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Migration of risk elements within the floodplain of the Litavka River, the
Czech Republic

Article  in  Geomorphology · December 2018

DOI: 10.1016/j.geomorph.2018.12.010

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 Geomorphology 329 (2019) 46–57

Contents lists available at ScienceDirect

Geomorphology

journal homepage: www.elsevier.com/locate/geomorph

Migration of risk elements within the floodplain of the Litavka River, the
Czech Republic
K. Kotková a,b,⁎, T. Nováková c, Š. Tůmová b,d, T. Kiss e, J. Popelka d, M. Faměra b,f
a
Institute of Geochemistry, Mineralogy and Mineral Resources, Faculty of Science, Charles University, Prague, Czech Republic
b
Institute of Inorganic Chemistry, Czech Academy of Sciences, Řež, Czech Republic
c
Institute of Geology, Czech Academy of Sciences, Prague, Czech Republic
d
Faculty of Environment, J. E. Purkyně University, Ústí nad Labem, Czech Republic
e
Department of Physical Geography and Geoinformatics, University of Szeged, Szeged, Hungary
f
Faculty of Science, Palacký University, Olomouc, Czech Republic

a r t i c l e i n f o a b s t r a c t

Article history: Floodplains are one of the most complex sedimentary environments used for the reconstruction of human im-
Received 16 August 2018 pacts on fluvial deposition and catchment pollution. Studies of polluted floodplains require an interdisciplinary
Received in revised form 13 December 2018 approach, including tools from geomorphology, geophysics, and geochemistry. The spatial distribution of pollut-
Accepted 14 December 2018
ants can reflect not only pollution history but also post-depositional transfers of pollutants. The Litavka River (SW
Available online 20 December 2018
Czech Republic) was impacted by historical mining and processing of Ag-Pb-Zn-Sb sulfidic ores, which resulted in
Keywords:
a severely polluted floodplain. Previous studies revealed that nearly all of the floodplain deposits of the Litavka
Floodplain sediments River downstream from the ore district are polluted, indicating massive floodplain aggradation. Our aim was
The Litavka River to decipher the role of aggradation in floodplain development by investigating the pollutant distribution in the
Post-depositional migration floodplain fill. Another important goal was to distinguish polluted (modern) sediments from secondarily polluted
Secondary pollution sediments (which were previously pristine) caused by extensive lateral and vertical post-depositional chemical
migration of risk elements within the floodplain fill.
The floodplain topography was characterized via a digital terrain model (DTM); the internal structure of the
floodplain was determined by electrical resistivity tomography (ERT). Sediment samples were collected from
hand-drilled cores across the floodplain along the ERT line, and their elemental composition and magnetic sus-
ceptibility were analysed. Dating of sediments was performed via optically stimulated luminescence (OSL).
The concentrations of Zn, Pb and Cd, along with values of magnetic susceptibility decreased with increasing dis-
tance from the current river channel. However, the spatial patterns of risk elements were more complicated than
expected in a fluvial sedimentary environment. Inter-element relationships of risk elements exhibited a complex
pattern, with abundant outliers that required the use of robust regression. The results helped distinguish the geo-
chemical difference between proximal and distal floodplains, and to identify zones of anomalous inter-element
ratios attributed to post-depositional element migration. The observed migration was significant, and not only
vertical but horizontal, spanning a distance of approximately half the floodplain width. Metal migration explains
why unpolluted sediments are practically missing from the floodplain fill of the Litavka River. Use of pollution
chemostratigraphy, without considering the possibility of post-depositional migration of risk elements, could
lead to overestimation of the volume of younger sediments deposited directly within the floodplain and to over-
estimation of the role of aggradation processes.
© 2018 Elsevier B.V. All rights reserved.

1. Introduction should be performed with respect to the knowledge of floodplain archi-

Floodplain sediments are natural archives of both natural processes
and past human activities. Environmental monitoring and management
⁎ Corresponding author at: Charles University, Faculty of Science, Albertov 6, 128 43
Prague, Czech Republic.
E-mail addresses: kristynakotkova@seznam.cz (K. Kotková), novakova@gli.cas.cz
(T. Nováková), Jan.Popelka@ujep.cz (J. Popelka), famera@iic.cas.cz (M. Faměra).
tecture and fluvial depositional dynamics. Sedimentary archives can be
used to describe the development of historical pollution of the area or to
estimate potential environmental risk related to legacy pollution
(e.g., James, 2013; Lecce and Pavlowsky, 2014).
Studies performed in previous decades have shown that many
European floodplains are contaminated with potentially toxic sub-
stances, which can pose a problem for the environment. These studies
have also shown that pollutant concentrations are spatially variable in

