URANIUM

HISTORY

Berlin-Mitte, Spandauer Strasse 25

Klaproth discovers the new element

uranium in 1789 from silver ore
near Johanngeorgenstadt, Erzgebirge

Joachimsthal/Jachymov (Czech Republic)

Marie Curie
Nobel-Preis fr Physik 1903
Nobel-Preis fr Chemie 1911

Lise Meitner
Otto Hahn
Nobel-Preis fr Chemie 1955

Experiment on nuclear fission of uranium, December 1938

235U

Fission

Manhattan Project
First nuclear reactor:
Chicago Pile-1,
2 December 1942:
First controlled
self-sustained
chain reaction
250 t graphite
36 t UO2
6 t U metal

Little Boy: Gun-style uranium bomb, exploded over Hiroshima, 6 Aug 1945

Hiroshima Atomic Bomb Dome

Hiroshima bomb over Clausthal-Zellerfeld

Large H bomb over Clausthal-Zellerfeld

= 8,750 billion USD (2014)

1963:
Partial Test-Ban Treaty
(USA-UK-USSR)
(Atmosphere-Oceans-Space)
1996:
Comprehensive
Nuclear-Test-Ban Treaty
(UN)

Kristensen and Norris (2013) Bull Atomic Scientists 69 (5): 75-81

Aue: Wismut Museum

Power Reactor and Nuclear Fuel Development Corporation (PNC)

Ningyo Toge, Japan

Years of demand coverage for oil resources

Prediction in 1974:
'The end of the oil age is in sight,' says U.S. petroleum geologist
M. King Hubbert.... If present trends continue, Dr. Hubbert estimates,
production will peak in 1995 -- the deadline for alternative forms of energy
that must replace petroleum in the sharp drop-off that follows."

Chernobyl, 26 Apr 1986 (melt-down with

no confinement, XY deaths)
Three Mile Island, 28 Mar 1979
(partial melt-down, no deaths)

Chernobyl

Kiev

Chernobyl today

Reactor
building

The Sarcophagus

Chernobyl, Ukraine:
Reactor (graphite) burning

Lava of reactor fuel in steam

safety valve below the reactor

Chernobyl

The New Safe Confinement

(NSC) to be constructed until
2013 at 1-2 billion EUR
Span: 270 m; Height: 100 m;
Length: 150 m)

Exclusion zone:
30 km radius around
Pripyat, plus some
hot spots
More than 100,000
people evacuated.

The Chernobyl explosion put 400 times more radioactive material into the Earth's atmosphere than the
atomic bomb dropped on Hiroshima.
Atomic weapons tests conducted in the 1950s and
1960s all together are estimated to have put some
100 to 1,000 times more radioactive material into the
atmosphere than the Chernobyl accident.

Jaworowski (1999) Physics Today 52 (9): 24-29

Chernobyl consequences
47 workers killed (including those who died within three months after the
accident), plus possibly 4000 extra-cancer deaths among the 300,000 most
exposed people (UNSCEAR/United Nations Scientific Committee of the Effects
of Atomic Radiation 1996). This number is much lower than recent estimates
by UNSCEAR 2006).
Contaminated area: Exclusion zone with 30 km radius around Chernobyl
(areas outside this radius are now considered safe for settlement and
economic activity).
Five million people in the border area of Ukraine, Belarus and Russia received
in between 2 mSv (towns) and 300 mSv (villages) in the 10 years from 1986-1995.
The global average lifetime dose (70 years) is in between 70 and 700 mSv.
The global average is 170 mSv.
Fewer than 10 percent of the 116,000 people evacuated from the "exclusion
zone received doses greater than 50 mSv; fewer than 5 percent received
more than 100 mSv.
Economic long-term cost is estimated at 200 billion USD.

The Chernobyl Forum 2003-2005: Chernobyls Legacy: Health, EnvironMental and Socio-Economic Impacts. IAEA 2006, page 12:

The general public has been exposed during the past twenty years after the
accident both from external sources (137Cs on soil, etc.) and via intake of
radionuclides (mainly, 137Cs) with foods, water and air. The average effective
doses for the general population of 'contaminated' areas accumulated in
1986-2005 were estimated to be between 10 and 30 mSv in various
administrative regions of Belarus, Russia and Ukraine. In the areas
of strict radiological control, the average dose was around 50 mSv and more.
Some residents received up to several hundred mSv.
It should be noted that the average doses received by residents of the
territories 'contaminated' by Chernobyl fallout are generally lower than those
received by people who live in some areas of high natural background
radiation in India, Iran, Brazil and China (100-200 mSv in 20 years).

