Journal of Hydrology 414415 (2012) 211219

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Journal of Hydrology
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Variable inltration and river ooding resulting in changing groundwater

quality A case study from Central Europe
Konrad Miotlinski a,, Dieke Postma b, Andrzej Kowalczyk a
a
b

University of Silesia, Faculty of Earth Sciences, 41-200 Sosnowiec, Poland

GEUS Geological Survey of Denmark and Greenland, . Voldgade 10, DK-1350 Copenhagen K, Denmark

a r t i c l e

i n f o

Article history:
Received 31 January 2011
Received in revised form 9 September 2011
Accepted 29 October 2011
Available online 7 November 2011
This manuscript was handled by Laurent
Charlet, Editor-in-Chief, with the assistance
of Peter Wolfgang Swarzenski, Associate
Editor
Keywords:
Groundwater quality
Pyrite oxidation
Nickel mobilisation
Flooding
Climate change

s u m m a r y
The changes in groundwater quality occurring in a buried valley aquifer following a reduction in groundwater exploitation and enhanced inltration due to extensive ooding of the Odra River in 1997 were
investigated. Long-time series data for the chemical composition of groundwater in a large well eld
for drinking water supply indicated the deterioration of groundwater quality in the wells capturing water
from the ooded area, which had been intensively cultivated since the 1960s. Inltration of ooded river
water into the aquifer is suggested by an elevated chloride concentration, although salt ushing from the
rewatered unsaturated zone due to the enhanced recharge event is much more feasible. Concomitantly
with chloride increases in the concentrations of sulphate, ferrous iron, manganese, and nickel imply
the oxidation of pyrite (FeS2) which is abundant in the aquifer. The proton production resulting from pyrite oxidation is buffered by the dissolution of calcite, while the Ca:SO4 stoichiometry of the groundwater
indicates that pyrite oxidation coupled with nitrate reduction is the dominant process occurring in the
2+
aquifer. The pyritic origin of SO2
4 is conrmed by the sulphur isotopic composition. The resultant Fe
increase induces Mn-oxide dissolution and the mobilisation of Ni2+ previously adsorbed to Mn-oxide surfaces. The study has a major implication for groundwater quality prediction studies where there are considerable variations in water level associated with groundwater management and climate change issues.
Crown Copyright 2011 Published by Elsevier B.V. All rights reserved.

1. Introduction
Pristine aquifers are often considered as a reliable source of potable quality water, which will inevitably lead to enhanced exploitation of these aquifers. However, the variations in groundwater
quantity affected by changes in exploitation, prolonged droughts,
or events of enhanced recharge including river oods may easily
result in long term deterioration of groundwater quality. In addition, climate change may affect recharge and changes in recharge
rates of groundwater bodies in recent years have already been reported in various areas around the world (Loaciga et al., 2000; Ma
et al., 2004; Hanson et al., 2006; Holman et al., 2009; Crosby et al.,
2010). However due to a delayed response between changing recharge rates and the resultant groundwater quality, the inuence
of climate change on the quality of groundwater resources has received little attention in the literature to date.
Reduced or enhanced recharge results in induction of geochemical processes including pyrite oxidation (e.g. Baszyk and Grski,
Corresponding author. Present address: CSIRO Land and Water, Water for a
Healthy Country Flagship, Private Bag 2, Glen Osmond, SA 5064, Australia. Tel.: +61
8 8303 8742.
E-mail addresses: konrad.miotlinski@csiro.au (K. Miotlinski), dieke.postma@gmail.com (D. Postma), andrzej.kowalczyk@us.edu.pl (A. Kowalczyk).

1981; Kinniburgh et al., 1994; Larsen and Postma, 1997; Prommer

and Stuyfzand, 2005), precipitation and dissolution of carbonates
(Hanshaw and Back, 1979; van Breukelen et al., 1998), sulphates
(Postma, 1983; Kinniburgh et al., 1994), iron (Magaritz and Luzier,
1985) and manganese oxides (Larsen and Postma, 1997).
This paper demonstrates the results of a detailed study in a
highly cultivated agricultural region of the Odra Valley in Racibrz,
Poland where the quality of groundwater has dramatically deteriorated over a number of years. Most water quality changes occurred after an extreme precipitation event and the ood of the
Odra River in July 1997 (Kundzewicz et al., 1999). Prior to this
aquifer recharge occurred via inltration of precipitation followed
by inow from the surrounding aquifers. The rising water table
associated with reduced abstraction, enhanced recharge, and the
ooding event resulted in groundwater contamination in abstraction wells. The objective of this study is to elucidate the geochemical processes that are responsible for groundwater quality
changes.