https://doi.org/10.1016/j.geomorph.2018.12.010
0169-555X/© 2018 Elsevier B.V. All rights reserved.
 K. Kotková et al. / Geomorphology 329 (2019) 46–57
river systems, as a consequence of complex river floodplain architecture
(e.g., Miller et al., 1998; Notebaert et al., 2011; Ciszewski et al., 2012,
2014; Matys Grygar et al., 2016a). Deposits in the channel belt and espe-
cially at eroding banks are often prone to be reworked (e.g., Lewin and
Macklin, 2003); thus, studying overbank sediments seems to be the best
choice to adequately describe the spatial distribution of risk elements.
Such an approach requires intergrated knowledge of geomorphology,
geophysics and analytical geochemistry.
Pollution chemostratigraphy is commonly used to search for iso-
chrones within the sedimentary strata to identify the onset or climax
of mining activity, or mark disasters, such as tailing ponds failures.
Chemostratigraphy is based on the spatial distribution of pollutants in
the floodplain deposits, which provides a record of pollution as well as
a history of deposition or erosion (Miller et al., 1998; Notebaert et al.,
2011; Ciszewski et al., 2012, 2014; Matys Grygar et al., 2016a). How-
ever, credible interpretation of pollution chemostratigraphy requires
post-depositional stability of risk elements, which is not always guaran-
teed (Hudson-Edwards et al., 1998). Diffuse transport of risk elements
along the river course (Hudson-Edwards et al., 1999; Coulthard and
Macklin, 2003) is known to contribute significantly to the overall flow
of contaminated metals into rivers, where metals stored in floodplains
can have a significant long-lasting impact on water quality due to remo-
bilization of sediments during flood events (Lynch et al., 2014).
Migration of risk elements occurs mostly in layers associated with
groundwater level fluctuations, which promotes decomposition of or-
ganic matter and dissolution and re-precipitation of Fe and Mn oxides.
Those processes occur mainly in coarse, well-sorted, and thus permeable
sediments, especially in sand layers (Hudson-Edwards et al., 1998), and
can lead to the vertical migration of risk elements previously bound to
the clay size fraction (as was observed for example, in the Odra River
beds, Ciszewski et al., 2008). Infiltration, evaporation, and water table
fluctuations have the potential to cause changes in redox potential and
pH, resulting in changes of the forms of the risk elements (Du Laing
et al., 2009; Palumbo-Roe et al., 2012; Aleksander-Kwaterczak and
Ciszewski, 2016), and consequent increases in toxic elements through
floodplain sediments (Naiman et al., 2010; Byrne et al., 2012; Ciszewski
et al., 2012; Lynch et al., 2014).
Vertical migration of risk elements is often observed in sediments
polluted by past mining activities and has been documented in several
European rivers (Hudson-Edwards et al., 1998; Ciszewski and Malik,
2004). Downward migration of Cd and Zn, for example, within the
floodplain sediments and soils polluted by material from tailings was
observed in the Guadiamar River Valley, Spain (Kraus and Wiegand,
2006). Horizontal migration can also be relevant - especially in ground-
water flow (e.g., Aleksander-Kwaterczak and Ciszewski, 2016). The rate
of migration is element specific. For instance, faster vertical migration of
Zn and Cd than of Pb has been observed in the Toka Creek, Hungary
(Ódor et al., 1998), and in sediments of the Merse River, Italy
(Pagnanelli et al., 2004). Actual distances and rates of migration of risk
elements in floodplains have not been described in detail.
The secondary mobilization of risk elements deposited earlier in
overbank sediments may affect the geochemical record in sediments
and complicate the reconstruction of the river basin's pollution history
and the estimation of trace metal background values (Cappuyns and
Swennen, 2004; Cappuyns et al., 2006; Matys Grygar et al., 2013;
Faměra et al., 2018). Migration of risk elements in floodplain sediments
is often studied through element solubility tests (single and sequential
extractions) and leaching tests (e.g., Cappuyns and Swennen, 2004;
Vaněk et al., 2005; Ettler et al., 2006; Lynch et al., 2014; Rennert and
Rinklebe, 2017; Rinklebe and Shaheen, 2017). However, such tests only
characterize the current potential for migration, although chemical
forms of risk elements are less likely to be the same as their forms imme-
diately after their deposition in floodplains. We therefore prefer to char-
acterize the overall consequences of past migration, i.e., stratigraphic
misfit of the current pollutant distribution in floodplain fill (e.g., Matys
Grygar and Popelka, 2016).
47
The town of Příbram (SW Czech Republic) is known as an area of
long-term mining and processing of polymetallic sulfidic ores. Mining
and smelting of Ag-Pb-Zn-Sb-bearing ores in Příbram Ore District, in-
cluding processing of other ore types (e.g., Au, Sb) imported from
other regions, resulted in well-documented contamination of alluvial
soils (Borůvka and Drábek, 2004; Vaněk et al., 2005, 2008) and stream
sediments (Ettler et al., 2006; Sýkorová, 2014). Previous studies
mapped pollution only within riverbank sediments and proximal flood-
plain sediments (Navrátil et al., 2008; Dlouhá et al., 2013; Nováková
et al., 2015), or considered transport of material in suspension (Žák
et al., 2009). Distal floodplain areas were considered to be old and
thus unpolluted. In the past, polluted sediments of the Litavka River
were supposed to have originated mainly by vertical accretion pro-
cesses, such as overbank floodplain aggradation (e.g., Nováková et al.,
2015), causing severe pollution of the upper layers of the floodplain.
The consequences of secondary migration of risk elements have already
been identified on the basis of the geographical variations in Zn/Pb ra-
tios in sediments (Nováková et al., 2015). These studies have also sug-
gested that the distribution of unpolluted sediments is limited (Žák
et al., 2009; Nováková et al., 2015; Faměra et al., 2018). Secondary mi-
gration of risk elements in the Litavka River sediments was observed
not only in lower parts of profiles, due to reductimorphic processes
and changes of redox conditions (Nováková et al., 2015), but also in
upper parts of profiles, due to secondary migration caused probably
by infiltration and/or evaporation processes (Faměra et al., 2018).
The aim of this study is to describe the chemical migration occurring
within the polluted floodplain fill. More specifically, the intent of the
study was to (1) map the structure and historical development of the
floodplain to describe the spatial distribution of pollutants, and (2) eval-
uate their lateral post-depositional migration within the floodplain fill.
Contrarily to previous studies, we focused on distal floodplain segments
deposited farther from the active channel belt. These deposits seem to
have been stable for N150 yr, and their analysis was thought to increase
the probability of finding older, pre-mining sediments, the scarcity of
these was discussed in previous papers (Nováková et al., 2015;
Faměra et al., 2018).
2. Materials and methods
2.1. Study area
The Litavka River flows through one of the most important mining
and polymetallic ore processing areas in the Czech Republic – Příbram
Ore District, located 60 km SW of Prague, the capital of the Czech
Republic (Fig. 1). The total channel length is 54.6 km, and the entire
catchment area covers 629 km2. The climate is temperate, with an an-
nual mean temperature ranging from 6.5 to 7.5 °C and an annual
mean precipitation of 600–800 mm. The mean annual discharge is
~2.6 m3 s−1, although the uneven distribution of precipitation and the
relatively small catchment area cause large fluctuations in flow (Žák
et al., 2009). The soils in the catchment are classified as Fluvisols (FL)
and Gleyic Fluvisols (FLg). The land is covered with grass without exten-
sive agricultural use (Dlouhá et al., 2013).
The study area consists of a 2-km-long reach of floodplain (35–37
river km) in “Valcha-Jih”, situated 5 km downstream from the town of
Příbram. The current single-thread river channel is located on the east
edge of the 160–230 m wide valley. The active channel is ~8 m wide
and slightly sinuous (sinuosity = 1.2). Based on the topography of the
area and historical maps, the channel shifted within a range of 15 m dur-
ing the last ~170 yr, reworking older floodplain deposits. An artificial
ditch situated on the western side of the floodplain also contributes to
water and flood conveyance. The ditch is located under the terrace,
composed of Pleistocene Aeolian sediments (Fig. 1B). The entire course
of the Litavka River has been strongly influenced by human activities;
88% of the channel underwent some type of river engineering in the
past (Taufmannová, 2007), including channel straightening, dredging,
48 K. Kotková et al. / Geomorphology 329 (2019) 46–57

Fig. 1. (A) The Litavka River study site in the Czech Republic. (B) Positions of drilled cores and OSL sampling along the ERT line transect across the Litavka River floodplain on the digital
terrain model (DTM) map. The historical development of the channel in the 1840s (pink line), 1953 (grey line) and the current channel position in 2013 (blue line).

