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Selected Topics

Geochemistry

Abbreviated Course Notes

Main tasks of geochemistry:

determine relative and absolute abundances of elements

and isotopes (in Earth and elsewhere)
understand distribution and migration of elements in
various parts of the Earth (crust, mantle, core,
atmosphere, oceans) and in minerals and rocks.

Part 1: Cosmochemistry

Elemental abundance in Universe determined from

1. analyzing spectra of outer portions of stars and from

nebulae
2. then averaging many stars of different kinds

Estimates constantly change.

Specifics almost certainly not known (exact %, for example)
but some general facts (or "rules") known.

Only 10 elements - H, He, C, N, O, Ne, Mg, Si, S, and Fe - all

with atomic numbers less than 27, show appreciable
abundance. Of these, H and He far outweigh the other 8.
Abundances show a rapid exponential decrease for
elements of the lower atomic numbers, followed by an
almost constant value for the heavier elements.
Elements adjacent to Helium (i. e. Li, Be) are very low in
relative abundance
Elements of even atomic number are more abundant
than those of odd atomic number on either side. This
regularity was first recognized by Oddo and Harkins (c.
1915) and is sometimes referred to as the Oddo-Harkins
rule.
Isotopes with mass numbers which are multiples of 4
(alpha particle mass number) have enhanced
abundances.
There is a pronounced abundance peak at atomic
number 26 and smaller peaks at several other heavier
atomic numbers (such as Oxygen)

We can explain relative abundances of elements by seeing

how elements form in stars.

A typical star might go through several stages - for example:

nebula, proto-star, main sequence star, red giant,
supernova/neutron star, black hole
Main sequence stage of star's life: Fusion of hydrogen into
helium
Several possible routes -
in one route, C acts as a catalyst; intermediate steps result in
the production of N and O, explaining their abundance
Some elements (such as Li, Be, Bo, Sc) used up as part of H
fusion process

Red giant stage: In core, He converted to C and O, explaining

their abundance
C + O yields Ne, Na, P, Mg, Si, S, Cl and Ar
Mg, Si, S then form Fe, Ni

Supernova stage: Implosion to form neutron star forms

some exotic heavy elements.
In fact, can correlate half lives of some short lived heavy
elements (like Cf254) with half life of luminosity of
supernova.
Explosion results in dispersion of elements into space.

Neutron star: Addition of neutrons to Fe forms heavier

elements which are less stable than Fe.
For these heavier elements, relative abundance depends on
relative stability.
Elements with even numbers of protons and neutrons are
more stable because they have greater nuclear binding
energy.

For second, third, etc. generation stars, different processes

occur because they have different starting materials as well
as being at different stages in their lives.
Composition of our Sun results from its present state of
evolution
Most striking feature is extreme abundance of H and He.
About 70 elements found in Sun so far.

Part 1a: Solar System Composition

Brief look at composition of other bodies in solar system

in order to compare with Earth:

meteorites
Moon
other planets (including their atmospheres)
asteroids

Meteorites - chunks of rock from space that land on Earth

Common minerals in meteorites:

kamacite, taenite (both Ni-Fe alloys, different crytal

structures)
pyroxene (especially bronzite)
olivine
plagioclase

Kinds of meteorites:

irons
stones
stony-irons
Iron meteorites:
Predominantly Ni-Fe alloys
Minor amounts of other minerals such as troilite (FeS)
Types classified according to % Ni:

hexahedrite
octahedrite (has Widmanstatten structure, exsolution
feature formed by slow cooling)
ataxite

Stone meteorites:
Chiefly silicates, mostly ferromagnesian
Up to 1/4 metallic Ni-Fe
Types:

Chondrites
Achondrites

Chondrites: Contain chondrules (BB-sized round bodies)

Composed chiefly of silicates such as olivine, pyroxene, and
plagioclase or glass
Important type is carbonaceous chondrite.

High content of volatiles, including water and non-

biogenic carbon (will later show how determined to be
non-biogenic)
Have same composition as Sun's atmosphere

Achondrites: no chondrules
 Same composition as terrestrial mafic and ultramafic
rocks
Most achondrites are breccias

Stony-iron meteorites: Equal amounts of silicates and Ni-Fe

alloys
Many are crystallized silicates which have been brecciated,
then invaded by metallic and sulfide melts
Classified according to kind of silicate:

pallasite (olivine)
mesosiderite (plagioclase, pyroxene)

Some questions on meteorite origins:

formed under low pressure? (void spaces in some) or

high pressure? (diamonds in some)
Why are most meteorites breccias?
Generally believed that meteorites formed from breakup
of minor planets (asteroids) which were large enough to
be differentiated into Ni-Fe cores and silicate mantles.
(explanation leads to more questions - number and size
of the bodies? what caused the breakup?)
What process produces chondrules?
Lunar regolith contains round bodies similar to
chondrules, formed by meteorite impact. Maybe surfaces
of minor planets had similar material.
Some chondrules are indistinct. Did some chondrules
form by recrystallization?
Are meteorites that we know about representative of the
whole solar system or just the part near Earth?
Moon:

basalt maria (with extra Fe and Ti)

anorthosite highlands
4 most common moon minerals:
pyroxene (augite and others)
plagioclase (Ca-rich)
olivine (Mg-rich)
ilmenite (iron titanium oxide)
No hydrated minerals.
No minerals formed by chemical weathering or life
processes.
Depleted in volatiles (probably as a result of how Moon
was formed.)

Other planets, etc.:

Mercury: silicates; relatively large iron core

Venus: basalt
Mars: basalt covered with iron oxides; more sulfur in
core
Jupiter and other giant planets in outer solar system:
mostly hydrogen
asteroids: silicates

Part 2: Composition and Early History of Earth

Most information about Earth's interior comes from

geophysical studies:

Density
 Moment of inertia (gives density distribution)
Seismic data (gives elastic constants of materials,
presence of fluids, location of discontinuities, etc.)
Heat flow data (gives temperatures, locations and
abundances of radioactive elements, mantle convection)
Magnetic data (gives possible core materials)

Outer core

liquid - fact helpful in determining internal temperature

Source of Earth's magnetic field
Composition of core:
Iron-Nickel alloy
Lesser amounts (10 % -20 %?) of S, C, Si, and/or iron
oxides

Mantle

Heterogeneous vertically (layered) and laterally due to

differences in composition and phase changes
Composition of upper mantle pretty much limited by
geophysics studies and petrological considerations to
eclogite and peridotite.
Olivine-pyroxene most common type of xenolith in
magmas which apparently have deep enough origins
to have come from mantle. Assumption is these are
leftover material after basalt has been removed
Original composition thus peridotite and basalt in
some ratio - generally assumed to be 3 parts peridotite
to 1 part basalt (called pyrolite)
 This composition doesn't account for volatiles which
erupt from volcanoes.

Crust:

Heterogeneous in composition
Varies in thickness -
5-8 km thick under oceans (under 4 km of water and 1
1/2 km of sediments)
about 35 km thick under continents
up to 60 km thick under active mountain belts
Gradual change to more mafic composition with depth
But not two layers as sometimes said

4 approaches to obtain overall composition of crust:

1. averaging of available rock analyses

2. as #1, but weighted in proportion to rocks' occurrences
3. abundance based on crustal models
4. indirect assessment - estimating mass balance of mafic
and felsic rocks to give, through weathering, etc., the
observed average composition of sediments (or selected
sediment)

Approach #2 used by Clarke and Washington, 1889

Calculations based on more than 5000 "superior" rock
analyses
Problem of how to weight different kinds of rocks to strike a
reasonable average
 Great bulk of crust is igneous rock or metamorphic rock
that was once igneous
Clarke estimate for upper 10 miles - 95 % igneous or
metamorphic, 4 % shale, 0.75 % sandstone, 0.25 %
limestone
Most common rocks by far are granite and basalt.
Use some combination of these 2 rocks.
What combination?
Continents - geologic observation and seismic
evidence suggest 1:1 ratio
Ocean floors - more basalt

Ronov-Yaroshevsky, 1969, used approach #3.

