Research Articles Titration Curves

Research Articles

Titration Curves
A Useful Instrument for Assessing the Buffer Systems of Acidic Mining Waters
Oliver Totsche1*, Andrew Fyson1,2, Margarete Kalin2 and Christian E.W. Steinberg1,3
1 Leibniz Institute of Freshwater Ecology and Inland Fisheries, Post Box 850119, 12561 Berlin, Germany
2 Boojum Research, Ltd., 468 Queen St. Toronto M5A 1T7, Ontario, Canada
3 Humboldt-Universität zu Berlin, Unter den Linden 6, 10099 Berlin, Germany

* Corresponding author (totsche@igb-berlin.de)

sociated with coal seams and mineral veins), and consequent

DOI: http://dx.doi.org/10.1065/espr2005.09.284
acidification. Acidic mine waters are generated when water
Abstract comes into contact with these weathering products. This can
Background, Aims and Scope. The acidification of mine waters happen in the mines and in mining waste tailings piles. After
is generally caused by metal sulfide oxidation, related to mining mine closure, mines fill with acidic water and tailings piles
activities. These waters are characterized by low pH and high develop seepages. Opencast mines become acidic mining lakes
acidity due to strong buffering systems. The standard acidity (Fig. 1), and at the foot of the tailings piles streams of acidic
parameter, the Base Neutralization Capacity (BNC), is deter- mining waters are emerging (Fig. 2). Acid mine waters have
mined by endpoint titration, and reflects a cumulative param-
eter of both hydrogen ions and all buffering systems, but does
low pH-values (pH 2–pH 4), and typically high concentra-
not give information on the individual buffer systems. We dem- tions of sulfate, iron and non ferrous metals (Klapper &
onstrate that a detailed interpretation of titration curves can Schultze 1995), which serve as buffering systems.
provide information about the strength of the buffering systems.
The buffering systems are of importance for environmental stud-
ies and treatment of acidic mining waters.
Methods. Titrations were carried out by means of an automatic
titrator using acidic mining waters from Germany and Canada.
The curves were interpreted, compared with each other, to
endpoint titration results and to elemental concentrations con-
tained therein.
Results and Discussion. The titration curves were highly repro-
ducible, and contained information about the strength of the buffer
systems present. Interpretations are given, and the classification
and comparison of acidic mining waters, by the nature and strength
of their buffering systems derived from titration curves are dis-
cussed. The BNC-values calculated from the curves were more
precise than the ones determined by the standard endpoint titra-
tion method. Due to the complex buffer mechanisms in acidic
mining waters, the calculation of major metal concentrations from
the shape of the titration curve resulted in estimates, which should Fig. 1: The partly flooded mining Lake Greifenhain, Lusatia, Germany,
not be confused with precise elemental analysis results. still exhibits the characteristics of an open cast mine but also already pos-
sess traits of a developing lake
Conclusion. Titration curves provide an inexpensive, valuable
and versatile tool, by which to obtain sophisticated information
of the acidity in acidic water. The information about the strength
of the present buffer systems can help to understand and docu-
ment the complex nature of acidic mining water buffer systems.
Finally, the interpretation of titration curves could help to im-
prove treatment measurements and the ecological understand-
ing of these acidic waters.
Keywords: Acid-base titration; acidity; acid mine drainage; base
neutralization capacity (BNC); mine waters; pH-buffering

Introduction
During mine operation, the groundwater is lowered by pump-
ing and a vast quantity of tailings as well as waste material
is exposed. The exposure of these materials to oxygen re- Fig. 2: Acid mine seepage water from tailings near Sudbury, Ontario,
sults in the oxidation of sulfide minerals (which are often as- Canada