2. Hydrogeology
The study area is located in the Upper Odra River Valley (Fig. 1)
near the city of Racibrz in southern Poland. Fig. 2 shows a cross

0022-1694/$ - see front matter Crown Copyright 2011 Published by Elsevier B.V. All rights reserved.
doi:10.1016/j.jhydrol.2011.10.034

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K. Miotlin

Fig. 1. Sketch of the study area presenting land use and the location of the selected wells with the capture zones.

Fig. 2. Hydrogeochemical cross-section (SeptemberDecember, 2005): 1 water level in the Quaternary aquifer, 2 boreholes, 3 well permeable units, 4 poorly
permeable units, 5 semi-permeable units, 6 directions of groundwater ow, 7 directions of groundwater seepage, 8 boundary between Quaternary and Neogene
(Kotlicka, 1978), 9 Pie diagram with a borehole number and a scale of diameter representing Total Dissolved Solids (TDS).

section through the buried valley deposits. One can distinguish two
aquifers in the prole: a Pleistocene and a Miocene (Sarmatian)
aquifer (Miotlinski, 2008). The Pleistocene aquifer, which is of particular interest here, comprises a heterogeneous mixture of coarse
and ne-grained material rich in organic matter (Kotlicka, 1978;
Fabianska et al., 2008). The aquifer can be subdivided into the three
hydrofacies; an upper (Upper Pleistocene) and a lower (Lower
Pleistocene) outwash facies composed of sands and gravels deposited by the glacial meltwater, and the intervening silt-rich

semiconning unit (Middle Pleistocene). In the central part of the

buried valley, the thickness of the ne-grained layer seldom exceeds 10 m, and therefore a hydraulic connection exists between
the two coarse-grained layers (Miotlinski, 2008). Perpendicular to
the axis of the valley, the ne-grained layers outweigh the sandy
layers in the upland areas towards the west. In these areas, the outwash deposits of the Lower Pleistocene, that form the most permeable part of the buried valley aquifer, do not occur. The aquifer,
varying in thickness from about 10 m to more than 40 m, is

 ski et al. / Journal of Hydrology 414415 (2012) 211219

K. Miotlin

covered by a poorly permeable layer and is underlain by the Miocene clay. The hydraulic conductivity of the permeable deposits
ranges from 1.6  105 m/s to 9.2  103 m/s. The lower values reect the upland areas in which the glacial sandy deposits contain
clay-rich layers, whereas the higher values are typical of the outwash gravel layers of Lower and Upper Pleistocene ages
(Miotlinski, 2008). All pumping wells penetrate the lowest part
of the aquifer (10 m), where hydraulic conductivity is the highest.
The capture zone of the Boguminska well eld is the largest in the
area covering a broad range of land use activity including urban
and residential areas, agricultural elds, and the area ooded by
the river in July 1997 (Fig. 1). The Miocene (Sarmatian) aquifer in
the area consists of the one layer of sandy deposits with an approximate thickness of 2030 m. The hydraulic conductivity of this
layer varies in the range of 4  1055  104 m/s. This aquifer
plays a minor role in groundwater provision in the area of Racibrz
(Witczak et al., 2007).
Extensive groundwater abstraction from the Pleistocene aquifer
during the twentieth century resulted in a water level decline of
about 20 m. A maximum drawdown was observed in the 1980s
in the Boguminska well eld. At that time the extraction from
the aquifer was in excess of 25,000 m3/d. Since 1994, a recovery
of the groundwater level has been observed (Fig. 3) which can be
attributed to a gradual decrease in groundwater exploitation and
an increase in rainfall over the preceding years. Groundwater
extraction reduced to 16,700 m3/d and 11,600 m3/d in 1997 and
2005, respectively. The mean annual precipitation also increased
from 530 mm (19821994) to 680 mm (19952001). At the beginning of July 1997 some areas of the Odra catchment received over
450 mm of rainfall within a couple of days (Kundzewicz et al.,
1999; Fenske et al., 2001) which resulted in an extensive ood
event in Racibrz (Fig. 1). The concomitant increase in the groundwater table (Fig. 3) indicates major inltration into the aquifer. In
2005, the drawdown in the Boguminska well eld had reduced to
less than 12 m. Since 1997 the area has not been ooded. The study
area is not irrigated.
A transient groundwater ow model (19912006) constrained
by isotopic (18O, 2H, 3H, 14C, 13C and 4He) data indicates that the
Pleistocene groundwater system is primarily recharged by precipitation (85%), although ascending ow from the Miocene aquifer
contributes to recharge as well (15%; Miotlinski, 2008). Streamow loss from the Odra River was taking place for the ooding period solely while is insignicant under normal water levels in the
river. Net recharge rates as a part of the annual precipitation vary