Based on many thousands of specimens from continents,
ocean floors, continental shelves and slopes

Goldschmidt used approach 4

Based on glacial clays in Norway
Gives lower values for Na, Ca (easily removed in weathering)

Material Earth formed from most easily studied by

considering the Fe-Mg-Si-O-S equilibrium system, when
O>>S and O+S<Fe+Mg+Si (you will get to this kind of
equilibrium system later)
Results in 3 essentially immiscible phases (iron present in
all):

iron-magnesium silicate
iron sulfide
free iron
Arrange these in order of density and this looks like Earth.
Other elements concentrated in these phases according to
their chemical properties (not density)

Chemical properties of elements determined primarily by

their electronic configurations; that's why elements in the
same group on the periodic table have very similar
properties.
Examples:

Uranium and thorium tend to form silicates and are

concentrated in crust.
Gold and platinum have no tendency to form oxides or
silicates but do allow readily with iron and are
presumably concentrated in core.

Goldschmidt first recognized primary geochemical

differentiation of the elements in 1923.
Coined terms siderophile, chalcophile, lithophile, atmophile

Part 3: Currently accepted theory for origin and

early history of Solar System and Earth:

Step 1: Rotating cloud of gas and dust (nebula) over

volume larger than orbit of Pluto

Questions:

Where did it come from?

Why was it rotating?
Step 2: Condensation of nebula

Questions:

Why? (nearby supernova explosion?)

When? (can get clues from radiometric dating - discussed
later)

Step 3: Material collects in central portion of nebula to

form Sun.
In remaining material, small groupings of particles form
randomly
Because of combined gravitational pull of the group, they
attract other particles.
Many bodies grow until they are several kilometers in
diameter
Larger bodies sometimes join together by collision and
sometimes become fragmented.
Bodies which continue to grow become planets and satellites;
those that fragment become interstellar dust, asteroids,
comets, etc.

Question: Did Earth form from cold fragments or hot

fragments?

Evidence favors cold accretion

Compare inert gases to other gases of approximately
same molecular weight (water, carbon dioxide,
ammonia)
Inert gases deficient in Earth
 Earth's present gravity field strong enough to hold them;
must have been lost by smaller aggregating particles
Other gases held by particles that formed Earth because
they were tied up in compounds such as hydrates,
carbonates, etc.
These compounds would have broken down at
temperatures of few hundred degrees so fragments from
which Earth formed would have to have been relatively
cool.

Question: Was early Earth homogeneous or heterogeneous

to start with?
(Reference: Grossman, 1972, Condensation in the primitive
Solar nebula, Geochim. Cosmochim. Acta, 36, 597-619)

Grossman took a gas believed to be similar to nebula

material, cooled it and observed order in which material
condensed.
Order was:
metallic iron-nickel
silicates
volatiles
Suggests that at least part of observed differentiation of
Earth and other bodies due to condensation order.

Step 4: planets heat up

Questions:

Why?
How hot were they to begin with?
 How much did they heat up?
How long did it take?
Are they still heating up?

Two sources of heat:

1. Gravitational potential energy from collapse

2. Radioactive decay (most important)

How fast and how far temperature rose is debatable

Depends on:

rate of infall
original distribution of radioactive elements

Also not known whether present temperature rising,

falling, or remaining constant
Depends on:

how much radioactive material still present

how it's distributed
amount of heat lost to space

None of which known accurately

Heating up could produce:

differentiation to form core and mantle?

crust formation
plate motions
magnetic field generation
 loss of volatiles from interior to form atmosphere and
ocean

Step 5. Differentiation to form core and mantle? and

crust formation.
"iron catastrophe"

Fe and FeS would be lowest melting material in body of

Earth's overall composition and interior pressure.
As Earth heated, various levels of interior became hot
enough to melt iron, perhaps at different times.
This liquid would aggregate and sink to center
Time required? (perhaps as little as 100 million years)

Questions:

How did crust form?

What was original extent and composition?

Overall chemistry of crust -

granitic rocks at high levels,

more mafic rocks toward base,
ultramafic rocks in mantle underneath

This is reminiscent of layering in differentiated igneous rock

bodies and of differentiation observed in labs.
Suggests similar process for formation of crust
Further evidence from Moon - anorthosite layer, flooded by
basalts derived from underlying ultramafic layer
When Earth heated, heavier Mg, Fe silicate would move to
or remain in mantle; scum of material rich in Al, Si, K, Ca,
etc. would rise to surface
Process might take place piecemeal over Earth, because of
slightly different temperature, so entire outer part of Earth
not necessarily molten at once

None of original crust preserved

Time between accretion and formation of oldest existing
rocks would have been tumultuous.
Moon's surface, as well as Mercury, Venus and Mars,
indicates intensive meteorite bombardment producing
cratered surface; almost certainly Earth's was too
Some of the chemical heterogeneity of Earth's crust and
upper mantle may be heritage from the variety of meteor
masses that were incorporated into surface material.
Might explain some odd concentrations of tin, iron, and
copper ore.
Could it have produced present (and past?) lopsided
distributions of continents and ocean basins?

Question: How did continents originate and grow?

At end of intense bombardment, crustal material

probably covered entire planet
Early crust mostly basalt (inferred from dominance of
mafic metamorphic rocks amongst oldest dated varieties)
Some granitic rocks and ocean basins (inferred from
presence of quartzite and a little marble)

Questions:
 Was early crust uniform or contain thicker parts which
might have been embryo continents?
How large were granitic continents?
How did they originate?
When did plate motions begin?

It is currently commonly thought that continents:

were end product of differentiation of mafic magma

were originally small and scattered
were moved about by slow currents in mantle beneath
coalesced and broke apart repeatedly
grew larger

Mafic lavas came to surface from deep in upper mantle,

formed by partial melting of garnet peridotite
Solidifying, lavas became oceanic crust, carried away from
spreading centers
At other places, oceanic crust and sediments which had
accumulated on it were carried back down and became hot
enough to generate felsic and andesitic magmas which
produced volcanoes and batholiths on the edges of granitic
islands, thus enlarging continents
Process much smaller in scale than at present
Slow and inefficient process but result was silica, alumina,
and alkali metals enriched in continents and olivine and
pyroxene enriched in upper mantle

Question: Is differentiation to produce continents continuing

or are continents simply rearranging themselves?
Other ways of asking same question:
 is total mass of continental material increasing?
is continental crust generation a one-way process or
cyclical?

Evidence for one side:

General decrease in age of granite bodies toward

continental margins suggests amount of continental
material increasing.

Evidence for other side:

no long-term decrease in amount of granite produced per

million years
(one way process should terminate when mantle loses
sufficient felsic components and becomes a cumulus of
olivine and pyroxene from which basalt can no longer be
generated)
no long term change in composition of granitic rocks
(granites do become more felsic in preCambrian and
Paleozoic but more mafic in Mesozoic)

Questions:
What kind of change in composition might occur in one way
process?

Should granites be more mafic, since felsics decreasing in

mantle?
Or, should granites be more felsic, since felsic
sedimentary material is recycled again and again through
subduction zones?
Step 6. Origin of atmosphere and ocean
Cold primitive Earth had virtually no atmosphere because
gases tied up in compounds or in frozen particles.
As Earth heated up (due to gravitational collapse and
radioactivity) gases would be released and accumulate at
surface
(This would presumably include water vapor which would
condense to form oceans, to be looked at later.)
Gravity would be sufficient to retain all gases except H and
He

Example of evidence for degassing: Argon comes from

decay of Potassium. Not enough K in surface rocks to supply
all Ar in atmosphere. Some Ar must have come from interior.

Questions:

Did all degassing take place at once, in some warmer

stage?
Or is degassing a gradual process which is still going on?
If all at once, when?
If continually, at what speed?

Clues:
Evidence from elemental abundance studies suggest that
isotopes of atomic number greater than about 40 are present
in about equal amounts.
So when elements in solar system formed, Ar36 = Ar38 = Ar40
But Ar40 also forms from radioactive decay of K so ratios
Ar40/Ar36 or Ar40/Ar38 constantly increasing
In Earth's interior, ratio is about 5000/1 at present (found in
diamonds which are heated to carbonization)

Look at 2 possible extremes:

all outgassing early, later gases still trapped; Ar40/Ar36

ratio in atmosphere should be small
all outgassing later or continuous; ratio should be closer
to 5000/1

Ratio in atmosphere at present is about 300/1 (that is, small);

indicates most of atmosphere formed early
Estimates that about 80 % formed in first 500 my; remaining
20 % from volcanic eruptions since then.

Average product of current degassing (from analysis of

gases from volcanoes):

water vapor
hydrogen
carbon oxides
sulfur gases
hydrogen halides
nitrogen
ammonia
possible hydrocarbons

Bears little resemblance to composition of present

atmosphere. Why?

Hydrogen escapes
 Sulfur and halogen gases dissolve in surface waters and
react with rocks
Carbon dioxide is removed by biologic activity
Oxygen is added by biologic activity, etc.

