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GS537 Geochemistry Autumn15 PDF
GS537 Geochemistry Autumn15 PDF
GS537 Geochemistry Autumn15 PDF
GS537
Geochemistry
Lectures, H. C. Sheth, Dept. of Earth Sciences, IIT Bombay
GS 537 Geochemistry
Syllabus
Chemical composition of the Earth and its constituent reservoirs; meteorite
evidence; elementary statistics for geochemistry; major, minor and trace
elements including rare earth elements; element partitioning between
minerals and melts; oxide-element conversions; radioactivity and
geochronology; chemical and isotopic fractionation; application of Rb-Sr
and Sm-Nd isotope geochemistry to rock dating, petrogenesis, and crust-
mantle evolution; mixing phenomena in elements and isotopes; related
numericals.
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Cosmochemistry
is a still broader
science, and
involves chemical
studies of stars,
planets, asteroids,
meteorites,
comets, etc.
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Formation of
different types of
meteorites due to
planetary
differentiation
followed by
explosions or
asteroid impacts
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He
9
8
O
C
7 Ne MgSi
6
Fe Note the saw-tooth or zig-zag abundance
N S Ar
5 Ca Ni pattern (Oddo-Harkins effect)
4 Na
AlP Ti
3
K
2 F Cl
Li V
1 B Sn Ba
Sc Pt Pb
0
-1 Be Th
-2 U
-3
0 10 20 30 40 50 60 70 80 90 100
Atomic Number (Z)
He
9
8
O
C
7 Ne MgSi
6
Fe
N S Ar
5 Ca Ni
4 Na
AlP Ti
3
K
2 F Cl V
1
Li Sn Ba
B Sc Pt Pb
0
-1 Be Th
-2 U
-3
0 10 20 30 40 50 60 70 80 90 100
Atomic Number (Z)
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Frank W. Clarke
(1847-1931)
Victor Goldschmidt
(1888-1947), the father
of modern geochemistry
Granite
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The main elements that make up the Earth’s crust (by mass and by volume)
Texts
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Example: Geochemical analysis of a basalt lava flow SH88 from the Deccan Traps
LOI includes the volatiles (H2O+, H2O–, and CO2), where H2O+ is structurally bound
water, and H2O– is simply the dampness in the rock powder.
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Example:
Wt.% oxide Conversion Atom Wt.% atom
Oxide Factor
SiO2 48.70 0.4675 Si 22.80
TiO2 1.29 0.5995 Ti 0.77
Al2O3 16.60 0.5292 Al 8.78
Fe2O3 2.05 0.6994 Fe3+ 1.43
FeO 8.29 0.7773 Fe2+ 6.44
MnO 0.16 0.7745 Mn 0.12
MgO 6.63 0.6031 Mg 4.00
CaO 10.70 0.7147 Ca 7.65
Na2O 2.83 0.7419 Na 2.10
K2O 0.47 0.8301 K 0.39
P2O5 0.81 0.4364 P 0.76
H2O+ 0.20 0.9445 OH– 0.09
CO2 0.09 0.2729 C 0.02
Total 99.49 55.35
(O=44.1)
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Major element variation in the most common silicate magmas and rocks
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The concentration of a
major element in a
phase is usually
buffered by the
system, so that it
varies little as the
system composition
changes. Here, at a
given T we could vary
Xbulk from 35 → 70 %
Mg/Fe without Trace elements behave as dilute
changing the solutions (Henry’s Law), and their
composition of the activity varies in direct relation to
melt or the olivine. their concentration in the system.
Thus if XNi in the system doubles
the XNi in all phases will double.
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Ni, Co, Cr Highly compatible elements. Ni and Co are concentrated in olivine, and Cr in spinel and clinopyroxene. High
Zr, Hf Very incompatible elements that do not substitute into major silicate phases (although they may replace Ti in titanite or
Nb, Ta High field-strength elements that partition into Ti-rich phases (titanite, Ti-amphibole, Fe-Ti oxides. Typically low
Ru, Rh, Pd, Platinum group elements (PGEs) are siderophile and used mostly to study melting and crystallization in mafic-ultramafic
Re, Os, systems in which PGEs are typically hosted by sulfides. The Re/Os isotopic system is controlled by initial PGE
Ir, Pd differentiation and is applied to mantle evolution and mafic melt processes.