Environ Sci Pollut Res 13 (4) 215 – 224 (2006) 215

© 2006 ecomed publishers (Verlagsgruppe Hüthig Jehle Rehm GmbH), D-86899 Landsberg and Tokyo • Mumbai • Seoul • Melbourne • Paris
Titration Curves
It is important to distinguish between the intensity factor,
namely pH, and the capacity factor, namely the acidity of
acidic systems. The acidity of water is defined as the amount
of strong base necessary to increase the pH-value of a solu-
tion to a reference value (Stumm & Morgan 1996a). There-
fore the acidity includes the amount of base necessary to
overcome the buffers in the particular range as well.
Acidity of waters can be calculated from water chemistry, as
well as measured directly by titration. Calculations use either
the equivalents of weak acids and bases, or the equivalents of
strong acids and bases (Stumm & Morgan 1996b). Measur-
ing acidity is routinely determined by endpoint titrations, with
NaOH as titrant. Automated microprocessor-controlled in-
struments allow very precise titrations. From the measurement
of the dispensed titrant volume the acidity is calculated.
Total acidity is defined as titrations to pH 8.3 (or 8.2 in
Germany) which represents the upper limit of the carbonate
buffer (German Standard Methods 1979; US Standard Meth-
ods 1998). Since the carbonate buffer system is negligible in
acidic waters (pH < 3), other reference pH-values, for ex-
ample the neutral point (pH 7), are common. Because of the
neutralization reaction acidity is also called base neutraliz-
ing capacity (BNC). In environmental science acidity has
the unit of mmol L–1, in applied fields the unit of meqv
CaCO3 L–1 is commonly used.
Complete titration curves – instead of endpoint titrations -
can be carried out and analyzed by linearization techniques
if high precision endpoints in weakly buffered samples are
required (Michalowski et al. 2005, Vasjari et al. 2000, Stumm
& Morgan 1996c). Titration curves are not only used to de-
termine high precision endpoints, they also hold additional
information about the buffering systems in the water sam-
ple. In combination with geochemical models, titration curves
were used to analyze the pH-buffering systems of acidic
mining water (Totsche et al. 2003, Uhlmann et al. 2004b),
sea water (Butler 1992), humic water (Clair et al. 1992, Hruska
et al. 1996), and volcanic crater lake water (Marini et al. 2003).
In unpublished literature – 'grey literature' such as confer-
ence proceedings or technical reports, titration curves were
already used for acidity determination and characterization
of acidic mining waters (Fyson & Kalin 2000, Totsche et al.
2002). A systematic analysis and description of the possi-
bilities and limitations of the application of complete titra-
tion curves for acidic mining waters has not been published.
In acidic waters, pH, acidity and buffering systems are of
special importance for: (1) the evaluation and optimization
of acid mining water treatment options; (2) environmental
studies, because environmentally important issues as min-
eral solubility, metal toxicity and nutrient availability are
governed by these factors (Nixdorf et al. 2001), and (3) water
quality forecasts in mining regions. For these forecasts not
just the actual acidity, but also the potential acidity, which is
the acidity of anoxic waters after oxidation through atmos-
pheric oxygen, is important (Uhlmann et al. 2004a).
The aim of this article is to summarize knowledge of the
buffer systems in acid mining waters, and demonstrate in
several examples, the superiority of the recording and inter-
pretation of titration curves compared to the standard
method of endpoint titration.
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Research Articles
1 Methods
1.1 Sampling
Water samples were collected from lignite mining lakes in
Lusatia, Germany and from base metal mine waters in Canada.
Epilimnion and stream water samples were taken from the
water surface. Hypolimnion samples were collected with a
water sampler 1 m above the deepest point of the lake and
stored in completely filled bottles under a nitrogen atmosphere.
1.2 Titrations
Titration curves were collected (if not mentioned otherwise)
using a Titrino 702 autotitrator (Metrohm) through addition
of 0.1 N NaOH by a combined method of drift control (0.5
mV min–1) and maximum waiting time (30 min). Endpoint
titrations were carried out by the same titrator. The param-
eters for the endpoint method were adjusted for high preci-
sion (adjustment range: 15, minimum flow rate: 1µL min–1)
and a waiting time of 5 min at the end of the measurement.
1.3 Chemical analyses
Chemical analyses were carried out according to modified
German Standard Methods (Zwirnmann et al. 1999). Sulfate
and chloride were measured by an ion chromatography sys-
tem (Shimadzu). The high sulfate concentrations (up to al-
most 40 mmol L–1) would have disabled the chromatogra-
phy column, hence the sample had to be diluted. Because of
this dilution, the values of other parameters (e.g. nitrate),
which could also have been measured by ion chromatogra-
phy were too low to obtain reliable determinations, and were
therefore measured by independent methods. Nitrate and
ammonia were determined photometrically using an auto-
mated flow through photometer (Flow Solution III, Perstop).