213

from 5% in the upper parts of the catchment to 25% and in the

oodplain areas where the transmissivity of the overlying deposits
is the lowest (Miotlinski, 2008).
3. Methods
3.1. Water sampling and analysis
Targeted groundwater sampling was undertaken during large
eld campaigns in October 2002, September 2005, September
October 2006, December 2006, and July 2007. Measurements of
pH, electrical conductivity, Eh, O2 and temperature were carried
out in line on unltered groundwater with electrodes in a ow cell
to prevent exposure to the atmosphere. Alkalinity and acidity were
determined shortly after sampling by the Gran titration method
(Stumm and Morgan, 1996). Samples for cations: Ca2+, Mg2+, Na+,
K+, NH4+ were ltered through 0.42-lm cellulose acetate lters,
collected in 100-ml polyethylene bottles and preserved with 2%

(v/v) 7 M HNO3 solution, whereas samples for anions: SO2
4 , Cl ,

3

NO
,
NO
,
F
,
PO
were
collected
in
100-ml
polyethylene
bottles
3
2
4
without ltering. Samples for the analysis of Fe, Mn, Ni, Cd, Cu, Co,
Zn, Al, As and Si were ltered through 0.42-lm lters and preserved with 1 ml of a Suprapure 65% v/v Merck HNO3. For ferrous
iron, an unltered subsample and one pure-water sample (blank
solution) were reacted in the eld with an acetic acid and phenantroline, and Fe2+ was measured by the spectrophotometric Ferrozine method (Stookey, 1970) immediately after transferring to
the laboratory. A similar procedure was also applied for sulphide
(Cline, 1967). Samples for 34S and 18O in sulphate were collected
in 1.5 l polyethylene bottles. All water samples collected in the
eld were refrigerated at 4 C until analysis.
To obtain water samples in a depth prole, four observation
wells were drilled: #10 and #15 in September 2005 and #12 and
#17 in December 2006. Groundwater was sampled during breaks
in drilling using a submersible pump lowered in a short-screen
0.1 m pipe.
The water samples were analysed for Ca2+, Mg2+, Na+, K+, NH
4,




SO2
4 , Cl , NO3 , NO2 and F concentrations by ion chromatography
(IC). Analyses of Fe2+, Mn2+, Ni2+, Cd2+, Cu2+, Co2+, Al3+ and Zn2+
were performed by ame atomic absorption spectrometry (AAS).
These metals as well as As and Si were additionally determined
by using ICPOES. Concentrations of ferrous iron, sulphide and
phosphate were quantied using spectrophotometry. Tritium measurements were performed by liquid scintillation coating of water

Fig. 3. Groundwater level elevation at the Boguminska well eld in the period of 19912005. The location of piezometers is depicted in the inserted map of the well eld in
Fig. 1.

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ski et al. / Journal of Hydrology 414415 (2012) 211219

K. Miotlin

after electrolytic enrichment of 3H (Eichinger et al., 1980). Prior to

the examination of d34S, d18O isotopes of sulphate, BaSO4 was precipitated. The BaSO4 was ground together with Cu2O and quartz
glass and reduced to SO2 by heating at 1120 C, as described by
Coleman and Moore (1978). The oxygen isotope composition of
the sulphate was determined on CO2 prepared by reduction of
BaSO4 with spectrographic graphite heated inductively in molybdenum crucibles (Mayer and Krouse, 2004).
In addition, monthly monitoring data for the Racibrz Waterworks wells since 1991 are included in this paper. The long-time
series renders it possible to identify temporal trends in groundwa2

ter chemistry. Determination of Ca2+, Mg2+, Na+, K+, NH
4 , SO4 , Cl ,

NO
,
NO
concentrations
was
undertaken
by
spectrophotometry
3
2
and alkalinity by Gran titration (Stumm and Morgan, 1996) by
the Racibrz Waterworks. The local laboratory, analysing these
samples, does not measure the concentrations of Na+ and K+, and
thus the accuracy of the chemical analyses could not be evaluated
by calculation of charge balance. The accuracy of the analyses provided by the Racibrz Waterworks was tested on several occasions
by inter-laboratory comparison. The variation in the concentra2

