HIDROKIMIA

AIR ASAM TAMBANG

Peristilahan
Acid Mine Drainage (AMD)
Air yang terkontaminasi akibat
kontak dengan aktivitas
penambangan

Acid Rock Drainage (ARD)

Batuan alami yang bersifat
asam

Keduanya menghasilkan air

asam Bagaimana
membedakannya?

KARAKTERISTIK AMD

Meningkatnya keasaman = Penurunan pH

Peningkatan konsentrasi logam
Peningkatan Sulfat
Peningkatan zat padat terlarut

Metals

Hg, Pb

As, Se
Cd, Sb,
Ag, CN
Cu, Zn
Pb, U
Cr, Fe
Hg

Efek thd Aliran Sungai

Air menjadi berwarna:
Yellow boy
Oksida besi, umumnya
memperlihatkan karat di
dasar aliran

Putih
Aluminum

Hitam
Mangan

Ditentukan oleh besarnya

pH-nya.

Perubahan dalam teknologi

tambang
Produk lama
Tambang yg sdh ditutup
Tumpukan tailing
/waste rock
ARD

Cara Baru
Pengolahan dengan teknologi sianida heap
leach

Kimia AMD
Pelapukan Pirit

+
Jenis Logam: Kaya As, Sb, Zn, Cu
Fe, Al, Mn
Kaya Sulfate

pirit
air
udara

pH rendah
+ Logam

Mineral yang kaya Pirit

Logam-logam sulfida
Fe - pyrite, marcasite, pyrrhotite
Hg - cinnabar
Pb galena
Ag acanthite, galena
As arsenopyrite, As-rich pyrite, orpiment, tetrahedrite, enargite
Ni pentlandite, millerite
Cu covellite, chalcocite, djurleite, bornite, chalcopyrite, enargite
Cd greenockite
Zn spahlerite
Co cobaltite

Besi-Sulfida
Pyrite (FeS2)
Marcasite (FeS2 )
Galena (PbS)
Arsenopyrite (FeAsS)

Pyrrhotite (Fe(1-x)Sx)
Chalcopyrite (CuFeS2)
Sphalerite (ZnS)
Bornite (Cu5FeS4)

Kimia AMD

Oksida besi

4FeS2 + 14 H2O + 15 O2 4Fe(OH)3 + 8 SO42- + 16 H+

Keseluruhan
menghasilkan air asam

Oksidasi Pirit: II
FeS2 + 7/2O2 + H2O Fe2+ + 2SO42- + 2H+
FeS2 + 14Fe3+ + 8H2O 15Fe2+ + 2SO42- +16H+

Fe(II) + S2

2-

+ O2
FeS2 (s) + O2

Fe (II) + SO4

2-

fast
microbial
+ O2
+ FeS2 (s)
slow
fast
inorg.
Fe(III) = Fe(OH)3 (s)
Sumber:
Stumm and Singer (1980)

Kinetik Oksidasi Pirit

Assumed Conditions/Predicted Half Times
Oxidants
pH
log[O2]
log[Fe3+] log[Fe2+]
t1/2
________________________________________________________
O2
2.0
-7.0
--780y
-3.6
--16y
Fe3+

2.0

--

-2.0
-2.0

-4.0
-2.0

Sumber: Langmuir (1996) menggunakan kecepatan rekasi dari

Williamson & Rimstidt (1994), PyArea=0.05 m2/g

4.4d
150d

Oksidasi Pirit: III

Kimia
Oksigen, Fe(III), Air, Larutan
buffer

Fisika
Tekstur, Ukuran Butir
Temperatur

Biologi
Oksidasi Fe- dan S-oleh bakteri

Bakteri sebagai Katalisator

Reaksi AMD

Efek Temperatur thd Oksidasi

Proses buffering ARD selama Oksidasi

Mineral

Proses buffering ARD selama

Oksidasi Mineral
Buffering of Mineral A
(e.g. calcite, dolomite)
Buffering of Mineral B
(e.g. ankerite, siderite)
Buffering of Mineral C
(e.g. Al(OH)3)
pH

Buffering of Mineral D
(e.g. feldspars)
Time

Kimia AMD
Luas permukaan kontak
Semakin luas permukaan semakin cepat bereaksi
Lebih kecil butiran lebih luas permukaannya

Pengolahan AMD
Cara Aktif dan Pasif
Aktif
Penambahan alkalinitas untuk meningkatkan pH
Efektif tetapi mahal

Pasif
Menggunakan cara-cara alami
Perawatan mudah dan murah
Tergantung dari volume

Contoh Pengolahan AMD cara

Pasif

Pengolahan AMD cara Pasif

Input
Fe , SO , H , Me
3+

24

Plant uptake

Output=
Cleaner

[inc. pH]

Oxidizing
ppt of Fe-OH-O-SO4
adsorption
See Kwong & Stempvoort (1994)
(Mt. Washington, B.C.)