Total dissolved metal concentrations were determined by
atomic absorption spectrometry (Al, Fe, Mn, Ca, Mg) and
atomic emission spectroscopy (Na, K) (AAS 3300, Perkin
Elmer). Iron(II) was analyzed photometrically (Photometer
UV 2101, Shimadzu) using the 1,10-phenanthroline method.
1.4 Acidity calculations
The calculation of acidity was based on two different con-
cepts: weak acids and bases and strong acids and bases
(Stumm & Morgan 1996b). These concepts were adapted
for Lusatian acidic mine lakes (Eq. 1: weak acid and base
concept (Peine & Peiffer 1998), Eq. 2: strong acid and base
concept (Uhlmann et al. 2004a)).
Aci = [H+] + 3[Al3+] + 2[AlOH2+] + [Al(OH)2+]
+ 3[Fe3+] + 2[FeOH2+] + [Fe(OH)2+] + 2[Fe2+]
+ [HSO4–] (Eq. 1)
Aci = 2[SO42–] + [Cl–] + [NO3–] – 2[Ca2+] – 2[Mg2+]
– [Na+] – [K+] – [NH4+] – 2[Fe2+] (Eq. 2)
Calculations for ion balance and speciation were carried out
by the hydrogeochemical simulator PHREEQC (Parkhurst
& Apello 1999).
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2 Overview of the Buffering Systems in Acidic Mining Waters
As the basis for the interpretation of titration curves, cur-
rent knowledge about buffering systems in acidic mining
waters is now summarized. The basis of each acid-base-ti-
tration curve is the theoretical titration of pure water with-
out any buffer system. On the basis of the ion product of the
water and the logarithmic nature of pH, the curve is sig-
moid shaped with its inflection point at pH 7 (Fig. 3). Typi-
cal titrations are run up to pH 10, therefore the most alka-
line part of the curve (pH > 10) plays hardly any role in
acidic mine water titrations.
Fig. 3: PHREEQC simulation of a titration curve of pure acidified (pH =
2.6) water without any buffering system
Buffer systems locally reduce the slope of the curve, sometimes
up to almost zero; these sections are called buffer plateaus.
As it is common knowledge, buffers are a combination of
weak acids and their conjugated bases. Weak acids are partly
dissociated (split) in water, and are able to keep the pH value
of a solution nearly constant in a certain range, by reacting
with the acid or the base. By addition of acid / base, the pH-
value will stay moreover constant as long as there is enough
buffer present. When the whole buffer is used up, the buff-
ering capacity is exhausted, and the pH-value will fall / rise
again with respect to the acid / base addition.
The most important buffering system in acidic mining wa-
ters will be discussed by means of the titration curve and
elemental water analysis taking the Lusatian acidic mining
Lake Plessa 111 as an example (Fig. 4). The titration curve
Fig. 4: Titration curve of the acidic mining Lake Plessa 111 and the concen-
trations of major buffering substances during the titration. Dissolved
aluminum and iron concentrations were measured directly. Hydrogen sulfate
concentrations were calculated from the sulfate and pH measurements.
The scaling of the ordinates allows a direct comparison between the buffer-
ing substances. The marked ranges (I to IV) reflect different buffer systems
Environ Sci Pollut Res 13 (4) 2006
Titration Curves
of Plessa 111 can be divided into four ranges (I to IV) by its
different slopes.
2.1 Hydrogen sulfate buffer
In the first range (0–2 mmol added alkalinity per liter sam-
ple water) the curve is raising steadily with alkali addition.
In this range a decrease of hydrogen sulfate ions can be ob-
served. The hydrogen sulfate [HSO4–] / sulfate [SO42–] buffer
system is also known from extremely acidic volcanic crater
lakes (Marini et al. 2003). In this buffer system, hydrogen
sulfate is the acid, and sulfate the conjugated base. If alka-
linity is added, the hydrogen sulfate ion becomes a sulfate
ion and therefore, the pH is changing much less than ex-
pected from the amount of added alkalinity. At the end of
range I there is still some hydrogen sulfate in the solution,
so the buffering continues in the second range.
2.2 Iron buffer
In the second range (see Fig. 4, 2–10 mmol L–1), the much
stronger iron(III) [Fe3+] / iron(III) hydroxide [Fe(OH)3] buffer
masks the effect of the hydrogen sulfate buffer. The iron(III)
buffer is a multi level buffer system (see Eq.. 1), in contrast
to the hydrogen sulfate buffer. Hereby the dissolved triva-
lent ferric iron [Fe3+] plays the role of the acid, and the pre-
cipitating iron hydroxide [Fe(OH)]3 the role of the base. The
intermediate steps act amphoterically, meaning they can act
both as acid and base, depending on their partner. In the
typically sulfate rich mine waters, it is unlikely that iron
precipitates as pure hydroxide, it usually precipitates as some
kind of hydroxy sulfates. In the case of Plessa 111, the pre-
cipitate was determined as schwertmannite with a molar
ratio of about 5.6:1 (Fe:S) (Totsche et al. 2003). Since each
sulfate ion replaces two hydroxy ions, the iron buffer pla-
teau was considerably shortened. Other studies found a for-
mation of jarosite (Koschorreck et al. 2003, Göttlicher et al.
2003), which contains potassium in addition to iron and
sulfate. The iron buffer is the only visible buffer system in
acidic mining lakes, high concentrations of dissolved ferric
iron cause an orange brown to brown-red color of the wa-
