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Journal of Hydrology
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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).
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
212
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
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
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.
214
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.
215
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.
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.
216
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.
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-
217
4
5FeS2 14NO3 4H ! 5Fe2 7N2 10SO2
4 2H2 O
8
With the ratio Ca: SO4 = 1: 1,
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
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.
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.
References
Baszyk, T., Grski, J., 1981. Ground-water quality changes during exploitation.
Ground Water 19 (1), 2833.
Bhlke, J.K., Denver, J.M., 1995. Combined use of groundwater dating, chemical, and
isotopic analyses to resolve the history and fate of nitrate contamination in two
agricultural watersheds, Atlantic coastal plain, Maryland. Water Resour. Res. 31,
23192339.
Broers, H.P., 2004. Nitrate reduction and pyrite oxidation in the Netherlands. In: IAH
Selected Papers, No 5, Balkema, Rotterdam, pp. 141147.
Caneld, D.E., Raiswell, R., Westrich, J.T., Reaves, C.M., Berner, R.A., 1986. The use of
chromium reduction inorganic sulfur in sediments and shale. Chem. Geol. 54,
149155.
Chao, T.T., 1972. Selective dissolution of manganese oxides from soils and
sediments with acidied hydroxylamine hydrochloride. Soil Sci. Soc. Am.
Proc. 36, 764768.
Chester, R., Hughes, M.J., 1967. A chemical technique for the separation of ferromanganese minerals, and adsorbed trace elements for pelagic sediments. Chem.
Geol. 2, 149262.
Cline, J.D., 1967. Spectrophotometric determination of hydrogen sulde in natural
waters. Limnol. Oceanogr. 14, 454458.
Coleman, M.L., Moore, M.P., 1978. Direct reduction of sulfates to sulfur dioxide for
isotopic analysis. Anal. Chem. 50, 15941595.
Crosby, R.S., McCallum, J.L., Walker, G.R., Chiew, F.H.S., 2010. Modelling climatechange impacts on groundwater recharge in the Murray-Darling Basin,
Australia. Hydrol. J. 18, 16391656.
Eichinger, L., Forster, M., Rast, H., Rauert, W., Wolf, M., 1980. Experience Gathered in
Low-level Measurements of Tritium in Water. TECDOC-246. IAEA, Vienna, pp.
4364.
Fabianska, M., Miotlinski, K., Kowalczyk, A., 2008. Geochemical features of redeposited organic matter occurring in uvioglacial sediments in the Racibrz
region (Poland); a case study. Chem. Geol. 253, 151161.
Fenske, C., Westphal, H., Bachor, A., Breitenbach, E., Buchholz, W., Jlich, W.-D.,
Hensel, P., 2001. The consequences of the Odra ood (summer 1997) for the
Odra lagoon and the Beaches of Usedom: what can be expected under extreme
conditions? Int. J. Hyg. Environ. Health 203, 417433.
Hanshaw, B.B., Back, W., 1979. Major geochemical processes in the evolution of
carbonate aquifer systems. J. Hydrol. 43, 287312.
Hanson, R.T., Dettinger, M.D., Newhouse, M.W., 2006. Relations between climatic
variability and hydrologic time series from four alluvial basins across the
southwestern United States. Hydrogeol. J. 14 (7), 11221146.
219
Holman, I.P., Tascone, D., Hess, T.M., 2009. A comparison of stochastic and
deterministic downscaling methods for modelling potential groundwater
recharge under climate change in East Anglia, UK: implication for
groundwater resource management. Hydrol. J. 17, 16291941.
Huerta-Diaz, M.A., Morse, J.J., 1990. A quantitative method for determination of
trace metals concentrations in sedimentary pyrite. Mar. Geol. 29, 119144.
Kay, J.T., Conklin, M.H., Fuller, C.C., ODay, P.A., 2001. Processes of nickel and cobalt
uptake by a manganese oxide forming sediment in Pinal Creek, Globe Mine
District, Arizona. Environ. Sci. Technol. 35, 47194725.
Kinniburgh, D.G., Gale, I.N., Smedley, P.L., Darling, W.G., West, J.M., Kimblin, R.T.,
Parker, A., Rae, J.E., Aldous, P.J., OShea, M.J., 1994. The effects of historic
abstraction of groundwater from the London Basin aquifers on groundwater
quality. Appl. Geochem. 9, 175195.
Kotlicka, G.N., 1978. Stratygraa osadw czwartorzedowych w dolinie Odry koo
Raciborza. [Stratigraphy of Quaternary deposits in the Odra Valley near
Racibrz]. Biuletyn Instytutu Geologicznego 300, 303387 (In Polish,
extended abstract in English).
Kundzewicz, Z.W., Szamaek, K., Kowalczak, P., 1999. The great ood of 1997 in
Poland. Hydrol. Sci.-J.-des Sci. Hydrol. 44, 855870.