We have implied that early atmosphere may have been

different than present one.
Look at CO2 and oxygen for evidence

Question: Was there less CO2 in past?

Continued evidence of life for more than 3 billion years
establishes a fairly definite minimum for the amount of CO2
in the atmosphere for at least 3 billion years

Question: Was there more CO2 in past?

Extremely high amounts would produce highly acidic
surface waters and greatly speed chemical weathering
(will look at results now, chemical reasons why later)

silicates would be broken down to free silica

ions from weathering would accumulate in an
enormously concentrated ocean
highly acid waters would prevent carbonate deposition
(at low pH, Ca+2 and Mg+2 don't readily combine with
HCO3-2)

Question: Is there evidence of silicates broken down into

free silica?
Banded iron formation - high amounts of silica (chert) in
alternating layers with various iron minerals such as
magnetite and hematite; restricted to period 2.5 to 1.8 by in
age

Question: Evidence of high ion concentration in oceans?

Significant evaporites older than latest preCambrian not
found

Question: Evidence of high acid waters preventing

carbonate deposition?
Carbonate rocks uncommon in most of preCambrian;
become abundant near close of era (especially dolomite) and
are continuing to form in large amounts today

Question: Was there less oxygen in past?

placer deposits of "not too oxidized" minerals (Ex.-

uraninite) restricted to early preCambrian
"red beds" (hematite rich rocks) became more extensive
in late preCambrian
gypsum (a sulfate) deposits rare in preCambrian

Conclusion:
Early preCambrian atmosphere had more carbon dioxide,
less oxygen (about 0.1 % of present value)
Great increase in abundance and complexity of organisms in
late preCambrian changed carbon dioxide rich
atmosphere to oxygen rich atmosphere

Life probably began in oceans.

Water would shield from ultraviolet radiation (ozone does
now but little oxygen in primitive atmosphere)
Organisms produce oxygen; some is used to form oxides,
some released to atmosphere
PreCambrian banded-iron formations probably formed
when iron weathering from rocks in an almost oxygen free
environment was washed into plant-containing oxygenated
water, oxidized, and precipitated
Later oxygen in atmosphere provided shield, life forms
expanded dramatically and moved from water environment.
Little change in atmospheric composition since then.

Origin of oceans:
Water condensed from atmosphere
pH dependent on composition of atmosphere because of
dissolved gases included
present pH 8.1- 8.4 in surface waters, slightly lower at depth

Early ocean more acidic (because more carbon dioxide in

atmosphere, and thus more dissolved)
Ocean should have obtained dissolved material fairly rapidly
in history (due to extensive early weathering)

Question:
Any large changes since?

more Ca+2 would mean more gypsum

less Ca+2 would mean more Na+ minerals (since Ca+2 less
soluble than Na+; will look at relative solubilities later)
more Mg+ would mean more sepiolite and brucite
less Mg+ would mean less dolomite
Rock record shows no evidence of change since late
preCambrian

For a few elements (notably chlorine, bromine, sulfur, and

boron), concentrations in seawater much higher than in
surface rocks
Common products of volcanoes and probably added
directly to seawater by volcanic activity rather than by
erosion
Elements involved with biological activity (C, O, N, P) vary
horizontally and vertically because of concentration of
organisms in surface layers in warmed waters and because
of decaying organisms returning material to seawater

Part 4: Radiometric Dating

Geochronology - concerned with determining age and

history of geologic materials by studying their isotopes

Radioactivity
Discovered in 1896
Natural change from one element to another by emission of
particles from nucleus or addition of particles to nucleus

Particles include:

helium nuclei (alpha particles)

electrons (beta particles)
high energy electromagnetic waves (gamma rays)
Decay occurs at constant rate and is not affected by
temperature, pressure, chemical combination or any other
known thing

Radioactive isotopes - an element capable of spontaneously

changing into another element by the emission or addition of
particles to its nucleus
Stable isotopes - an isotope which is not radioactive

Radiogenic isotopes - an isotope produced by radioactive

decay
Non-radiogenic isotopes - an isotope not produced by
radioactive decay

Half-life - time for half of element to decay

Parent - the radioactive element which decays

Daughter - an element formed from another by radioactive
decay

T (half life) = ln 2/ = 0.6931/

The equation which represents radioactive decay is (derived

in most geophysics texts for those who are interested and
know a little calculus):

solved for t (age of rock):

Assumptions made in radiometric dating:

no loss or gain of parent or daughter

decay rate constant
half life known
can measure amounts of parent and daughter accurately
(usually use mass spectrometer)

Part 4a: RbSr dating

Rb87 -> Sr87 (could also write 87Rb, etc.)

Rb commonly substitutes for K in minerals; so method used
on K-bearing minerals or rocks which contain them

Decay equation reads:

(Subscript m stands for measured, or in other words, now; o

stands for original)

It is easier to measure ratios of atoms rather than absolute

numbers so expression usually written:

Could solve for t (age of mineral):

Now measure Sr87/Sr86 and Rb87/Sr86 ratios and for
reaction ( = 1.39 x 10-11/yr)
Then estimate (Sr87/Sr86)o (Can measure this ratio in
coexisting undisturbed minerals which contain no Rb)

Note: Sr86m = Sr86o since Sr86 is stable and non-radiogenic

Sr86, Sr84, and Sr88 are all stable and non-radiogenic.
Any could be used; Sr86 most abundant and therefore most
often used.

Easier mathematics and more accurate way of

determining (Sr87/Sr86)original:
Equation for straight line is y = ax + b, (where a is slope, b is
intercept on y axis)

Equation is in that form (actually y =

b + ax) when t is constant (for several minerals in a rock or
several rocks of the same age)

If we plot (Sr87/Sr86)m vs (Rb87/Sr86)m, the values should be

different for different rocks and minerals because they
would have different initial amounts of Rb.
The slope of the line obtained by connecting these points is
-1 and the intercept is (Sr87/Sr86)o
Thus we can obtain both the age of the suite and the
initial strontium ratio.
These plotted lines are called isochrons.

Isochrons can also be used to determine age of

metamorphism.
If whole rock hasn't lost Rb or Sr, but minerals have passed
them around during metamorphism, two ages will be
obtained - one from dating whole rock and one
(metamorphism age) from dating individual minerals in
rock.

Another Sr isotope use:

First must know Sr87/Sr86 in material that made up primitive
Earth.
Usually assume it was same as non-Rb87 bearing meteorites
or about 0.699

During differentiation of crust, behavior of Rb and Sr would

be different (different charge, different size).
Rb concentrated in crust, Sr evenly distributed between crust
and mantle.
Production of Sr87 should thus be faster in crust than in
mantle and Sr87/Sr86 ratios should be higher for crustal
material.
Difference in Sr87/Sr86 ratios, then, is a means for
distinguishing igneous rocks that have formed by partial
melting of crustal rocks from those that have their origin
in differentiation or partial melting of mantle material

Present Sr87/Sr86 ratio for mantle rock estimated from

analyses of recent basalts and gabbros from oceanic
environments (direct origin from mantle assumed and no
contamination by continental material)
Value is about 0.704
Extrapolation between 0.699 and 0.704 gives reasonable
estimate for ratio in mantle at any time in past.
Look at Sr87/Sr86 ratios for rocks when they formed to
determine origin.
(ratio above or consistent with expected mantle ratio?)
(Remember can get Sr87/Sr86 ratios from isochrons.)

Part 4b: Uranium, Thorium - Lead dating:

U238 -> Pb206

U235 -> Pb207

Th232 -> Pb208

Commonly use ratio with stable Pb204

One equation might be written:

or:

Must determine ratio (Pb206/Pb204)o and .

Can find original ratio from associated lead minerals (such
as galena) or can use mineral for study that wouldn't have
had any original lead (zircon, uraninite, sphene, apatite,
monazite, etc.)
By using U238, U235, and Th232, theoretically you get three age
determinations and they should agree (concordant ages).
If disagreement, ages are said to be discordant.
This is probably due to gain or loss of material.

Lead-lead method

If equation for U235 is divided by equation for U238, we get

another equation:

Use of this equation called lead-lead method.

Handy because U235/U238 ratio known, as are decay
constants.
Can't solve remaining equation directly for t but ages
corresponding to different isotope ratios have been plotted
and can be obtained from published graphs or tables

Use of Pb-Pb method is good check on U235, U238, and Th

methods because if lead lost, the ratio of isotopes of
remaining lead should not be changed and valid age should
still be given.

