Geochemical evolution of active porphyry

copper tailings impoundments:

From alkaline deposition towards acidification

Jochen Smuda
General introduction Dr. Jochen Smuda

Outline

Introduction
Mining as environmental factor, Processing of ore, acid-producing
processes, aims of the thesis, locations, method
Results I: Carén tailings impoundment
Results II: Talabre tailings impoundment
Conclusions
General introduction Jochen Smuda

Mine wastes - the largest volume of materials

handled in the world
> 5 billon tons handled per year 1
~ 1,000 times the pyramid of Cheops!

Principal problem: Exposure to weathering

1: ICOLD (1996)
General introduction Jochen Smuda

Processing of Cu-Mo ore, transport and

deposition of tailings
Copper production: 17,974,300 tons per year (London Metal Exchange, 2007),
mainly from porphyry copper deposits with 1-2 wt.% Cu

Cu and Mo
concentrate: Tailings:
1-2 % sandy/silty
98-99 % ca. 50 vol% water, including
“non-economic” sulfides,
Flotation e.g., pyrite, enargite, galena, ...

Milling
Crushing

Open pit Tailings impoundment

Underground
mine Acid Mine Drainage
Sulfide ore
General introduction Jochen Smuda

Mining, flotation and tailings discharge

General introduction Jochen Smuda

Acid Producing Processes

Sulfide oxidation (e.g., pyrite)

FeS2 + 7/2 O2 → Fe2+ + SO42- +2 H+
FeS2 + 14 Fe3+ + 8 H2O → 15 Fe2+ + 2 SO42- + 16 H+
Fe2+ + ¼ O2 + H+ ↔ Fe3+ + ½ H2O
(microbiological catalyzed e.g., A. ferrooxidans)

Hydrolysis
Fe3+ + 3 H2O → Fe(OH)3 + 3 H+
Precipitation
4 Fe(OH)3 → 2 Fe2O3 • ½ H2O + 5 H2O
Ferrihydrite

Transformation
2 Fe2O3 • ½ H2O + H2O → 4 FeO(OH)
Ferrihydrite Goethite
General introduction Jochen Smuda

The porphyry copper systems

El Teniente and Chuquicamata
Arica
Cu-Mo porphyry
Chuquicamata
copper deposits (>70 Mt
Mine Cu)
Main sulfide ore
minerals: Pyrite,
Santiago chalcopyrite, digenite,
El Teniente Mine
bornite, molybdenite,
sphalerite, galena and
Porphyry tennantite
copper
Chile belt Gangue: quartz, alkali-
feldspar, biotite,
anhydrite-gypsum and
Punta Arenas carbonates
General introduction Jochen Smuda

Aim of the presented site studies

In the framework of similar studies of mine waste impoundments
in different climates and with different deposition techniques, we
try to identify:

- Water sources and pathways in active tailings systems

- Geochemical processes of Acid Mine Drainage in fresh
tailings
- Transport processes in mine waste systems
- Climatic influences on the above mentioned processes

Final aim: Early control of AMD formation

Methods Jochen Smuda

Sampling
Sediments Water
coring up to 2.5 m depth at Carén Piezometer up to 4 m depth
up to 8 m at Chuquicamata

Field measurements
Eh, pH
Pore air
Electrical conductivity
O2, CO2 and H2S in
the vadose zone Alkalinity
Methods Talabre Jochen Smuda

Mineralogical and Geochemical Approach

Solid samples (coring up to 8m)

- Optical microscopy, XRD, SEM-EDS
- Major and trace elements (XRF)
- Sequential extractions
- δ34Sprimary sulfate/sulfide, δ18Oprimary sulfate
Water samples (vadose zone, groundwater zone)
- Mayor (HPIC) and trace elements (ICP-MS), As (HG-AAS)
- δ2Hwater , δ18Owater
- δ34Sdissolved sulfate, δ18Odissolved sulfate
- Geochemical modeling: PHREEQC2 (speciation of
elements, saturation indices of minerals) and
Hydra/Medusa (predominance diagrams)
Introduction Carén Jochen Smuda

Geochemistry of fresh alkaline porphyry

copper tailings: Implications on sources and
mobility of elements during transport and
early stages of deposition
Introduction Carén Jochen Smuda

The Carén Tailings Impoundment

Climate: Mediterranean (412 mm precipitation/year)

Fresh tailings: alkaline pH (10.5)
Introduction Carén Jochen Smuda

Focus of research

Impact of long transport way

on tailings
Sulfide oxidation in totally
water-saturated systems with
constant deposition of fresh
tailings
Climatic influences (dry
summer, wet winter) on (the
evolution of) the system
Results Carén Jochen Smuda

Geochemical processes in the tailings channel

pH: alkaline
(9.2-10.2)
Eh: oxidizing
(243-267 mV)
Results Carén Jochen Smuda

Isotopic composition of tailings water

• Group I: Tailings pore
water with low influences of
tailings weathering,
evaporation and mixing
with catchment water
• Group II: Tailings pore
water mixed with winter
catchment water (origin:
rain)
• Group III: Tailings pore
water with high water-rock
interaction (e.g., gypsum
dissolution)
•Group IV: Tailings water
influenced by evaporation
and high water-rock
interaction (e.g., gypsum
precipitation)
Data for Santiago MWL: IAEA, Vienna, Austria,1990-1999
Results Carén Jochen Smuda

Water sources and pathways

TL-28
Results Carén Jochen Smuda

Cu and Zn mobilization in deep tailings

TL-26

(from Smith et al., 1992)

Concentrations:
Cu = 0.41µM
Zn = 10.0 µM
S = 10.0 mM
Cl = 0.73 mM
C = 0.68 mM
Results Carén Jochen Smuda