tions of Ca2+, Mg2+, HCO
3 , SO4 and Cl measured at the two laboratories was less than 5%.
3.2. Sediment sampling and analysis
Sediments were sampled in December 2006 (during drilling of
wells #12 and #17) and the analyses were performed from January
to May 2007 at the Faculty of Earth Sciences of the University of
Silesia.
The extraction of Mn-oxides, Fe-oxides and sulphides was
undertaken via a three-step procedure. A sample of frozen sediment (5 g) was rst extracted by shaking it with 35 mL of a
0.2 M hydroxylamine hydrochloride (HA) solution in a v/v 25% acetic acid for 1 h (Chester and Hughes, 1967; Chao, 1972; Larsen and
Postma, 1997). The suspension was centrifuged at 3500 rpm for
20 min, and the supernatant was removed. The sediment was then
rinsed twice with distiled water, immersed in 35 ml of a 6 M
hydrochloric acid (HCl) solution, and again shaken for 1 h (Chester
and Hughes, 1967). The suspension was centrifuged at 3500 rpm
for 20 min, and the supernatant was removed. The sediment was
then rinsed twice with distiled water and placed into a glass vessel.
Subsequently, the sample was boiled in a concentrated nitric acid
(HNO3) (Huerta-Diaz and Morse, 1990). The supernatant of each
extraction step was ltered through a 0.42-lm membrane lter
and acidied with 0.5 ml of a Suprapure 65% v/v Merck HNO3.
The samples were stored at 4 C until analysis. The metals including Ni2+ were analysed with ame AAS.
Sulphide and sulphur were determined in sediments using a
modied Cr(II) reduction method (Caneld et al., 1986). Chromium
reducible sulphur was measured spectrophotometrically, instead
of by iodometrical titration as proposed by Caneld et al. (1986).
Also chromium powder dissolved in HCl was used as an alternative
to using chromium chloride solution (Sullivan et al., 2000).
Water soluble sulphates were determined after displacement of
the pore water. Initially the frozen sediment samples were rinsed
with ethanol at room temperature to displace pore water and the
remaining ethanol was removed by evaporation overnight. The dried
samples were then shaken for 2 h in demineralised water and centrifuged at 3500 rpm for 15 min. In the ltered (0.42-lm) supernatant,
Ca2+ and SO2
4 were determined by ion chromatography.
Pyrite and other heavy metals were extracted from selected
sand samples for microscopy and isotope analyses by density separation. Bromoform (CHBr3) with a density of 2.8 g/cm3 was used
for the separation. The sulphur isotopic composition of pyrite
was determined from SO2 prepared from the oxidation of pyrite
by Cu2O at 1100 C (Taylor et al., 1984).

4. Results
4.1. Water chemistry
The major features of the studied aquifer are distinct temporal
variations in water quality. Those changes are observed chiey in
the Boguminska well eld (wells #11, 13, and 14) after 1997 as depicted in Fig. 4. Prior to 1995, sulphate and Fe2+ were low (0.8
1 mM and 0.025 mM, respectively) and the Cl was around
0.75 mM. From 1995 to the 1997 ooding event a small increase
in SO2
4 was visible evident in well #13, and to a lesser extent also

for Cl. After 1997 the increases in SO2
4 and Cl were more dra2+
2+
matic followed by the increases in Fe , Mn and Ni2+. The increases in SO2
and Cl correspond to declines in alkalinity and
4
pH. Remarkably, the alterations in Fe2+, Mn2+ and Ni2+ are signicantly delayed in comparison to sulphate. As a result of these
changes, the water types evolved from a CaHCO3 type towards a
CaSO4HCO3 water type. Other indicators of the water quality
changes include the gradual evolution towards the (a) undersaturation with respect to calcite and (b) negative d34S(SO2
4 ) values.
The tritium concentration in well #11 indicates that part of the extracted water must have recharged the aquifer after the 1960s.
The changes in water chemistry observed since 1995 result in
spatial variability within the aquifer. The changes along the regional direction of groundwater ow (from the east to the west) crossing the Boguminska well eld in the year of 2005 are shown as pie
diagrams in Fig. 2. Groundwater in the well eld is characterised by
the highest TDS which is reected by the area of the circle. This

