Ore Deposits

Definition of stable isotope:

Characteristics of useful isotopes:

Abundance of light stable isotopes

Element
Hydrogen
Boron
Carbon
Nitrogen
Oxygen
Silicon
Sulfur

Isotope
1H
2H
10B
11B
12C
13C
14N
15N
16O
17O
18O
28Si
29Si
30Si
32S
33S
34S
36S

Abundance
99.9844%
0.0156%
18.98%
81.02%
98.89%
1.11%
99.64%
0.36%
99.763%
0.0375%
0.1995%
92.27%
4.68%
3.05%
95.02%
0.75%
4.21%
0.02%

Variation
D/H = 700
11B/10B
13C/12C

= 60
= 100

15N/14N
18O/16O

= 50
= 100

30Si/28Si

34S/32S

=6

= 100

Causes of isotope variations in nature:

Fractionation factor: relative difference in isotopic ratio between two substances

A B =

Stable isotopes

RA

RB =

H 1 Ha

H 1 Hb

Ore Deposits
Kinetic effects are associated with unidirectional processes:

K. E .= 1 2 mv 2

1
1
m1v12 = m2 v 22
2
2

v1
=
v2

m2
=
m1

20
= 1060
.
18

Isotopic contour map of North America

Stable isotopes

Ore Deposits
Equilibrium effects are associate with exchange reactions:

12

CO+ 13CH4 13CO+ 12CH4

(13CO)

RCO2
(13CO)(12CH4 )
(12CO)
Keq = 12
=
=
RCH4
( CO)(13CH4 ) (13CH4 )
12
( CH4 )
is related to the equilibrium constant by:
= K1/n
where n is the number of substituted atoms

Measurement of stable isotopes:

It is easier and more precise to measure relative differences in isotopic
ratios rather than absolute differences between two substances
Normally this is reported as a value in permil (parts/thousand)
The measured value then can be related to :

A =

RA Rstd
103
Rstd

A = A 1 103
Rstd

A B =

RA

RB

A = ( 1) 103

A = 1000 A Std 1000

A + 1000
= A Std
1000

Stable isotopes

Isotopic composition of primary standards

Vienna Standard Mean Ocean Water (VSMOW)
Hagemann et al., 1970

D/H=155.76x10-6

Vienna Standard Mean Ocean Water (VSMOW)

Baertschi, 1976

18O/16O=12005.2x10-6

Pee Dee Belemnite (PDB) (original supply exhausted)

calculated using 18OVSMOW = 30.91

18O/16O=2067.2x10-6

Pee Dee Belemnite (PDB) (original supply exhausted)

Craig, 1957

13C/12C=1123.75x10-5

Air, NBS-14
Junk and Svec, 1958

15N/14N=367.6x10-5

Canon Diablo Troilite

Thode et al., 1961

34S/32S=449.94x10-4

Ore Deposits
Factors affecting the sign and magnitude of :
Temperature

Chemical composition:
Fractionation between metal carbonates and water
Metal

18O(25C)

18O(240C)

radius

mass

Mg

31.2

0.72

24.3

Ca(ar)

28.7

1.18

40.1

Ca(cc)

28.0

7.2

1.00

40.1

6.8

0.83

54.9

Mn
Sr

26.8

6.2

1.16

87.6

Cd

26.1

6.0

0.95

112.4

Ba

24.5

4.7

1.36

137.4

4.5

1.18

207.2

Pb

Crystal structure:

Oxidation state:

Pressure:

Stable isotopes

Ore Deposits

Fractionation between phases

H in gases:
H2<H2S,CH4<NH3,H2O
C in gases:
CO<CH4<graphite<CO2<calcite
H, O in minerals:
oxides < water < micas < simple silicates < cc
< feldspars < quartz
S-bearing minerals:
sulfides < sulfates

Stable isotope thermometry

1-2

4
3

400

abmt
mt

600

qtz
-mt

1000

an-

2
1

c
qtz-c

Stable isotopes

Ore Deposits
Stable isotope thermometry

Sulfide-sulfide pairs
Sulfide-sulfate pairs

Stable isotopes

Ore Deposits
Stable isotopes and water types:

Primary ore fluids might include seawater, meteoric water, magmatic

water, metamorphic water, and brines
Seawater:
Stable isotopic standard for H and O, but actually varies worldwide (-7 < D <
+5; -1.0 < 18O < 0.5) and through time
13C close to 0 but has varied through time (-1<marine carbonates<3)
May be significantly enriched in closed anoxic basins because of removal of organic C
34S variable through time, presently +20.9 (reflecting contributions of basaltic S,
terrestrial sulfate, and evaporite sulfate)
Evaporites/Brines
Essentially modified seawaters having seawater compositions but elevated D (to
+30 ) and 18O (to +10) values

Stable isotopes

Ore Deposits

Meteoric water:
From evaporation of seawater along MWL D = 818O + 10
13C signature buffered by atmospheric C (-7.0) and organic C (-25)
34S signature dependent on wallrock S (sulfide oxidation, sulfate dissolution,
biogenic S)
Magmatic water:
Comprises exsolved and equilibrated fluids from magmas, containing H2O; CO2;
SO2, H2S, HCl, HF, etc.
18O signature dominated by equilibration of water with magmatic rock oxygen;
generally 5.5 < 18Owater < 10
D signature dominated by water from the magma
positive correlation between D and degree of degassing of magmas
suggests kinetic isotope effects
generally ranges -30 < D < -60 for water from felsic magmas
(dehydrated oceanic crust); slightly lower -30 < D < -60 for more
mafic magmas (MORB = -8010)
13C probably mantle buffered (-3 < CO2 < -5) but may shift due to
crustal contamination
34S signature is a function of deep magmatic signature (i.e. origin of the
magma) and redox state; also potential crustal contamination
15N signature poorly known
Metamorphic water:
Comprises fluids associated or equilibrated with metamorphic rocks
Fluid composition is highly variable, dependent on type of rock undergoing
metamorphism, and P & T parameters of that metamorphism
18O signature dominated by equilibration of water with rock oxygen; generally
5.5 < 18Owater < 25
D signature ranges 0 < D < -70
13CCO2 is strongly affected by redox state (-2 < CO2 < +6 if CO2 >> CH4;
~ 13 if CO2 << CH4)
34S signature is poorly characterized probably because it is highly variable and
a function of the S in the metamorphic pile and its redox state

Stable isotopes

Ore Deposits
Modification of meteoric waters by evaporation

Modification of meteoric waters by water-rock interaction

Stable isotopes

Ore Deposits

Stable isotopes

10

Ore Deposits

veins
meteoric
water
circulation

prop
phy

veins

pot

Stable isotopes

11

Ore Deposits

Hypogene vs. supergene processes

Stable isotopes

12

Ore Deposits
Sulfur in igneous systems

Disproportionation reaction:

2 SO2 + 2 H2 O H2 SO4 + H2 S + O2

Effects of degassing:

Stable isotopes

13

Ore Deposits
Sulfur in magmatic-hydrothermal fluids
(mixing calculations)

S isotopes in fo2-pH space

S isotopes in the weathering environment

Stable isotopes

14