and the building of revetments along the banks. Most of the upper
course has been channelized. As a consequence, the course of the river
and the rate of lateral channel migration changed several times during
the last few centuries. In the nineteenth century, part of the water in
the study area was diverted by a canal. In the mid-twentieth century,
the channel was straightened along its entire length (Fig. 1B).
2.2. History of mining and ore processing
The entire catchment of the Litavka River consists of sedimentary
and magmatic rocks, ranging from slate and sandstone to greywacke,
accompanied by basaltic rock dykes and intrusive bodies of granites,
granodiorites and diorites. Most of the upper part of the river valley is
covered by Quaternary loams, slope sediments and fluvial sands and
gravels. More detailed information about the geology of the area can
be found elsewhere (e.g., Bambas, 1990; Žák and Dobeš, 1991; Vurm,
2001; Ettler et al., 2006). The margins of the floodplain are defined by
accumulations of Aeolian sediments, which are present at the elevated
floodplain edges and on upper Pleistocene or lower Holocene terraces
situated along the river valley.
Polymetallic ore deposits are composed of Ag-bearing galena (PbS),
antimonite (SbS), sphalerite (ZnS), and gangue materials, such as siderite
(FeCO3) (Bambas, 1990). In the SE area of the Příbram Ore District, ura-
nium deposits, mainly consisting of uraninite (UO2), are present. The
first mining activities started in the sixth century during the Celtic civiliza-
tion and became more intensive during the sixteenth century (Ettler et al.,
2001). The most extensive polymetallic ore mining peaked between 1850
and 1950, when approximately 3.5 kt Ag, 480 kt Pb and 260 kt Zn were
mined in the Bohutín and Březové Hory ore regions (Bambas, 1990).
Smelting and processing of the mined Pb\\Ag ores occurred in Lhota u
Příbramě from 1786 to 1972. Since 1972, the smelter was used for pro-
cessing of secondary scrap, such as used car batteries. Mining of uranium
ores and their processing in Bytíz produced 48 kt U between 1948 and
1989 (Kafka, 2003).
Mining and ore processing activities finally ceased with the closure
of the mines in 1972 as a result of changes in smelting technology
(Ettler et al., 2005) that accompanied increased environmental concern
 K. Kotková et al. / Geomorphology 329 (2019) 46–57
at the end of twentieth century. However, the legacy of mining is still
present in the form of waste dumps near the deposits of Příbram-
Březové Hory and Bohutín and in the form of processing slag near the
town of Lhota u Příbramě. Historical tailing ponds at Březové Hory
were repeatedly ruptured and partly destroyed during extreme precip-
itation events in 1932 and 1952, and a large amount of polluted material
was transported downstream with large flood waves. The tailing mate-
rials were subsequently deposited onto the floodplains along the river
(e.g., Žák et al., 2009; Nováková et al., 2015). The severely polluted allu-
vium is a source of secondary pollution of the Litavka River (Navrátil
et al., 2008; Žák et al., 2009; Nováková et al., 2015; Faměra et al., 2018).
2.3. Sampling, analyses and data processing
Channel dynamics were evaluated using geo-corrected Imperial
Obligatory Imprints of the Stable Cadastre maps (1840s, scale: 1:2880)
and ortho-photos (1953 and 2013, scale 1:5000). A digital terrain model
(DTM) was obtained from a laser-scanning dataset (Digital Model of the
Relief of the fifth generation, DMR-5G, made in 2011) purchased from
the State Administration of Land Surveying and Cadastre (ČÚZK) and
from the Military Geographic and Hydrometeorology Office (VGHMÚŘ).
The data were processed using the desktop version of ArcGIS 10.3.1.
A subsurface image of the floodplain fill was obtained using electric
resistivity tomography (ERT) acquired with the ARES system (GF Instru-
ments, the Czech Republic). To obtain imagining up to the depth of 4 m,
the electrodes were arranged in a Schlumberger electrode configuration
at a distance of 0.5 m from each other (for a more detailed description,
see Faměra et al., 2018).
Floodplain sediments were sampled along a W-E cross section, per-
pendicular to the active channel and the former artificial canal. These sed-
iments were used to analyse the horizontal migration of pollutants and to
identify the lithology of major sedimentary bodies with different resistiv-
ity present within the floodplain fill. Samples were collected using a
hand-drilled groove corer (Eijkelkamp; the Netherlands) with an internal
diameter of 3 cm. The maximum depth (80–170 cm) of the drilled cores
was limited by the presence of coarse sediments. Samples from a core sit-
uated on a terrace above the range of the historical floods were also col-
lected. The drilled cores were subdivided into 5-cm-long segments and
stored in polyethylene bags. The samples were air-dried, and element
analysis was performed on dry non-homogenized samples with a
handheld (portable) X-ray fluorescence (XRF) spectrometer (Niton
GOLDD3+, Thermo-Fischer Scientific, Germany). The XRF was cali-
brated using internal calibration provided by producer.
Rouillon and Taylor (2016) have shown that a portable XRF instru-
ment can provide fast and low-cost measurements with high quality re-
sults, depending on the textural properties of measured standard
reference materials. Further calibration of the hand-held XRF spectrome-
ter was performed via measurements of 10 certified reference materials,
where the concentrations of Al, Si, Pb, Zn, Fe, Rb, and Ti and their ratios
were measured four times. Repeated measurements were made to
Table 1
Results of Al and Fe for reference materials measured using the hand-held XRF instrument.
Certified reference material Al (%)
Certified
NIST 2702 inorganics in marine sediment 8.41 ± 0.22
METRANAL 31 light sandy soil 8.156
METRANAL 34 loams (metals) 6.933
NIST 2704 buffalo river sediment 6.11 ± 0.16
NIST 2711a Montana II soil 6.72 ± 0.06
NIST 1646A estuarine sediment 2.297 ± 0.018
IAEA-314 stream sediment
IAEA SL-1 (lake sediment)
IAEA SL-3 (lake sediment) 2.45 ± 0.12
CTA-FFA-1 fine fly ash 14.87 ± 0.39
a
Median of 4 measurements.
49
determine outliers. Consequently, the median values of all measurements
for each element and their ratios were calculated and further compared
with the certified reference material values. The results of the Fe and Al
measured in certified reference materials using the portable XRF instru-
ment are presented in Table 1. The content of Cd was measured using a
table-top ED-XRF (Epsilon 3×, PanAnalytical, the Netherlands), equipped
with an internal calibration system, after homogenization in the planetary
mill (Pulverisette 6, Fritsch, Germany). Analysis of the reference material
SRM2711a Montana II Soil (NIST, USA) was used for verification of results.
Magnetic susceptibility data were measured using KLY-4S Kappabridge
equipment (Agico, the Czech Republic). More details about the measure-
ment can be found in Faměra et al. (2013).
Calculation of local enrichment factors (LEFs) was used to evaluate
the content of Fe. Concentrations of Pb, Zn, and Cd were found to be
too scattered through the floodplain deposits (Faměra et al., 2018)