Public exposure to radiation from global sources

(average shown by a bar, and typical range shown by a
line) (Source: UNSCEAR [30] and WHO [29].)

IAEA (2013)

Key Growth: Brazil, Egypt, Indonesia, Iran, Mexico, Nigeria, Saudi Arabia, South Africa, Thailand and Turkey

ExxonMobil (2015)

CO2 and temperature during the Phanerozoic

Royer et al. (2004) GSA Today 14/3: 6

URANIUM
ECONOMY

Uranium world mine production

in 2013 (59,370 t U)

Uranium mine
production 2002-2012

Uranium resources in 2011 (IAEA): ~7 Mt U

Fukushima: 11 March 2011

2014

Entwicklung der Preise fr Energietrger (constant USD)

(normiert auf boe=barrel oil equivalent)

Red Book (2006)

Three Mile Island, 28 Mar 1979

(partial melt-down, no deaths)

Uranium exploration expenditure and drilling in Canada

Uranium exploration expenditure and drilling in USA

2012

Gap in between uranium production and demand since

about 1990 filled by recycled uranium and conversion of military
stockpiles

URANIUM
GEOCHEMISTRY

Th

232

232.03806
t=14.05 billion yrs
100%

Igneous geochemistry of uranium and thorium

Uranium and other large highly charged cations
(Th4+, Zr4+, REE3+) dissolve in silicate melts according to
the degree of melt depolymerization, which depends on
the temperature and excess of alkalies and Ca relative
to Al. U solubility increases from ppb to percent levels
with increasing [(Na+K)/Al] from 0.7 (peraluminous) to
1.6 (peralkaline).
Therefore, peraluminous granites have early monazite
[(REE,Th)PO4] and zircon [ZrSiO4] fractionation which leads
to strong Zr, Th, REE depletion. On further fractionation,
U continues to be enriched until uraninite saturation.
Th-poor UO2 crystallizes which represents the most easily
leachable uranium source for aqueous fluids.

Aqueous geochemistry of uranium versus thorium

(1) There are two main uranium species: U6+ and U4+.
The hydrothermal solubility of uranium is redoxdependent: U6+ is easily soluble in water,
U4+ is insoluble and fixed in uraninite (UO2+x),
where it forms a wide variety of hydrothermal
ore deposits.
U6+ (aqueous) + 2 e- = U4+ (solid)
UO2(CO3)22- + 2 H+ = UO2 + O2 + 2 CO2 + H2O
(2) There is one main thorium species: Th4+.
Thorium is essentially insoluble in water, and forms no
hydrothermal ore deposits, but can form heavy mineral
placer deposits from weathering of granitic rocks.

Rich et al (1977) Hydrothermal uranium deposits. Elsevier.

Eh-pH plot for the

U-CO2-H2O system
at 25C for pCO2 100 b
UO2 solution boundaries
are drawn at 10-6 M
(0.24 ppm U)

Nash et al (1981)
EG Anniv Vol: 68

Aue (Erzgebirge): Shear-zone controlled hematite alteration

Oberschlema-Aue, Erzgebirge: BiCoNi + U, As: black, Ag: grey

Aue: Longitudinal section: Ore shoots in black schist

Total production: 73,000 t U; Grade: 0.4 % U

Hematite Pitchblende Pyrite

Bertholne, Massif Central, France

Rozna, Czech Republic: Bituminous uraninite ore

URANIUM
ORE DEPOSIT STYLES

Biblis 1974

India 2010

UK 2009

Krmmel
1984

Tricastin 1980

,00
10

Cigar Lake

Sandstone/Roll front

t
00
0,0
10

0t

10

Volcanic-hosted deposits

t
00
10

Calcrete deposits

Collins Bay

Black shale deposits

McClean Lake

Leucogranite deposits
Key Lake

Nabarlek

IOCG
Paleoplacers

Midwest

0t
10

Shinkolobwe

Menzenschwand

Pribram

Grade (% U)

Unconformity-related
Vein deposits

McArthur River

Jabiluka 1
Rozna

Aue/Niederschlema
Ranger
Streltsov

Yeelirrie
Ronneburg
Quirke Lake
Zobes

Fanay

0.1

Jabiluka 2

Inkai
Langer Heinrich

West Rand
Rssing

Mynkuduk
Olympic
Dam

Welkom
0.01
0.01

0.1

10

Tonnage (Mt)