Reducing
2SO4 to H2S
ppt (Fe,Me)S

Pengolahan AMD cara Pasif

O2 H2O
2+

Fe

SO4

Mine Tailings

2-

Fe(OH)3
Al(OH)3
FeCO3
after Ptacek and Blowes (1994)

CaCO3

Other authigenic ppts:

Goethite, jarosite, schwertmannite

Mekenisme pengendalian ARD

pada Waste Batuan
Precipitation

Surface Discharge
Tailings
Oxidation Zone
Neutralization Zone

Dam
Process Water

Seepage

Mekenisme pengendalian ARD

pada Tailing
Precipitation

Sulfide Waste Rock

Infiltration

Surface Runoff

Basal
Drainage
Seepage
Collection
Ditch

Mekenisme pengendalian ARD

pada Open Pit
Precipitation

Surface Water Runoff

Pre-Mining
Groundwater
Table

Infiltration
ARD Seepage

Post-Mining
Groundwater
Table

Residual Sulphide
Rock Debris

Residual
Sulphides

ARD Seepage

Ore Body

ARD Seepage

Groundwater Flow
Through Rockmass

Mekenisme pengendalian ARD

pada Underground
Precipitation
Backfill Alternatives

Open Pit
Water
Flow

GloryHole

Sulphide
Exposure

Infiltration

Mine
Workings

Open Stope

Rockfill
Residual
Sulphide Exposures
(see inset backfill
alternatives)

ARD

Mine
Workings

ARD

Ore Body
C

Tailings
(uncemented)

Tailings
(cemented)

Pre-Mining
Groundwater
Table

Post-Mining
Groundwater
Table

Pengolahan cara aktif

Umumnya menggunakan cara :
- Oksidasi
- Penambahan Alkali
- Sedimentasi

Alkali Minerals
Jenis
Karbonat
Kalsit (CaCO3)
Dolomit (Ca,Mg(CO3)2)

Hidroksida
Fe(OH)3
Al(OH)3

Silikat
Lempung

Contoh Pengolahan Aktif

Iron Mountain, California

Pengolahan Cara Baru

Cyanide Heap Leach Penumpukan
dan Peluluhan dgn sianida.
Umum pada pengolahan emas
Ekstraksi Au dari bijih berkadar rendah
Bijih dihancurkan, ditempatkan di ruang
terbuka untuk proses CHL
Sianida disemprotkan di atas tumpukan
Luluhan Au mengalir melalui bijih
Larutan disaring dihasilkan Au
Cara yang mudah?

Kerangka & tahapan

Penelitian ARD
Kimia air tergantung kepada:

Derajat & tingkat oksidasi

Derahat & tingkat pelepasan logam
Jumlah material
Contained metals
Hidrologi dan iklim lolasi hydrology and
Akumulasi produk yang
mudah teroksidasi
pH/kontrol kelarutan,
reaksi selama aliran
Kontrol Teknologi

Site Characterization

Design
Field investigation & Sampling
Lab testing

New Mines vs. Existing Mines

New Mines
ARD probably not evident
Objective is to determine ARD potential
Fresh samples used for testing and prediction
Long term behavior based on kinetic testing, modeling and
prediction
Existing and Abandoned Mines
ARD may be evident/mature
Field reconnaissance used to define ARD
Historic data (time trends) extremely useful
Limited laboratory testing required
Field instrumentation and monitoring possible
Background altered, requires simulation

Design

Review existing data, e.g:

Geology & mine plan

Drill core logs
Water quality monitoring results
Assays on ore/waste rock and tailings
Waste type volumes
Waste placement history

Develop reconnaissance & sampling

plan

Field Investigations
Objectives
Detect early signs of ARD
Determine potential for ARD
Assess factors that control ARD
Evaluate control measures
Determine environmental impact
Assess compliance with regulatory
standards

Field Investigations
What to bring:
Eyes that know what to look
for
pH and conductivity meters
Acid bottle, hydrogen
peroxide, sulfate kit
Geological pick, hand lens,
sampling bags, camera,
GPS unit
Site map, history, data

2.2

Field Investigations
Things to look for:
Visible pyrite or other sulfides (oxidation) & calcite
Red, orange, yellow, white, blue staining (precipitates, water)

Dead vegetation or bare ground

Melting snow or steaming vents on waste
Dead fish or other biota
Low pH in seeps, groundwater, decants & streams

