rare earth element deposits: their genesis and …...rare earth element deposits: their genesis and...
TRANSCRIPT
Rare Earth Element Deposits: Their
Genesis and Exploration
A.E. Williams-Jones
Department of Earth and Planetary Sciences
McGill University, Montreal, Canada
By
McGillQuébec Mines, 2016
The REE and the Periodic Table
Li3
H1
Na
K
Rb
Cs
Fr
Be
Mg
Ca
Sr
Ba
Ra
Sc
Y
La
Ac
Ti
Zr
Hf
Rf
V
Nb
Ta
Db
Cr
Mo
W
Sg
Mn
Tc
Re
Bh
Fe
Ru
Os
Co
Rh
Ir
Ni
Pd
Pt
Ag
Au
Cd
Hg
B
Al
Ga
In
Tl
C
Si
Ge
Sn
Pb
N
P
As
Sb
Bi
O
S
Se
Te
Po
F
Cl
Br
I
At
He
Ne
Ar
Kr
Xe
Rn
11
19
37
55
87
4
12
20
38
56
88
21 22 23 24 25 26 27 28
Cu Zn29 30 31 32
39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54
36
18
10
2
5 6 7 8 9
1716151413
33 34 35
57 72 73 74 75 76 77 78 79 80 81 82 83 84 85 86
89 104 105 106 107
Hs Mt Ds Uuu Uub Uuq108 109 110 111 112 114
Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu58 59 60 61 62 63 64 65 66 67 68 69 70 71
Light REE Heavy REE
Th Pa U Np Pu Am Bk Cf Es Fm Md No Lr90 91 92 93 94 95 97 98 99 100 101 102 103
Cm96
Why we Need the REE
The REE and Wind Power
Wind power now supplies 11.4% of
the European Union’s electricity
(141.6 GW; growing at 15.6% /yr).
Wind turbines are driven by
(Nd,Dy)2Fe14B magnets requiring
730 Kg of Nd and Dy per MW.
In the U.S., wind power supplies
4.4% of electrical energy (74.5
GW); also growing at 15.6%/yr.
In 2015, China overtook the EU with
145.1 GW of installed wind turbine
power capacity, a 27% 1 yr growth
(supplies ~4% of electrical energy)
Not all REE are Equally Critical
Medium term criticality matrix (2015 -2025)
U.S. Department of Energy (2011)
The Strategic Importance of the REE
US Production Chinese Production
Rare Earth Element Deposits
Nechalacho
Strange LakeBayan Obo
Maoniuping
Lovozero
Mt Weld
Mountain
Pass
Lofdal
Bear Lodge Kipawa
CarbonatiteNepheline syeniteGraniteHydrothermal
Ion adsorption clay
Mine
Prospect
Ilímaussaq
Relative Abundance of the REE in
the Earth’s Crust Normalized to
Primitive Mantle
0,1
1
10
100
La Ce Pr Nd Sm Eu Gd Tb Dy Ho Er Tm Yb Lu Y
LREE
HREE
HREE
The Hosts to REE Deposits
Alkaline igneous rocks and carbonatites
Carbonatites; LREE deposits, main ore
minerals, monazite-(Ce), basnäsite-(Ce)
Nepheline syenites;
HREE deposits,
A-type granite pegmatites; HREE
deposits, ore minerals, secondary
gadolinite-(y), bastnäsite-(Ce)
main primary ore mineral,
eudialyte; secondary
fergusonite-(Y)
0,85
0,90
0,95
1,00
1,05
1,10
1,15
1,20
1,25
La Ce Pr Nd Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
Ce4+
Eu2+REE3+
Ionic
radiu
s (
Angstr
om
s)
Y3+
HeavyLightY3+
The Lanthanide ContractionIncompatible elements are concentrated by low degrees of partial melting
Light and Heavy REE deposits
Carbonatite-hosted
deposits are invariably light
REE-rich.
Nepheline-syenite- and A-
type granite-hosted REE
deposits are relatively
enriched in the heavy REE.
Carbonatites are the
products of either very low
degrees of partial melting
or liquid immiscibility, both
of which favour the most
incompatible elements, the
LREE.
Chakhmouradian & Zaitsev. (2012)
Oceanic
Alkaline
Magmatism
Continental
Alkaline
Magmatism
Depleted Upper
Mantle
Undepleted
Lower Mantle
The Source of Alkaline Magmas
Environments of Alkaline
Magmatism
Back Arc Intraplate
Continental Swell
Continental Rift
Mountain Pass Strange LakeMaoniuping Lovozero
Nechalacho
Oka Carbonatite
Nepheline syenite
Carbonatite
Québec Separation and the REE
Mont Saint Hilaire
HREE
LREE
Monteregian Hills deliniate a failed rift – alkaline magmatism
produced nepheline syenites, carbonatites and REE
Carbonatite-hosted REE Deposits
Magma evolutionCalcio-carbonatite magnesio-carbonatite ferrocarbonatite
CaO
MgO FeO + MnO
Ferrocarbonatite
Calcio-carbonatite
Ferruginous
carbonatite
Magnesio-carbonatite
The REE mineralisation
is progressively enriched
from magnesio-
carbonatite to
ferrocarbonatite
The example of the
Eldor carbonatite,
Québec; bulk-rock
compositional data.