ter body (Fig. 5).
Fig. 5: The shoreline of Lake Plessa 76. The brown-red color of the
water is due to the very high concentration of dissolved ferric iron. The
small picture demonstrates the water color without the influence of the
sediment
217
Titration Curves
2.3 Aluminum buffer
In the third range (see Fig. 4, 10–14 mmol L–1)
the trivalent
aluminum buffer operates analogous to the iron buffer. The
aluminum phase precipitates as a mixture of various hydroxy
sulfates with different stoichiometric compositions (Totsche
et al. 2003, Ulrich & Pöthig 2000). In lake Plessa 111 a
molar Al : S ratio of 2.7 : 1 was found (Totsche et al. 2003).
2.4 More metal buffers
Iron and aluminum buffers are the most frequent metal buffer
systems in acidic mining waters. Especially in heavy metal
mines, other metal buffer systems such as copper [Cu2+],
nickel [Ni2+], and zinc [Zn2+] can also form buffering pla-
teaus. One example with zinc as an additional buffer is pre-
sented in Fig. 6.
Fig. 6: Titration curve and concentrations of Fe, Al and Zn from a Cana-
dian base metal waste rock pile seepage. The solid lines represent the
buffer ranges
2.5 Solid phase buffer
The last range (IV) of the titration curve of Plessa 111 (see
Fig. 4, >14 mmol/L) is dominated by an ion exchange buffer.
Hereby the solid phase of the sample, namely the iron and
aluminum precipitates, act as exchange matrix. The pro-
posed reactions include protonation and deprotonation of
the hydroxyl groups, the adsorption of calcium and magne-
sium, and the desorption of sulfate, which adsorbed in range
II and III. If the exchange processes include not only adsorbed
sulfate, but also sulfate from the mineral structure, this leads
to a mineral transformation. In Plessa 111 a mineral trans-
formation from schwertmannite to goethite was observed
(Totsche et al. 2003). This solid phase buffer may not be the
most important buffer in the water phase. However, the same
mineral transformation is also known from the sediment of
acidic mining waters (Peine & Trischler 2000, Jönsson et al.
2005). Considering the neutralization of whole lakes the
hydroxy sulfates in the sediments may contribute a large
Table 1: pH-range for metal precipitatation from Canadian acidic mining waters (Liu & Kalin 1992) and the Lusatian mining lakes from the present study
Fe3+
pH-range of Canadian acidic mining waters < 3.2
pH-range of Lusatian acidic mine lakes < 3.8
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buffer capacity. This solid phase buffer will probably play a
major role during whole lake neutralization, especially for
lakes with little acidity in the water column.
2.6 pH-range of metal precipitation
The pH-range in which some metals precipitate, and there-
fore build buffer plateaus, were determined for some Cana-
dian acidic mining waters. However, they do not entirely
correspond with the data of the present study (Table 1). This
variation can be due either to different experimental condi-
tions or to different water chemistry.
It is known that experimental conditions such as the rate of
base addition (Smith & Hem 1972) and mixing efficiency
(Clark et al. 1993), have an influence on the titration curve
because they can lead to different mineral phases. For exam-
ple, inefficient mixing during a titration increases the portion
of polymeric aluminum species, which leads to an earlier
and shorter aluminum buffer plateau (Clark et al. 1993).
The influence of the experimental conditions on the pH-
range is probably quite small compared to the influence of
the water chemistry, which is the major determinant for the
kind of mineral precipitating. Different minerals have dif-
ferent solubility constants, and even the solubility of a sin-
gle mineral is not only a function of pH but also varies with
the concentrations of solutes, water temperature and ionic
strength (Stumm & Morgan 1996d). The differences in metal
precipitation between the Canadian and the German mine
waters could therefore have many reasons. Since it is well
known that aluminum precipitates at lower pH-values in
the presence of sulfate than without it (Chapman et al. 1983,
Nordstrom & Ball 1986, Ulrich & Pöthig 2000), the higher
pH-range for aluminum precipitation in the Lusatian sam-
ples could, for instance, be due to lower sulfate concentra-
tions in Lusatian mining lakes.
3 Methodical Aspects
For systematic analysis, the reproducibility of titration curves
and the influences of the titration time were investigated.
The reproducibility was determined by titrating different
(n = 13) sub-samples of the same water sample using the
same method. This test showed a very good reproducibility
(Fig. 7), with an average coefficient of variance (CV) across
the whole margin of values of 0.7%. As a result of error
propagation, the CV value increased towards the end of the
titration curve.
Sometimes, at the beginning of the iron buffer (here around
4 mmol L–1 added alkalinity), a small drop in pH was appar-
ent. This could be the result of supersaturation of the solid
phase due to the lack of suitable nucleation sites or slow crys-
tallization kinetics (Chapman et al. 1983, Diz et al. 1999).
Precipitation of
Al 3+ Cu2+ Zn2+ Fe2+
3.0–4.5 5.0–6.5 6.5–7.5 5.5–6.5
3.5–5.0 – – 7.0–9.0
Environ Sci Pollut Res 13 (4) 2006
