Static Geochemical Tests

For Mine Drainage Prediction

Acid Base Accounting
Net Acid Generating Test
Mineralogy- Optical, X-ray Diffraction
Elemental X-ray Florescence
Sampling
Acid Base Accounting
Maximum Potential Acidity (MPA), also called Acid Production
Potential (APP)
Neutralization Potential (NP), also called Acid Neutralizing Capacity
(ANC)
Net Neutralization Potential (NNP), also called Net Acid Production
Potential (NAPP)
NNP = NP - MPA
Paste pH, Fizz
Does not predict pH or concentrations of metals and sulfate
Acid Base Accounting Stoichiometry
FeS
2
+ 2 CaCO
3
+ 3.75 O
2
+ 1.5 H
2
O
2 SO
4
2-
+ Fe(OH)
3
+ 2 Ca
2+
+ 2 CO
2

One mole of pyrite oxidizes to produce 4 moles of acidity, sulfate and Iron Hydroxide.
Two moles of calcium carbonate (calcite) are required to neutralize the acidity.
On a mass basis, 200 grams of calcium carbonate are required for 64 grams of sulfur
from pyrite, or ratio of 3.125. When Acid Base accounting is expressed in parts per
thousand, the mass ratio is 31.25.
+
+
=
=
Neutral
Neutral
Water
Water
Acid Base Accounting Stoichiometry
One Mole Pyrite Two Moles Calcite
Maximum Potential Acidity
Calculated from total sulfur measurement. ABA assumes all
sulfur present as pyrite. For many rocks this is a valid
assumption.
Ore bodies and waste rock at metal mines usually contain
different sulfide minerals such as sphalerite (ZnS), galena
(PbS), and others, in addition to pyrite.
Not all sulfide produce acidity when oxidized, so total sulfur
will probably over estimate potential acidity. For these mines,
identification of specific sulfide minerals is helpful, using X-
ray diffraction (XRD) and x-ray florescence (XRF) or optical
techniques. The samples may also be tested using kinetic
methods
If sulfate minerals or organic sulfur are present, fractionate
into sulfide, sulfate and organic. Organic S considered non-
acid forming
Maximum Potential Acidity
Sulfate minerals like gypsum CaSO
4
* 2 H
2
O do not form
acid drainage.
Metal sulfate salts such as copiapite Fe
II
Fe
III
4
(SO
4
)
6
(OH)
2
* 20
H
2
O, represent stored acidity. They generate acidity by
dissolving and metal hydrolysis.
Fe
II
Fe
III
4
(SO
4
)
6
(OH)
2
* 20 H
2
O Copiapite dissolution
Fe
2+
+ 4 Fe
3+
+ 6 SO
4
2-
+ 2 OH
-
+ 20 H
2
O
Fe
3+
+ 3 H
2
O Fe(OH)
3
+ 3 H
+
Oxidation and Hydrolysis of
5 moles of Fe yields 14 moles H
+
, minus 2 moles OH
- .
Sulfate fractionation does not identify the minerals.
Sulfate Salts on Coal
Neutralization Potential
A measure of acid neutralizing capacity of a
rock.
NP represent mostly carbonates, and small
amounts of exchangeable bases and soluble
silicate minerals.
Modification of a test method designed to
measure the calcium carbonate content of
agricultural lime
Neutralization Potential Siderite interference
The iron carbonate, siderite can interfere with the determination of neutralization
potential. Siderite will produce a net neutralization of zero.
FeCO
3
+ 2 H
+
Fe
2+
+ CO
2
+ H
2
O (Neutralization)
Fe
2+
+ 0.25 O
2
+ H
2
O + H
+
Fe
3+
+ 1.5 H
2
O (Oxidation)
Fe
3+
+ 3H
2
O Fe(OH)
3
+ 3H
+
(Hydrolysis)
FeCO3 + 1/4 O2 + 3/2 H2O Fe(OH)3 + CO2
Summary reaction
A modified test using H
2
O
2
is used in some laboratories to correct for siderite
Effects of Siderite and Test Method
on Neutralization Potential
926 926 90%
Calcite
56 64 8% Siderite
55% Clays
16 70 49% Siderite
NP (ppt)
H
2
O
2
Method
NP (ppt)
Standard
Method
Sample
Composition
Data from Skousen et al, 1997
Example Acid Base Accounting Data
1.37 Coal
-37.65 13.6 51.25 1.64 0.36 Sandstone,
gray
-14.16 15.22 29.38 0.94 0.3 Shale,black
2.16 18.21 16.25 0.52 0.3 Shale,black
3.36 8.05 17.5 0.56 0.8 Shale,black
5.88 10.57 15.94 0.51 0.9 Shale,gray
4.33 9.02 4.69 0.15 0.9 Shale,gray
696.3 701 4.69 0.15 0.58 Limestone
760.3 765 4.69 0.15 0.3 Limestone
816.3 821 4.69 0.15 0.3 Limestone
NNP
(ppt)
NP
(ppt)
MPA
(ppt)
% S Thickness
(meter)
Rock Type
Summary Interpretation Acid Base Accounting
Ratio of NP:MPA.
Ratio <1, likely acid producer
Ratio 1<Ratio<2, Variable, some acid, most alkaline
Ratio> 2, acid neutralizer, source of alkalinity
Neutralization Potential
NP>20ppt, acid neutralizer, source of alkalinity
10<NP<20, Variable, some acid, most alkaline
NP<10, likely acid producer
Net Neutralization Potential
NNP>12, acid neutralizer, source of alkalinity
0<NNP<12, Variable, some acid, most alkaline
NNP<0, likely acid producer
Net Acid Generating Test (NAG), Australia
React sample with H
2
O
2
overnight to oxidize pyrite. Acid formed
should react with neutralizers.
Measure pH, Acidity, sulfate, specific conductance and others. Titrate
solution to pH 7.Calculate H
2
SO
4
equivalent
Repeat sequence for samples with more than 1.5% S
Suggested Interpretation of NAG Test
If pH=4.5 , NAG = 0, does not form acid
If pH<4.5 , NAG < 5, low acid former
If pH<4.5 , NAG > 5, likely to form acid
Interpretation may vary by site conditions
Example NAG Data, Australia
0.4 4.0 13 11 24 0.8 C
6.3 78 124 202 6.6 B
7.3 243 205 450 14.7 A
NAG NAG
pH
NAPP ANC MPA % S Sample
From ARD Test Handbook, 2002, AMIRA International, Melbourne, Australia
NAG Sample Interpretations
Sample A. Mineralogy shows all S in pyrite, but oxidizing slowly.
Reactive neutralizers present. May generate acidity long term after
carbonates are reacted.
Sample B. Much of S present in Galena (PbS) and sphalerite (ZnS),
which do not form acid. Sample has enough neutralizers present to
produce non acid water.
Sample C. Low acid forming potential, but also low acid neutralizing
capability.
Mineralogy
Identify specific minerals present using optical methods, X-ray diffraction,
scanning electron microscope
Calcite and dolomite Illite