Rim
BD Zone
A-Zone
MHREO-Zone
B-Zone
Beland & Williams-Jones. (in prep)
Carbonatite-hosted REE Mineralisation
Dolomite 1 (primary); Dolomite
2 (hydrothermally altered
Dolomite 1); and Dolomite 3
(hydrothermal dolomite filling
vugs with bastnäsite-(Ce) and
parisite-(Ce)
XFe = 0.41
XFe = 0.30
XFe = 0.24
The example of the Wicheeda LREE carbonatite Deposit,
British Columbia (11.3 Million tons grading 1.95 wt% REE)
In most carbonatite-hosted deposits, the REE mineralisation is hydrothermal.
Trofanenko et al. (2016)
Carbonatite-hosted REE Mineralisation
At Wicheeda, the calcio-carbonatite has a mantle isotopic signature, the
dolomitic carbonatite an igneous signature and the vug-filling dolomite
accompaning bastnäsite-(Ce), a hydrothermal signature.
A model is proposed in
which the REE
mineralisation was the
product of late
magmatic carbo-
hydrothermal fluids at ~
300 C.
Trofanenko et al. (2016)
Strange Lake Nechalacho
Silica-saturated
magma
Silica-undersaturated
magma
Mafic magma
Mantle
Felsic magma
Crust
Rifts, Plumes and REE-Rich Magmas
Peralkaline granite (A-type) Layered nepheline syenite complex
Nepheline Syenite REE Deposits
REE mineralisation develops in alkaline layered igneous complexes as a
result of extreme fractional crystallisation, which saturates the incompatible
REE, Zr, and Nb as eudialyte in the last aliquot of liquid.
The Ilímaussaq layered complex, Greenland
Eudialyte cumulates (pink)
Na15(Ca, REE)6(Fe,Mn)3Zr3NbSi25O72(O,OH,H2O)3
Cross-Section through the
Nechalacho Layered Suite, NWT
100 m
Long Lake
Basal Zone
Upper Zone
Sodalite Foyaite
Micro-layered Agirine Nepheline Syenite
Thor Lake
Syenite Grace Lake
Granite
Nepheline syenite
Möller & Williams-Jones (2016)
The Ore Zones
Bt
Zrn
Bt, Mt0.5 cm
0.5 cm
Eud
Bt, Mt
Na15(Ca, REE)6(Fe,Mn)3Zr3NbSi25O72(O,OH,H2O)3
Eudialyte
Upper
ore zone
Basal
ore zone
Albitite
Unaltered
aegirine
nepheline
syenite
Sodalite
syenite
Basal Zone REE Mineralisation
Pseudomorphs after eudialyte
0.5 cm
Bt, Mt, Hm
Pseudomorph after eudialyte
in plane polarised light
Qtz
Mt
MnzZrn
Bt
Cal
0.1 cmFer
Yttrium
20µm
Yttrium
100µm
Yttrium
40µm
Zircon
Fergusonite
Progressive alteration of zircon
100µm
Zirconium
100µm
YttriumAlteration of eudialyte to zircon
and REE minerals
Hydrothermally Unlocking the REE
LREE mobilised upwards and
deposited as Bastnäsite-(Ce)
and monazite –(Ce)
Sheard et al. (2012)
HREE deposited locally, mainly
as fergusonite-(Y) {Y,NbO4}
Magmatic concentration of the REE in
Nechalacho Layered Complex
Sodalite
Zr Silicate
Aegirine Nepheline
Crystallisation
from roof down
and floor up
Residual, volatile
(F, Cl)- and HFSE-
rich magma
saturates with
REE-bearing
zirconosilicates
(zircon, eudialyte)
A hydrothermal
fluid is released.
The REE “stew in
this juice” and are
mobilised
Granite-hosted REE Deposits
1 km
Subsolvus
granite
Hypersolvus
granite
B-Zone M-Zone
Hypersolvus
granite
Strange Lake, Québec, the type example
Pegmatite border Pegmatite core
The Strange Lake Pegmatite Ores
REE MineralsTitanite
(CaTiSiO5)
Gittinsite
(CaZrSi2O7) Fluorite
Nb Ce Eu Dy YBeZr
F
Porous
Porous
15
20
25
30
Pegm
atite
Distribution of REE and Zr in Pegmatite
Melt Inclusions in Hypersolvus Granite
Melt Inclusions are evident by their
spherical shape. They vary from
being silicate-only, to fluorite-bearing
to fluorite-only.
