Development of a European standard for the determination of acid

potential and neutralisation potential of sulfidic waste

Tommi Kaartinen1 and Margareta Wahlström1
1
VTT Technical Research Centre of Finland, P.O. Box 1000, FI-02044 VTT, Finland tommi.kaartinen@vtt.fi,
margareta.wahlstrom@vtt.fi

ABSTRACT
European Directive (2006/21/EC) on the management of waste from the extractive industries
requires guidance on waste characterization as a basis for the development of waste
management plans. CEN, the European standardization organization, has commenced work
on standards for extractive waste. One of the work tasks is to develop tools for determination
of “acid generation behavior”.
Test methods for the determination of acid generation behavior can be divided in static and
kinetic tests. A static test is usually relatively fast to perform, but gives only indicative
information based on total composition of the waste material. The kinetic test gives more
detailed information on behavior based on reaction rates under specified conditions.
This paper describes a European static method draft developed for waste characterization of
sulfide bearing materials which may generate sulfuric acid when subjected to weathering. In
the test draft specified methods for determining both the acid potential (AP) and the
neutralization potential (NP) of the material are presented. Here the focus is more on the
determination of NP. From these results the net neutralization potential (NNP) and the
neutralization potential ratio (NPR) are calculated.
Basis for the standardization work were the existing static test methods applied in the
extractive industry and research. Background for the choice of the method to be standardized
is discussed in the paper.

INTRODUCTION
Acid drainage is considered as one of the most significant environmental problems associated
with extractive industry. Iron sulfide oxidation is responsible for the majority of the acid
production by mine wastes. Iron sulfides (e.g. Pyrite) in tailings or waste rock are stable as
long as reducing conditions are maintained, but as soon as oxygen and moisture are present
iron sulfides begin to oxidize. The resulting acidic, iron and sulfate rich pore water may (i)
enhance the weathering process by reacting with sulfide minerals (ii) evaporate to precipitate
e.g. hydrated iron-sulfates (iii) react with the waste and, depending on the buffering capacity,
leave the mining waste as acid drainage (Lapakko, 2002).
Acid drainage from pyrite oxidation may occur if the acid potential exceeds the acid
neutralization potential of the minerals in the waste. However, kinetics describe the reaction
pathways towards equilibrium. Only if the acid production rate exceeds the rate at which the
buffering minerals can neutralize the produced acidity or if the buffering minerals simply
become exhausted, acid generation reactions will result in a decrease of pH in the drainage
that may lead to e.g. high metal leaching from the waste.
The mining waste directive (2006/21/EC) lays down requirements for the safe
management of extractive waste including proper characterization of the waste. In 2006
European Commission gave a mandate to CEN, the European standardization organization,
for the development of standardized methods relating to the characterization of wastes from
the extractive industries. One of the work tasks covered by the mandate includes the

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development of a standardized static test with the status of a European norm (EN) for the
determination of net acid production potential in sulfidic waste.
A variety of non standardized static tests methods exists for rough estimation of whether a
waste material will potentially generate acid drainage. Methods usually include the
determination of sulfur/sulfide content of waste and based on this the calculation of acid
potential (AP). Determination of neutralization potential (NP) is usually done by digesting a
finely ground sample with acid and measuring the acid consumed by the waste. The ratio of
AP and NP or the subtraction NP-AP is then used in the judgment of potential risk for acid
drainage.
Static tests are designed for the single purpose of measuring extractive waste’s capacity
for producing acidity and its acid neutralization capacity. Accordingly, static tests are
commonly used for screening purposes and to provide an answer to whether the mine waste
material has a potential to be an acid producer or an acid neutralizer. These tests do not
consider parameters such as the actual availability of acid-producing and acid-neutralizing
minerals and differences between the respective dissolution rates of acid-producing and acid-
neutralizing minerals. Kinetic tests which allow determination of oxidation rates of sulfides
and the release rates of acid-producing and neutralizing minerals as well as e.g. metals are
needed for deeper characterization of extractive waste.

Here we describe the development of a static test to a European Norm (EN).