Can also directly use ratio:

These two quantities increase with time at different rates
and if plotted against each other, a curved line is formed
(called a concordia curve because all points on the curve
have concordant U238/Pb206 and U235/Pb207 ages).

If a rock sample has lost no Pb, calculated ages from U238

and U235 would be concordant and a point representing the
ratio of the above quantities would lie on the concordia
curve.

If Pb has been lost, the ages will be discordant and the point
representing the ratio will lie below the curve.

Since lead loss would presumably be different for different

areas in the sample, several different analyses from different
locations in the sample should give several different ratios
and thus several different points below the concordia curve.
It can be determined mathematically that these several
points will lie on a straight line (called a discordia).

If the discordia line is extended to intersect the concordia

curve, upper intersection gives age of rock.
Lower intersection supposedly gives time lead lost but
almost never accurate since lead almost never lost all at once
but gradually over long time.

Technically could use U238 -> He4, U235 -> He4, or Th232 ->
He4
But, helium may be lost since a gas.
Assume that any He present when rock was molten escaped
Therefore, any He present now formed from U or Th after
solidification.
He ages thus give solidification ages
(Example: how long it takes for granite batholith to solidify).

Part 4c: Other Pb uses

1. Can measure average amounts of U238 and Pb206, or U235

and Pb207 in rocks at the Earth's surface (usually use recent
marine sediments).
Assume no radiogenic lead to start with, can calculate age of
Earth's outer portion.

2. Begin with primeval lead (lead present when Earth

formed): Pb204, Pb206, Pb207, Pb208 in certain ratios for Earth
as whole (usually assume this to be same as ratios in
meteorites without U, Th).
With time, radiogenic lead increases, thus higher
Pb206/Pb204, etc., ratios with time.
Can get age of Earth (4550-4750 my).

3. (variation on 2)
After a time, ore might form (example: galena).
This ore would "sample" the lead at time of formation, which
would consist of the primeval lead plus all radioactive lead
formed before the time of ore formation (total lead called the
common lead).
Thus, age of ore can be determined by comparing its lead
ratios to the ratios which would have existed at various
times.

4. Stable nuclei atomic weight about 40 and above are

present in about same abundance.
Assume when elements formed, same rule applied to
unstable elements.
Now U238 is 140 times as abundant as U235.
If both once equally abundant, would take 6 billion years to
reach present proportion.
Age of Universe? of our part of Universe? of our Solar
System nebula?

Part 4d: Fission-track dating:

U238 spontaneously breaks down by fission (splits into two

large parts).
This is a rare occurrence.
These fission particles pass through the surrounding
material with very high energy and leave tube-shaped
damage tracks.

These tracks can be counted (etch mineral with HFl, look at

under microscope) and thus the number of spontaneous
fissions may be counted.
This gives amount of daughter product in sample.

Can determine (generally from measurement of amount of

radiation being emitted) current U238 content in sample.
Essentially have number of daughter atoms and number
of remaining parent atoms and can thus determine age.

Useful because can be used on wide variety of substances

of wide range of ages.

Disadvantage which turns out to be an advantage:

Fission tracks are "healed" by prolonged heating (millions of
years).
Temperature at which healing occurs is different for
each mineral.
Each different mineral thus can yield a different age
(apparent disadvantage) because each mineral has its clock
"restarted" by healing at different temperatures and thus
different times.
But temperature history of sample can be determined by
comparing different minerals in sample.

Part 4e: Potassium-Argon dating:

K40 undergoes 2 principal kinds of decay, to Ca40 and to

Ar40.
Decay to Ca40 not useful, because Ca40 most common isotope
of Ca and small amount produced radiogenically would be
undetectable.
Therefore, use K-Ar.

Since 2 separate decay types are possible, decay equation

somewhat more complicated.
Let be total decay constant, Ar be decay constant for K-Ar
reaction, and Ca be decay constant for K-Ca reaction.
Then decay equation can be written:

Ar40original = 0 for all but very exotic minerals (original Ar a

gas, wouldn't survive formation except under very unusual
circumstances, such as enormously high pressures).
Therefore, substituting 0 for original Ar and also substituting
decay constants:

t = 1.88 x 109 ln (1+ 9.07 Ar40/K40)

If metamorphism occurs, Ar40 already formed will probably

be lost and clock reset.
K-Ar methods can therefore be used to date metamorphic
events.

Disadvantage to method:

Ar is gas and will often escape

Advantages to method:

can be applied to very common and abundant rocks and

minerals, since K one of major elements in Earth's crust
Glauconite in sedimentary rocks can be used and other
methods not generally useful for sedimentary rocks
schists and slates can be dated
 since Rb usually found with K, 2 independent ages can
usually be obtained from same sample and compared
wide range of ages because of length of halflife (from age
of Earth to about 5000 years old); no other methods allow
dating of rocks a few tens of thousands of years old
(important for establishing chronology of recent
magnetic reversals)

Part 4f: Samarium-Neodymium dating:

Techniques same as for Rb-Sr or K-Ar.

Has advantage that both elements are members of rare-

earth group and have virtually identical chemical properties.
Both similarly affected by weathering and metamorphic
processes.
Sm/Nd ratios would remain unchanged, giving reliable date
for original crystallization.

Part 4g: Carbon dating:

Carbon 14 dating (also called radiocarbon dating)

C14 formed in upper atmosphere by reaction of N2 with

neutrons produced by cosmic rays.
Reaction is: 0N1 + 7N14 -> 6C14 + 1H1
then C14 decays -> 7N14 + -1 0
Thus, total amount of C14 in atmosphere constant.
Carbon in organism has same C14/C12 ratio as air or water
does as long as organism alive.
When organism dies, C14 not replenished, disappears, and
C14/C12 ratio decreases to zero.
C14/C12 ratio thus gives age since death.

Limited to very young samples (less than 70,000 years)

because of short half-life (5730 years).

Instead of measuring C14/C12 ratio in material directly,

normally we compare C14 in sample to C14 in air by
comparing radioactivity of the 2 samples (number of decays
per minute per gram of carbon).
A is activity of C14 in material to be dated and Ao is activity of
air.
(Age of sample) t = 19,035 log Ao/A.

Is % C14 really constant?

Known that C14 content of atmosphere increased 10 % in
period 6000 to 2000 years ago.
Found by studying tree rings.
Cause not known.
Now changing because of:

burning of fossil fuels

nuclear explosions
possibly through changes in intensity of Earth's magnetic
field

Part 5: Stable Isotopes

Commonly used stable isotopes in geology:

H1, H2
C12, C13
O16, O18
S32, S34

Atoms of 2 different isotopes of the same element in the

same molecule or crystal structure will vibrate at different
frequencies.
The difference in frequency depends on the relative
difference in mass between the isotopes.
It would be a significant difference for isotopes of hydrogen
(where H2 is twice the mass of H1) and insignificant for
isotopes of elements such as tungsten (W186 is 1.03 times
mass of W180).

The lighter isotope vibrates at a higher frequency than the

heavier one and is therefore less strongly bonded.

It can, therefore, be more easily removed by physical,

chemical, or biological processes.
Degree to which separation occurs is called fractionation.
Theoretical calculations for fractionation are very difficult or
impossible.
Therefore, data is usually merely observed experimentally
and then one uses tables, graphs, etc. to study natural
occurrences.
The extent of isotopic separation (or fractionation) can be
expressed by a ratio called the fractionation factor, .
= (Ra/Rb) - 1
where Ra is ratio of isotopes in phase a, Rb is ratio in phase b.

Example: for oxygen at 25 degrees C,

No fractionation number is very far from zero.

Differences between fractionation numbers are very

small, so we usually use comparisons between isotopic
separation in a particular sample and the corresponding
isotopic separation in some standard.
Standards used:

O, H - sample of sea water called standard mean ocean

water (SMOW)
C and sometimes O - belemnites of the Cretaceous Peedee
Formation of South Carolina
S - troilite from the Canyon Diablo (Arizona) meteorite
Si - a quartz vein in the Mother Lode of California

These comparisons are given in terms of delta values, , in

permil units (parts per thousand).
A positive means the sample contains a higher % of the
heavier isotope than a standard and a negative means the
sample contains a lower % of the heavier isotope than the
standard.
Examples:

1. physical process
Evaporation of water leads to concentration of lighter
isotopes of H and O in the vapor phase and heavier isotopes
of H and O in the fluid phase.
O in fresh water has values down to -60 permil because light
isotope concentrated in vapor escaping from the sea (and
then precipitating to form fresh water).