water is also enriched in Ca2+, SO2
4 , and Cl , among the major ions

and depleted in HCO3 . Such high concentrations do not occur in
other wells located in the central part of the buried valley (see well
#1 in Table 1). Hence, the following broad factors must be responsible for the spatial variability of water quality: (a) the geology
(permeability of the formation overlying the aquifer, geochemistry,
heterogeneity), (b) the hydrodynamics (the areas contributing to
recharge to the individual pumping wells as well as the upward
movement of the water table in the Boguminska due to enhanced
recharge rates including ooding in 1997 and diminishing groundwater abstraction), and (c) the anthropogenic inuences (the land
use including agriculture and urban areas).
The depth proles, that were sampled at the Boguminska well
eld, in 2005 and 2006, also show signicant changes over depth
(Fig. 5). Boreholes #12 and #17 display the water chemistry of
the rewatered part of the saturated zone, whereas the much deeper
wells #10 and #15 mainly represent the water chemistry of the
deeper part of the aquifer. The water chemistry of the rewatered
zone (Fig. 5, # 12 and 17) is oxic with up to 0.22 mM of O2, and

up to 0.05 mM NO
3 . Further downward the O2 and NO3 concentra2+
tions decrease while there is a signicant Fe increase and the
SO2
concentration is around 3 mM. The deeper groundwater
4
(Fig. 5, #10 and 15) is anoxic with only traces of nitrate but contains both ferrous iron and manganese, reaching 244 lM Fe2+
and 44 lM Mn2+. Sulphate concentrations are between 1 and
2 mM and show no clear depth trend.

4.2. Sediment chemistry

The sediment chemistry of the rewatered zone (wells #12
and #17) is shown in Fig. 6. Borehole #17 exhibits enhanced
concentrations in particular for Fe, Mn and Ni in the depth range
914 m. The 6 M HCl and hydroxylamine hydrochloride extractions both show high Fe concentrations from 10 to 14 m. HA reduces poorly crystalline iron oxyhydroxides and the similar
distribution for HCl-extractable-Fe suggests that 6 M HCl extracts
more crystalline iron oxyhydroxides (e.g. goethite). However, the

 ski et al. / Journal of Hydrology 414415 (2012) 211219

K. Miotlin

215

Fig. 4. The variations in selected ions concentrations in groundwater over time.

Table 1
Chemical parameters of groundwater and river water from Racibrz. In the heading the name of sampling point and date is given.

Hydrochemical type
TDS (mg/L)
pH
O2 (mM)
Ca2+ (mM)
Mg2+ (mM)
Na+ (mM)
K+ (mM)
SO2
4 (mM)
NO
3 (mM)
HCO
3 (mM)
Cl (mM)
2+
Fe (mM)
Mn2+ (mM)
Ni2+ (lM)
SIcalcite
SIsiderite
SIrhodochrosite
SIgypsum
d34S(SO4) ()
*

Well #1
27/09/2006

Well #11
11/12/2006

Well #13
27/05/1991

Well #13
16/06/2005

River water*
26/11/2004

CaHCO3
525
7.14
<0.003
2.49
0.68
0.41
0.03
0.29

CaSO4HCO3
810
6.52
<0.003
3.35
0.96
0.93
0.15
3.8

CaHCO3
550
6.43
n/a
2.64
0.73
0.41
0.04
0.7

CaHCO
3 SO4
640
6.71
<0.003
2.72
0.87
1.01
0.19
1.86

NaCl
950
7.25
0.35
3.2
1.27
6.91
0.22
1.33

<0.02
5.8
0.37
0.02
0.002
<0.017
0.01
0.08
0.63
2
6.12

<0.02
2.25
1.03
0.26
0.004
3.8
1.03
0.22
1.33
0.9
5.44

<0.02
5.03
0.75
0.025
0.002
n/a
0.77
0.52
1.33
1.62
n/a

<0.02
3.8
1.13
0.2
0.013
<0.017
0.65
0.54
0.38
1.23
n/a

0.23
2
8.46
<0.002
0.01
<0.017
0.59
10.8
0.19
1.9
3.02

Note that the river water sample represents a non-ooding period; n/a value not available.

amount of iron extracted with hydrochloric acid is far greater

than by HA. Hydroxylamine hydrochloride also reduces Mn from
the sediment, indicating the presence of Mn-oxides and again
the concentration extracted is approximately an order of magnitude greater in the extraction with HCl than for HA. In contrast,
oxidative dissolution by HNO3 which will dissolve pyrite,

releases little Mn. The leaching of Ni by hydroxylamine hydrochloride suggests a Ni liberation during reductive dissolution of
Fe- or Mn-oxides and the amount of Ni2+ released by HCl is
comparable to the HA extraction. Up to ten times more Ni2+ is
released by HNO3, suggesting that pyrite is the primary source
of this metal.

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ski et al. / Journal of Hydrology 414415 (2012) 211219

K. Miotlin

Fig. 5. The variations in selected ions concentrations in groundwater over depth.