Sources and pathways of dissolved sulfate

A B 15.5 ‰
12
12 El Teniente mine δ34Sprimary sulfates
δ18Osulfate (‰ VSMOW)

Primary sulfates

δ34Ssulfate (‰ VCDT)
6
8
34 group II
δ Sprimary sulfides Mixing
0
zone
group I
4
-6
δ18Owater
-12 δ34Sprimary sulfides
0
-8 -4 0 4 8 12 16 1500 1750 2000 2250 2500
34
δ Ssulfate
C (‰ VCDT) 15.5 ‰ SO4 (mg/L) – 6.7 ‰
D
12 12
δ18Osulfate (‰ VSMOW)

10

δ34Ssulfate (‰ VCDT)
δ18Oprimary sulfates δ34Sprimary sulfates
8 8

6
group II
group I
4 4 δ34Ssec.
group I group II efflor.
salts
2 δ18Osecondary efforescent salts
δ34Sprimary sulfides
0 0
-15 -12 -9 -6 -3 0 -15 -12 -9 -6 -3 0
δ18Owater (‰ VSMOW) – 6.7 ‰ δ18Owater (‰ VSMOW)
+ decantation lake and river downstream $ tailings sediments (0m) / secondary efflorescent salts
( tailings channel and discharge & tailings sediments (1-4m) " sulfuric acid (acid flotation)
Primary sulfides and sulfates (El Teniente deposit): Data from Kusakabe et al. (1984) and this study
Conclusion Carén Jochen Smuda

Efflorescent salts

1 cm - Na-K-Ca sulfates (mirabilite

Na2SO4 *10H2O, syngenite
K2Ca(SO4)2(H2O), gypsum)
- Mo concentration up to 0.28
wt.%, most probable as
powellite (CaMoO4)
- lower δ34Ssulfate and δ18Osulfate
values in comparison to
dissolved sulfate of tailings
pore water
Conclusion Carén Jochen Smuda

Conclusions I
Carén impoundment in winter

Stage I
Deposition
New tailings
Water table
pH

7 pH 10
Conclusion Carén Jochen Smuda

Conclusions I
Carén impoundment in winter

Stage I Stage II
Deposition Dry out
New tailings Sulfide oxidation
Water table
pH pH

7 pH 10

7 pH 10 7 pH 10
Conclusion Carén Jochen Smuda

Conclusions I
Carén impoundment in winter

Stage I Stage II Evaporation

Deposition Dry out Rain events
New tailings Sulfide oxidation
Water table
pH pH δ18Owater
δ2Hwater

Catchment water
infiltration

-90 ‰ VSMOW -50 (δ2H)

7 pH 10 7 pH 10
-12 ‰ VSMOW -5 (δ18O)
Conclusion Carén Jochen Smuda

Conclusions II
Carén impoundment in summer

Stage I
Deposition
New tailings
Water table
pH

7 pH 10
Conclusion Carén Jochen Smuda

Conclusions II
Carén impoundment in summer

Stage I Stage II
Deposition Dry out
New tailings Efflor. salts
Sulfide Water table
pH oxidation
pH
δ18Owater, δ2Hwater

7 pH 10 -12 -5 δ18O
-90 -50 δ2H

7 pH 10
Introduction Talabre Jochen Smuda

Element cycling during the transition from

alkaline to acidic environment in an active
porphyry copper tailings impoundment,
Chuquicamata, Chile
Introduction Talabre Jochen Smuda

The Talabre tailings impoundment

5 years

2 years

DISCHARGE 3 years
POINT

4 years
Introduction Talabre Jochen Smuda

Overview

Dry tailings
Tailings discharge

Water sampling by piezometer

Results Talabre Jochen Smuda

Geochemical evolution of the tailings system

Results Talabre Jochen Smuda

Isotopic characteristics of tailings water

-20

.8
e

+9
lin
n
io

O
1

WL
-30 s 9.

8
s

.3δ 1
e 2
gr 8 O -

CM
re

=8
1
re 5 δ
b 4.
δ2H (‰ VSMOW)

la

δ 2H
-40 T a =
2H
δ

-50

-60
groundwater
salar water
fresh tailings
tailings vadose pore water (0-2m)
-70
tailings shallow groundwater (2-8 m)

-10 -8 -6 -4 -2 0 2
18
δ O (‰ VSMOW)
Results Talabre Jochen Smuda

Water in the vadose zone

Results Talabre Jochen Smuda

Deep tailings water

Results Talabre Jochen Smuda

Sources of dissolved sulfate

Results Talabre Jochen Smuda

Secondary mineral precipitation

Precipitation with the time sequence:

- Na-Ca-Mg sulfates and halite
- Cu sulfates, Cu clorides
In the seepage zone: Atacamite, halite
Conclusions Talabre Jochen Smuda

Conclusions

Hydrology of tailings in hyper-arid climate

Vadose zone

Groundwater
zone
Conclusion Jochen Smuda

General conclusions

Geochemical, mineralogical and stable isotope

studies on fresh tailings impoundments help to
identify:

- Water sources: Tailings water, infiltrating groundwater, percolating

neutral mine drainage (former AMD), condensated water in the
vadose zone (hot climates)
- Sulfate sources: Discrimination of dissolved sulfate from primary
sulfates, sulfates from the bedrock and secondary sulfate derived
from sulfide oxidation
- Transport processes in deep tailings: Depending on infiltrating
waters and changes of the discharge point
- Climatic influences: Infiltration of rain water, vaporation and
condensation of water in the vadose zone, capillary rise
 Jochen Smuda

Gracias!
Preguntas?