2. chemical process
If one mixes water made of only O16 with CO2 made of only
O18, the isotopes will exchange to yield water and CO2 with
both kinds of isotopes but the water will wind up with a
slightly different ratio of O16/O18 than the CO2, because of
different bond strengths in the two compounds.

3. biological process
Biological processes are complex and not well understood.

Example 1: The reduction of sulfate to sulfide uses

bacteria as a catalyst.
The production of sulfide is faster for the lighter isotope
of sulfur and this means sulfides have a concentration of
lighter isotopes of sulfur and sulfates have a
concentration of heavier sulfur isotopes.
Example 2: Photosynthesis by plants favors carbon 12
over carbon 13
Hydrocarbons formed from living organisms have a
C12/C13 ratio higher than non-biogenic hydrocarbons.
 The high C12/C13 ratios of coal, petroleum, etc. are a
principle evidence of biogenic origin.

Temperature effects:
At high temperatures, the difference between vibrational
frequencies of different isotopes is much smaller than at low
temperatures.
Thus less separation of isotopes occurs at high temperatures.

This fact can sometimes be used to determine the

temperature that prevailed when a certain process was
occurring.
Example:
Temperature at time of formation of CaCO3 precipitated in
ocean can be determined by measuring oxygen isotope
composition of the carbonate.
Ideally, temperature differences of less than 1 degree C can
be determined.

Shows decrease in average temperature of seawater of 5 to

10 degrees C in past 150 my.

Use of stable isotopes to determine source of fluids: (Big ore

deposit debate).
Comparison of H2/H1 ratios and O18/O16 ratios for
hydrothermal fluids to same ratios for rainwater in that area
and to magmatic water.
Ratios of hydrothermal fluid almost same as rainwater but
not quite.
Indicates most fluid from rainwater in vicinity but some
possibly from magmatic source.
 Part 5a: Meteorite Impacts and Extinctions

Geochemical evidence for impact:

Rocks deposited in the Cretaceous/Tertiary boundary clay
layer contain substantial amounts of elements such as
iridium which are common in extraterrestrial rocks but rare
in Earth rocks.

Geochemical evidence against impact:

These anomalies could also be produced by:

extensive volcanic activity

a decrease in sedimentation as a result of extinction of
plant and animal species

Part 6: Low Temperature Geochemistry or Water

Geochemistry

Will now look at some chemical reactions of rocks at the

surface of the Earth:

during weathering
during transportation
during deposition
post deposition

Important reminder: "Chemists" usually deal with very

simple solutions where they can control the conditions.
Geologists must deal with several complications:

complex composition of rocks and minerals

 slow rates of reaction (especially at low temperature of
Earth's surface)
grain size and amount of fracturing can significantly
influence rates of reaction

Mechanical weathering:

frost action
organic activity
exfoliation
etc.

Chemical weathering:

solution
colloidal suspension
hydration
oxidation
carbonation

At this point, you should review your introductory geology

coursework on weathering of rocks and minerals.

Part 6a: Chemical Equilibrium

For the reversible reaction aA + bB + ... <-> yY + zZ + ...

the equilibrium constant K is defined as

[Y]y [Z]z ...

K = ---------------
[A]a [B]b ...
where values in brackets are concentrations and the
coefficients in the equation determine the powers to which
the concentrations are to be raised.

Example:

Values of K are given for 25 degrees C and 1 atmosphere

pressure, unless otherwise specified.

Concentrations of gases are expressed as partial pressure

in atmospheres
(In a mixture of gases, each gas behaves approximately as
though it were alone and exerts a pressure independently of
the the others. This is its partial pressure.)

Concentrations of solutes in water solutions are given

either as moles of solute per liter of solution (molarity) or as
moles of solute per kilogram of water (molality)
In dilute solutions (types usually dealt with in geology), the
difference between molarity and molality is negligible.

Concentrations of pure solids and pure liquids and of

water are included in the equilibrium constant and hence do
not appear in the formula.
Once equilibrium is established, a change in concentration
of one constituent will lead to changes in the others
(le Chatelier's Principle)

Example: What would be the effect of more CO2 in the

atmosphere? (as in the early history of Earth)
From 2nd equation, increasing [CO2] results in increased
[H2CO3].
From 1st equation, increased [H2CO3] means more solution
of CaCO3.
Thus, explains why decrease in CO2 in late preCambrian
resulted in more carbonate deposition.

Note that in discussion of equilibrium, nothing has been said

about rates of reaction.
Has significance in geology.

Some rules:

Reactions involving ions in water solution generally

almost instantaneous.
Reactions of ions in silicate melts slow because
movements of ions impeded by extreme viscosity of
liquid.
Reactions speeded by rise in temperature (apparently
because molecules must be broken down before the
substances can react)

(Important)
Many natural systems not in equilibrium but may be
considered "stable" because reactions are so slow
 Part 6b: Solubility Products

Solubility product - equilibrium constant for solution of a

substance in water

Example: CaSO4 <-> Ca+2 + SO4-2

K = [Ca+2] [SO4-2] = 3.4 x 10-5

Example of how used:

Determine solubility of CaSO4
Solubility is maximum amount that can be dissolved.
Solubility (in moles per liter) = concentration of Ca+2 in
saturated solution [Ca+2]; also = [SO4-2]
(Solubility)2 = [Ca+2] [SO4-2] = K = 3.4 x 10-5
Solubility = 5.8 x 10-3 M

Solubilities are given for ideal solutions at 25 degrees C.

Effect of raising temperature is usually increased solubility

Some exceptions if solubility reaction gives off heat.

For real solutions:

Some compounds, when dissolving, react with water

(hydolysis) and increase the solubility.
This is true for many silicates.
Some compounds, when dissolving, form complex ions
with other ions already present in solution, increasing
solubility.
 Important process in solution of minerals during
weathering.
Also important in many hydrothermal solutions.
For non-dilute solutions, ions don't behave
independently, and thus we must consider the "activities"
(or effective concentrations) of the substances rather
than their concentrations
Some substances produce colloidal suspensions, not true
solutions, and don't follow any simple rules or equations.

Uses of solubilities:
From table, determine solubility of ion.
Compare to measured concentration (or activity of non-
dilute solution).
This will tell degree of undersaturation and often indicate
whether a small change will lead to precipitation.

Example of use:
order of precipitation of evaporites when water evaporates
is least undersaturated first to most undersaturated last

Common ion effect -

the decrease in solubility of a salt due to presence of one of
its own ions already in the solvent

Example:
(remember, solubility of CaSO4 in water is 5.8 x 10-3 M)
Calculate solubility of CaSO4 in 0.1 M CaCl2
Solubility of Ca+2 = x (from CaSO4) + 0.1M (since 0.1M already
in solution)
Obviously, solubility of SO4-2 is also x.
K (from table) = 3.4 x 10-5 = (x + 0.1) (x)
Use quadratic formula and x = 3.4 x 10-4 M
Thus solubility of CaSO4 less in CaCl2 solution than in water.

Most important solvents at Earth's surface are rainwater and

other natural waters.
Rainwater and surface waters are not neutral but actually
weak acids or bases.
(reminder: pH = - log [H+]
In nature, observed pH's lie mostly in the range of 4 to 9; a
typical value for surface waters might be 5.7
Since natural waters are weak acids and bases, we must
consider solubility of rocks in weak acids and bases rather
than in pure water.

Part 7: Carbonates

An example of a substance dissolving in a weak acid,

calcium carbonate dissolving in surface waters, is
represented by the following compound reaction (Equation
is not balanced.):

H2O + CO2 <-> H2CO3 <-> H+ + HCO3-

CaCO3 <--> Ca+2 + 2HCO3-

This reaction describes the following:

the weathering of limestones

the dissolving of limestone to form caves
 the dissolving of marble by ore-bearing solutions in
the walls of a fissure
the precipitation of limestone in the sea
the precipitation of calcium carbonate as a cementing
material in sedimentary rocks
the precipitation of calcium carbonate where droplets
evaporate at the tip of a stalactite
etc.

We will use this reaction to look at the effect of real life

complications on what at first glance might seem to be a
relatively simple chemical reaction:

1. effect of pH
Dissolving of CaCO3 uses up H+ (to form HCO3-)
Addition of H+ (lowering the pH) should increase the
solubility
Addition of OH- (raising the pH) should favor precipitation

2. forest fires, air pollution, volcanic eruptions (all

sources of CO2)
More CO2 in atmosphere, more H2CO3
More CaCO3 dissolves.

