PRINCIPLES OF GEOCHEMISTRY

GEOL 423
FALL 2004
TEST 4 - ANSWERS
PROBLEM 1 (15 points):
a)
87Sr
+
=

86
86
Sr Sr 0
87

Sr

87

Rb

86

Sr

(e

b) To use the isochron method, you must make a plot like the one below, and fit a straight line to
the data (in your case using a straight edge to fit a line by eye):
0.95

0.85

87

86

Sr/ Sr

0.90

Intercept = 0.7027
Slope = 0.05218
2
r = 0.9946

0.80

0.75

0.70
0

2
87

86

Rb/ Sr

87 Sr
= 0.7027. The age
The initial Sr isotope ratio is given by the intercept of this plot, thus

86
Sr 0
can be derived from the slope, but first we must calculate the decay constant from the half-life:
=

0.693
t 12

0.693

= 1.42 1011 a

48.8 Ga

(et 1) = 0.05218
et = 1.05218
(1.42x10-11 a-1)t = 0.05086
t = 3.58 Ga
c) Actually, the crust did not separate from the mantle until ~ 2.7 Ga, so at ~ 3.6 Ga, there was
no crust to be involved with. So it has to be mantle-derived. However, if you did not realize this,
87 Sr
= 0.7027 falls within the mantle range, so I accepted this answer.
the correct value of

86
Sr 0

PROBLEM 2 (10 points):

a) The appropriate equation is:

Hf 176Hf
=
177
Hf 177Hf
176

+
0

176
177

Lu t
(e 1)
Hf

b) The 176 Hf/177 Hf ratio in the mantle will be higher at any given time than the same ratio in the
crust. This is because the parent radionuclide, 176 Lu, is enriched in the mantle. Thus, at any given
time, more 176 Hf will be produced in the mantle than in the crust, because production of a
daughter isotope is proportional to the amount of parent isotope present. Because the percent
mass difference between the two Hf isotopes is small, chemical and physical processes cannot
separate the two. Thus, when the crust and mantle separated, each initially had the same
176
Hf/177 Hf ratio, but different 176 Lu/177 Hf ratios. After separation of the crust from the mantle,
the 176 Hf/177 Hf ratio increases with time in both the crust and mantle owing to decay of 176 Lu to
produce 176 Hf, but the ratio increases faster in the mantle because there is relatively more parent
176
Lu.
PROBLEM 3 (15 points):
The solubility of calcite decreases with depth because of: 1) increased PCO2 owing to the
decomposition of organic matter; 2) decreased temperature (calcite solubility is retrograde); 3)
increased total pressure. At shallow depths in the ocean, seawater is supersaturated with respect
to calcite and once formed, calcite does not dissolve. With increased depth, we reach a depth
called the lysocline where the saturation index is just equal to one. Above this depth, no net
calcite dissolution occurs; below this depth calcite can begin to dissolve. However, calcite can
still accumulate if the rate of supply from the sinking of biogenic calcite particles exceeds the
rate of dissolution. With further increase of depth, the saturation index continues to decline
below one and so the rate of dissolution increases. At the CCD (calcite compensation depth), the
rate of dissolution is just equal to the rate of supply of calcite particles. Below the CCD, calcite
dissolves faster than it is supplied, so no calcite can accumulate. Vast portions of the seafloor are
at depths greater than the CCD, so they do not contain carbonate sediments because the
carbonate particles dissolve before reaching the seafloor. See the sketch below for more details.
degree of saturation
() for calcite
undersaturated
1

depth (km)

1
2

supersaturated
2

calcite

calcite does not dissolve

3
Lysocline
4
CCD
5

calcite dissolves but

not faster than it is supplied

calcite dissolves
faster than it is
supplied

PROBLEM 4 (15 points):

The plot should look like that below:

a) The fact that the data plot along a single straight line (discordia) implies that a single stage of
lead loss occurred.
b) The upper intercept gives the age of formation of the zircons (~2.87 Ga), and the lower
intercept gives the age of the single stage of lead loss (~1.05 Ga).
PROBLEM 5 (10 points):
a) The sketch of the concentration vs.salinity profile for a conservative trace element in an
estuary is given below:
River water

Concentration

Co
n

se
r va

tiv
e

Seawater

Salinity

b) The sketch of the concentration vs.salinity profile for a removed trace element in an estuary is
given below:

Concentration

Seawater

al
ov
m
Re
River water

Salinity

PROBLEM 6 (15 points):

Rubidium is a conservative element. It occurs as the ion Rb +, which has a rather low Z/r
value, meaning it is highly soluble and not scavenged. It is also not involved in biological
cycling. Its depth profile is shown below:

Depth

Concentration

The concentration is constant with depth because conservative elements are not scavenged or
involved in biogeochemical cycles. They have long residence times and therefore are well mixed
in the ocean.
Phosphorus is a nutrient element, required in biological molecules such as ATP, and is a
major component of teeth and bones in vertebrates. Its depth profile is shown below:

Depth

Concentration

This profile has the shape it does because nutrient elements are depleted in the near surface
waters where biological activity is the greatest. When animals and plants die, they fall through
the water column and begin to decompose, causing an increase in concentration, perhaps to a
maximum, at some intermediate depth. Thereafter, the concentrations decrease and then level off
as for a conservative element.

