Geochemistry / Technical Note

Acid Base
Accounting
Acid Base Accounting (ABA) is a set of laboratory methods which
are used to identify the acid-production and acid-consumption
properties of a geological material. The methods are designed to
produce the best estimate of how likely a material is to be a net acid
producer or net acid consumer, therefore how likely to produce
Acid Rock Drainage (ARD). If minerals that neutralise acid are pres- Sobek Method
ent, then the hydrogen ions produced by the breakdown of The ABA method proposed by Sobek
sulphides will not migrate as they will be buffered. To prevent the et.al. (1978) assumes all sulphur in a
sample is present as pyrite and the
occurrence of ARD during mining and storage of waste and ore,
oxidation of that pyrite by oxygen. Each
the charac-teristics of the rocks being disturbed needs to be mole of sulphur produces two moles
of acid which is neutralised by one
determined to effectively plan mitigation measures.
mole of calcium carbonate. The molar
ARD can occur when sulphide minerals neutralising or acid producing) or ratio of sulphur to calcium carbonate is
are exposed to oxygen and water negative number (net acid producing). therefore 1:1. This gives a weight ratio
(surface conditions) and break down, The MPA is often referred to as the Acid of 100 g CaCO3/mole CaCO3 to 32g S/
releasing H+ ions. These H+ ions Production Potential (AP). The unit of mole S, or in standard AP units 31.25
decrease the pH and can result in acidic measurement for these values is kg kg/tonne CaCO3 per % S. To perform a
waters which can maintain more CaCO3 per ton. or tCaCO3/1000t ore. Sobek measurement a known amount
elevated concentrations of metals than of hydrochloric acid (HCl) is added to
Methods for determining the NNP have the sample and reacted. The amount
would occur in neutral pH water. These
been proposed by multiple research of HCl that is added to the sample
metals can have an adverse impact on
groups and some have been selected is determined by a preliminary fizz
aquatic life along with the low pH of
by government organisations to be part test. After the HCl-sample mixture is
water itself. Other impacts of low pH can
of mine development reporting combined, it is heated to near boiling
be the corrosive effect on pipes, and
requirements. The method required in to facilitate the reaction. When the
concrete infrastructure (Tarr and White,
2015). a particular jurisdiction varies, and this reaction has reached completion it is
information should be obtained from titrated with a base (sodium hydroxide
ABA laboratory methods produce the relevant government organisations. NaOH) to pH7.
values for both Maximum Potential ALS offers a wide range of methods for
Acidity (MPA) and Neutralisation This test has an upper boundary of
ABA estimation: Sobek, Modified
Potential (NP) which can then be used to sulphide content, if >9% of the material
Sobek, Siderite correction, Modified
calculate the Net Neutralisation is sulphide sulphur it will be acid
Neutralisation Potential from MEND,
Potential (NNP) of the material (balance producing. This is because if ~9.5% of
and EN 15875 methods. A brief
between acid production and acid material is sulphide sulphur (assumed
description of these methods and how
neutralisation). As the NNP is the NP to be pyrite) the rest of the material
they differ from one another is given on would have to be CaCO3 to neutralise
minus the MPA, it can be a positive
the following page.
(net acid neutralising), zero (neither the amount of acid produced.

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Modified Sobek (M) hydrogen peroxide (H2O2) is added to pH range is from 2- 2.5 and the end
the filtrate of hydrochloric acid (HCl) point of the titration is pH 8.3.
The Modified Sobek method bases the
digested siderite sample in order
AP on sulphide sulphur instead of total Paste pH
to oxidise ferrous iron to ferric iron
sulphur. A total sulphur method does
before back-titration. Because the Paste pH is measured on a mixture of
not take non-acid producing sulphates
resulting ferric iron is precipitated as sample and deionised water before
(e.g. gypsum and barite) into
iron hydroxide (Fe(OH)3) upon titration, any reactions are performed. This
consideration and can overestimate the
the solution yields a more accurate NP value is used to indicate if there is
AP of a sample. The Modified Sobek
value for siderite bearing material. readily available acidity or alkalinity
method uses a fizz test to determine
in the sample material (MEND 1991).
how much HCl is added to a sample MEND Method (B)
A pH below 5 is used to suggest that
(Lawrence and Wang, 1997). However,
This method uses the modified the material contains acidity due to
the titration endpoint is 8.3 instead of
neutralisation potential as outlined in acid generation prior to the test. The
7.0 as in the standard Sobek method.
MEND (1991). Two grams of pulverised measurement is performed on 10g
Also the temperature of reaction, 25-30°
sample are treated with an appropriate of sample material and saturated to
C (room temperature), is lower than the
amount of HCl at ambient temperature. form a paste which is measured with a
standard Sobek method which heats the
The pH of the slurry is checked twice to pH electrode (method code OA-ELE07).
sample to near boiling.
ensure the HCl levels in the flask are
Total Sulphur
Siderite Correction (S) sufficient for the reaction to proceed
and the resulting slurry is titrated The sample is heated to greater than
Meek (1981) suggested that the NP
with sodium hydroxide (NaOH) to a pH 1000°C in an induction furnace while
of rock units is overestimated when
endpoint of 8.3. The measured passing a stream of oxygen through the
siderite (FeCO3) is present. During
neutralisation potential is reported sample. Sulphur dioxide formed by
the standard Sobek method there
as calcium carbonate equivalents. This combustion is measured by an infrared
is insufficient time for ferrous iron
method uses the total sulphur detection system and the total S from
oxidation and subsequent precipitation
determined for the calculation of MPA. the sample reported.