3a. decay of organic matter in air or in aerated water

Produces CO2
More CO2, more CaCO3 dissolves.

3b. decay of organic matter when air is restricted or cut

off
Produces CO2 and/or H2S and/or ammonia (process varies)
CO2 and H2S would make CaCO3 more soluble
NH4OH would raise pH and make precipitation of CaCO3
more likely.
Hard to predict what will happen.

4. temperature changes

a. the solubility of most salts increases with increasing

temperature
2. the opposite is true of CaCO3; its solubility decreases with
increasing temperature.
3. the solubility of CO2, like any other gas, decreases with
increasing temperature.

Effect b is greater than effect c.

Thus increasing temperature leads to precipitation.

As an illustration of the effect of temperature, CaCO3

dissolves at great depth in the ocean, where the water is
perennially cold, but precipitates near the surface, especially
in the tropics, where the water is warm.

5. effect of pressure
Increase of pressure increases solubility by increasing
solubility of CO2 in water.
In deep parts of ocean, pressure alone would increase the
solubility of CaCO3 to about twice its surface value.
In near surface environments, changing atmospheric
pressure can theoretically change amount of CO2 that
dissolves and thus effect solubility of CaCO3.

6. organic activity

6a. Many organisms use calcium carbonate in the

construction of their shells. How they accomplish this is not
certain.
Biological precipitation of CaCO3 is extremely important,
however.

6b. Green plants cause precipitation of CaCO3 by removing

CO2 from water in the process of photosynthesis.
Example: Abundant green algae in the warm waters of the
Bahama Banks aid in the precipitation of the limy mud and
sand with which the banks are covered.

More exotic complications:

7. CaCO3 is polymorphous.
The two commonly occurring natural forms are calcite and
aragonite; at least one other form (vaterite) can be prepared
artificially and is known as a rare mineral in nature.

Solubilities of the various forms are different.

K = 4.5 x 10-9 for calcite
K = 6.0 x 10-9 for aragonite

Suppose we establish equilibrium between solid aragonite

and its saturated solution.
Then the product of the concentration of the two ions is:
[Ca+2] [CO3-2] = 6.0 x 10-9
This number is larger than the equilibrium product for
calcite; that is - there are too many ions present for the
solution to be in equilibrium with solid calcite.
The excess Ca+2 and CO3-2 should therefore combine to form
calcite.

This process does happen but not rapidly enough to be

observed under natural conditions.
Main reason is that in many cases nuclei are not present for
calcite to precipitate around.
Therefore if aragonite is present, it will remain apparently
stable for a long time but eventually turn into calcite.

Important question:
If calcite precipitates at lower ion concentrations than are
necessary for the precipitation of aragonite, how does
aragonite get produced in the first place?
In fact, experiments show that calcite and aragonite often
precipitate together.
No satisfactory answer to this question has been found.
It is an observed fact that many polymorphic substances
show this same tendency to precipitate first in metastable
forms, which change only slowly to the stable varieties.
Living creatures that use CaCO3 in their shells may
precipitate either polymorph, some species favoring one and
some the other. Many pelecypods precipitate both in
alternate layers.

8. effect of grain size

Very tiny grains show a greater solubility than do large
crystals.
(Ions escape most easily from corners and edges; more of
these per volume on small grains.)
We should then have two solubility products for each
reaction, one for small grains and one for large grains.
(Technically, we should have an infinity of solubility
products.)

A solution in equilibrium with small grains will be

oversaturated with respect to large grains and therefore the
small grains should eventually dissolve and the large ones
grow at their expense.
This is common and produces such effects as growth of large
grains in limestone and conversion of opal to chalcedony
and quartz after precipitation.

9. effects of other electrolytes (electrolyte - something that

produces ions when dissolved)

9a. Common ion effect (covered previously) - decrease in

solubility of a salt due to the presence of one of its own ions.

9b. Electrolytes which do not supply a common ion generally

have the opposite effect; they make the solubility greater.

Consider a Ca+2 ion in water.

Water is a polar molecule; one end positively charged, the
other negative.
All the negative ends of the H2O molecules surrounding the
Ca+2 ion should be close to the ion, the positive ends pointing
outward.
The CO3-2 ions should be similarly surrounded.
Thus the H2O molecules serve as a shield between the
positive ions and the negative ions, making it harder for
them to get together and precipitate.
(This is why electrolytes tend to dissolve better in water than
in non-polar compounds.)
Now if another electrolyte (say NaCl) is added, the Na+ and
Cl- ions as well as the water molecules will be attracted to the
Ca+2 and CO3-2 ions.
This will mean each Ca+2, for instance, will be at the middle
of a cluster of water molecules and Cl- ions.
Thus the shielding is increased and the Ca+2 and CO3-2 ions
will have even more trouble getting together.

In general, the greater the concentration of the second

electrolyte, the more ions of it are present for shielding, and
the greater the solubility of the CaCO3.
Divalent ions shield better than monovalent ions and this
effect means that CaCO3 is more soluble in a solution of 0.1
molar MgSO4 than in a 0.1 M solution of NaCl.

Of course, the presence of electrolytes should have little

effect on the solubility of things that don't ionize much when
dissolved, such as H2CO3.

10. possible associations of ions to form complexes such

as UO2(CO3)2-2
This removes CO3-2 ions from solution and makes CaCO3
more soluble.
Thus there are so many things that can effect the solubility of
CaCO3 in H2CO3 that in many cases it is impossible to
predict whether CaCO3 will dissolve or precipitate or
only qualitative reasoning can occur.
Example: We might be able to predict that precipitation
would occur as temperature was raised but not be able to
predict at exactly what temperature the precipitation would
occur.

The fact that CaCO3 is observed to be dissolving in some

parts of the ocean and precipitating in other parts and that
only slight shifts in the ocean environment can change
precipitation to dissolving implies that seawater is
essentially saturated in CaCO3.

Other simple carbonates enter into equilibria like the

CaCO3 equilibrium according to reactions that can be
symbolized:
XCO3 + H2CO3 <--> X+2 + 2HCO3- with X standing for Fe, Sr,
Mn, etc.

Replacement of one carbonate by another is often observed,

both in sedimentary rocks and veins.
For example, the replacement of calcite by siderite should
follow the equation:
CaCO3 + Fe+2 <--> Ca+2 + FeCO3

We can obtain the equilibrium constant for this reaction as

follows:
 [Ca+2] [Ca+2][CO3-2] 4.5 x 10-9
K = -------- = ------------- = ------------ = 225
[Fe+2] [Fe+2][CO3-2] 2.0 x 10-11

This means that a solution of 1 M [Ca+2] would be at

equilibrium with 1/225 M [Fe+2].
If the ratio of Ca+2 to Fe+2 were decreased (more Fe+2 added
or Ca+2 removed), in order to reestablish equilibrium, some
of the iron would replace the Ca+2 in CaCO3 to produce more
siderite.

The Dolomite Problem:

Dolomite rock is one of the commonest sedimentary
materials.
There are thick and extensive beds in strata of all ages.
But - Efforts to prepare dolomite in the laboratory under
normal sedimentary conditions have failed.
No dolomite is observed forming in nature today in ordinary
sedimentary environments.
There is no geologic evidence to indicate that formation took
place in the past under unusual conditions of temperature
and pressure.
So how does dolomite form?

Clue 1 - look at structure of dolomite

Anions are CO3-2 group.
Cations are regularly alternating Ca+2 and Mg+2.
The regular alternation is important.
This is a special, highly-ordered crystalline structure;
perhaps it takes a long time to grow.
Clue 2 - free energy levels indicate the following reactions
which produce dolomite can occur spontaneously:
(will explain later how free energy works)

CaCO3 + Mg+2 + 2HCO3- <--> CaMg(CO3)2 + H2CO3

2CaCO3 + Mg+2 <--> CaMg(CO3)2 + Ca+2

Clue 3 - geologic evidence

Poor preservation of fossils in dolomite
Coarseness of grains
Commonly observed cavities and pore spaces

All clues suggest that dolomites in older strata did not form
as primary deposits but are instead altered CaCO3
deposits.

Currently accepted theory:

Dolomite is formed by a reaction between Mg+2 ions and a
CaCO3 sediment.
The Mg+2 may come from seawater in contact with the limy
sediment or buried with it, from ions taken up in the original
CaCO3 structure (particularly in shells), or from later
solutions moving through the sediment.

