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Advanced Aqueous Geochemistry DM Sherman, University of Bristol

22010/2011

Geochemical Modelling of Acid Mine Drainage !


Advanced Aqueous Geochemistry DM Sherman, University of Bristol

What is Acid Mine Drainage? !


"Pollution associated with abandoned mines resulting from the oxidation of FeS2 (pyrite). "Very acid streamwaters with mobilized heavy metals. "Some AMD is natural (the mining industry prefers that it be called acid-rock drainage)

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Advanced Aqueous Geochemistry DM Sherman, University of Bristol

22010/2011

The Rio Tinto (Spain) !


SW Spain, mining activity for > 3000 years.

Pyrite (FeS2) !
Pyrite is the most common sulfide mineral and occurs associated with hydrothermal ore deposits and in coal derived from marine deposits.

In pyrite the oxidation state of sulfur is -1 (S2-2)

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Advanced Aqueous Geochemistry DM Sherman, University of Bristol

22010/2011

Pyrite/FeOOH Stability !
(species in italics are aqueous complexes)

Acid Generation by S22- Oxidation !


Oxidation of S22- generates H+ FeS2(s) + (7/2)O2(g) + H2O ! Fe2+ + 2SO42-(aq) + 2H+(aq) Oxidation of S2- does not generate H+ CuFeS2(s) + 4O2(g) ! Cu+2 + Fe2+ + 2SO42-(aq) FeS(s) + 2O2(g) ! Fe2+ + SO42-(aq) ZnS(s) + 2O2(g) ! Zn2+ + SO42-(aq)

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Advanced Aqueous Geochemistry DM Sherman, University of Bristol

22010/2011

Fundamental Reactions in AMD !


FeS2(s) + (7/2)O2(g) + H2O ! Fe2+ + 2SO42-(aq) + 2H+(aq)

4Fe+2 + O2 + 2H+ ! 2Fe+3 + H2O

Fe+3 + 2H2O = FeOOH (goethite) + 3H+

PHREEQC Generation of AMD !


We can model these reactions using a simple input:

TITLE Generate Acid mine water vi REACTION! SOLUTION 1 PURE WATER! pH 7.0! temp 25.0! EQUILIBRIUM_PHASES 1 !! !Pyrite 0.0 0.1! !Goethite 0.0 0.0! REACTION 1! O2 1.0! 0.5 moles in 100 steps!

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Advanced Aqueous Geochemistry DM Sherman, University of Bristol

22010/2011

Reaction Simulation of Pyrite Oxidation !


Extremely acidic solutions result

High concentrations of dissolved Fe+2

Precipitation of FeOOH !
Iron(III) (hydr)oxides precipitate out from solution when pH > 3.

Goethite ("-FeOOH)

Schwertmannite (Fe8O8(OH)6SO4)

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Advanced Aqueous Geochemistry DM Sherman, University of Bristol

22010/2011

Evaporite Deposits of FeSO4 !


Under acidic conditions, abiotic oxidation of Fe2+ is slow. In the Rio Tinto, FeSO4.nH2O precipitates upon evaporation.

PHREEQC Generation of AMD !


Inclusion of K-Feldspar and Secondary Phases
TITLE Generate Acid mine water vi REACTION! SOLUTION 1 PURE WATER! pH 7.0! temp 25.0! EQUILIBRIUM_PHASES 1 !! !Pyrite 0.0 0.1! !Goethite 0.0 0.0! !K-Feldspar 0.0 1.0! !Alunite 0.0 0.0! !Kaolinite 0.0 0.0! !Chalcedony 0.0 0.0! REACTION 1! O2 1.0! 0.5 moles in 100 steps!

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Advanced Aqueous Geochemistry DM Sherman, University of Bristol

22010/2011

Pyrite+K-Feldpar !
Dissolution of K-Felspar buffers pH to high values.

Remediation of Acid Mine Waste I !


A plausible method to deal with acid mine water would be to neutralize it using carbonate (Calcite, CaCO3). 2H+ + CaCO3 = Ca+2 + CO2 Trials of this method in Cwm Rheidol, Wales were not encouraging. A precipitate of CaSO4 formed on the surface of calcite and prevented the above reaction.!