and lacking knowledge of their geochemical background values simply
prevented the calculation of their local enrichment factors. The local en-
richment factor (e.g., Matys Grygar and Popelka, 2016) was calculated
as the ratio of the actual concentration of the target element (M) to its
background concentration (MBG), which was calculated using a local
geochemical background function, where:
LEF ¼ M=MBG ð1Þ
The local geochemical background function was obtained empiri-
cally from the unpolluted part of the sedimentary profiles. The back-
ground function was defined by the relationship between the actual
concentration of the target element (M) and the concentration of the se-
lected reference element (MREF), preferably with the same grain size:
MBG ¼ f ðMREF Þ ð2Þ
In the case of the Litavka River sediments, the local background func-
tion of Fe was obtained using Al in the unpolluted samples from proxi-
mal and distal floodplain profiles as the reference element (Fig. 2). The
contents of both Fe and Al measured with a hand-held Niton XRF spec-
trometer had to be calibrated by comparison with values measured
using the Epsilon3x table XRF spectrometer, using the calibration equa-
tions presented in Table 2. The local geochemical background function
used for the calculation of the Fe LEF is shown in Fig. 2.
Samples for optically stimulated luminescence dating (OSL - LIT 1, 2,
and 3) were collected from sampling points along the ERT profile. Back-
ground samples were collected from above and below the OSL samples.
All samples were dried in the laboratory for 24 h at 50 °C, and the mois-
ture content was determined.
The contents of U, Th and K in the samples were established via high-
resolution gamma spectrometry using an HPGe detector (Canberra,
Australia). The dose rate of cosmic radiation was determined on the
basis of the geographical position and depth of the samples below
ground level using the equation from Prescott and Hutton (1994).
Fe (%)
a
Measured Certified Measureda
4.929 8.85
3.616 3.308 3.501
3.53 4.071 4.319
3.547 4.11 ± 0.1 4.543
3.363 2.82 ± 0.04 2.941
1.158 2.008 ± 0.039 2.175
4.961 3.324
4.502 6.74 ± 0.17 7.354
1.008 1.107
6.677 4.89 ± 0.14 5.161
50 K. Kotková et al. / Geomorphology 329 (2019) 46–57
Fig. 2. The lithogenic background concentrations of Fe plotted against the reference element (Al) from all samples originating from unpolluted parts of all studied profiles in the distal (grey
squares) and proximal (black circles) floodplain were used for obtaining of local geochemical background function (y = 1.7892x, r2 = 0.409), which was further used for calculation of the
local enrichment factor (LEF) of Fe. All unpolluted and polluted samples are shown for comparison (white circles).
The OSL measurements were performed after separation and sedi-
mentation of the 11–20 μm fractions, which were extracted from the
sediment samples and treated with 10% hydrochloric acid (HCl) and
10% hydrogen peroxide (H2O2); this step was repeated twice to remove
the organic and carbon contents. The quartz grains for OSL were sepa-
rated from feldspar by etching in 20 ml H2SiF6 for seven days. The re-
maining acid in the samples was subsequently neutralized with HCl.
All OSL measurements were made using a RISOE TL/OSL-DA-20 auto-
mated luminescence reader. Radioactive irradiation was performed
using a 90Sr/90Y beta source with a calibrated dose rate of 0.12 Gy/s.
Equivalent doses were determined using the Single Aliquot Regenera-
tion (SAR) protocol (Wintle and Murray, 2006). The results were evalu-
ated using the RISOE Analyst and Microsoft Excel software packages. For
age calculations, we applied the unlogged minimum age model and the
central age model depending on the distribution of equivalent dose
data. These were divided by the calculated dose rate values of each sam-
ple (Table 3).
2.4. Statistical analysis
Ratios between risk and reference elements were estimated using
ordinary least squares (OLS) regression or robust linear regression, set-
ting the intercept to zero for all functions. Because outliers (even a sin-
gle outlier) in the dataset (i.e., possibly polluted sediment samples) may
cause serious problems for ordinary least squares (OLS) regression, the
least trimmed squares (LTS) (Rousseeuw and Yohai, 1984) robust re-
gression method was used. This method provides identification of all
of the important outliers, vertical outliers (outliers in the response
variable representing a model failure, e.g., the presence of individual
anthropogenically polluted sediments), leverage points (cases in
which some values are far away from the bulk of the other data), and in-
fluential points (observations whose inclusion or exclusion result in
Table 2
Equations used for calibration of Fe and Al.
Calibration equation n r2
Al Al (%) = 2.023x 8 0.9438
Fe Fe (%) = 0.9289x 7 0.9969
substantial changes in the fitted model) in both simple and multivariate
settings (Blatná, 2014; Matys Grygar and Popelka, 2016). LTS regression
is more popular than other robust estimates (S-, M-, MM-estimates)
mainly because of its computability and intuitively appealing definition
(Willems and Van Aelst, 2005). Although highly resistant to outliers, LTS
suffers from a low efficiency of approximately 0.08 relative to OLS esti-
mates (Stromberg et al., 2000). Conversely, various mechanisms en-
hance the natural variability of element concentrations in sediments,
and it is unrealistic to optimize statistical procedures exclusively for
the highest efficiency of estimated parameters (Matys Grygar and
Popelka, 2016). LTS robust regression estimates were computed in the
R software using the ltsReg function provided by the robustbase package
(for details, see Rousseeuw et al., 2015). LTS regression was used to es-
timate Zn/Pb and Cd/Zn ratios (Figs. 3 and 4). Common statistics (means
and standard deviations) were computed in Microsoft Excel and in
Origin Pro ver. 8.0.
3. Results
3.1. Topography and lithology
Based on spatial data from maps and ortho-photos, the historical
changes of the channel during the last centuries were evaluated
(Fig. 1B). In the 1840s, the river had a sinuous channel (sinuosity of
1.3), and the channel-belt represented about one-fifth of the floodplain
width. Within the NE part of the study area, an artificial channel (ditch)
was created to support outflow from a mill. The extensive river channel
engineering works in the target area can be identified in the 1953 ortho-
photo (Fig. 1B), and shows that river was artificially straightened. How-
ever, due to the high slope and the lack of revetments, the channel
started to erode its banks, resulting in the renewed development of a
sinuous channel. However, by 2013, its sinuosity (1.2) had not reached
the pre-regulation value.
The contemporary channel is ~8 m wide and lacks well-marked
overbank aggradation; instead, the channel is characterized by slight in-
cision, as is reflected by eroding banks and the small ravines crossing
the bank lines (Fig. 1B). Within the channel-belt, there are two aban-
doned channel fragments. The surface of the distal floodplain (outside
the current channel-belt) is relatively flat; remnants of older forms are
 K. Kotková et al. / Geomorphology 329 (2019) 46–57 51