Research Articles
Fig. 7: Mean titration curve and the area of twice the standard deviation of
the acidic mining water of Plessa 111 calculated from 13 parallel titrations
After the first nuclei are formed, the sample is equilibrating.
This results in the precipitation of more iron than induced
by the last alkalinity addition, and a drop in pH.
Acid-base reactions are generally quite fast. However, if
precipitation or ion exchange processes are involved, fast
reactions can be slowed. If the time between the additions
of alkalinity is shorter than the time necessary to reach the
chemical equilibrium, this has an influence on the shape of
the curve. Differences in waiting time between the alkalin-
ity additions causes slight shifts in the iron buffer ranges
and bigger shifts in the solid-phase buffer ranges (Fig. 8).
In the iron buffer range, the extension of the total titration
time from 1.5 hour to and 80 hours (3 days 8 hours) causes
a shift of the buffer plateau to a lower pH-value. This is
probably caused by a kinetic inhibition of precipitation (e.g.
by slow crystallization kinetics) of the solid iron phase.
At the beginning of the solid phase buffer, the opposite ef-
fect can be observed. The slope of the titration curve becomes
steeper with extension of the titration time. This means that
buffer capacity of the solid phase buffer decreases in the long
time titration. The reason for this is not readily apparent. One
explanation could be that the rate of mineral crystallization
increases over time. Therefore, the higher degree of crystalli-
Fig. 8: Titration curves of the acidic mine Lake Plessa 111. The titrations
were carried out with three different waiting times between the alkalinity
additions. The waiting times of 1, 5, and 60 minutes resulted in total titra-
tion times of 1.5, 7, and 80 hours
Environ Sci Pollut Res 13 (4) 2006
Titration Curves
zation of the iron and aluminum precipitates in the long
time titration results in less surface sites for ion exchange,
and therefore in a reduction of the solid phase buffer.
At the end (pH > 9), the curve of the long time (80 h) titra-
tion flattens much more than the other curves (see Fig. 8).
This is probably caused by a newly formed carbonate buffer.
The carbonate buffer usually does not play any role in acidic
mining waters, since in waters with pH values below 4.3,
the DIC (dissolved inorganic carbon) concentration is very
low. Under neutral and alkaline conditions, carbon dioxide
from the surrounding atmosphere can enter the water phase.
In normal acidic mining water titrations, the time between
neutrality and the end of the titration is quite short. How-
ever, with very long waiting times, the sample is for about
12 hours in the range between pH 7 and pH 10. During
this relatively long period, some carbon dioxide can enter
the sample from the atmosphere and start to build up a
carbonate buffer.
Recapitulating one can say, that if the titration is carried
out too fast, the kinetic inhibition of iron hydroxide pre-
cipitation shortens the iron buffer plateau. If the titration is
carried out too slowly, the built up of a carbonate buffer
changes the shape in the alkaline part of the titration curve.
Therefore the titration time should be moderate to avoid
both effects.
To optimize the results and to reduce the time exposure, a
drift control instead of predefined waiting times can be used.
The drift control allows measurement of fluctuations in the
pH-value or its primary signal, the input voltage. If the fluc-
tuation declines under a predefined value the pH is defined
as stable, the next unit of alkalinity is added. In practice, a
combination of drift control and defined maximum wait-
ing time has proofed itself. If the fluctuation is falling un-
der the predefined value before the maximum waiting time
is reached, the titration continues. If not it continues after
the waiting time.
4 Classification and Characterization of Acidic Mining
Waters by Titration Curves
The high precision and reproducibility of titration curves
makes them an ideal tool for characterization of acidic min-
ing waters. The advantage of titration curves over the BNC-
values alone is the information about the individual buffer
systems. The latter sum up all buffer systems and the change
in H3O+-ions. This information is important for the evalua-
tion and optimization of treatment options for acidic min-
ing waters and for environmental studies. For most eco-
logical characteristics such as metal toxicity and nutrient
availability, pH, and not acidity, is a determining factor.
However, the buffer systems are very important, because
the pH-value and its stability are governed by them. For
example the buffer system indirectly controls the level of
biomass and species composition by affecting nutrient avail-
ability (particularly phosphorus and carbon) (Nixdorf et
al. 2001, Nixdorf et al. 2003). Due to this, many iron buff-
ered lakes show hypolimnetic plankton maxima and a
switch to littoral colonization (Nixdorf et al. 2001).
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Fig. 9: Titration curves of mining Lake Felixsee (Felix) and all mining lakes (Plessa 75, 76, 77, 78, 99, 107, 108, 110, 111, 112, 113, 114, 116, 117 and 118)
of the former open cast mine Plessa