Sr Substitutes for Ca in plagioclase (but not in pyroxene), and, to a lesser extent, for K in K-feldspar. Behaves as a
compatible element at low pressure where plagioclase forms early, but as an incompatible element at higher pressure
REE Myriad uses in modeling source characteristics and liquid evolution. Garnet accommodates the HREE more than the
LREE, and orthopyroxene and hornblende do so to a lesser degree. Titanite and plagioclase accommodates more
Y Commonly incompatible. Strongly partitioned into garnet and amphibole. Titanite and apatite also concentrate Y, so the
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Where
CL = concentration of an element in the liquid;
Lord Rayleigh
CO = concentration of the element in the original (John William
(unmelted) source rock Strutt), 1842-
1919
F = melt fraction (weight fraction of produced
melt);
DO = bulk distribution coefficient prior to the onset
of melting
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As F → 1 the
concentration of
every trace element
in the liquid = the
source rock (CL/CO
→ 1)
Rayleigh fractionation
Rayleigh fractionation represents the idealized case of a
closed system (magma chamber), without magma recharge or
magma/wallrock mixing.
Q: Imagine a closed magma chamber with a cooling magma
body. No new magma is entering the chamber. Crystals of
three different minerals are forming from the magma, and
sinking to the base of the magma chamber. The starting
magma contained 100 ppm of a perfectly incompatible
element “X”. What will be the concentrations of X in the
residual liquids?
A: As the element X is perfectly incompatible in each of the
three fractionating minerals, Kd values for X for all three are
zero. Hence, D also equals zero. The concentrations of X will
be
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• Large-ion-lithophile
elements (LILE) have large
ionic size and low ionic
charge, and ionic potential
< 2.0. They are also known
as low-field-strength
elements (LFSE).
Examples are Cs, Rb, K,
Ba, Pb2+. They are more
mobile, especially if fluids
are present.
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• As for other
elements, partition
coefficients for the
REE even in the same
mineral depend on
magma composition
(indirectly,
temperature).
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He
9
8
O
C
7 Ne MgSi
6
Fe
N S Ar
5 Ca Ni
4 Na
AlP Ti
3
K
2 F Cl V
1 Li Sn Ba
B Sc Pt Pb
0
-1 Be Th
-2 U
-3
0 10 20 30 40 50 60 70 80 90 100
Atomic Number (Z)
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• Granites of
the continental
crust also have
high
LREE/HREE
ratios.
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10.00
8.00
sample/chondrite
?
6.00
4.00
2.00
0.00
56 La58
Ce 60Nd 62Sm 64
Eu 66
Tb 68Er 70 Yb 72
Lu
L
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Problem 2: Using the data in the table below, find out the REE abundances in an andesite magma after 40%
plagioclase fractionation, using the relationship CL = COFD-1. Will a rock formed by the solidification of this residual
magma have a Eu anomaly in its REE pattern?
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Exercise: Interpret
the three patterns
given in the figure.
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REE concentrations
(normalized to
chondrite) for melts
produced at various
values of F via
melting of a
hypothetical garnet
lherzolite using the
batch melting
model.
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• Cs, Rb, K, U…
abundances are
affected by
weathering and
alteration.
• Th, Nb, Ta, Ti
etc. are little
affected by
weathering and
alteration.
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Spiderdiagram for a typical alkaline ocean island basalt (OIB) and tholeiitic
mid-ocean ridge basalt (MORB). Data from Sun and McDonough (1989).
