Mineral dissolution/precipitation

To determine whether or not a water is saturated with an aluminosilicate such as K-feldspar, we could write a dissolution reaction such as: KAlSi3O8 + 4H+ + 4H2O K+ + Al3+ + 3H4SiO40 We could then determine the equilibrium constant: 3 aK a Al 3 aH 4 SiO4 K 4 aH

from Gibbs free energies of formation. The IAP could then be determined from a water analysis, and the saturation index calculated.

INCONGRUENT DISSOLUTION
Aluminosilicate minerals usually dissolve incongruently, e.g., 2KAlSi3O8 + 2H+ + 9H2O Al2Si2O5(OH)4 + 2K+ + 4H4SiO40

As a result of these factors, relations among solutions and aluminosilicate minerals are often depicted graphically on a type of mineral stability diagram called an activity diagram.

ACTIVITY DIAGRAMS: THE K2O-Al2O3-SiO2-H2O SYSTEM

We will now calculate an activity diagram for the following phases: gibbsite {Al(OH)3}, kaolinite {Al2Si2O5(OH)4}, pyrophyllite {Al2Si4O10(OH)2}, muscovite {KAl3Si3O10(OH)2}, and K-feldspar {KAlSi3O8}. The axes will be a K+/a H+ vs. a H4SiO40. The diagram is divided up into fields where only one of the above phases is stable, separated by straight line boundaries.

Activity diagram showing the stability relationships among some minerals in the system K2O-Al2O3-SiO2-H2O at 25C. The dashed lines represent saturation with respect to quartz and amorphous silica.
6 5

Muscovite

Amorphous silica
K-feldspar Pyrophyllite
-3
4 4

log (aK+/aH+)

4 3

Gibbsite
2 1 0 -6 -5 -4

Quartz
Kaolinite

-2

-1

log aH SiO 0

Aluminum
2

-2

+++

log a Al

Gibbsite
-4

Al

+++

-6

Al(OH)4

-8

25oC
-10 2 3 4 5 6 7 8 9 10 11 12

pH

Greg Mon Nov 01 2004

Diagram A l

+ AlOH Al(OH)2

++

+++

, T = 25 C , P = 1. 013 bars , a [ H 2O] = 1

14

12

Fe(OH)4

10

pH

Fe(OH)3

Fe(OH)3 (ppd)

Fe(OH)2
++

FeOH
2

25C +++
4 2 0
Lab user Fri Oct 02 2009

0 10

log a Fe

Diagram Fe

Fe

+++

+++

Fe2 (OH)2

++++

, T = 25 C , P = 1.013 bars, a [H 2O] = 1; Suppressed: FeO(c), Hematite, Goethite

Linking nutrient cycling and redox chemistry in fresh water lakes

P cycling and sediment microbes

PO43- PO43-

Iron reducers
Sulfate Reducers

PO43-

PO43-

FeOOH
PO43-

Fe2+
FeS2

H2S

PO43- PO43Blue Green Algae blooms?

N cycling and sediment microbes

NO3Ammonifying bacteria

NH4+

Solid State Analysis

X-Ray Fluorescence Spectroscopy (XRF)

X-ray Diffraction (XRD)

Extractions
Using selected acids, bases, organics, chelators to dissolve a subset of minerals Many possibilities for this We will look at 2 used to investigate Fe, Mn, P:
Aqua Regia Combination of Nitric Acid and Hydrochloric acid, heated to just below boiling dissolved most stuff (but not all!!) Ascorbic Acid extraction Combination of ascorbic acid and bicarbonate

FeOOH/MnOOH in sediments
Ascorbic acid extraction technique specific to reactive Fe and Mn (Kostka and Luther, 1994) XRD data confirms reactive stuff is ferrihydrite Size is nanloparticulate, sensitive to degree of recycling!

Where is the Phosphorus?

P mobility measured through hundreds of sediment digests for samples in Missisquoi Bay collected at different times, places, and depths
P vs. Fe

2008 Sediment Extraction Correlation Statistics Ascorbic Acid (reactive) R2 0.8952 0.6561 0.6895 0.4653 p-value 6.4 x 10-100 3.1 x 10-48 2.7 x 10-27 1.5 x 10-26 n
202 202 184 184

Aqua Regia (total) R2 0.1940 0.3026 0.1709 0.6883 p-value 3.5 x 10-10 5.0 x 10-16 5.0 x 10-9 3.4 x 10-48 n
185 185 185 185

Only strong and consistent correlation is with reactive Fe, present predominantly as nanoparticulate FeOOH particles

P vs. Mn P vs. Ca P vs. Al

2007 Reactive Fe & Mn vs Reactive P

0.700 0.600 0.500 0.400 0.300 0.200 0.100 Fe vs P P vs. Mn

2008 Reactive Fe vs P
1.2 1 mg P/g dry sed. 0.8 0.6 0.4 0.2 0 y = 0.0626x + 0.1195 R = 0.8952

y = 0.0779x + 0.0928 R = 0.8862 y = 0.4726x + 0.2519 R = 0.5681

1.000 2.000 3.000 4.000 5.000 6.000 7.000

0.000 0.000

10 Fe mg/g dry sed.

15

20

2008 Total Fe and Mn vs P

2.50

2007 Total Fe vs Total P

2.50

mg P/g dry sed.

2.00

y = 0.04x - 0.4575 R = 0.5946 mg P/g dry sed

y = 0.6168x + 0.6817 R = 0.6537 2.00

1.50 y = 0.5057x + 0.6956 R = 0.6325

1.50 T Fe vs. P TMn vs. P y = 0.026x + 0.081 R = 0.909

1.00

1.00

0.50 p < 0.001 0.00 0.00 20.00 40.00 60.00

0.50

0.00 0.00

20.00

40.00 60.00 80.00 mg Mn or Fe/g dry sed

100.00

mg Mn or Fe/ g dry sed.