of ferric hydroxide. Therefore,
only half of the siderite reaction is EN15875 Method Sulphur in Sulphate
considered, the base generating step of The method developed by Technical All ABA methods estimate how
the reaction. If precipitation of ferric Committee CEN/TC 292 2011 is much S is present in the sample and
hydroxide has time to occur, then an the European Standard (EN 15875, most assume all is hosted in sulphide
equal amount of acid is generated, “Characterisation of waste – Static test minerals. This can overestimate the acid
resulting in a net zero NP for siderite. As for determination of acid potential and production potential of a sample and
only the base generating part of the neutralisation potential of sulphidic so methods to determine how much of
reaction is counted an erroneously high waste”). The main difference between the total S in a sample is hosted in
NP values can be reported for samples this method and others offered is that sulphates are available. This can be
containing siderite (Fey, 2003). the amount of HCl added to the sample useful as sulphates will not form part of
To compensate for the short analysis is not estimated using a fizz test but the acid generating component of a
time that doesn’t allow the full reaction is calculated based on the amount of material so can be excluded from the
to occur, a small quantity of 30% carbonate in the sample. The digestion estimate for MPA (or AP).
Sulphate content can be determined in Other methods These tests are referred to as kinetic
several ways, total sulphate by testing because of the time component
Net Acid Generation (NAG) is the
carbonate leach (S-GRA06), when of the measurement. They are designed
quantitative estimate of acid that can be
measured by ICP-AES (S-ICP19) and to mimic the weathering of samples
generated by a material. This is a stand-
HCl leachable sulphate (S-GRA06a). The (typically tailings or crushed rock) in
alone package in which H2O2 is used to
HCl leachable sulphate doesn’t fully a controlled fashion at bench scale.
rapidly oxidise sulphides in a sample.
dissolve barite and celestite so where Humidity Cell tests determine the rate
After the room temperature reaction
these minerals are expected S-GRA06 is of acid generation and the variation
has ceased, the slurry is then heated
recommended. Also, by performing over time in leachate water quality.
until the reaction reaches completion.
both analyses (as is the case in ABA- Typically one kilogram of dry, crushed
On cooling the pH of the solution is read
PKG05) it is possible to estimate the (< 6.5 mm) rock samples is placed into
and then it is titrated to an end pH of 4.5
species of sulphate minerals present a specially designed humidity cell
using NaOH. The concentration of the
(e.g. proportion of sulphate in gypsum apparatus, and is then subjected to
NaOH used for titration is based on the
vs barite). weekly cycles that alternate between
pH reading taken after the reaction
the circulation of dry air and moist
Carbonate Carbon finalised (Miller et al., 1997). Titration to
air over the samples to simulate
an end point pH 7 and
Many ABA packages include precipitation cycles.
the associated NAG value can also be
measurement of inorganic C. This is
reported. Values from NAG analysis are
carbon in carbonate minerals, and it
reported in H2SO4/tonne. ABA and NAG
is determined by reacting the sample
tests are referred to as static tests as
with an acid in a heated container
they record a single measurement for
and then measuring the evolved
how a rock is expected to behave.
CO2. Alternatively, the C in carbonate
Other more involved methods such as
minerals can be calculated by
Humidity Cell use customised testing
determining total C and organic C, the
and take measurements over time.
difference is then the inorganic C in the
sample.
ABA-PKG01 ABA-PKG02 ABA-PKG03 ABA-PKG04 ABA-PKG05 ABA-
PARAMETERS
(M/S) (M/S) (M) (M/S) (M/S/B) PKG06E*
Net Neutralisation Potential (NNP) √ √ √ √ √
Maximum Potential Acidity (MPA) √ √ √ √ √
Neutralisation Potential (NP) & Fizz √ √ √ √ √
Ratio (NP : MPA) √ √ √ √ √
Neutralisation Potential (EN 15875 NP) √
Acid Potential (EN 15875 AP) √
Maximum Acid Potential (EN 15875 AP Max) √**
Neutralisation Potential Ratio (EN 15875 NPR) √
Net Neutralisation Potential (EN 15875 NNP) √
Paste pH √ √ √ √ √
Sulphate by ICP √
HCl-leachable Sulphate √ √ √ √
Total Sulphate (Carbonate Leach) √ √
Sulphide (calculated) √ √ √
Sulphide (analysed) √** √** √ √** √**
Total Sulphur √ √ √** √ √ √
Inorganic Carbon (CO2) √ √
Inorganic Carbon (calculated) √
Organic Carbon √
Total Carbon √
*meets EU regulations
** optional parameter, use A after the package name to indicate the optional extra analysis.
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References E [email protected]
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Toxicity Potential of Mine-Waste Piles Workshop. applicable to overburdens and mine-soils. WPA T +27 11 608 0555
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DC.
E [email protected]
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Municipality, Nova Scotia: in Geoscience and T +55 31 3045 8400
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