Normal-MORB
Enriched-MORB
Ocean island basalt
Rock/Primitive Mantle
10
1
Rb Ba Th U K Nb Ta La Ce Pr Pb Sr Nd P Zr Sm Eu Ti Gd Tb Dy Y Ho Er Tm Yb Lu
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100
Rock/Primitive Mantle
10
1
Rb Ba Th U K Nb Ta La Ce Pr Pb Sr Nd P Zr Sm Eu Ti Gd Tb Dy Y Ho Er Tm Yb Lu
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Cs - 5.6 - 0.079 - - -
Rb 22 112 49 0.635 34.64 176.38 77.16
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Transitional-MORB
Upper continental crust
T-MORB:UCC mix (80:20)
Bushe (JEB185), Deccan
100
Rock/Primitive Mantle
10
1
Rb Ba Th U K Nb Ta La Ce Pr Pb Sr Nd P Zr Sm Eu Ti Gd Tb Dy Y Ho Er Tm Yb Lu
200
175
Sr (ppm)
150
125
100
0 100 200 300 400 500 600 700 800 900 1000 1100
Ba (ppm)
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4.5
4.0
Rb/Th
3.5
3.0
2.5
2.0
0.00 1.00 2.00 3.00 4.00 5.00
Ba/Sr
10
9
8
Rb/Th
7
6
5
4
3
2
0.00 1.00 2.00 3.00 4.00 5.00
Ba/Sr
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Isotope geochemistry
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Amedeo Avogadro
(1776-1856)
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( 18 O/ 16 O) sample − ( 18 O/ 16 O) SMOW
18 16
x1000
( O/ O) SMOW
Thus, clouds have negative values of delta. Most
evaporation occurs over the Equator, clouds are formed,
and drift towards the poles.
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Relationship
between
d(18O/16O) and
mean annual
temperature for
meteoric
precipitation,
after Dansgaard
(1964).
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• Take a garden with many dogs and cats. They are different
animals (= elements). During a fight cats would climb a tree,
the dogs will stay on the ground below (stable equilibrium
positions). This is akin to chemical fractionation.
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• Yet, within cats, which are more or less the same weight (=
mass), but of different colours (white and black), the
white:black ratio of cats now in the tree will be the same as
what it was when they were below. This is akin to lack of
isotopic fractionation, a most useful property of many
geological processes.
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87Sr
86Sr
t1
c1
b1
a1
()87Sr
86Sr
to
a
o
b c
87Rb
86Sr
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At time t2 all rock sample points have again shifted and define
a new line. Thus at all times the rocks are on a straight line
which becomes steeper with time (i.e., slope is proportional
to age of the rocks.) The line’s Y-intercept is however fixed
(the initial ratio).
t2
87Sr
c2
86Sr
t1
b2 c1
a2 b1
a1
()87Sr
86Sr
o a b c to
87Rb/86Sr
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Gerald Wasserburg
Donald J. DePaolo
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Estimated Nd
isotopic evolution
of the Earth’s
upper mantle,
assuming a large-
scale melting or
enrichment event
at 3.0 Ga.
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The Nd isotopic
evolution
curves are the
opposite of Sr
isotopic
evolution
curves.
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RXA XA f + RXB XB (1 – f)
RXM = ____________________
XA f + XB (1 – f)
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(143Nd/144Nd)M
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0.730
0.725
0.720
Sr/ Sr
86
0.715
87
0.710
0.705
0.700
150 200 250 300 350 400 450 500
Sr (ppm)
0.740
0.735
0.730
Sr/ Sr
0.725
86
0.720
87
0.715
0.710
0.705
0.700
0.512 0.5122 0.5124 0.5126 0.5128 0.513 0.5132
143 144
Nd/ Nd
Observation: Isotopic ratio vs. isotopic ratio (different
elements) = hyperbola usually
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0.725
0.720
Sr/ Sr
86
0.715
87
0.710
0.705
0.700
0.512 0.5121 0.5122 0.5123 0.5124 0.5125 0.5126 0.5127 0.5128 0.5129 0.513 0.5131
143
Nd/144Nd
Answer:
• For simple binary mixing, the curvature of the mixing
hyperbola depends on (Sr/Nd)A / (Sr/Nd)B.