Larsen, F., Postma, D., 1997. Nickel mobilization in a groundwater well eld: Release
by pyrite oxidation and desorption from manganese oxides. Environ. Sci.
Technol. 31, 25892595.
Loaciga, H.A., Maidment, D.R., Valdes, J.B., 2000. Climate-change impacts in a
regional karst aquifer, Texas, USA. J. Hydrol. 227, 173194.
Ma, T., Wang, Y., Guo, Q., 2004. Response of carbonate aquifer to climate change in
northern China: a case study at the Shentou karst springs. J. Hydrol. 297, 274
284.
Magaritz, M., Luzier, J.E., 1985. Water-rock interactions and sea-water freshwater
mixing effects in the coastal dunes aquifer, Coos Bay, Oregon. Geochim.
Cosmochim. Acta 49, 25152525.
Mayer, B., Krouse, H.R., 2004. Procedures for sulfur isotope abundance studies. In:
Handbook of Stable Isotope Analytical Techniques, Elsevier, Amserdam, pp.
538596.
McKenzie, R.M., 1980. The adsorption of lead and other heavy metals on oxides of
manganese and iron. Aust. J. Soil Res. 18, 6173.
McMahon, P.B., Dennehy, K.F., Bruce, B.W., Bhlke, J.K., Michel, R.L., Gurdak, J.J.,
Hurlbut, D.B., 2006. Storage and transit time of chemicals in thick unsaturated
zones under rangeland and irrigated cropland, High Plains, United States. Water
Resour. Res. 42, W03413. doi:10.1029/2005WR00441.
Miotlinski, K., 2008. Hydrogeochemical Evolution in the Buried Valley in the
Racibrz area. PhD Dissertation. University of Silesia, Faculty of Earth Sciences,
Sosnowiec, Poland.
Postma, D., 1983. Pyrite and siderite oxidation in swamp sediments. J. Soil Sci. 34,
163182.
Postma, D., 1985. Concentration of Mn and separation from Fe in sediments I.
Kinetics and stoichiometry of the reaction between birnessite and dissolved
Fe(II) at 10 C. Geochim. Cosmochim. Acta 49, 10231033.
Postma, D., Appelo, C.A.J., 2000. Reduction of Mn-oxides by ferrous iron in a ow
system: column experiment and reactive transport modelling. Geochim.
Cosmochim. Acta 64, 12371247.
Postma, D., Boesen, C., Kristiansen, H., Larsen, F., 1991. Nitrate reduction in an
unconned sandy aquifer: water chemistry, reduction processes, and
geochemical modeling. Water Resour. Res. 27, 20272045.
Prommer, H., Stuyfzand, P., 2005. Identication of temperature dependent water
quality changes during a deep well injection experiment in a pyritic aquifer.
Environ. Sci. Technol. 36, 22002209.
Stollenwerk, K.G., 1994. Geochemical interactions between constituents in acidic
groundwater and alluvium in an aquifer near Globe, Arizona. Appl. Geochem. 9,
353369.
Stookey, L.L., 1970. Ferrozine a new spectrophotometric reagent for iron. Anal.
Chem. 42, 779781.
Stumm, W., Morgan, J.J, 1996. Aquatic Chemistry. Chemical Equilibria and Rates in
Natural Waters, third ed. Wiley and Sons.
Sullivan, L.A., Bush, R.T., McConchie, D.M., 2000. A modied chromium reducible
sulphur method for reduced inorganic sulphur: optimum reaction time for acid
sulphate soil. Aust. J. Soil Res. 38, 729734.
Taylor, B.E., Wheeler, M.C., Nordstrom, D.K., 1984. Stable isotope geochemistry of
acid mine drainage: experimental oxidation of pyrite. Geochim. Cosmochim.
Acta 48, 26692678.
Tesoriero, A.J., Liebscher, H., Cox, S.E., 2000. Mechanism and rate of denitrication in
an agricultural watershed: electron and mass balance along ow paths. Water
Resour. Res. 36, 15451559.
Tonkin, J.W., Balistrieri, L.S., Murray, J.W., 2004. Modeling sorption of divalent metal
cations on hydrous manganese oxide using the diffuse double layer model.
Appl. Geochem. 19, 2953.
van Breukelen, B.M., Appelo, C.A.J., Olsthoorn, T.N., 1998. Hydrogeochemical
transport modelling of 24 years of Rhine water inltration in the dunes of the
Amsterdam Water Supply. J. Hydrol. 209, 281296.
_ ski, K.,
Witczak, S., Szklarczyk, T., Kmiecik, E., Szczepanska, J., Zuber, A., Rzan
Dulinski, M., 2007. Hydrodynamic modelling, environmental tracers and
hydrochemistry of a conned sandy aquifer (Kedzierzyn-Gubczyce
Subtrough, SW Poland). Geol. Quart. 51 (1), 116.