Fig. 6. Geochemical properties of sediments. Symbols represent the solution being used for the extraction: HA (hydroxylamine hydrochloride), HCl (hydrochloric acid), HNO3
(nitric acid), CrCl2 (chromium (II) chloride), H2O (pure water). n/anot applicable.

SEM analysis revealed the persistence of euhedral pyrite in the

rewatered zone (Miotlinski, 2008) indicating that all iron sulphides
were not completely oxidised when the water table was low. In
good agreement (Fig. 6) the concentration of Cr(II)-reducible sulphur, comprising pyrite, ranges from 75 to 100 mM/kg S. The gypsum content was assayed by measuring H2O-extractable sulphate
and concentrations of up to 6 mM/kg S were measured (Fig. 6).

5. Discussion
5.1. Hydrogeology and water quality of enhanced inltration
The regional groundwater ow eld indicates that the vast
majority of groundwater extracted in the Boguminska well eld
comes from the upland areas (Fig. 2). Nevertheless, the water de-

 ski et al. / Journal of Hydrology 414415 (2012) 211219

K. Miotlin

rived directly from the upland areas is of a reasonably good quality

(e.g. wells #1 and #6 in Table 1). The tritium data and particle
tracking modelling indicate that at least part of this water must
have recharged the aquifer during the period of intensive agricultural fertilisation since the 1960s (Miotlinski, 2008).
Prior to the ooding event, there was little variation in the
chemical composition of groundwater which may suggest that
the ooding event from 1997 was responsible for the changing
water quality. This hypothesis nds a conrmation in the sudden
rise of the water table following the ood. Wells #13 and #14,
whose capture zones were covered by the ood waters in
1997, show an increase in the Cl concentration (Fig. 4), which
could be considered to be of the river origin, as river water is
generally higher in chloride than the groundwater (Table 1).
The midpoints of the chloride breakthrough curves in Fig. 4 occurred in October 1999 (Well #13) and April 2000 (Well #14),
corresponding to travel times for inltration of river water of
27 and 33 months respectively. Estimating a horizontal distance
of 500 m from the ooded area and a vertical distance of 40 m
towards the well screens, the breakthrough curves correspond
to a high estimate for the average groundwater velocity of
240 m/year. A linear groundwater velocity in this range seems
to be unlikely, because the supercial and upper sections of
the aquifer consist of ne grained material of relatively low
hydraulic conductivity. Moreover, the chloride signature of the
river water is believed to be diluted during the ooding events
due to very large runoff rates associated with the episodes of
heavy precipitation (Fenske et al., 2001).
Concomitantly with Cl, the sulphate concentration increases in
wells #13 and 14 (Fig. 4) which points towards a related mechanism for increase. For the same timespan as the chloride breakthrough with a rise of about 0.75 mM Cl, the increase in SO2
4
are is up to 1.9 mM. However, in the river water the Cl/SO4 ratio
is higher than 6 (Table 1). The implication is that the river water
cannot be the main source of SO2
for the observed increase in
4
SO2
4 after ooding. More likely the inltrating river water and diffuse recharge from rainfall are ushing the products of agricultural
activity, which had accumulated here during the relatively dry
conditions before 1995, from the unsaturated zone. Many authors
(e.g. Postma et al., 1991; Bhlke and Denver, 1995; Tesoriero et al.,
2000) have previously reported that in addition to nitrate loading,
agricultural activity may result in the increases of sulphate, chloride or calcium in groundwater. Also, some water of elevated sulphate concentration may have accumulated in a relatively poor
permeability zone of the upper part of the saturated zone prior
to 1997 and have been washed out with increased recharge following the ood event. In addition wells #13 and #14 showed an increase in SO2
4 before ooding (Fig. 4) in response to a rise in the
groundwater table of a few metres as a result of the reduction in
pumping.
A possible source of sulphate to be ushed from the rewatered
unsaturated zone is gypsum that is being dissolved. The presence
of gypsum in the unsaturated zone of dewatered aquifers has previously been reported elsewhere. In the London basin aquifer up to
1.7 weight percent of gypsum was found (Kinniburgh et al., 1994)
and up to 6 mM/kg of water-soluble sulphur was measured in the
Beder well eld (Larsen and Postma, 1997). In both cases the dissolution of gypsum was associated with recovery of water level.
Although the oversaturation of groundwater with respect to gypsum has been never conrmed in Racibrz, traces of gypsum were
identied in the unsaturated zone (Fig. 6). The dissolution of gypsum will release Ca2+ and SO2
4 in a 1:1 stoichiometry according to
the reaction:

CaSO4  2H2 O $ Ca2 SO2

4 2H2 O

217

5.2. Pyrite oxidation

The increases in the concentration of sulphate and iron, following the ooding event (Fig. 4) suggest that pyrite oxidation is involved or at least the ushing of the oxidation products of pyrite
oxidation from the unsaturated zone takes place. Pyrite oxidation
as a result of groundwater exploitation and a corresponding decline in the water level is a well documented issue in many aquifers (Baszyk and Grski, 1981; Kinniburgh et al., 1994; Larsen
and Postma, 1997).
Pyrite oxidation by reduction of oxygen may either proceed
with oxidation of both sulphur and iron:

FeS2 15=4O2 7=2H2 O ! FeOH3 2SO2

4 4H

or, when insufcient electron acceptor is present, by oxidation of

sulphur only:

FeS2 7=2O2 H2 O ! Fe2 2SO2

4 2H

Pyrite oxidation may also be coupled to nitrate reduction in

aquifers (Postma et al., 1991; Bhlke and Denver, 1995; Tesoriero
et al., 2000; Broers, 2004). When nitrate is the electron acceptor,
the reactions are:

5FeS2 15NO3 10H2 O ! 5FeOH3 15=2N2 10SO2

4 5H

4
5FeS2 14NO3 4H ! 5Fe2 7N2 10SO2
4 2H2 O

In the presence of CaCO3 and at near neutral pH, these reactions

are buffered by the reaction:

CaCO3 H ! Ca2 HCO3

Combining reactions (2)(5) with (6) leads to:

FeS2 15=4O2 7=2H2 O 4CaCO3

2
! FeOH3 2SO2
4HCO3
4 4Ca

With the stoichiometric release ratio Ca: SO4 = 2: 1,

2
FeS2 7=2O2 H2 O 2CaCO3 ! Fe2 2SO2
2HCO3
4 2Ca

8
With the ratio Ca: SO4 = 1: 1,

5FeS2 15NO3 10H2 O 5CaCO3

2
! 5FeOH3 15=2N2 10SO2
5HCO3
4 5Ca

With the ratio Ca: SO4 = 1:2,

5FeS2 14NO3 4Ca2 4HCO3

! 5Fe2 7N2 10SO2
4 2H2 O 4CaCO3

10

Note that reaction (5) is proton consuming and therefore reaction (10) may precipitate CaCO3. The corresponding stoichiometric
ratio is Ca:SO4 = 1:2.5.
From the foregoing it becomes clear that the predominant pyrite oxidation reaction can be identied from the Ca:SO4 ratio even
when the electron acceptor is no longer present. Nonetheless, the
approach presented for identifying the reaction path in the pyrite
oxidation process is based on the following assumptions:
1. The amount of sulphate originating from pyrite must exceed the
amount derived from agricultural sources. The latter could be
conrmed by the isotopic examination of sulphur.
2. The uptake and release of calcium by ion exchange must be
small.

218

ski et al. / Journal of Hydrology 414415 (2012) 211219

K. Miotlin

communism in Poland in 1989 around 200 kg N/ha/year was

used while the current level is 120 kgN/ha/year. McMahon
et al. (2006) studied the effect of irrigation on the behaviour
of nitrogen and chloride in thick unsaturated zones beneath cultivated areas, in the high plains of central USA, and concluded
that the induced inltration results in the mobilisation of 60%
of nitrogen (mostly in the form of NO
3 ) and as much as 80%
of chloride previously stored in the prole. Most probably the
ooding alongside enhanced recharge from precipitation has
ushed nitrate, or the oxidation products of pyrite oxidation,
that had accumulated in the soil and unsaturated zone.
5.3. Nickel mobilisation

Fig. 7. Relation between dissolved Ca2+ and SO2

4 in groundwater and corresponding stoichiometry of major reactions.

Using the Ca2+ and SO2

4 contents of the pristine groundwater
(Table 1, well #1) as starting point the lines corresponding to these
different stoichiometries are shown in Fig. 7 together with data
from the different wells that were sampled over time (Fig. 4).
Clearly most data-points fall within the nitrate reduction window.
Since the amount of Fe2+ released, as compared to sulphate, is lower than predicted by reaction (10) the overall reaction stoichiometry must be somewhere between reactions (9) and (10), as is also
apparent from Fig. 7. On the other hand, pyrite oxidation by oxygen
does not appear to be important in the development of the groundwater chemistry as data points do not plot in the oxygen reduction
window of Fig. 7. The ratio Ca:SO4 = 1:1 is predicted for partial oxidation of pyrite (reaction (8)) as well as for dissolution of gypsum
(reaction (1)). Although there are a few data that plot near this line,
in general neither of the two processes has a major inuence on the
groundwater composition. The only well that indicates an inuence of pyrite oxidation by oxygen is well #11. Nevertheless, this
well was drilled after the ood (in 2001) and might contain a signicant admixture of water from shallower parts of the aquifer.
Otherwise its data plot between the oxygen and nitrate windows
which would imply that both processes contribute in the capture
zone of this well.
An intriguing question is the source of nitrate required for
pyrite oxidation according to reactions (9) and (10). Their stoichiometry predicts that to produce 3 mM SO4 about 4.5 mM
NO3 is needed. Inspection of the composition of the present
day river water (Table 1) shows that this is an insufcient
source. Similarly, the present day supercial groundwater is
low in nitrate (Fig. 5). However, historically the lands in the area
have been intensively fertilised. Before the collapse of