Part 8: Colloids

Colloidal dispersion - particles in size range between that of

true solution (10-7 mm) and suspensions (greater than 10-3
mm)
How to tell colloidal dispersion from suspension:

even in field of microscope, colloidal particles can't be

seen
when allowed to stand, colloid doesn't change; particles
in suspension settle out

How to tell colloidal dispersion from true solution:

colloids scatter light (Tyndall effect), often look milky

when seen in reflected light
can observe Brownian motion of colloidal particles under
microscope (result of bombardment by water molecules)
colloids diffuse very slowly (through a membrane, for
example)
colloids effects on vapor pressure, boiling point and
melting point of water not predictable
(unlike substance in solution; for example: solution
lowers freezing point)
colored diffusion bands form in colloidal gels when an
electrolyte is allowed to diffuse (Liesegang rings); process
not understood; may be origin of colored bands in agate

Electric charges characteristic of colloids.

Due to adsorption of ions on particles
What determines amount of charge and sign of charge not
understood.

Colloids are thermodynamically unstable.

According to free energy calculations (will look at later), the
particles should spontaneously grow larger.
Electric charge is what keeps colloid particles dispersed.
Reducing or removing charge causes flocculation.
Thus most colloidal dispersions destroyed by adding
electrolytes.

Apparent confusion:
Must have electrolyte to form colloid (to get ions which are
adsorbed) but more electrolyte causes precipitation.
Key apparently is amount and kind of ions present, but
process not completely understood.

Protective colloids - the presence of a second colloid

sometimes makes a colloid more stable
Examples:

organic colloids protect iron hydroxide and manganese

dioxide colloids
silica colloids protect gold and mercury sulfide and may
have an important effect in ore formation

The role of electric charge in colloidal flocculation leads to

three general rules useful in geology:

particles remain suspended in fresh water longer than in

sea water
salt lakes are clear due to flocculation of colloidal
material carried into them
many "poisonous" materials (copper, selenium, arsenic,
lead, etc.) are removed by this process; obviously good for
us
Some ions adsorbed on colloids are held tightly; some
weakly.
Depends on type of force, type of colloid and type of ion.
Usually attachment is weak enough so some ions are easily
replaced by others.
Important fact is that some surfaces or some kinds of
colloidal particles hold adsorbed ions more strongly.

In geology, ion exchange is very important.

Examples:

mechanism for redistribution of metal ions between

solutions and sediments
Explains why cobalt and lead found with manganese
since these ions are easily adsorbed on manganese
diioxide sols
influence of adsorbed ions on substance

Especially important for clays.

Clays with adsorbed Na+ are sticky and impervious to water;
clays with Ca+2 are granular, easily worked, readily
permeable.
That's why gypsum often added to yards to convert Na+ clays
to Ca+2 type.

The effect of heat on colloids not understood.

Important because of hydrothermal studies.

Two forms of colloidal dispersions:

1. sol
 clear, transparent liquid
individual particles?
example: dissolved gelatine

2. gel

solid network of fibers in which water trapped?

Which form depends on:

concentration
methods of preparation
time of standing

Two types of colloidal substances:

1. hydrophilic

probably have much adsorbed water

dissolves directly to form colloidal dispersions
dispersion stable indefinitely
readily forms gels and process of gelation reversible

2. hydrophobic

must be obtained indirectly (by precipitation from a

true solution, passage of electric current, etc.)
less stable than hydrophilic
hard to form gels and gelation not reversible

Some compounds difficult to classify.

Example: silica
 stable indefinitely
forms gel readily
doesn't spontaneously disperse

Some common natural colloids:

silica
clay minerals
limonite
manganese dioxide

1. silica

Colloidal characteristics:

cryptocrystalline or amorphous
has Liesegang rings
coagulated by electrolytes
round nodules resemble laboratory made gels
shrinkage cracks in nodules
etc.

silica in the laboratory:

solution represented by equation: SiO2 + 2H2O <-->

H4SiO4 (silicic acid)
all silica in solution above equilibrium amount is slowly
converted to sol
in concentrated solutions, sol is converted to gel

silica in nature:
 at super low concentration conditions (stream water,
ground water), silica is in true solution
in oceans, organisms remove silica (probably producing a
gel in the process)
Some precipitates as silicate (glauconite, chlorite, illite,
etc.)
the only place where silica concentration is high enough
to directly form appreciable amounts of gel is in hot
water (near underwater lava flows, hot springs, etc.)
replacement of other minerals by silica is common but
not understood, partly because never studied

2. clay minerals

Colloidal characteristics:

flocculation by electrolytes
ion-exchange behavior
ability to adsorb water

Clays are very important in the study of differences in

weathering environments (warm, humid, arid, polar,
underwater, etc.)
Decay is faster and penetrates deeper in warm humid
climates but the products of weathering in all environments
are the same except for differences in clay minerals.

Why do we have different clay minerals in different

environments?
Formation of clay minerals during weathering is essentially
a hydrolysis reaction.
Example:

4KAlSi3O8 + 22H2O --> 4K+ + 4OH- + Al4Si4O10(OH)8 + 8H4SiO4

Evidence from laboratory work:

acid solutions favor kaolinite

basic solutions favor montmorillonite
K+ abundance favors illite

Mechanism for producing clay minerals not understood.

How do we go from chain structures (amphiboles, etc.) or 3
dimensional structures (feldspar, etc.) to sheets?
Two possibilities:

1. modification of structure perhaps by formation of

colloidal particles which then recombine
Illite currently being studied for clues.
2. breakdown into Al-O and Si-O which then recombine

Evidence from nature:

Kaolinite forms in humid climates on well-drained slopes

where abundant vegetation makes soil solutions acid and
cations are removed.
Montmorillonite forms in less humid climates where
solutions are alkaline and have more cations.
Illite forms in soils where potassium fertilizers have been
long used, from igneous rocks rich in potassium, or in
 desert areas with little leaching.

Laterites - soils with little or no clay but with AlO and FeO
(and SiO2 which is removed in solution)
Why do we get laterites in tropics?
Apparently where weathering is intense, clays break down
further.
This is an important process in forming 75 % or world's
aluminum ore, 80 % of Ni, 50 % of Fe, etc.

Part 9: Hydration

Other examples of hydration reactions common in nature:

CaSO4 . 2H2O (gypsum) <--> CaSO4 (anhydrite) + 2H2O
Fe2O3 (hematite) + H2O <--> 2FeOOH (limonite)

Both of these reactions are simple but not well understood.

Common occurrence of both hydrated and anhydrous
forms suggests that the difference in stability is not large
and the reactions are extremely slow.

Part 10: Oxidation

Oxidation reactions in nature are simple but not well

understood.

At ordinary temperatures, oxidation is slow.

Water speeds up oxidation (probably by dissolving to
produce ions which then react more quickly).
Oxidation reactions probably take place in stages.
To understand how complex the situation may be, use pyrite
as an example:
In an arid region:

Step 1: 2 FeS2 +7O2 + 2H2O --> 2Fe+2 + 4SO4-2 + 4H+

Step 2 (which one occurs depends on the pH):
4Fe+2 + O2 + 4H+ --> 4Fe+3 + 2H2O
or 4Fe+2 +O2 + 4H2O --> 2Fe2O3 + 8H+
Step 3: Fe+2 + SO4-2 --> FeSO4
Step 4 (only if enough water is present): Fe+3 + H2O -->
FeOH+2 + H+

Other reactions are possible.

Also, can have significant time intervals between steps.

Part 11: Eh-pH Diagrams

In chemistry, oxidation is defined as a loss of electrons.

Reduction is defined as a gain of electrons.
A substance which is oxidized is said to be a reducing agent
(because it reduces something else) and vice versa.

Examples of oxidation:

Fe(0, +2) --> Fe+3

S(0, -2) --> SO4-2
Mn(0, +2) --> Mn(+3, +4)
Currents flow when there is a difference in electrical
potential energy (voltage).
This voltage can be measured with a galvanometer.
If we take 2 metals, attach a wire between one end of each
and put the other two ends in a solution which contains ions,
a current will flow along the wire.
Electrons lost by one metal are being gained by the other.
An oxidation-reduction reaction is thus occurring.

The oxidation potential (or technically, the oxidation-

reduction potential, symbol Eo) of a substance is that voltage
which would occur between an electrode of that substance
and an electrode of hydrogen (formed by letting H2 at 1
atmosphere pressure bubble over a platinum rod) at
standard conditions.
For the oxidation potential of a natural solution the symbol
used is not Eo but Eh (called redox potential).
A positive Eh means hydrogen would be oxidized by the
substances in the solution.