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Advanced Aqueous Geochemistry DM Sherman, University of Bristol

22010/2011

Simulation of CaCO3 Addition !


TITLE Titrate AMD with Calcite! SOLUTION 1 PURE WATER! pH 7.0! temp 25.0! EQUILIBRIUM_PHASES 1 !! !Pyrite 0.0 0.1! !Goethite 0.0 0.0! !O2(g) ! ! -0.7 1000.! SAVE SOLUTION 2 # Generated AMD solution! END! USE SOLUTION 2! REACTION 1! CaCO3 1.0! 0.3 moles in 100 steps! EQUILIBRIUM_PHASES! Goethite 0.0 0.06! Gypsum 0.0 0.0! Calcite 0.0 0.0! END!

Simulation of CaCO3 Addition !


We can remediate AMD using CaCO3.

The major problem in active remediation using CaCO3 is pptn of gypsum.

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Advanced Aqueous Geochemistry DM Sherman, University of Bristol

22010/2011

Kinetics of Pyrite Oxidation by Oxygen !


FeS2(s) + (7/2)O2(g) + H2O ! Fe2+ + 2SO42-(aq) + 2H+(aq)

rate (moles/m -s) = 10

!8.10

[O2 ]0.5 [H ]0.11

At pH 2.0 in air-saturated conditions [O2] = 10-3.6 mol/ kg, t1/2 = 16 years for 0.05m2/g.

Fe2+ Oxidation facilitated by Bacteria !


Thiobacillus ferrooxidans is the most important bacteria that facilitates the oxidation of pyrite by generating Fe3+ !

4Fe2+(aq) + O2 + 4H+ ! 4Fe3+(aq) + 4H2O Thiobacillus ferrooxidans is acidophillic, autotropic and fixes its carbon from atmospheric CO2.

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Advanced Aqueous Geochemistry DM Sherman, University of Bristol

22010/2011

Kinetics of Pyrite Oxidation by Fe3+ !


FeS2(aq) + 14Fe3+(aq) + 8H2O(l) ! 15Fe2+(aq) + 2SO42-(aq) + 16H+(aq)

rate (moles/m2 -s) = 10!8.58

[Fe 3+ ]0.3 [Fe 2+ ]0.47 [H ]0.32

At pH 2.0 with [Fe]tot = 10-2 and [Fe2+]/[Fe3+] = 0.01, t1/2 = 150 days for 0.05m2/g.

Pyrite Oxidation Summary !


(a) FeS2(s) + (7/2)O2(g) + H2O ! Fe2+ + 2SO42-(aq) + 2H+(aq) (b) 4Fe2+(aq) + O2 + 4H+ ! 4Fe3+(aq) + 4H2O Slow

Via Fe2+ oxidizing chemolithoautotrophs

(c) FeS2(aq) + 14Fe3+(aq) + 8H2O ! 15Fe2+(aq) + 2SO42-(aq) + 16H+(aq) Fast, autocatalytic mechanism

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Advanced Aqueous Geochemistry DM Sherman, University of Bristol

22010/2011

Kinetics of AMD formation !


TITLE Generate Acid mine water vi REACTION! SOLUTION 1 PURE WATER! pH 7.0; temp 25.0! EQUILIBRIUM_PHASES 1! Goethite 0.0 0.0001! O2(g) -0.7 1000.! KINETICS 1! Pyrite; m0 0.1! -step 9e8 in 100 # 28 years! RATES! Pyrite # rates from data compiled by! # Williamson and Rimstidt 1994, GCA 58, 5443! -start! 1 A = 0.3 * m0 # surface area in m2/dm3! 10 if SI("Pyrite")>0 then goto 100! ...! END!

Kinetics of AMD formation !

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Advanced Aqueous Geochemistry DM Sherman, University of Bristol

22010/2011

Summary !
"Acid Mine Drainage results from the oxidation of pyrite. "Geochemical modelling can be used to test if a rock is suseptible to AMD "Geochemical modelling can also be used to test the effect of active remediation strategies.

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