Table 3
Main features of the collected OSL samples: moisture content (W); environmental dose rates of U, Th and K; total dose rate (D*) and equivalent dose (De) and age of samples.

Sample ID (profile) Depth (cm) W (%) U (ppm) Th (ppm) K (%) D* (Gy/ka) De (Gy) Age (ka)

OSL-LIT 1 (KL 81) 50–57 23.4 ± 5 2.45 ± 0.05 7.40 ± 0.18 1.06 ± 0.03 1.95 ± 0.06 2.03 ± 0.05 1.04 ± 0.04
OSL-LIT 2 (KL 77) 64–74 16.5 ± 5 1.31 ± 0.03 4.09 ± 0.10 0.68 ± 0.02 1.29 ± 0.06 8.71 ± 0.06 6.72 ± 0.33
OSL-LIT 3 (KL 74) 105–115 12.5 ± 5 1.66 ± 0.03 5.72 ± 0.14 0.69 ± 0.03 1.52 ± 0.07 11.52 ± 0.08 7.56 ± 0.35

not visible. In the NW part of the study area, a lower-lying area remains.
Two crevasses join this area from the south, and the ERT section crosses
them. On the western edge of the study area, an artificial ditch was
created.
The elevation changes on the floodplain along the studied profile are
b1 m (Fig. 5A). As a result, the flat surface does not reflect the litholog-
ical heterogeneity of the floodplain fill obtained by ERT imaging. The
ERT image was acquired across nearly the entire floodplain on the left
riverbank (Fig. 1B). It ranged from the terrace edge (KL78 profile) and
the ditch in the distal floodplain to the edge of the active channel-belt
(KL82 profile, 75 m from the active channel).
Field observations of lithology within cores drilled along the ERT line
were used to confirm the results of the ETR imaging (Fig. 5B). The bot-
tom part of the floodplain fill that could not be sampled by hand-
drilling is composed of coarse sediments with the highest resistivity
(N600 Ω⋅m). These sediments are overlain by sandy strata with lower
resistivity (500–550 Ω⋅m). On this coarse floodplain base, finer sandy-
silty sediments (150–300 Ω⋅m) are deposited and covered by the finest
sediments (20–80 Ω⋅m), from where the majority of the cores were
obtained.
The ERT image also revealed coarse sandy material with high resis-
tivity (N600 Ω⋅m) located very close to the floodplain surface under
the profile KL77 situated in the middle of the floodplain (Fig. 5B). This
coarse body is most likely an abandoned channel. This channel physi-
cally and geochemically (see more below) divides the floodplain into
two parts: (1) a proximal floodplain covered with coarser sediments
with higher resistivity situated from the profile KL77 towards the river
channel (KL83), and (2) a distal floodplain that extends to the small
ditch in the west. This area is covered by much finer sediments and
loams with very-low-resistivity.
To verify the different age of the sedimentary bodies divided by the
abandoned channel, OSL dating was applied (Figs. 1B and 5C, Table 3).
The oldest sample (OSL – LIT 3: 7.56 ± 0.35 ka) represents the finer
sandy-silty sediments (resistivity: 150–300 Ω⋅m) at the distal part of
the floodplain (KL74 core). The age of the second sample situated be-
tween the distal and proximal floodplain (KL77 core, coarse sandy ma-
terial, resistivity: N600 Ω⋅m) is slightly younger (OSL-LIT 2: 6.72 ±
0.33 ka). These samples likely represent the same sedimentary body:
the sandy material of a paleo-channel and its finer overbank deposit.
However, the third sample collected in the proximal floodplain (KL81)
is considerably younger (OSL-LIT 1: 1.04 ± 0.04 ka). This slightly coarser
material (resistivity ≥300 Ω⋅m) was deposited in historical times.
3.2. Depth distribution of Pb, Zn, Cd and magnetic susceptibility in
floodplain profiles
Chemostratigraphic correlations of depth profiles of Zn/Pb ratios,
which were successfully used in previous studies to distinguish the mi-
gration zones of Zn and Pb (Nováková et al., 2015), are shown as red di-
amonds together with the concentrations of Cd (black circles) in Fig. 5C.
Based on the statistical analysis and differences in the concentrations of
risk elements, the profiles were classified as (1) upper Pleistocene or
lower Holocene terrace (profile KL79), (2) distal floodplain (KL 73-78)
and (3) proximal floodplain (KL80-83). Floodplain sediments of the

Fig. 3. Sediments of proximal (black circles) and distal floodplain (red circles) were distinguished using the least trimmed squares regression method. Anomalous Pb (black crosses) and Zn
(red crosses) concentrations were used to mark the migration zones and Zn-enriched and Pb-enriched samples in Fig. 5C.
52 K. Kotková et al. / Geomorphology 329 (2019) 46–57
Fig. 4. Concentrations of Cd from all samples plotted against concentrations of Zn, where outliers (grey crosses) were identified using the least trimmed squares regression method and
further used to distinguish parts of profiles prone to the Cd migration (solid and dashed black line rectangles) in Fig. 5.
Litavka River are severely enriched in Cd, Pb and Zn compared to abun-
dance of these elements in upper continental crust (UCC), where the av-
erage values of Pb, Zn, and Cd are 17, 63, and 0.09 mg/kg, respectively
(Rudnick and Gao, 2003).
Assessment of pollution of the sediments can be performed using
local enrichment factors, which are calculated using lithogenic back-
ground functions (e.g., Bábek et al., 2015; Matys Grygar and Popelka,
2016). However, in the case of the Litavka River, the pollution of flood-
plain sediments is widespread throughout the sedimentary profiles,
probably due to the secondary migration of Zn, Pb and Cd into previ-
ously pristine sediments (Nováková et al., 2015; Faměra et al., 2018).
Thus, simple curves of geochemical background functions based on
the collection of pristine sediments cannot be obtained. Therefore, the
calculation of the local enrichment factors was performed for Fe only,
which was shown to be elevated in the strata from the climax of Pb
and Zn pollution (Faměra et al., 2018). The local background function
of Fe was obtained from the regression line between Fe and a reference
element (Al) from unpolluted samples; their correlation is shown in
Fig. 2. The Fe/Al ratios in unpolluted samples were generally greater in
the proximal floodplain (~2.1) than in the distal floodplain (~1.7). Ac-
cording to Faměra et al. (2018), who suggested that values of the Fe
LEF in severely polluted sediments exceed 1.4, calculation of the values
of the Fe LEF allowed us to distinguish severely polluted strata within in-
dividual profiles (shown as the dark grey area in Fig. 5C).
Similar to the findings of Faměra et al. (2018), the Pb concentrations
and mass magnetic susceptibility (χ) values in our sedimentary profiles
were interrelated (Fig. 6A, B). Most of the points were clustered in two
main areas (Fig. 6A) - area I included values under the thresholds,
i.e., values of Pb b3000 mg/kg and χ b 25·10–8 m3 kg −1 (68% of
samples), and area III exhibited values of Pb and χ higher than these
thresholds (19% of samples). The remaining areas, II (below the χ
threshold, above the Pb threshold), and IV (above the χ threshold,
below the Pb threshold) included 10 and 3% of samples, respectively.
The data points in the quadrant II may indicate post-depositional Pb
enrichment, whereas in quadrant IV there is a possibility of post-
depositional Pb depletion.
Therefore, non-normalized threshold values of Pb N 3000 mg/kg and
threshold values of χ N 28·10−8 m3 kg−1, derived from the distribution
of Pb and χ values (Fig. 6), were used for chemostratigraphic correlation
of polluted sedimentary strata in the upper part of the proximal and dis-
tal floodplain (shown as the light grey area in Fig. 5C). The base of this
polluted layer is also shown as a red line on the valley cross-sectional
profile (Fig. 5A). The marked polluted layer in the proximal floodplain
exhibited mean values of Zn, Pb, and Cd of 5384, 4238 and 41 mg/kg, re-
spectively, and the mean χ value was 37·10−8 m3 kg−1. The mean
values in the top part of the distal floodplain in the topmost polluted
layer were lower: 1795, 2003 and 30 mg/kg for Zn, Pb and Cd, respec-
tively, and 23·10−8 m3 kg−1 for χ. Relatively unpolluted sediments
are deposited under the polluted layer in the distal floodplain profiles
(Fig. 5C), whereas in the proximal floodplain, unpolluted sediments
simply no longer exist within the studied depth (≤1.7 m). The elevated
concentrations of Zn, Pb, and Cd observed at greater depths in all pro-
files were attributed to the lateral or vertical post-depositional migra-
tion of risk elements (Fig. 5C).
3.3. Post-depositional migration of risk elements
Heterogeneous distribution of risk elements (stratigraphically non-
correlated) and signs of horizontal migration of risk elements were ob-
served in all compared neighbouring profiles. Scatter plots of Cd vs. Zn
and Zn vs. Pb for all data points showed large variability with abundant
outliers instead of the expected simple trend of nearly constant inter-
element ratios expected for the average ore composition. To process
the interelement ratios, we applied a robust regression method to all
sedimentary samples to limit the influence of outliers. This regression
helped us to find a geochemical difference between samples from the
proximal and distal floodplain, and to reveal samples with anomalous
contents of Zn, Pb and Cd. This analysis showed a systematic difference
between proximal and distal floodplain sediments.
The correlation between Zn and Pb, and Zn and Pb outliers (Zn-
enriched and Pb-enriched samples) are shown in Fig. 3. Proximal
and distal floodplain sediments were also distinguished by distinct
 K. Kotková et al. / Geomorphology 329 (2019) 46–57 53