100

1000

10000

Saskatchewan, Canada

Southern Saskatchewan, Canada: Les Prairies

Northern Saskatchewan, Canada

Northern Saskatchewan, Canada

Athabasca Basin, northern Saskatchewan, Canada

Total resource: ~600,000 t U, average grade: ~2% U

Key Lake Mine: Grtner pit

Key Lake Mine: Deilmann pit

Deilmann + Grtner: 40,000 t U (Grade: ~1 % U)

Key Lake Mine: Deilmann pit

Deilmann pit: Basal unit of 1.7 Ga Athabasca Sandstone

Deilmann pit: Basal unit of 1.7 Ga Athabasca Sandstone

Deilmann pit: Archean basement with sheared graphite-rich rocks

Deilmann pit: Archean basement with sheared graphite-rich rocks

Key Lake Mine: Deilmann pit

>2.6 Ga

1.7 Ga

1.3-1.6 Ga

Geology of the Key Lake uranium deposits

Dahlkamp (1978) EG 73: 1430-1449

Cross section of the

Deilmann orebody, Key Lake

Orebodies with up to 30 % U
and 15 % Ni

Dahlkamp (1978) EG 73: 1430-1449

Cross section of the

Grtner orebody, Key Lake

Dahlkamp (1978) EG 73: 1430-1449

McArthur River mine, metal tonnage: 80,000 t U (measured)

at 15 % U + 63,000 t U (inferred) at 22%U

McArthur River high-grade drill core, density around 7 g/cm3

530 m level (fresh air)

McArthur River:
Raiseboring after
wall freezing

640 m level (remote control)

Raisebore drilling
at
McArthur River

High-grade uranium ore slurry is trucked 80 km from the McArthur Mine

to the Key Lake mill

McArthur River
Geology

P2 thrust fault

Cigar Lake underground uranium mine

Metal tonnage (measured): 87,000 t, Grade: 21% U

Cigar Lake

Cigar Lake:
Bulk ore freezing and water jet
mining

CIGAR LAKE PROJECT

Cigar Lake mine has made use of pre-cast concrete tunnel liners to help secure
development in areas of poor ground.

Rabbit Lake: Metal tonnage 24,000 t U, 0.3 % U

Geological
situation at
Collins Bay and
Rabbit Lake

Pine Creek Orogen, Northern Territory, Australia

Ranger: Historic production: 110,000 t U3O8
Remaining resource 128 Mt @0.09 % U3O8

Model for Rum Jungle Creek South deposit, Northern Territory, Australia
The mineralization is controlled by graphitic schist near the unconformity
on top of the Coomalie dolomite.

Geology of
the Yeelirrie
calcrete deposit,
western Australia
35 Mt @ 0.15 % U3O8
52,500 t U
U is in carnotite,
at the surface, in a
calcrete cemented
paleochannel

Model for rollfront uranium deposits in sandstone

Metamorphic basement

Red zone

Uranium front

White-green zone

Roll front
uranium
deposits

Mercadier et al. (2010) Miner Deposita

Roll front uranium deposits in Colorado

Qidwai and Jensen (1979 MD

Tyuyamunite (Ca-U-V hydrate) from evapotranspiration.

Wyoming, USA

Lodve, France: Rotliegendes

Cameco's Highland in-situ leach (ISL) uranium mine

in Wyoming, USA

Beverley ISL uranium mine

in South Australia (Heathgate Resources)

Beverley ISL uranium mine in Australia (Heathgate Resources)

In Situ Leaching (ISL)

In Situ Leaching (ISL)

Balkash

Chu-Sarysu and Syrdarya basins in central Kazakhstan:

Resource in Late Cretaceous to Paleogene sandstone: 1.1 Gt U

Paleozoic basement
Karatau Mountains

Lake Balkash

,00
10

Cigar Lake

Sandstone/Roll front

t
00
0,0
10

0t

10

Volcanic-hosted deposits

t
00
10

Calcrete deposits

Collins Bay

Black shale deposits

McClean Lake

Leucogranite deposits
Key Lake

Nabarlek

IOCG
Paleoplacers

Midwest

0t
10

Shinkolobwe

Menzenschwand

Pribram

Grade (% U)

Unconformity-related
Vein deposits

McArthur River

Jabiluka 1
Rozna

Aue/Niederschlema
Ranger
Streltsov

Yeelirrie
Ronneburg
Quirke Lake
Zobes

Fanay

0.1

Jabiluka 2

Inkai
Langer Heinrich

West Rand
Rssing

Mynkuduk
Olympic
Dam

Welkom
0.01
0.01

0.1

10

Tonnage (Mt)

100

1000

10000

Olympic Dam mine

Roxby Downs

Olympic Dam resources (2013):