4.1 Classification of acidic mining waters

Iron rich waters with pH-values below 4 are usually classi-

fied as iron buffered (Geller et al. 2000). If the buffering is
named after the buffering system which is currently buffer-
ing against small acid or base additions, this is not entirely
correct. Despite the fact that the iron and the aluminum
buffers are the strongest, and therefore the most important,
buffer systems in acidic mining waters, the hydrogen sulfate
buffer is the actual active buffer system in typically sulfate
rich mine waters below pH 3 (see Fig. 4). This means that
all Plessa lakes in Fig. 9 except for the least acidic ones (Plessa
117 and Plessa 118) belong to the hydrogen sulfate buffered
lakes. Plessa 117 and Plessa 118, which lack the hydrogen
sulfate plateau, are iron buffered. Waters with pH-values
between 4 and 5 such as Lake Felixsee (see Fig. 9) lack the Fig. 11 : Lake Plessa 111 and a close-up view of its orange colored sediment
iron buffer plateau. These are aluminum buffered lakes.
4.2 Characterization of acidic mining waters
Aluminum buffered lakes often have gray sediments (Fig. 10),
due to the high amount of precipitated white aluminum hy- Most acidic mining lakes in Lusatia are hydrogen sulfate
droxides and hydroxy sulfates. In contrast, hydrogen sulfate buffered lakes. If the waters belong to the same class of buffer
and iron buffered lakes often have a red brown sediment systems, the differences between the lakes are quantitative
similar to that of Plessa 111 (Fig. 11), due to the high con- rather than qualitative in nature. Even in this situation, the
centration of ferric iron minerals. titration curves are a very useful tool with which to charac-
terize and compare the waters. Lake Plessa 77 and lake Plessa
110 are both hydrogen sulfate buffered lakes. From the shape
of the curves (Fig. 12), one can see that the iron buffer of

Fig. 10: Lake Felixsee and a close-up view of its gray sediment with black Fig. 12: Titration curve of the mining Lakes Plessa 77 and Plessa 110 and
lignite fragments their belonging BNC(4.3)-, BNC(7)- and BNC(8.2)-values

220 Environ Sci Pollut Res 13 (4) 2006

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Lake Plessa 77 is stronger than the one of Plessa 110. In
contrast there is a very strong aluminum buffer plateau in
Plessa 110, whereas in Plessa 77 almost no aluminum buff-
ering can be detected. These qualitative differences are the
reason why the two lakes would react very differently to an
addition of neutralizing substances or flooding with neutral
river water. Although both lakes have approximately the
same pH-value at the beginning, during the addition of the
first 4 mmol L–1 alkalinity, the pH-value of Lake Plessa 110
would rise much more. Then, the pH-value of Lake Plessa
110 will stay almost the same for a long time, while the pH
of Lake 77 will rise to neutral and then to alkaline. This
uneven distribution of buffering capacity can be seen from
the titration curves, but not be from single BNC-values.
4.3 Anoxic waters
Anoxic waters such as hypolimnetic water, sediment pore
water, seepage and groundwater are of special interest for
treatment options, water quality forecasts and environmen-
tal studies. In contrast to the oxic epilimnion samples, an-
oxic samples can change quite rapidly if they come in con-
tact with the oxygen in the air. Oxidation processes can be
very fast, especially in the neutral and alkaline range of the
curve. Oxidation processes can produce or consume acid,
and are therefore able to substantially influence the shape
of the curve. Sometimes the pH-value falls, despite the added
alkalinity (data not shown). To prevent these changes, the
anoxic samples can be titrated under an inert gas (N2 or
Ar) atmosphere.
The shape of titration curves from anoxic samples, such as
the anoxic hypolimnion of Lake Plessa 111, is usually dis-
tinct from those of the oxic epilimnion (Fig. 13). In the
hypolimnion there is a higher initial pH-value, and the fer-
ric iron buffer (thus far referred to simply as iron buffer) is
absent or at low concentrations. Instead, a very strong buffer
plateau around pH 7 often dominates the shape of the curve.
Chemical analysis show that this buffer is also an iron buffer,
but a ferrous iron buffer. In contrast to ferric iron, which
precipitates around pH 3, ferrous iron precipitates in near
neutral conditions.
Fig. 13: Titration of the anoxic hypolimnion and oxic epilimnion water of
the acidic mining Lake Plessa 111. One part of the hypolimnion water
sample was titrated under nitrogen atmosphere; the other one was titra-
tion after one week of aeration
Environ Sci Pollut Res 13 (4) 2006
Titration Curves
If the anaerobic hypolimnion sample is aerated, the ferrous
iron will be oxidized to ferric iron. Since the solubility of
ferric iron is limited at this pH, not all ferrous iron becomes
dissolved ferric iron. Another part precipitates as ferric iron
hydroxide. This process produces acid, which causes a de-
crease in pH. The aerated hypolimnion water still contains
more dissolved iron than the epilimnion water, this also re-
sults in a higher BCN-value.
The interpretation of base neutralization capacity values of
anoxic samples such as this hypolimnion sample of Lake Plessa
111 are problematic. The epilimnion sample shows a typical
curve for Lake Plessa 111, with a BNC(7.0)-value of approxi-
mately 14 mmol L–1. The hypolimnion sample has a higher
pH-value and a BNC(7.0)-value of less than 9 mmol L–1. This
persists as long as the hypolimnion water does not come into
contact with air, for example, during the turnover of the lake.
If this happens, the aerated hypolimnion water will attain
approximately the same pH as the epilimnion water, and the
BNC(7.0)-value will be even higher (19 mmol L–1). Without
knowledge of the shape of the titration curve, single BNC-
values of anoxic samples can lead to misinterpretations.
Curves of the fresh sample and of the fully oxidized sample,
contain valuable information. Determination of the actual
acidity of anoxic samples is carried out under an inert gas
atmosphere, and represents the actual buffer conditions; the
potential acidity is determined from completely oxidized
samples, and represents the pH and buffer conditions after
a possible oxidation. For reliable water quality forecasts for
actual or former mining regions, both actual acidity and
potential acidity are important parameters (Uhlmann et al.
2004a). Complete oxidation can be achieved by bubbling
with air or oxygen, or by the addition of hydrogen peroxide
(H2O2) (Brugam & Stahl 2000).
4.4 Acidity development
Titration curves are additionally very useful for illustration
of changes of chemical parameters in a water-body over time
(Fig. 14). The results of a whole lake treatment with phos-
phate rock for a Canadian mining-influenced lake are shown
in Fig. 14. At treatment time the titration curve shows two
buffer plateaus, the ferric iron buffer plateau between pH 3
Fig. 14: Titration curves of a shallow lake (Mud Lake, Ontario, Canada)
receiving acid mine drainage ground water, before and after the treatment
of the sediment with phosphate rock. The vertical lines show the BNC(8.3)
values of the curves
221
Titration Curves Research Articles