Fig. 5. (A) Cross-sectional profile of the valley along the ERT transect showing the positions of cores and the base of the contaminated layer (red line) and the base of the fine sediments
(black line). (B) ERT image of the floodplain fill. (C) The depth profiles of Zn/Pb ratios (red diamonds) and concentrations of Cd in mg/kg (black circles) along the floodplain transect. Base
of the contaminated layer indicated with a red line in panel A presents severely polluted upper part of profiles in panel C exhibiting values of Pb N 3000 mg/kg and of χ N 25.10−8 mg3 kg−1
(denoted by the light grey area), and values of LEF Fe N 1.4 (denoted by the dark grey area). Sediments with anomalous concentrations of Zn, Pb or Cd identified as post-depositional
migration are also marked (dotted red line rectangles for Zn, blue circles for Pb, and black solid and dashed line rectangles for Cd). OSL dating points are also shown.

relationships between Zn and Pb: Zn = 1.26 ∗ Pb in proximal and Zn =
0.63 ∗ Pb in distal floodplain (both equations were significantly different
at p b 0.01). This difference may point to different pathways of pollution
of proximal and distal floodplains. Mean ratios of Zn/Pb were 0.9, 2.5,
and 3.4 within terrace (profile KL79), distal and proximal floodplain
sediments, respectively. Robust regression on Zn and Cd values was
used to distinguish zones prone to Cd post-depositional migration and
identification of Zn-enriched and Cd-enriched sediments (Fig. 4) as out-
liers from the regression Cd = 0.0093 ∗ Zn (p b 0.01). The mean ratio of
Cd/Zn was 0.010 in the distal and 0.021 in the proximal floodplain.
The sediment samples with anomalous relative concentrations of Zn,
Pb, and Cd were then used for identification of Zn-enriched (red dashed