Zirconium is a scavenged element. The Zr4+ ion is small and highly charged, yielding an
intermediate Z/r, implying Zr is relatively insoluble and readily scavenged onto particles. Its
depth profile is shown below:

Depth

Concentration

This profile arises because scavenged elements are supplied to the ocean predominantly via
atmospheric input. This leads to a maximum concentration of the element at the very surface.
With depth, the concentration decreases due to scavenging of the element by particles including:
calcite, silica, Fe/Mn oxyhydroxides, and organic matter. With further increase in depth, the
concentration of a scavenged element increases as the particles with which it are associated begin
to dissolve or decompose. The profile may continue to increase all the way to the ocean bottom,
or it may level off.
PROBLEM 7 (10 points):
a) Rivers, atmospheric deposition, and seafloor hydrothermal activity
b) There are several possibilities for this answer, including:
1) Sea-to-air fluxes: bubble bursting and wave breaking. Converts some salts to aerosols
that are removed to the continents. Examples: Na and Cl.
2) Evaporite formation: precipitation of minerals owing to seawater evaporation in
restricted basins, followed by burial. First calcite, then gypsum/anhydrite, then halite, and
then bittern salts precipitate. Examples: Na, Cl, Ca, sulfate (generally minor sink for all).
3) Ion-exchange on clays (halmyrolysis): the elements Na, K and Mg are exchanged for
Ca adsorbed onto the surfaces of clay particles. Examples: Na, K, and Mg.
4) Carbonate precipitation: surface seawater is supersaturated with respect to calcite and
aragonite (and also dolomite), but calcite and aragonite are mainly precipitated by
biological activity. This becomes a sink if the carbonates do not dissolve before reaching
the seafloor, and are permanently buried. Examples: Ca, Mg and bicarbonate.
5) Silica precipitation: biologically produced as skeletons of phytoplankton (diatoms,
etc.). If these skeletons are buried before they can dissolve, they lead to removal of silica.
6) Sulfide formation: within the pore water of sediments, sulfate is reduced to sulfide.
This sulfide can combine with Fe(II) to form amorphous FeS, and then eventually pyrite.

A number of trace metals can be co-precipitated as sulfides. Examples: Fe, S, Zn, Cd, Pb,
etc.
7) Seafloor hydrothermal activity: there are several ways hydrothermal activity on the
seafloor can act as a sink for elements. On the cooler flanks of a mid-ocean ridge, where
cold seawater sinks into oceanic crust and begins to become heated, several constituents
such as Mg and sulfate are removed nearly quantitatively. Another example is the case of
the REE. Pristine seafloor hydrothermal vent fluids are enriched in REE compared to
seawater. However, such fluids are also enriched in reduced Mn and Fe. When these
fluids mix with oxidized seawater, plumes of Mn and Fe oxyhydroxides form in the water
column above the vent. These phases are excellent scavengers of REE, such that they
remove not only the REE input into seawater from the pristine hydrothermal fluids, but
also REE provided to seawater by atmospheric and riverine input. Thus, hydrothermal
activity is a net sink for the REE, and perhaps also other elements that are scavenged by
Mn and Fe oxyhydroxides.
8) Reverse weathering: involves the conversion of kaolinite to illite. This is a mechanism
for the removal of K from seawater.
9) Permanent burial in pore waters of sediments: all constituents of seawater are subject
to permanent trapping and removal of pore water into sediments.
PROBLEM 8 (10 points):
The big four major compone nts of seawater are Na, Cl, Mg and sulfate. The major
components of most rivers are Ca, Mg, Na and K, and bicarbonate. Also, seawater has a mucher
higher ionic strength, and is much more uniform in composition than rivers. Finally, rivers tend
to have higher Al, Fe, Mn, and perhaps Si than seawater. Much of the river load of these
elements is lost in estuaries due to flocculation.
EXTRA CREDIT (10 points):
The equation required to solve this problem is:
90

90

90

Sr =90 Sr0 e t

Sr = (1.5 g) e-t

Sr = (1.5 g) e-(0.02467 a
90

-1 )(18)

Sr = 0.96 g

Note that t = 21 3 = 18. It is the time since the ingestion of 90 Sr that is relevant here.