Following the recharge event the quality of groundwater also

declined with respect to nickel, with concentrations in the Boguminska well eld up to 340 nM (Fig. 4) or up to eight times the recommended EU drinking water limit. The increase in the Ni2+
concentration suggests that Ni mobilisation is related to pyrite oxidation as has been reported from other well elds (Larsen and
Postma, 1997; Broers, 2004). The high content of Ni extracted by
HNO3 in the sediments at Racibrz (Fig. 6) suggests that the pyrite
is rich in Ni and therefore probably is the primary source of dissolved Ni2+ in groundwater. However, Fig. 4 shows that there is
no simple relation between the groundwater sulphate and Ni2+
concentrations and an additional process affecting the mobilisation
of Ni2+ in the aquifer must be operative.
Fig. 8 displays that the concentrations of Ni2+ and Co2+ in the
groundwater correlate well with that of Mn which suggests a
coupled mobilisation process, most likely the reduction of Mnoxides. Mn-oxides are known to be important scavengers of
trace metals due to their high surface area and a large negative
surface charge (McKenzie, 1980; Tonkin et al., 2004). An almost
complete uptake of both Ni2+ and Co2+ in the presence of
Mn-oxides was observed by Kay et al. (2001) during a column
experiment. Larsen and Postma (1997) found a strong association between Ni2+ and Mn-oxides in aquifer sediments. Probably
the Ni2+ released during pyrite oxidation has predominantly become adsorbed on the surfaces of Mn-oxides. Subsequent reductive dissolution of the Mn-oxides will cause the mobilisation of
Ni2+ as well (Stollenwerk, 1994; Larsen and Postma, 1997; Kay
et al., 2001). In particular, during a rising water table, the mobilisation of Fe2+, for example by partial oxidation of remaining
pyrite, can drive the reaction (Postma, 1985; Larsen and Postma,
1997; Postma and Appelo, 2000):

2Fe2 MnO2 4H2 O ! 2FeOH3 Mn2 2H

11

The time series displayed in Fig. 4 support this scenario, showing how Fe2+ builds up followed by the increases of Mn2+ and Ni2+.

Fig. 8. Relations between trace metals and Mn2+ in the shallow wells.

 ski et al. / Journal of Hydrology 414415 (2012) 211219

K. Miotlin

6. Conclusions
The reduction in groundwater extraction, an increase in recharge, and the 1997 ooding event of the Odra River rendered
the recovery of the water level in the Quaternary aquifer at Racibrz, Poland. The inltration event is reected in the groundwater
quality of the pumped wells by sharp increases in the Cl and SO2
4
concentrations.
The enhanced inltration resulted in increases in dissolved sulphate and iron and decreases in pH and alkalinity. These changes
were attributed to ushing of oxidation products from pyrite.
The calcium-sulphate-stoichiometry suggests nitrate accumulated
in the unsaturated zone from fertilizer application to be the main
electron acceptor for pyrite oxidation.
In addition the upward movement of the water level has resulted in increases in the Ni2+ concentration. The rise in Ni2+ is
strongly correlated to an increase in Mn2+ and it is inferred that
Ni2+ is mainly present adsorbed on the surfaces of Mn-oxide. Subsequent reductive dissolution of Mn-oxide is presumably caused
by reaction with Fe2+ and releases Ni2+ to the groundwater.
Acknowledgements
The project was funded by the Ministry of Science and Higher
Education of Republic of Poland (Research Project N 521 001 31/
0335) under the PhD scholarship project of the rst author. We
appreciate the constructive comments by two anonymous reviewers. It is a pleasure to thank Joanne Vanderzalm from CSIRO Land
and Water for her comments and linguistic guidance. Jacek Wrbel
and Alina Niewiadomska are acknowledged for eld and laboratory
assistance.
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