Fig. 6. (A) Relationship between concentrations of Pb and magnetic susceptibility (χ) in sediments from this study. (B) Data from other sites in the Litavka River floodplain shown for
comparison (Faměra et al., 2018).
54 K. Kotková et al. / Geomorphology 329 (2019) 46–57
rectangles), Pb-enriched (blue circles) and Cd-enriched (solid black
squares) and Cd-depleted (dashed black squares) zones in individual
profiles in Fig. 5. Such enriched sediments can be found in both proxi-
mal and distal floodplain profiles. Most of them were located within
the polluted layer in the upper part of profiles marked in Fig. 5C; how-
ever, some of them were also found in deeper parts of profiles and
marked as potential migration zones.
The upper parts of four proximal floodplain profiles (KL80–83) ex-
hibited Zn-enriched sediments not only in the upper parts of profiles
(KL81–83 down to the depth of 20 cm) but also in the deeper strata
(N100 cm), while Pb-enriched sediments (outliers) occurred only as in-
dividual points only in the upper part of profiles KL80–82, maybe as a
result of Zn depletion. Similarly, Cd-depleted zones were found in
all proximal profiles up to the depth of 60 cm, whereas Cd-enriched sed-
iments were found mainly in the lower parts of profiles (KL83, 50–
80 cm; KL81, 90–140 cm).
Distal floodplain profiles (KL73 to KL78) also exhibited Zn-enriched
sediments in the entire upper part of neighbouring profiles with de-
creasing thickness of the Zn-enriched layer with increasing distance
from the ditch (up to 70, 80, 120 and 160 in profiles KL77, KL76, KL75
and KL74, respectively (Fig. 5C). Although this may suggest a possible
pathway of Zn migration from the ditch, the profile closest to the
ditch exhibited Zn-enriched sediments only in the upper part to a
depth of 30 cm. Most of Cd-enriched sediments were located within
the boundary of the most-polluted sediment layer, and also in deeper
parts of KL75 (60–100 cm) and KL74 (80–90 cm). Samples enriched in
Pb were present as individual scattered points in profile KL76 (~20
and 40 cm), and also at greater depths in profiles KL78 and KL73. This
suggests a similar pathway as for Zn migration within the deeper
parts of profiles due to the presence of the ditch, which influences the
ground-water table levels and consequently enhances lateral migration
of risk elements.
4. Discussion
4.1. The Litavka floodplain architecture
Faměra et al. (2018) rejected previous hypotheses (Žák et al., 2009;
Nováková et al., 2015) regarding anthropogenically triggered aggrada-
tion as the main mechanism of fine sediment deposition for the Litavka
River floodplain. Žák et al. (2009) assumed such an aggradation scenario
as a consequence of (1) forest clearance in the river catchment due to
need of charcoal for metallurgy and (2) failures of settling ponds in
Fig. 7. Models of the historical development of the Litavka River floodplain. (A) Model based on prevailing lateral reworking with negligible aggradation nearby the channel belt.
(B) Prevailing aggradation of anthropogenic material from mining activities into empty space in the river valley (scenarios are based on work done by Faměra et al., 2018).
the twentieth century. The model of prevailing aggradation of anthro-
pogenic material in the floodplain is shown in Fig. 7B and is consistent
with a classical concept of a sediment wave introduced to the river sys-
tems by historical mining (Miller et al., 1998). Faměra et al. (2018),
however, preferred another scenario for the Litavka River: prevailing
continuous lateral reworking of the floodplain fill (Fig. 7A) analogous
to the Holocene floodplain dynamics found in several other Czech rivers
(Matys Grygar et al., 2013, 2016b).
The scarcity of unpolluted sediments in the floodplain sections pre-
sented by Faměra et al. (2018) was, however, a challenge for their
reworking model. In this study we decided to test whether that scarcity
resulted from the intentional focus of Faměra et al. (2018) on
floodplain sections with clear signs of recent lateral channel movements
(i.e., sections with the channel belt that represented only about a half of
the total floodplain width). We therefore selected a floodplain section
with a much narrower active channel belt for our study to increase
chance to finding more pre-mining sediments. Our findings indeed sup-
port the model of Faměra et al. (2018) because the majority of the flood-
plain fill in our floodplain section is older than mining activities
according to the OSL dating. We thus adapted the model according to
Fig. 7A and modified it for our particular study area (Fig. 8).
The real role of floodplain aggradation, particularly the magnitude of
its anthropogenic component, is rather difficult to assess (Erkens et al.,
2009), and it has apparently tended to be overestimated in most of
the past studies. To evaluate the role of floodplain aggradation, it is nec-
essary to exclude the impact of recycled older sediments (autogenic
forcing) and climate changes (allogenic forcing), and even then the
resulting proportions of human impact may be minor, especially in
larger river systems (Erkens et al., 2009; Verstraeten et al., 2017).
Lower than expected impact of aggradation in such a small river system
under such severe anthropogenic pressure like the Litavka River may
seem surprising.
The OSL dating, however, clearly showed that the deeper strata of
the fine floodplain fill were deposited before the mining period. Only
up to 20 cm of the floodplain fill in the distal floodplain were polluted
directly by fluvial aggradation and/or atmospheric deposition (Faměra
et al., 2018; this work). That polluted layer was originally even thinner,
increasing due to bioturbation that caused persistent percolation of
toxic elements to deeper layers (e.g., Wijnhoven et al., 2006).
Visualized using ERT (Fig. 5B), the pre-mining and mining-affected
floodplain fills of the Litavka River are separated by a buried paleo-
channel at the location of the KL77 drill core. Fluvially-deposited, con-
taminated sediments from the period after the pollution climax are
 K. Kotková et al. / Geomorphology 329 (2019) 46–57
Fig. 8. Model of the historical development of the Litavka River based on scenario in
Fig. 7A, adapted to our study area.
outlined by threshold values of the pollution parameters Pb
N 3000 mg/kg and χ N 28·10−8 m3 kg−1 suggested by Faměra et al.
(2018) (those thresholds are exceeded in quadrant III in Fig. 6). This
layer has a wedge shape with mean concentrations of ~3300 mg/kg
Pb, ~2500 mg/kg Zn and ~30 mg/kg Cd. The most polluted layer was
formed in the period from 1850 to 1950, when the smelting technology
had been improved by replacement of charcoal and wood by coke and
peak productions of Pb and Zn were achieved (Faměra et al., 2018).
The young age of the sediments deposited in the current channel
belt has also been shown by radiocarbon dating of charcoal fragments
found in eroded banks upstream from our study area to date to the nine-
teenth (Žák et al., 2009) and/or the eighteenth centuries (Nováková
et al., 2015). Our OSL dating also confirmed the young age of the sedi-
mentary body of the channel belt (younger than sediment with the
age of 1.04 ± 0.04 ka found near the KL81 core). Sediments from the
distal floodplain at depths larger than 20 cm, with Pb concentrations
and χ values below the above cited thresholds (red line in Fig. 5A, points
in quadrant II and IV in Fig. 6) is thus a product of secondary migration
of the risk elements. Neither of the previous studies (e.g., Žák et al.,
2009; Nováková et al., 2015; Faměra et al., 2018) expected such exten-
sive secondary pollution in the Litavka River floodplain.
4.2. Post-depositional migration within the floodplain fill
Post depositional migration is the only mechanism that can explain
the increased concentrations of Pb, Zn and Cd in deeper strata in the dis-
tal floodplain dated by OSL to the middle Holocene or earlier (Table 3).
These sediments were contaminated by horizontal post-depositional
migration of risk elements, in particular, Zn and Cd. Secondary pollution
by migration could explain the complete absence of the pre-mining un-
polluted sediments in some sections in the Litavka River floodplain,
such as “Valcha-Jih” site reported by Faměra et al. (2018).
The presence of labile elements in the Litavka River floodplain has
been found previously using sequential chemical extraction methods
(Vaněk et al., 2005; Ettler et al., 2006). Those researchers showed that
considerable portions of Pb, Zn and Cd are present in mobile fractions
(ion-exchangeable and soluble by weak acids): up to 30% Zn and
39% Pb. A less mobile fraction is bound to the Fe and Mn oxyhydroxides,
up to 61% Zn, 71% Pb, and 84% Cd, whereas primary sulfide ores were
responsible for only 8–19% Zn and 12–42% Pb of their total content
(e.g., Vaněk et al., 2005; Ettler et al., 2006). It is known that Zn is more
mobile in polluted floodplain fill than Pb (Hudson-Edwards et al.,
1998), however, Cd tends to have an even larger fraction in ion-
exchangeable and soluble forms than Zn (and Pb), and is usually the
most mobile among the three elements in sediment and soil profiles
(Cappuyns and Swennen, 2004; Aleksander-Kwaterczak and Helios-
Rybicka, 2009; Matys Grygar and Popelka, 2016; Rennert and
Rinklebe, 2017). We thus expected that post-depositional migration
would alter the ratios between those risk elements in polluted
sediments.
55
Zinc and cadmium are chemically similar, therefore, we expected
that they would exhibit nearly constant ratios in ore, smelting wastes
and polluted sediments in the study area. The polluted sediments in
the proximal floodplain (active channel belt) of our study area had
Cd/Zn ratio of ~0.01. The mean values of Cd/Zn ranged from 0.0087 to
0.0095 in datasets from Faměra et al. (2018), which contained mainly
severely polluted sediments. According to Cd/Zn ratios summarised
for major types of Zn ores by Wen et al. (2016), the Příbram ores
belonged to the low-temperature type.
The Cd/Zn ratios in the distal floodplain in our study area, however,
were elevated to ~0.021 (i.e., more than twice that of the proximal
floodplain). Cadmium-enriched bottom parts of sedimentary profiles
(below primarily polluted sediments) exhibited Cd/Zn values of 0.046