Gagarinite-(Y) NaCaY(F,Cl)6
Elpidite Na2ZrSi6O15·(3H2O)
Vasyukova & Williams-Jones (2014)
Fluoride-bearing Melt Inclusions
after Heating and Quenching
Transmitted Light SEM Image
1 – Silicate glass;
~3 wt.% Zr
2 – Ca-fluoride glass;
~10 wt.% REE
3 – REE-fluoride glass;
~47 wt.% REE
Acidic Alteration and REE Mobilisation
Autometasomatism
lead to acidic
alteration by HCl-HF-
bearing fluids that
destroyed the
primary mineralogy,
creating porosity
REE were mobilised,
replacing earlier
minerals and filling
vugs
Flc - fluocerite (REEF3)
Gysi & Williams-Jones (2013)
Mobilisation of the REE
Gysi et al. (2016)
The LREE were mobilised preferentially leaving the HREE concentrated
closer to the pegmatites (LREE are more mobile than HREE, discussed later)
Model of REE Accumulation
Al, Na, K, Fe + Zr
Ca, REE, F
Fractional crystallizatio
n
Silicate melt
Fluoride melt
c o o l i n g
Subsolvus
granite Pegmatite
Hydrothermal fluid
REE Mobilised
F
Porous
Porous
Zr Y
Hydrothermal REE Deposits
Monazite (LREEPO4) and bastnäsite
(LREECO3F), together with magnetite,
hematite and fluorite replaced H8 dolomite .
Fluids 5 – 15 wt% NaCl eq., T > 400 C.
Smith & Henderson (2000)
The Bayan Obo deposit, China, is thought by some to be carbonatite-hosted
and others to be hosted by dolomitic marble that was replaced by magnetite,
hematite, REE minerals, aegirine, and fluorite.
Bayan Obo replacement ore.
The Lofdal HREE Deposit, Namibia
The Lofdal HREE deposit is associated with 750 Ma
nepheline syenites and calcio-carbonatites that were
emplaced during intracontinental rifting which
preceded amalgamation of Gondwana.
REE-Mineralised StructuresThe REE-mineralised structures give the appearance of ferrocarbonatite
dykes but are instead fault-controlled sodic fenites (albitites) that have been
altered to calcite and/or ankerite. The red colour reflects pyrite oxidation.
Lithogeochemical SurveyThe potential ore deposit with zones of strong fenitisation/carbonate
alteration (dark grey) and weaker fenitisation (light grey). The coloured
dots show the distribution of Dy in surface rock samples. Xenotime-(Y)
concentrates in the structure and bastnäsite-(Ce) distally from it.
>700
300-700
100-300
<100
Dy ppm
106 ppm Ce
2987ppm Y
1124ppm Th
REE Mineralisation in Core
Albitite clast containing xenotime-(Y) in a dolomite-cemented breccia
Ce 152ppm
Y 1470ppm
Albitite containing HREE-enriched, biotite-filled shears
Dolomite Albite
Xenotime-(Y) Mineralisation
Albitite cut by xenotime-(Y)-zircon-biotite veins and then replaced by
calcite.
Calcite
Rutile
CalciteRutile
AlbiteXenotime
and zircon
100 µm
Calcite
Calcite
Albite
Why is the Lofdal Deposit So Enriched
in the HREE? The light REE were preferentially mobilised as chloride complexes by
hydrothermal fluids leaving behind the heavy REE.
Williams-Jones et al. (2012)
Control on REE Fractionation
Ion Adsorption Clay DepositsThe REE are leached by humic acids and transported down the soil profile
into the B-zone where they are concentrated by adsorption as the REE3+ onto
the surfaces of clay minerals, mainly kaolinite. Many of the deposits are
HREE-rich with grades between 0.2 and 0.35 wt.% REE2O3
A
B
C
Solution Mining For HREE, China
1) Ammonium sulphate is dripped
into weathered granite hill-tops, 2)
ion adsorbed REE leached, 3)
solutions collected down slope and
channeled into holding tanks,
4)REE precipitated with oxalic acid.
Recovery of the REE
(NH4)2SO4 + REE3+ = REESO4+ + 2(NH4)
+
The REE are dissolved to form REE sulphate complexes according to the
ion exchange reaction (NH4+ displaces the REE3+ on the clay mineral
surface):
and precipitate in the holding tanks as a result of the addition of oxalic acid.
2REESO4+ + 3H2C2O4 = REE2(C2O4)3 + 6H+ + 2SO4
2-
The REE oxalate precipitates
settle to the bottom of the
tanks and after draining of the
fluid, they are removed, dried
and bagged for transport to a
refinery.
The resulting concentrate
contains 60 – 90 wt% REE.
“These elements [the rare earths] perplex us in our researches, baffle us in our speculations and haunt us in our very dreams. They stretch like an unknown sea before us, mocking, mystifying and murmuring strange revelations and possibilities.”
(Sir William Crookes, February 16th, 1887)
Thank You