EAS 4550 Geochemistry

P. S. 6 Solutions Due Oct. 27, 2017

1. For a sodium carbonate solution titrated with HCl to the bicarbonate equivalence point, show that:
SCO2 = [Cl–] + [OH–]
At the bicarbonate equivalence point, [H2CO3] = [ CO2-
3 ] (1)
+ + –
We define components as: (H2O – implicit), H , Na , Cl , CO 2-
3

Our Proton Mole Balance is (alternatively, one could start with the proton balance
equation):
TOTH = [H+] + 2[H2CO3] + [ HCO2- –
3 ] – [OH ] (2)
Substituting (1) into (2)
TOTH = [H+] + 2[ CO2- –
3 ] + [ HCO 3 ] – [OH ]
2-
(3)

Before we begin the titration, TOTH = 0 (we have not added any component H to
our solution). After the titration begins, TOTH = [Cl–] since we added 1 mole of
component H for each mole of Cl- added to the solution. Hence:
[Cl-] = [H+] + 2[ CO2- –
3 ] + [ HCO 3 ] – [OH ]
2-
(4)
Our Conservation equation is:
SCO2 = [H2CO3] + [ HCO2-
3 ] + [ CO 3 ] = [ HCO 3 ] + 2[ CO 3 ]
2- 2- 2-
(5)
Substituting (5) into (4), we have:
[Cl-] = [H+] + SCO2 – [OH–] (6)
or SCO2 = [Cl-] + [OH–] + [H+]

A glance at figure 6.02 reveals that [H+] will be something like 3 orders of
magnitude lower than [OH-], so this reduces to:
SCO2 = [Cl-] + [OH–]

2. Using the composition given below, calculate the alkalinity of seawater at 25°C.

Na+ 0.481 M Cl- 0.560 M

Mg 2+ 0.0544 M SO 0.0283 M
Ca 2+ 0.0105 M HCO 0.00238 M
K + 0.0105 M
There are several possible approaches to this problem, but the best one is to use
equation 6.35:

Alk= Sconserv. cations - Sconserv. anions

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EAS 4550 Geochemistry
P. S. 6 Solutions Due Oct. 27, 2017
Alk = [Na+] + 2[Mg2+] + 2[Ca2+] + [K+] - [Cl–] - 2[ SO2-
4 ]

Alk = 0.481 + 2 x 0.0544 + 2 x 0.0105 + 0.0105 - 0.560 - 2 x 0.0283 = 0.0047

Comparing this with equation 6.33, we see that about half the alkalinity in
seawater is due to HCO-3 .

3. For the adsorption of Zn2+ on hydrous ferric oxide:

ºFeOH0 + Zn2+ ® ºFeOZn+ + H+
the apparent equilibrium constant is 100.99. For this problem, use the surface acidity constants (i.e.,
equilibrium constants for adsorption and desorption of H+) given in equations 6.98 and 6.99 (Example
6.11). Make a plot of QZn (fraction of sites occupied by Zn) vs. the aqueous concentration of Zn2+ at pH 7
and a total concentration of surface sites of 10-3 M. Assume that Zn2+ forms no complexes in solution.

(a) The quantity that we want is [ºFeOZn+]/[SºFeO]

We start with a conservation equation for surface sites:
Σ ≡ FeO = [≡ FeOZn+ ]+[≡ FeOH 2+ ]+[≡ FeOH ]+[≡ FeO − ] (a)
Our equilibrium constant expressions are:
[≡ FeOH 0 ][H + ]
K1 = (b)
[≡ FeOH 2+ ]
[≡ FeO − ][H + ]
K2 = (c)
[≡ FeOH 0 ]
[≡ FeOZn+ ][H + ]
K ad = (d)
[≡ FeOH 0 ][Zn 2+ ]
From these we can derive the following:
[≡ FeOH 0 ][Zn 2+ ]K ad
[≡ FeOZn+ ] =
[H + ] (b)

[≡ FeOH 0 ][H + ]
[≡ FeOH 2+ ] =
K1 (c)
0
K 2 [≡ FeOH ]
[≡ FeO − ] =
[H + ] (d)
Substituting these into (a) and rearranging, we have

⎛ [Zn 2+ ]K ad [H + ] K2 ⎞
Σ ≡ FeO = [≡ FeOH 0 ]⎜ +
+ +1+ ⎟
⎝ [H ] K1 [H + ] ⎠
(e)
Dividing (b) by (e), we have:

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EAS 4550 Geochemistry
P. S. 6 Solutions Due Oct. 27, 2017
[≡ FeOZn+ ] [Zn 2+ ]K ad
=
Σ ≡ FeO ⎛ 2+ [H + ]2 ⎞
⎜[Zn ]K ad + +[H + ]+ K 2 ⎟
⎝ K1 ⎠
log Zn Zn fract Zn sites
-10 1.0E-10 0.003
-9.5 3.2E-10 0.010
-9 1.0E-09 0.032
-8.5 3.2E-09 0.094
-8 1.0E-08 0.248
-7.75 1.8E-08 0.370
-7.5 3.2E-08 0.511
-7.25 5.6E-08 0.650
-7 1.0E-07 0.767
-6.9 1.3E-07 0.806
-6.8 1.6E-07 0.839
-6.5 3.2E-07 0.913
-6 1.0E-06 0.971
-5.5 3.2E-06 0.991
-5 1.0E-05 0.997
-4.5 3.2E-05 0.999
-4 1.0E-04 1.000

The plot is shown below:

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EAS 4550 Geochemistry
P. S. 6 Solutions Due Oct. 27, 2017
1

0.9

0.8

0.7

0.6
fract Zn sites

0.5

0.4

0.3

0.2

0.1

0
-10 -9 -8 -7 -6 -5 -4
log [Zn2+]aq

4. Make two rare earth plots for the following three samples. For the granite, MORB, and the Mn
nodule, plot them normalized to one of the chondritic values in Table 7.3 on a log scale. Make a second
REE plot normalizing the Mn nodule to average shale (also on a log scale). Describe the features of the
REE patterns.

La Ce Pr Nd Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
Granite 41 75 7.63 25 3.6 0.6 2.7 0.34 1.3 023 0.53 0.072 0.4 0.055
Ave. MORB 2.98 9.13 1.74 9.22 3.19 1.15 4.29 0.81 5.27 1.14 3.31 0.49 3.20 0.49
Mn-nodule 110 858 34.0 116 24 4.9 24 4.3 24.1 5.15 14.4 2.15 13 1.92

Tm should have been 0.072.

The granite and the Mn nodule are both light rare earth enriched with negative
Eu anomalies. The Eu anomaly results from some Eu being present in the 2+
valence making it more compatible and partitioning into plagioclase. This is
characteristic of upper continental crust. The Mn nodule is derived from

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EAS 4550 Geochemistry
P. S. 6 Solutions Due Oct. 27, 2017
seawater, which is in turn derived from continental crust. In addition, the Mn
nodule shows a positive Ce anomaly, a consequence of Ce being in the 4+ state in
the oceans and being more readily absorbed onto Mn nodules.
The Ce anomaly is also apparent when normalized to shale.

1000

100
sample/chondrites

10

1
La Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu

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EAS 4550 Geochemistry
P. S. 6 Solutions Due Oct. 27, 2017
100

10

1
La Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu

5. Calculate the enrichment in rare earth elements in an equilibrium partial melt of a mantle consisting
of 10% cpx, 5% gar, 25% opx and 60% ol, assuming modal (phases enter the melt in the same proportion
as they exist in the solid) batch melting for F = 0.02 and F = 0.10. Assume the concentrations in the
mantle are chondritic. Use the partition coefficients given in Table 6.5. Use only the following 8 rare
earths: La, Ce, Nd, Sm, Eu, Gd, Dy, and Lu. Plot the results on a semi-log plot of chondrite-normalized
abundance vs atomic number (i.e. typical REE plot). Draw a smooth curve through the REE,
interpolating the other REE. (Hint: since you are going to make an REE plot, work only with chondrite-
normalized abundances, don't worry about absolute concentrations, so the Co values will all be 1).

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EAS 4550 Geochemistry
P. S. 6 Solutions Due Oct. 27, 2017

A cpx opx ol gar D F

0.02 0.1
La 57 0.07 0.0007 0.000001 0.001 0.007 36.93 9.39
Ce 58 0.12 0.0017 0.000003 0.005 0.013 30.84 8.98
Nd 60 0.28 0.006 0.00004 0.07 0.033 19.10 7.71
Sm 62 0.42 0.012 0.0001 0.02 0.046 15.35 7.07
Eu 63 0.45 0.024 0.0005 0.4 0.071 11.13 6.09
Gd 64 0.49 0.04 0.002 0.6 0.090 9.23 5.52
Dy 66 0.62 0.08 0.009 1.7 0.172 5.29 3.92
Lu 71 0.8 0.22 0.022 7.1 0.503 1.95 1.81
mode 0.1 0.25 0.6 0.05

La 36.93 9.39
Ce 30.84 8.98
Pr 24.97 8.34
Nd 19.10 7.71

Sm 15.35 7.07
Eu 11.13 6.09
Gd 9.23 5.52
Tb 7.26 4.72
Dy 5.29 3.92
Ho 4.62 3.50
Er 3.95 3.07
Tm 3.29 2.65
Yb 2.62 2.23
Lu 1.95 1.81