Field Investigations
Things to log in the field:
Paste pH
Paste conductivity
Colour
Lithology
Sulfide content
Secondary mineralogy
Degree of fizz
Moisture content
Grain size

Field Investigations
General Methodology
Visual observation of site
Paste pH and water quality data
Field extraction testing
Classify types of wastes
Solids sampling (for lab testing)

Field Investigations
Geochemistry:

Low paste pH of mine wastes

High conductivity of waste paste
Contaminants in leach extraction tests
Static (ABA) tests

Products from Reconnaissance:

Physical disturbance and drainage map

Waste deposit map and characterization
Exposed rock map and characterization
Paste pH and conductivity survey
Observations and sampling map
ARD site assessment report

TDS vs pH
Field Paste pH vs. Field Paste TDS

Field Paste TDS

2200
2000

Dike samples

1800

Leach Pad Samples

1600

Pit Samples

1400

Waste Rock Samples

1200
1000
800
600
400
200
0
0.0

2.0

4.0

6.0

8.0

Field Paste pH

10.0

12.0

14.0

Sample Selection (New Mines)

Step 1: On geological sections:
Define rock types
Define sulfide and alkali mineral distribution
Preliminary rock units classification
Step 2: Sample each rock unit class allowing for:
Area distribution of class
Variability of rock
Step 3: Perform static lab tests and use results to refine rock unit
classification
Step 4: Sample each new rock class and repeat Step 3 until
satisfied.
Step 5: Sample each rock class for appropriate kinetic testing and
use results to refine rock classification
Step 6: Repeat Step 5 until satisfied with classifications and
characterization.

Sampling (existing mines)

Steps:

Define geology, mineralization,

waste types etc.
Define objectives (i.e. sampling for
reveg, cover, water quality
evaluations etc. may have different
focus)
Consider mine plan and waste
placement history
Identify sources of samples
Initial sampling and testing program
Further sampling if necessary

Sampling
(Existing Mines)

A Becker hammer-type drill rig

can be used in order to
minimize sample crushing and
the geochemical disturbance of
the samples
Samples typically collected at
specified intervals (e.g. every
10 ft) & paste pH and EC
measured,
A sub-set of samples can then
be selected using observations
and field measurements as a
guide for more detailed
laboratory testing

Test Methods
Static ARD Tests
balance between potentially acid generating and consuming
tool for waste management
includes geological/mineralogical
characterization
individual samples

Short-term Leaching Tests

readily soluble component

Kinetic Tests
oxidation and metal leaching rates
water chemistry prediction

Geochemical Static Tests

Objective:
Potentially Acid Generating Minerals
vs

Acid Neutralizing Minerals

Cautions for ARD assessment:
pH of alkalinity (NP) determination
Assumes instant availability of NP
Assumes all sulphur/sulphide
minerals reactive
Ignores reaction rates (kinetics)
Extrapolation to field

Geochemical Static Tests

Procedures
Paste pH and conductivity on the as received fines
Acid-Base Accounting Tests
Net Acid Generation (NAG) - also an accelerated kinetic test
B.C. Research Initial Test
Lapakko Neutralization Potential Test
H2O2 Oxidation (modified for siderite correction)
Net Carbonate Value (NCV) for ABA Tests
Leach extraction analyses
Forward acid titration tests
Multi-element ICP analyses

Geochemical Static Tests

Definitions:
AP
= acid potential
= % S x 31.25
NP
= neutralization potential
NNP = net neutralization potential
= NP - AP
NP:AP ratio
= NP/AP
All expressed as:
kg CaCO3 equivalent/tonne, or
CaCO3 eq./1000 tonnes

Example:
S=2%
AP = 62.5 kgCaCO3/t
NP = 90 kgCaCO3/t
NNP = 27.5 kgCaCO3/t
NP/AP = 1.4:1

Note: units and acronyms used are different in Australiasia, local references
should be sought for correct usage, terminology, guidelines etc.

Interpretation
20

NP (kg CaCO3/t equiv)

Non-acid
generating

1:1 ratio

3:1 ratio

15

Uncertain acid
generating potential
Potentially acid
generating

10

Start with
guidelines or
general criteria
for classification,
then develop
site- specific
criteria

12
Potentially acid
generating

10

0
5
AP (kg CaCO3/t equiv)

Typically criteria are

based on a set of
tests, not just one
type of test e.g. ABA
& NAG results

10

15

Paste pH

Uncertain acid
generating potential

Non-acid
generating

20

6
4
2
0
-50

-30
-10
10
30
Net Neutralisation Potential (NP-AP) (kg CaCO3/t equiv)

50