and pH 4 and the ferrous iron buffer plateau between pH 5

and pH 6. Both buffer plateaus had almost the same
strength. As the phosphate is dissolved slowly, total acidity
(BNC(8.3)) gradually decreased in 9 days from 12 to 7.4
due to formation of precipitates. The titration curves show
that the whole acidity reduction is related to the decrease
of the ferrous iron buffer. The ferric iron buffer plateau
was not affected. If only data for BNC-values, without ti-
tration curves, were available, a ferric and ferrous iron speci-
fication would be needed to identify the fraction responsi-
ble for the acidity reduction.

5 Estimation of Metal Concentrations from Titration Curves

There are different methods for quantification of buffering
substances based on the shape of the titration curve (Moisio
& Heikonen 1996, Kochana et al. 1992, Michalowski 1992,
Parczewski et al. 1994). These methods all work with rea-
sonable precision in relatively simple buffer solutions. How-
ever, acidic mining waters have complex buffer mechanisms,
and in these cases the results of such analyses do not always
give precise quantification. This is mainly due to additional
buffer systems of unknown water constituents (e.g. humic
substances) in the same pH-range as the buffering metal ions,
and the precipitation of other minerals in addition to pure
hydroxides such as hydroxy sulfates or polymeric species.
However, even if a precise quantification can not be achieved
for acidic mine waters, it is possible to get an estimate of the
concentration of the major buffering metal ions (Liu & Kalin
1992). The simplest method for estimation the molality of a
major buffering metal ion, is to measure the amount of ti-
trated alkalinity (in mole) which was added from the begin-
ning of the buffer plateau to its end, and divide this by the
valence of the metal ion.
The metal concentrations estimated from the curves of Fig. 9
and 13 as described above and the concentrations measured
by independent chemical methods are compared in Fig. 15.
The estimates show an acceptable agreement of the values
above 0.1 mmol L–1. Below this concentration the values
have much less precision, since the start- and endpoint of
the buffer plateaus are hard to determine.
6 BNC-values Determined from Titration Curves
BNC-determinations are usually carried out as endpoint
titrations. This means that alkalinity is added without any
recording of intermediate readings, until the measured pH
exceeds the predefined values (usually pH 4.3, 7.0, 8.2 or
8.3). Thus the size of overstepping is not considered by this
method. In contrast titration curves provide numerous data
points between the start and the end pH-value therefore, BNC-
values can be determined from titration curves by linear inter-
polation between the values directly below and directly above
the target value, with the advantage that the span of overstep-
ping is considered. This leads to higher readings and less pre-
cision in the endpoint titration [BNC(7.0) = 15.10 ± 0.13,
for 13 fold analysis of Lake Plessa 111 water] compared to
the interpolation of the titration curve values [BNC(7.0) =
Fig. 15: Estimation of the total iron(III), total aluminum and total iron(II)
concentrations from the titration curves of the lakes of Fig. 9 and 13, and
the comparison with the measured concentrations
14.70 ± 0.06]. If the chosen additions of alkalinity are too
large the interpolation method will just become a bit less
precise whereas endpoint titration can substantially overesti-
mate the acidity. Comparison of the acidity determination
methods on the basis of the lakes of the former opencast lig-
nite mine Plessa shows that indeed, all endpoint titration
acidity values exceed the titration curve values (Table 2).
The calculation of acidity from water chemistry requires
many different methods to analyze all important ions. Each
method has its own inaccuracies. The calculation using weak
acids and bases is the most straightforward method, because
weak acids and bases are responsible for pH buffering. For
this method, distinguishing between different species of an
ion [e.g. Fe3+, FeOH2+, Fe(OH)2+, ...] are necessary. The
speciations are calculated by stability constants from pH-
values and sum parameters [e.g. Fe(III)]. Because the pH is
used for the calculation of both the H+-ion concentration
and the speciation, this method is very dependent on the
precise determination of the pH-value. For the calculation
of acidity by strong acids and bases such speciation is not
necessary. This alternative method works by using the charge
balance to determine the equivalent of weak acids and bases.
As this only works when the ion balance error is low, a com-
plete chemical analysis of the water is necessary. If the ion
balance error is high, this calculation method can not be
used, or is limited. In the present study, the sulfate concen-
trations were fitted to compensate for the mismatches of the
ion balance. Sulfate was assumed to be the parameter with
the most uncertainties, because high dilutions made dilu-
tion failures likely. Although equation 2 was adapted for
Lusatian acidic mining lakes, it assumes sulfate as a con-
servative, not dissociated ion, and therefore underestimates
the acidity by neglecting the hydrogen sulfate buffer.