Measured resource 1.47 Gt @ 1.02 % Cu, 0.030 % U3O8, 0.35 g/t Au, 2.0 g/t Ag
Indicated resource 4.84 Gt @ 0.84 % Cu, 0.027 % U3O8, 0.34 g/t Au, 1.0 g/t Ag

BHP Billiton Annual Report 2013

Hitzman and Valenta (2005) EG 100: 1661

Geological map of Olympic Dam mine

Lehmann (2008) AMS

Rssing mine, Namibia

3000 m

Rssing mine, Namibia in alaskite: 100,000 t U (0.037 % U)

4,000 t U/a; 69 % Rio Tinto, 16 % Govnt of Iran

Rssing:
Alaskite (Leucogranite)

Calcrete uranium deposits

Langer Heinrich, Namibia

Paleochannel rooted in the Bloedkoppie Granite (up to 100 ppm U).
U mineralization is in carnotite. 72.3 Mt @ 0.06-0.07 % U3O8 44,000 t U3O8

Quartz-pebble meta-conglomerate, Ventersdorp, 2.8 Ga, Witwatersrand, S-Africa

Elsburg mine, pyrite pebbles, uraninite-thucholite, gold (polished section)

Elsburg mine, pyrite pebbles, uraninite-thucholite, gold (polished section)

Elsburg mine, pyrite, uraninite-thucholite with PbS, gold (oil immersion)

Kump (2008)
Nature 451: 278

Lehmann (2008) AMS

URANIUM
OKLO

Biblis 1974

India 2010

UK 2009

Krmmel
1984

Tricastin 1980

Natural self-sustained fission chain reactors

Predicted by Kuroda in 1956
Discovered in Gabon in 1972 during uranium mining
Conditions:
(1) High-grade uranium enrichment (up to 80 % U) exceeding
the critical mass of 235U (i.e. a 2 m thick layer of mineralized
sandstone with >10 % U and 15 % pore water as moderator)
(2) High 235U/238U ratio (today 235U: 0.072 %, at 2 Ga: 3.67 %)
(3) Low content of isotopes with high neutron-capture cross
section (i.e. low B, V, Ti, Mn, Fe, REEs
(4) High content of light isotopes to moderate the highenergy neutrons (2 x 106 eV) released from fission
reactions (i.e. water, liquid bitumen)

Uranium Isotopic Abundances

Solar system uranium today
238U
99.2745 %
235U
0.7202 0.0006 %
OKLO 235U
First measurement : 0.7171 % (a diff of 0.42 %)
Typical value in Oklo fossil reactors: 0.65 %
Lowest measurement : 0.29 %

Geological map of the

Franceville basin, Gabon
FC-FE Chert, dolomite,
volcanic rocks
FB Black shale
FA (100-1000 m)
Sandstone,
conglomerate

Franceville Series
(1000-4000 m) 2.0 Ga

Unconformity-related sandstone hosted deposits in sandstoneblack shale sequence on top of 3.0-2.6 Ga granite basement

U ore deposits are all

hosted in FA
(average 0.1-1.0 % U, ore
shoots up to 80 % U)
and formed
during early burial and
diagenesis from mixing
of oxidized uraniferous
basin fluids and oil.
Criticality in 15 high-grade
zones (14 at Oklo,
1 at Bangomb was reached
~1950 Ma ago
Evins et al. 2005, GCA 69: 1590

Stratigraphic column
(not to scale):
Note unconformityrelated situation,
uraniferous conglomerates
(leached monazite + zircon)
and redox trap (black shale
in the hanging-wall)

Jensen and Ewing

(2001) GSA Bull 113: 36

Mounana

Ore processing plant

Oklo Today

Mining ceased in 1979

Pourcelot and Gauthier-Lafaye (1999) Chem Geol 157: 156

Pourcelot and Gauthier-Lafaye (1999) Chem Geol 157: 157

Reactor zone:
a few m wide,
silica dissolution
leads to high-U
argile de pile
(illite-rich rock)

Jensen and Ewing

(2001) GSA Bull 113: 38

Temperature, C

Solubility of
quartz
in water

Jensen and Ewing (2001) GSA Bull 113: 39

10
13

14

12

Zones 7, 8 & 9

Zone 10

Zone 14
Doleritic
Dyke

Zone 13

Zone 2

Entrance to Zone 15

FB Pelites
FA Sandstones

Zone 15

Reflected light micrographs

of reactor zone ore (RZ16)
U = uraninite
G = galena
Ph = phyllosilicates (illite,
chlorite, kaolinite)
OM = organic matter
Cc = calcite
The Pb content in the reactor
uraninite (~5 wt% Pb) corresponds to a chemical age of
~550 Ma, i.e. there is Pb loss
since ore formation at ~2 Ga

Pb isotopic composition of uraninite

Evins et al. (2005) GCA 69: 1592

BSE images of reactor zone ore (RZOKE): Coffinite (USiO4) alteration of uraninite by
silica from dissolved sandstone. Abundant bitumen (formerly liquid petroleum).
Jensen and Ewing (2001:46).