in the proximal and 0.016 in the distal floodplain.
In the sites studied by Nováková et al. (2015), fluvially polluted sed-
iments deposited during the pollution climax had relatively stable Zn/
Pb ratio of ~1.5. However, in our novel floodplain section a Zn/Pb ratio
of ~1.26 was found in the proximal floodplain, but only 0.63 in the distal
floodplain (by robust regression, Fig. 3). Most polluted strata in the dis-
tal floodplain are thus Zn depleted relative to Pb, which might be caused
either by a larger contribution of atmospheric fallout that contains
much more Pb than Zn (Nováková et al., 2015), or the partial removal
of Zn by downward migration. Contrarily, deeper strata of the studied
floodplain (below primarily polluted strata) identified as outliers by ro-
bust regression (Fig. 3) are strongly enriched in Zn, with mean Zn/Pb ra-
tios of ~15 in proximal and 6 in distal floodplains. We attribute the
elevated Cd/Zn and Zn/Pb ratios in the distal floodplain and deep strata
(i.e., compared with the top ~0.7 m of the active channel belt) to post-
depositional migration of Cd and Zn from strata that were originally pol-
luted during the mining period, either laterally from the active channel
belt or ditch in the distal floodplain or vertically from atmospheric pol-
lution fallout.
It is impossible to decipher effective migration pathways for the
studied risk elements in the Litavka River floodplain based on the avail-
able data. All hypothetical migration pathways are shown in Fig. 5C. Pro-
cesses impacting the chemical migration of risk elements include
atmospheric deposition which still presents a substantial pollution
source in the entire floodplain, although to a much lower extent than
during the peak of mining and smelting. The Litavka River floodplain
in not entirely saturated by water and migration in non-saturated
upper parts of the sediment fill occurs during and after flood events
when the changes from oxidizing to reducing environments occur.
Fluctuations of the water table change the redox conditions and
consequently lead to dissolution and re-precipitation of Fe and
Mn oxyhydroxides, which can bind risk elements (Pb, Zn, Cd)
(e.g., Rennert et al., 2018). Consequences of such processes can be rec-
ognized visually, e.g., by colour changes and formation of concretions
within sedimentary deposits of the Litavka River at the depths N0.2 m
(Nováková et al., 2015). In this study, we observed those changes at
the depths N0.3 m. The redox changes are most intensive near the
water table level, creating accumulation zones in proximal floodplain
sediments (Fig. 5C).
Chemical migration of risk elements has also been reported in his-
torical or current mining materials after weathering and pH changes
(Lynch et al., 2014), particularly in sediments near the active channel
that are in contact with river water via hyporheic flow (e.g., Matys
Grygar et al., 2013, 2016b) (effluent and influent flow, Fig. 5). In our
study, lower parts of proximal floodplain seem to have been contami-
nated by lateral migration from the active channel, while lower parts
of distal floodplain exhibited potential lateral migration from the artifi-
cial ditch.
The data collected showed the consequences of risk element migra-
tion: formation of concentration depth profiles that cannot be laterally
correlated (Fig. 5). Chemostratigraphic correlation of such varied
concentrations may perhaps be performed between two or three
neighbouring profiles; however, it then quickly becomes more difficult
56 K. Kotková et al. / Geomorphology 329 (2019) 46–57
as these local correlations outline migration pathways rather than depo-
sition isochrones.
Migration of Pb and Zn described here and in previous studies
(e.g., Ettler et al., 2006; Žák et al., 2009; Nováková et al., 2015; Faměra
et al., 2018), and Cd shown in this work, not only complicates the inter-
pretation of floodplain development and pollution assessment, but it
also presents actual risk of persistent horizontal transfer of pollutants
from floodplain hot spots to the current river channel.
4.3. Relevance for floodplain architecture studies
Chemostratigraphic correlation of sedimentary profiles is often used
for floodplain pollution assessment (e.g., Lecce and Pavlowsky, 2014;
Pavlowsky et al., 2017; Lynch et al., 2018) as well as for floodplain archi-
tecture studies (Notebaert et al., 2011; Matys Grygar et al., 2016b;
Faměra et al., 2018). For the later it is necessary to combine pollution
chemistratigraphy with other chemical-analytical methods and dating
of sediments and also to focus on pollutants that do not undergo migra-
tion, such as anthropogenic magnetic grains in the Litavka River flood-
plain, which produce 11 laterally correlated depth profiles (Fig. 5).
Geophysical imaging (in this study, ERT) is another very efficient tool
for floodplain architecture studies.
On the basis of ERT imaging, drill coring, and pollution
chemostratigraphy, Faměra et al. (2018) suggested three possible
models for the development of the Litavka River floodplain. The most
likely model of Litavka floodplain development was consistent with
the Holocene evolution mechanisms described by Schirmer et al.
(2005) for central European rivers (e.g., Erkens et al., 2009; Macklin
et al., 2013). This model includes incision and narrowing of the channel
belt during the Holocene within the fluvial deposits accompanied by lat-
eral reworking. Aggradation occurred mainly as a process inherently as-
sociated with re-filing of laterally reworked channel belts, of which the
most recent generation shows anthropogenic imprints with elevated
overbank deposition (Fig. 7A). The second model possible for the
Litavka River (Fig. 7B) would include filling all available space created
by late glacial to early Holocene fluvial incision to Pleistocene valley
fill by anthropogenic alluvium derived from mining and ore processing,
including failure of settling ponds, which exceeded the channel belt
transport capacity (e.g., Miller et al., 1998; Žák et al., 2009; James, 2013).
Although it is impossible to directly confirm the recycling of the
older (Pleistocene) floodplain deposits because they were evacuated
mostly near the Pleistocene/Holocene transition, the OSL dating results
suggested the presence of mid-Holocene floodplain sediments in the
distal floodplain, and where the elevation of the floodplain surface is
similar to the present one. Anthropogenic accumulation of younger pol-
luted material from mining activities, discussed by Žák et al. (2009) and
Nováková et al. (2015), thus dominated only in the active channel belt.
The recognition of a surprisingly large extent of secondary pollution by
risk elements migrating through the pre-mining sediment fill was vital
for our study to interpret the floodplain architecture of the Litavka River.
The possible extent of the risk element migration must be taken into ac-
count whenever pollution chemostratigraphy is used in floodplain ar-
chitecture studies.
5. Conclusions
Pollutants in floodplains impacted by mining have an intricate risk-
element distribution because of complex sedimentation patterns;
therefore, the choice of sampling strategy is an important part of the
study of polluted floodplains. In this study, we have shown that combin-
ing a geomorphic assessment with geophysical methods and OSL dating
can be successfully used to decipher floodplain architecture. These
methods resulted in the proposal of lateral reworking with minor aggra-
dation as the main floodplain-forming process.
Pollution chemostratigraphy based on a depth distribution of risk el-
ements in combination with robust statistical analysis helped us to
distinguish between proximal and distal floodplain sediments and to
identify the consequences of post-depositional migration of risk ele-
ments. The use of pollution chemostratigraphy has a known limitation:
it assumes that pollutants do not migrate after deposition. It is necessary
to avoid sampling in zones prone to the migration of risk elements if
geochemical dating of sediments is desired. In the Litavka floodplain,
magnetic susceptibility (χ) analysis also proved to be a useful method.
Extensive vertical and horizontal migration spread contamination
by Cd, Pb, and Zn across nearly the entire floodplain width including
early to middle Holocene deposits. Proximal floodplain sediments
were impacted not only by lateral fluvial deposition of polluted sedi-
ments during the period of peak mining, but also by vertical and hori-
zontal element migration. The distal floodplain was polluted from
above by atmospheric fallout, minor aggradation, bioturbation and ver-
tical migration, as well as by lateral migration from the proximal flood-
plain. The risk element migration altered the inter-element ratios Zn/Pb
and Cd/Zn, and produced laterally non-correlated depth profiles in the
distal floodplain and in deeper strata in the proximal floodplain. Such
extensive post-depositional migration of Zn, Pb and Cd observed within
sediments of the Litavka River results in the potential transfer of pollut-
ants from hot spots in the floodplain to the current river channel,
thereby negatively impacting the quality of suspended particulate mat-
ter and river water.
Acknowledgements
We are grateful to an anonymous reviewer for key suggestions that
significantly improved the text. We thank T. Matys Grygar (IIC) for re-
search targeting and assistance with data interpretation, and the entire
team from the Institute of Inorganic Chemistry for helping with sample
processing, and interpretation and presentation of results. We also
thank György Sipos (University of Szeged) for performing of OSL dating.
This work was funded by the Grant Agency of the Charles University,
Czechia (GA UK project no. 925016) and partially by a student project
from Internal grant agency UJEP, Czechia (IGA project No. 44204 15
2076 01). We also acknowledge the support of IIC via a long-term re-
search programme project. Long-term research programme support at
the Institute of Geology was provided by institutional project
RVO67985831. Some of the laboratory analyses were financed by the
Czech Science Foundation (project number 15-00340S).
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