109. Miller, R.R., 1986, Geology of the Strange Lake Alkalic Complex and the associated Zr-Y-Be-REE mineralization: Newfoundland Department of Mines and Energy, Mineral Development Division Report 86-1, p. 1119. Olivo, G.R., and Williams-Jones, A.E., 1999, Hydrothermal REE-rich eudialyte from the Pilanesberg Complex, South Africa: Canadian Mineralogist, v. 37, p. 653663. Peiffert, C., Nguyen-Trung, C., and Cuney, M., 1996, Uranium in granitic magmas: Pt. 2. Experimental determination of uranium solubility and fluidmelt partition coefficients in the uranium oxide-halpogranite-H2O-NaX (X = Cl, F) system at 720770C, 2 kbar: Geochimica et Cosmochimica Acta, v. 60, p. 15151529. Pettke, T. Audtat, A., Schaltegger, U., and Heinrich, C.A., 2005, Magmaticto-hydrothermal crystallization in the W-Sn mineralized Mole Granite (NSW, Australia): Pt. II. Evolving zircon and thorite trace element chemistry: Chemical Geology, v. 220, p. 191213. Pidgeon, R.T., ONeil, J.R., and Silver, L.T., 1966, Uranium and lead isotopic stability in a metamict zircon under experimentally hydrothermal conditions: Science, v. 154, p. 15381540. Pinckston, D.R., and Smith, D.G.W., 1995, Mineralogy of the Lake zone, Thor Lake rare-metals deposit, N.W.T., Canada: Canadian Journal of Earth Sciences, v. 32, p. 516532. Pupin, J.P., 1980, Zircon and granite petrology: Contributions to Mineralogy and Petrology, v. 73, p. 207220. Rae, D.A., and Chambers, A.D., 1988, Metasomatism in the North Qroq Centre, South Greenland: Cathodoluminescence and mineral chemistry of alkali feldspars: Transactions of the Royal Society of Edinburgh, Earth Sciences, v. 79, p. 112. Rubin, J.N., Henry, C.D., and Price, J.G., 1989, Hydrothermal zircons and zircon overgrowths, Sierra Blanca Peaks, Texas: American Mineralogist, v. 74, p. 865869. 1993, The mobility of zirconium and other immobile elements during hydrothermal alteration: Chemical Geology, v. 110, p. 2947. Salvi, S., and Williams-Jones, A.E., 1990, The role of hydrothermal processes in the granite-hosted Zr, Y, REE deposit at Strange Lake, QubecLabrador: Evidence from fluid inclusions: Geochimica et Cosmochimica Acta, v. 54, p. 24032418. 1995, Zirconosilicate phase relations in the Strange Lake (Lac Brisson) pluton, Qubec-Labrador, Canada: American Mineralogist, v. 80, p. 10311040. 1996, The role of hydrothermal processes in concentrating high-field strength elements in the Strange Lake peralkaline complex, northeastern Canada: Geochimica et Cosmochimica Acta, v. 60, p. 19171932.

103

104

SHEARD ET AL. Sinha, A.K., Wayne, D.M., and Hewitt, D.A., 1992, The hydrothermal stability of zircon preliminary experimental and isotopic studies: Geochimica et Cosmochimica Acta, v. 56, p. 35513560. Smith, D.G.W., de St. Jorre, L., Reed, S.J.B., and Long, J.V.P., 1991, Zonally metamictized and other zircons from Thor Lake, Northwest Territories: Canadian Mineralogist, v. 29, p. 301309. Srensen, H., 1997, The agpaitic rocksan overview: Mineralogical Magazine, v. 61, p. 485498. Srensen, H., Bohse, H., and Bailey, J.C., 2006, The origin and mode of emplacement of lujavrites in the Ilmaussaq alkaline complex, South Greenland: Lithos, v. 91, p. 286300. Trueman, D.L., Pederson, J.C., de St. Jorre, L., and Smith, D.G.W., 1988, The Thor Lake rare-metal deposits, Northwest Territories: Canadian Institute of Mining and Metallurgy Special Volume 39, p. 280290. Ussing, N.V., 1912, Geology of the country around Julianehaab, Greenland: Meddr Grnland, v. 38, p. 376. Wallace, G.M., Whalen, J.B., and Martin, R.F., 1990, Agpaitic and miaskitic nepheline syenites of the McGerrigle Plutonic Complex, Gasp, Qubec: An unusual petrological association: Canadian Mineralogist, v. 28, p. 251266. Watson, B.E., 1979, Zircon saturation in felsic liquids: Experimental results and applications to trace element geochemistry: Contributions to Mineralogy and Petrology, v. 70, p. 407419.

2005, Alkaline granite-syenite deposits: Geological Association of Canada Short Course Notes, v. 17, p. 315341. Salvi, S., Fontan, F., Monchoux, P., Williams-Jones, A.E., and Moine, B., 2000, Hydrothermal mobilization of high field strength elements in alkaline igneous systems: Evidence from the Tamazeght Complex (Morocco): ECONOMIC GEOLOGY, v. 95, p. 559576. Schaltegger, U., 2007, Hydrothermal zircon: Elements, v. 3, p. 51 and 79. Schaltegger, U., Pettke, T., Audetat, A., Reusser, E., and Heinrich. C.A., 2005, Magmatic-to-hydrothermal crystallization in the W-Sn mineralized Mole Granite (NSW, Australia) Pt. I: Crystallization of zircon and REEphosphates over three million yearsa geochemical and U-Pb geochronological study: Chemical Geology, v. 220, p. 215235. Schilling, J., Michael, A.W., Marks, M., Wenzel, T., and Markl, G., 2009, Reconstruction of magmatic to subsolidus processes in an agpaitic system using eudialyte textures and composition: A case study from Tamazeght, Morocco: Canadian Mineralogist, v. 47, p. 351 365. Schmitt, A.K., Trumbull, R.B., Dulski, P., and Emmermann, R., 2002, Zr-NbREE Mineralization in peralkaline granites from the Amis Complex, Brandberg (Namibia): Evidence for magmatic pre-enrichment from melt inclusions: ECONOMIC GEOLOGY, v. 97, p. 399413. Schoenenberger, J., and Markl, G., 2008, The magmatic and fluid evolution of Motzfeldt Intrusion in South Greenland: Insights into the formation of agpaitic and miaskitic rocks: Journal of Petrology, v. 49, p. 15491577. Sinclair, W.D., Jambor, J.L., and Birkett, T.C., 1992, Rare earths and the potential for rare earth deposits in Canada: Exploration and Mining Geology, v. 1, p. 265281. Sinclair, W.D., Hunt, P.A., and Birkett, T.C., 1994, U-Pb zircon and monazite ages of the Grace Lake Granite, Blatchford Lake Intrusive Suite, Slave Province, Northwest Territories: Geological Survey of Canada, Current Research 1994-F, Report 8, p. 1520.

0361-0128/98/000/000-00 $6.00

104