• The more (Sr/Nd)A is different from (Sr/Nd)B, the greater is
the curvature of the hyperbola.
• When (Sr/Nd)A = (Sr/Nd)B, the mixing curve is a straight
line. Check the values in the last example.
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• If one wants to determine the age of the Earth, say with the
Sm-Nd method, one needs a reservoir in the Earth that has
not undergone any change in its Sm/Nd ratio since the
formation of the Earth.
• The continental crust, oceanic crust etc. have highly
variable Sm/Nd ratios today due to chemical fractionation of
Sm from Nd during previous and ongoing melting episodes.
• The existence of a primordial, undifferentiated reservoir is
theoretically improbable, and is not suggested by any
evidence.
• If such a reservoir does exist within the Earth, it is not
being sampled by any magmas and is therefore inaccessible
to us.
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• The Mantle
Array is believed
to be due to
mixing.
• However, with
many more
studies, two-
component
mixing cannot
explain the data,
many of which
are inclined to the
main array.
•“Mantle array” is an archaic concept
now, and many more components are
required in the oceanic mantle.
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Histograms
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• The median:
Given five variables 3,
12, 8, 11, 5, rearranging
from smallest to largest
gives 3, 5, 8, 11, 12:
value 8 is the median.
If the number of
variables is even, e.g., 3,
12, 8, 11, 5, 6,
Rearranging gives 3, 5,
6, 8, 11, 12; the median
is the average of the two
middle values, i.e., the
median is (6 + 8) / 2 = 7.
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• It is important to know
if the “average” being
reported is mean or
median. They can be
greatly different, and
can be used to mislead.
• Deviation (d) is a
measure of the difference
between an individual
value and the mean value,
i.e., d = Xi – x. It can be
measured as variance or
standard deviation.
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• The mode:
The mode is the value with the highest frequency in a
frequency histogram.
Given a dataset 3, 12, 8, 3, 11, 5, 3, 14, 25, 19, 3, 10
The mode is 3 (appears maximum – four – times).
• For a normal distribution, the mean, median and mode
are the same.
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In the figures
below,
a: Ten
measurements
that are both
accurate and
precise.
b: Ten
measurements
that are accurate
but not precise.
c: Ten
measurements
that are precise
but not accurate.
d: Ten
measurements
that are neither
precise nor
accurate.
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Calibration curves
• An analytical instrument gives a signal, never the value
directly. Rock standards are first used to make a calibration
curve (signal vs. known concentration). Unknown
concentrations of elements in samples to be analyzed are then
determined from the curve from the signals they produce.
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Regression
• Fitting a line to the
data points involves a
technique called
regression. Note that
all points have
associated errors on
both X and Y. The
line is fit such that
the sum of squares of
distances of points is
a minimum. This is
known as a best-fit
line.
Question: Why use squares of distances?
Calibration curves
• A calibration curve requires at least three standards. A blank
should plot at the origin.
• It is important to choose rock standards that are similar to the
unknown samples lithologically, and which bracket the
compositional range of the unknown samples. This means that
unknown samples should not be located outside the calibration
curve. Why so?
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(143Nd/144Nd)prock – (143Nd/144Nd)pCHUR
εNdprock = _________________________________ x 104
(143Nd/144Nd)pCHUR
(0.510487 – 0.512638)
εNdprock = ____________________ x 104 = – 41.96
0.512638
To determine the εNdtrock for 3.54 Ga, we must have the (143Nd/144Nd)t = 3.54 Ga ratio of
CHUR besides that of the rock.
(0.508075 – 0.508031)
∴ εNdtrock = ____________________ x 104 = 0.87
0.508031
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Nd model ages
• A model age is a
measure of the time a
rock sample has been
separated from its
(presumed) source
mantle (CHUR or DM,
Depleted Mantle).
• It is not a “real” or
direct age, but model-
dependent.
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