222 Environ Sci Pollut Res 13 (4) 2006

Research Articles Titration Curves

Table 2: Results of the acidity titrations by endpoint titration up to pH 7, titration curves, and the acidity calculation from water chemistry by the concepts
of weak acids and bases and strong acids and bases. The coefficient of variance (CV) is calculated across the different methods

Sampling site Acidity [mmol L–1] CV

[%]
Endpoint titration Titration curves Weak acids Strong acids
and bases and bases
Lake Plessa 75 17.8 17.5 17.8 19.0 3.6
Lake Plessa 76 6.0 5.9 5.0 5.6 3.1
Lake Plessa 77 6.2 6.1 5.5 5.6 4.5
Lake Plessa 78 6.0 5.7 5.6 5.7 2.6
Lake Plessa 99 8.5 8.2 7.8 7.8 3.7
Lake Plessa 107 45.2 44.8 55.3 56.3 10.4
Lake Plessa 108 4.5 4.3 4.0 4.1 4.7
Lake Plessa 110 8.1 7.8 7.4 7.5 3.1
Lake Plessa 111 14.3 13.9 14.4 14.5 1.7
Lake Plessa 112 4.2 4.0 3.8 3.8 4.0
Lake Plessa 113 14.8 14.5 13.6 13.8 3.1
Lake Plessa 114 7.7 7.3 6.9 6.5 6.0
Lake Plessa 116 3.1 2.9 2.8 2.9 4.2
Lake Plessa 117 1.5 1.4 1.3 1.3 5.2
Lake Plessa 118 1.2 1.1 1.0 1.0 8.2

Overall the acidity values from the different measuring and
calculation methods are in good agreement. The highest
coefficient of variance (CV, see Table 2) was determined for
the most acidic mining lake Plessa 107. This is also the only
lake with a positive ion balance (data not shown). This sug-
gests that the strong deviation between the calculated and
measured acidity values could be due to an error in analysis,
or that a relevant parameter is missing from the calculation.
7 Conclusion
Titration curves were demonstrated to be a versatile tool for
assessing the acidity of acidic mining waters. The interpre-
tation of titration curves provides information about the
strength of the buffer systems present. This offers the op-
portunity to characterize and compare the acidity of differ-
ent waters, and the development of an acidic mining water
over time. The additional information about the different
buffer systems, available from the titration curves compared
to traditional endpoint titrations, can help to improve wa-
ter quality forecasts, treatment measures, and the understand-
ing of environmental processes in these waters. In addition,
titration curves allow determination of BNC-values with
higher precision than the standard endpoint method, as well
as providing an estimate of the concentrations of major buff-
ering metal ions.
Acknowledgements.The authors gratefully acknowledge the assist-
ance with chemical analysis given by the staff of the IGB chemical
laboratory. We also thank Dr. Sarah Poynton, Dr. Jörg Gelbrecht and
the unknown reviewers for their help in improving the manuscript. This
study was partly funded by the scholarship program of the German
Federal Government Environment Foundation (DBU).
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Received: December 17th, 2004
Accepted: September 14th, 2005
OnlineFirst: September 15th, 2005
Environ Sci Pollut Res 13 (4) 2006