Example of use:
Consider a natural water (symbolized by x) with an Eh of 0.5
volt.
Would dissolved iron be present as Fe+2 or Fe+3?
Equation for oxidation of natural water:

x --> x+ + e- Eh = 0.5 volt

Equation for oxidation of iron:

Fe+2 --> Fe+3 + e- Eo = 0.77 volt

Interpretation:
Fe is more likely to oxidize hydrogen than the natural
solution is and thus Fe is more likely to oxidize the natural
solution and be itself reduced.
We would then expect to find Fe+2.

The usual natural values of Eh and pH are often plotted on

graphs with Eh as the vertical axis and pH as the horizontal
axis.
These are called Eh-pH diagrams.
The upper and lower limits of water stability are often
indicated as well as the pH-Eh relationships at these limits.

These diagrams can be interpreted to

obtain information about how substances behave under

various natural conditions
determine fields of stability for minerals

Part 12: Thermodynamics

Internal energy (E) - total energy of all kinds contained

within a system (sum of kinetic and potential energies of its
constituent atoms)
Cannot easily be determined in absolute values
Change in internal energy is factor which is most significant.

1st law of thermodynamics - energy can neither be created

nor destroyed (Law of Conservation of Energy)
If system undergoes a change of state, and E1 is internal
energy before change and E2 is internal energy after change,
then E = E2 - E1.
The change of energy is determined by

the amount of heat absorbed or lost by the system (Q) and

the amount of work done to or by the system (W).

By convention, + used for heat in, - used for work done by

system.

So E = Q - W, or for infinitesimal change: dE = dQ - dW

Since W = F x distance, pressure = F/A, and V = A x distance,

W = PV
or, at constant pressure, dW = PdV
thus dE = dQ - PdV and dE = dQ at constant volume

Enthalpy (H) defined as E + PV (Enthalpy sometimes called

heat content.)

Since H = E + PV, dH = dE + PdV + VdP

or, at constant pressure, dH = dQ - PdV + PdV + VdP = dQ +
VdP
or since pressure constant, dH = dQ
Also note that if pressure and volume both constant, dH = dE

The change in enthalpy (or in heat at constant pressure) is

given special names in certain circumstances:

heat of fusion - heat absorbed by a solid when it melts

 heat of vaporization - heat absorbed when liquid
changes to gas
heat of reaction - heat absorbed or given off in chemical
reactions
heat of formation - heat change produced in a reaction
of elements to form a compound

The amount of heat absorbed or given off (dH) during a

chemical reaction can be measured.
(For standardization, unless told otherwise, assume all
reactions occur at 25 degrees C and 1 atmosphere pressure,
and quantities of reactants are given in moles.)

Heat unit used is usually kcal and is often written as part of

the equation.

Example:
H2 + 1/2 O2 -> H2O + 68.3 kcal
and, since energy lost, dH = -68.3 kcal for this reaction.

(Reminder - the enthalpy change involved in forming a

compound from its elements is called the heat of formation.)
Thus the heat of formation of water is -68.3 kcal/mole.

By adding and subtracting heats of formation, the enthalpy

change for any reaction can be computed.
For example - the burning of hydrogen sulfide may be
written:
2H2S + 3O2 -> 2H2O + 2SO2
The heats of formation are:
 H2 + S -> H2S dH = -4.9 kcal
H2 + 1/2 O2 -> H2O dH = -68.3 kcal
S + O2 -> SO2 dH = -70.9 kcal

dH = sum of heats of formation for products minus sum of

heats of formation of reactants
= 2 (-68.3) + 2 (-70.9) - 2 (-4.9)
= -268.6 kcal

Entropy (S) - the degree of disorder in a system

In general, spontaneous processes in nature tend toward the
formation of less ordered structures, or entropy increases.

2nd law of thermodynamics:

For a system in equilibrium, dS = dQ/T or dQ = TdS
or since dE = dQ - PdV, dE = TdS - PdV
or since dH = dQ + VdP, dH = TdS + VdP
For non-equilibrium processes, dS > dQ/T

Helmholz Free Energy (A) defined as E - TS

Gibbs Free Energy (G) defined as H - TS

Look at Gibbs Free Energy: G = H - TS

Since H = E + PV, G = E - TS + PV
at constant pressure and temperature, dG = dE - TdS + PdV
and, if in equilibrium, dE = TdS - PdV (2nd law of
Thermodynamics)
so dG = TdS - PdV - TdS + PdV
or dG = 0
Therefore the criterion for a system to be in equilibrium
at constant pressure is that dG = 0.
Another way of saying this is that the Gibbs free energy of
the reactants must be equal to that of the products.
If dG for reaction not equal to 0, then system not in
equilibrium.
The farther the value is from 0, the farther the reaction is
from equilibrium (at standard concentrations).

If dG is a negative number, then reaction will proceed

spontaneously in direction written (although rate may be so
slow than no reaction is apparent.)
If dG is a positive number, then reaction will proceed in
reverse direction (or energy must be supplied from external
source to make reaction go in direction written.)

Refer back to dolomite problem.

Remember we said Gibbs Free Energy calculations showed
that dolomite could form from several reactions involving
calcite and Mg ions.

Similarly, we can determine that for a system in

equilibrium at constant volume, dA = 0
Since most chemical reactions of geologic interest take place
at constant pressure rather than constant volume, Gibbs Free
Energy more important to us than Helmholz Free Energy.

When substances have standard concentrations, free

energies of the products and the reactants can be combined
to obtain the free energy change for the reaction (like
combining enthalpies of formation)
Values for free energies can be found in tables. Free
energies, like enthalpy, are expressed in kcal.

Example of use: Take H2 at 1 atm., HI at 1 atm., and solid

Iodine.
1/2 H2 + 1/2 I2 <-> HI
Is this mixture in equilibrium?
dG = 0.3 kcal
Thus approximately at equilibrium, but not quite. A little bit
of HI would tend to break down.

Another example: S at 1 atm., O2 at 1 atm., SO2 at 1 atm.

S + O2 <-> SO2
dG = -71.8 kcal
Reaction far from equilibrium.
Mixture will react to produce much more SO2 before
equilibrium attained.

Normally tables give free energies of formation for

substances as follows:

1 atmosphere partial pressure for gases

1 molar for substances in solution
solids and liquids regarded as pure compounds

How often are standard partial pressures and concentrations

found in nature? never

At other concentrations, various formulas have been

developed by which free energies of reactions can be
calculated.
Won't derive formulas, but merely give examples:

[Y]y [Z]z ...

dG = dG0 + 1.364 log -----------------
[A]a [B]b ...

dG0 = free energy of reaction for standard "activities" (will

define activity later)

Example:
PbS + 2H+ <-> H2S + Pb+2
at H+, H2S, and Pb+2 all 1 molar, dG0 = + 11.1 kcal

(1)(1)
at H+ = 10-3 M, dG = 11.1 + 1.364 log ------- = +19.3 kcal
(10-3)2

Tables give free energies at 25 degrees C plus often give list

of coefficients A, B, and C
These coefficients used in an equation to calculate dG at
other temperatures.
dG = A + BT log T + CT

Example: Cu2O (s) <-> 2 Cu (S) + 1/2 O2

Table gives A = 40.5, B = .004, C = - 0.03
At 400 degrees C, dG = 40.5 + (.004) (673) (2.9) - (.03) (673) =
28.1 kcal

Additonal information (to show preceding has actually been

an over-simplification):
1. When 2 or more components are in a system, total Gibbs
Free Energy is not a simple sum of components' Gibbs
Free Energies because the process of mixing changes the
Gibbs Free Energy of each component.
Instead we have an "effective Gibbs Free Energy" for the
whole system called the chemical potential.
Rather complicated equations exist for calculating
chemical potential for a multi-component system.
2. For an ideal gas (no force acting between atoms, etc.),
chemical (including thermodynamic) equations are
relatively simple.
For real gases, equations are horrendous.
Fugacity is fudge factor needed to make the properties of
a real gas satisfy the equations of an ideal gas.
Can be found experimentally for each gas.
Tables are published.
Whenever pressure (P) occurs in an equation, we use
fugacity instead to get correct answer for real gases.
3. A similar fudge factor, called activity or effective
concentration, is needed for a real solution vs an ideal
solution.
Whenever concentration is called for, we use activity
instead to get correct answer for real solutions.
Activities not accurately known in most cases.