DETERMINATION OF NEUTRALISATION POTENTIAL

Background for the choice of method

In CEN/TC 292 Working group 8 “Wastes from the extractive industry” it was agreed from
the beginning that in the first place no completely new static test method would be developed.
Instead, already existing non standardized static test or tests would primarily form the basis
of a test to be standardized. The first step in this work was a review on the current approaches
to determine the net acid production in extractive waste (Stenvall 2006).
Based on the review as well as discussions among experts in Working group 8 a modified
acid-base accounting procedure introduced by Lawrence and Wang (1997) was agreed to be
the method for the determination of neutralization potential to form the basis of an EN.
Rationale listed below favored the choice of this method to be standardized. The method
itself along with development needs is described in detail further in the text.
• The method has been widely used in industry and research
• The test is relatively simple to perform
– Cost of a single test remains reasonably low
– It allows multiple samples to be tested simultaneously
• No expensive equipment is needed
• Test is performed in ambient temperature
– No overestimation of NP due to high temperature
• Test aims at final digestion-pH of 2,0-2,5
– No overestimation of NP due to extremely low digestion-pH

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• The method (with limited amount of modifications) has the potential to produce results
with good repeatability and reproducibility

Modifications to the method

Determination of neutralization potential as described in the modified acid-base accounting
by Lawrence and Wang (1997) is performed on a pulverized sample by adding water and pre-
determined amounts of acid to the suspension. The suspension is mixed throughout the test.
Acid is added at start and after two hours of mixing. After 22 hours the pH of the suspension
is measured and, if needed, adjusted between 2,0 and 2,5, After 24 hours the test is
terminated and the suspension is back-titrated with base to pH 8,3. The acid consumed in the
test is converted to neutralization potential (NP) in calcium carbonate equivalents (kg
CaCO3/t of waste).
The modified acid-base accounting method by Lawrence and Wang (1997) uses the so
called Fizz-test as a preliminary test to determine the amount of acid added to the test
suspension in the early stages of the test. In the Fizz-test a few drops of strong hydrochloric
acid is added to a small amount of pulverized sample. The rate of bubbling caused by the acid
is evaluated visually and the acid amount to be added is chosen from four alternative
categories based on the rate of bubbling. The idea behind the preliminary test is to adjust the
digestion-pH in the test to be on the same level for samples with different buffering
capacities.
The type of visual evaluation that the Fizz-test includes was seen impossible to be part of a
European Norm. A European Norm has to be such that tests performed in different
laboratories by different technicians produce as similar results as possible. It has been shown
that different Fizz-ratings with the same sample can cause significant differences in the
resulting NP (Stenvall 2006).
Another weakness in the modified acid-base accounting method by Lawrence and Wang is
that samples with high neutralization potential are digested most of the test time in a
relatively high pH. The highest amount of acid (1 M HCl) to be added corresponds to
neutralization potential of 125 kg CaCO3/t of waste and this amount of acid is soon consumed
by samples with high neutralization potential.
Particle size of the test sample has also been shown to have great impact on the results
(Stenvall, 2006, Tammelin, 2007), The modified acid-base accounting by Lawrence and
Wang does not fix the particle size though “pulverized” is mentioned in the procedure.
Table 1 shows the fundamental steps in the modified acid-base accounting procedure.
Along with these are the corresponding steps in the modified procedure prEN 15875 that now
has the status of a European standard draft. Explanations to modifications are given further in
the text.

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Table 1. Test parameters in the modified acid-base accounting by Lawrence and Wang and
prEN 15875.
Test parameter Modified acid-base prEN 15875 Remarks
accounting by Lawrence
and Wang (1997)
Particle size Pulverized 95 % <0,125 mm
Sample amount 2,00 g 2,00 g (dry mass)
Amount of water added 90 ml 90 ml
Acid used in digestion 1 M HCl 1 M HCl
Amount of acid added 1 to 3 ml based on 0,5 to 10 ml based on
at start bubbling in the Fizz-test carbonate content of the
sample
Amount of acid added 1 to 2 ml based on 0 to 10 ml based on
at time= 2 h bubbling in the Fizz-test carbonate content of the
sample
Amount of acid added So that pH of the So that pH of the In prEN 15875 not more
at time = 22 h suspension is between suspension is between than 50 % of the total
2,0-2,5 2,0-2,5 amount of acid is allowed
to be added at time = 22
h.
If pH of the suspension is
below 2 at 22 h the test
has to be redone with
reduced volume of acid
Test duration 24 h 24 h
Condition for final pH 2,0-2,5 2,0-2,5 If not in the domain test
of the suspension has to be redone
Base used in back 0,1 or 0,5 M NaOH 0,1 M NaOH
titration
End point of back 8,3 8,3
titration
Expression of NP kg CaCO3/t mol H+/kg In prEN 15875
conversion factors given
to kg CaCO3/t