Reactor Requirements
Uranium
Min U: 235U; 10%: 1%
Today 235U < 0.72%
Oklo (1.9 Ga) ~4%

U Fuel Quality
Free of neutron
poisons (Cd, REE)

FISSION REACTOR

Moderator
Thermalised neutrons
H2O or C

Reactor Size
Able to utilise neutrons
Fuel assemblage vol of
cubic metres

Oklo: a Breeder reactor

Atomic
Number
(Z)

Mass
Number
(Z+N)

239

~50 % of the total energy

released at Oklo (~15 GWa)
is from breeding of 239Pu
and decay to 235U

Pu

2.4x104a

239

Np

2.355 d
235

236

7.04x108a

Thermal Fission

237

Un

239U

4.5x109a

23.5 m

238

fast
fission

Retention of Fission Products at OKLO

1
H
3
Li

Mobilized

11 12
Na Mg
19
K
37
Rb
55
Cs

20
Ca
38
Sr
56
Ba

Partially retained

Retained

4
Be

21
Sc
39
Y
5771

22
Ti
40
Zr
72
Hf

23
V
41
Nb
73
Ta

24
Cr
42
Mo
74
W

5
B

Locally redistributed
25
Mn
43
Tc
75
Re

26
Fe
44
Ru
76
Os

27
Co
45
Rh
77
Ir

28
Ni
46
Pd
78
Pt

29
Cu
47
Ag
79
Au

30
Zn
48
Cd
80
Hg

6
C

7
N

8
O

9
F

2
He
10
Ne

13 14 15 16 17 18
Al Si P S Cl Ar
31
Ga
49
Sb
81
Tl

32
Ge
50
Sn
82
Pb

33
As
51
Sb
83
Bi

34
Se
52
Te
84
Po

35
Br
53
I
85
At

36
Kr
54
Xe
86
Rn

87 88
Fr Ra
57 58 59 60 61 62 63 64 65 66 67 68 69 70 71
La Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
89 90 91 92 93 94 95 96 97 98 99 100 101 102 103
Ac Th Pa U Np Pu Am Cu Bk Cf Es Fm Md No Lw

Ra
in
Oc

Bo
g

wa

2O

2 H2O = 2H2 + O2 (K = 10-83.1)

[H2]2 . [O2] = 10-83.1

ter

wa
te r
ea
nw

Gr

ate
r

ou
nd
w

ate
r

Garrels RM, Christ CL (1965)

Solutions. minerals, and equilibria.
Freeman, San Francisco.

Environment of ore formation at Oklo (reconstructed from mineralogy:

hematite + pyrite, carbonates, ie. dolomite, calcite, siderite)

Total dissolved Fe: 10-6 m, S: 10-3 m

Total dissolved U: 10-6 m, C: 10-2m

Brookins (1978) Chem Geol 23: 309-342

63

Eh-pH plots
Total dissolved metal species
at 10-4 and 10-6 m activity

93

94

95

Brookins (1978) Chem Geol 23: 309-342

40

41

42

43

75

Eh-pH plots
Total dissolved metal species
at 10-4 and 10-6 m activity

Brookins (1978) Chem Geol 23: 309-342

44

47

45

48

46

49

Brookins (1978) Chem Geol 23: 309-342

50

51

83

Eh-pH plots
Total dissolved metal
species at 10-4 and
10-6 m activity

Brookins (1978) Chem Geol 23: 309-342

52

84

Environment of ore formation at Oklo (reconstructed from mineralogy:

hematite + pyrite, carbonates, ie. dolomite, calcite, siderite)

Total dissolved Fe: 10-6 m, S: 10-3 m

Total dissolved U: 10-6 m, C: 10-2m

Brookins (1978) Chem Geol 23: 309-342

Summary
Isotopic studies of Oklo fossil reactors show:
Evidence of mobile fission products (FP) being
retained close to reactor zones
Most FP elements retained within reactor zones for
2000 million years
This immobility in spite of high overall rock permeability
is due to the reducing environment at low salinity, plus
absorption by iron oxides and clays: Note that salt rocks
represent the opposite environment, i.e. low permeability
but a chemically very mobile environment!