It is known that carbonate minerals are the biggest source of neutralization potential in
extractive waste. Therefore it was seen feasible to replace the subjective Fizz-test with the
determination of the carbonate content of the sample as a preliminary test to decide on the
amounts of acid added at start and after two hours. Now the amounts of acid added
correspond to stoichiometric neutralization potential in the carbonates assuming all
carbonates to appear as calcium carbonate. This will give more equal conditions in the test in
terms of digestion pH for samples with different neutralization potential.
However, in two types of cases the acid additions based on carbonate content may be
misleading. Firstly, not all carbonates have neutralization potential and the digestion pH
might fall two low. Then the test has to be done again with reduced volume of acid.
Secondly, extractive waste may contain other neutralizing minerals than carbonates e.g.
silicates some of which are reactive at the pH-domain of the test. In this case the pH of the
suspension can be found quite high at 22 hours. Then possibly quite a lot of acid is needed to
drop the pH back to the desired level. To have the testing conditions (digestion-pH) as equal
as possible throughout the test for samples with NP from different minerals an upper limit for
the volume of acid added at 22 hours is set to be 50 % of the total volume. If exceeded, the
test has to be redone with higher volume of acid.

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DETERMINATION OF ACID POTENTIAL
The potential of extractive waste to produce acid mainly originates from sulfides. However,
no standard methods for the determination of sulfur species (sulfate-, sulfide-, disulfide-
sulfur) are established for extractive waste. Analytical methods that are referred to in a
European Norm should also have a status of a standard method.
Analysis of total sulfur is a well established method and is regarded as a default method in
the standard draft prEN 15875. Total sulfur is determined either by bomb combustion
according EN 14582 or by high temperature combustion according to ISO 351 or ISO 15178.
If substantial part of total sulfur is in sulfate, then the calculation of acid potential based on
total sulfur will lead to significant overestimation of AP. prEN 15875 gives informative
guidance on the determination of sulfur species in this type of cases.
Calculation of AP as instructed by prEN 15875 assumes all sulfur to appear as pyrite. It is
done my multiplying the total-S in mass fraction (%) by 0,625 to yield acid potential (AP) in
mol H+/kg based on 1 mole of sulfur in pyrite creating 2 moles of H+.

FUTURE ACTIONS
A couple of major steps have to be taken before a standard draft prEN 15875 can be finalized
to a European Norm (EN). These major steps include robustness testing of the method for
determination of neutralization potential and a validation study of the method.
In the robustness testing some of the most critical test parameters are tested on their
sensitivity to affect the results. These could include e.g. the timing of the acid additions in the
test and the means of mixing the suspension during the test. The results from the robustness
testing are evaluated statistically and the testing conditions can be further adjusted.
In the validation study the idea is to see if results of same magnitude can be produced in
different laboratories. Extractive waste samples are shipped to participating laboratories and
by following the procedure the participating laboratories determine the neutralization
potential of the samples. The validation study also includes statistical evaluation of the
results. If the NP-values determined in different laboratories are within reasonable range then
the reproducibility of the method is adequate to be accepted as an EN.

ACKNOWLEDGEMENTS
European Commission is funding the development of the static test to a European Norm. The
work is planned to be ready and prEN 15875 finalized to EN in 2011.

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REFERENCES
European Committee for standardization. 2008. prEN 15875, Characterization of waste –
Static test for the determination of acid potential and neutralization potential of sulfidic
waste.
International Organization for Standardization. 1996. ISO 351 Solid mineral fuels -
Determination of total sulphur - High temperature combustion method
International Organization for Standardization. 2000. ISO 15178 Soil quality --
Determination of total sulfur by dry combustion
Lapakko, K. 2002. Metal mine rock and waste characterization tools: an overview, MMSD,
IIED, no 67, 30p.
Lawrence, R.W. and Wang, Y. 1997. Determination of neutralization potential in the
prediction of acid rock drainage. Proceedings of Fourth International Conference on Acid
Rock Drainage. Vancouver B.C. Canada. Volume I, pp.451-464.
Stenvall, M. 2006. Determination of neutralization potential in sulfide bearing mining waste.
Master’s thesis, Åbo Akademi Finland (In Swedish)
Tammelin, M. 2008. Development of a static test for determination of neutralization potential
in mining waste towards a European Norm. Master’s thesis, University of Turku Finland
(In Finnish)