ELSEVIER Journal of Geochemical Exploration 65 (1998) 27–45

Zn, Pb, Cu and As distribution patterns in overbank and medium-order

stream sediment samples:
their use in exploration and environmental geochemistry
R. Swennen a,Ł , J. Van der Sluys b
a Department of Fysico-chemical Geology, K.U. Leuven, Celestijnenlaan 200C, B-3001 Heverlee, Belgium
b Geological Survey of Belgium, Jennerstreet 13, B-1000 Brussels, Belgium

Accepted 27 July 1998

Abstract

Overbank and medium-order stream sediment samples were collected in Belgium and Luxembourg from 66 sampling
locations (area of about 33,000 km2 ) and analysed for major and trace elements among which Zn, Pb, Cu and As. At
each sampling location large bulk samples were taken, namely in the lower (normally at ½1.5 m depth, over an interval
of about 20–40 cm) and upper (normally upper 5–25 cm) parts of the overbank profiles and from the stream sediments.
Furthermore, at a number of these sites, a detailed geochemical analysis of vertical overbank sediment profiles (sampling
intervals of 10–20 cm) was subsequently carried out to unravel element variations through time and to help in the overall
evaluation. For most sampled sections evidences such as 14 C-dating and the absence of anthropogenic particles point
towards a pre-industrial and often pristine origin of the lower overbank sediment samples. From the latter bulk samples,
mean background concentrations were deduced. They reveal the existence of significant differences between the northern
and southern part of Belgium (incl. Luxembourg) which relate to the difference in geological substrate. In the north
dominantly non-lithified Quaternary and Tertiary sands, marls and clays occur while in the south Palaeozoic sandstones,
shales and carbonate rocks outcrop. Consequently separate mean background values were calculated for the two areas. In
the southern study area, some anomalous metal concentrations have been recorded in pre-industrial sediments. They are
derived from mineralised Palaeozoic rocks, a feature which could be of interest for base metal exploration. In the upper
overbank and stream sediments, in general, higher heavy metal and As contents were recorded with highest values in
areas with metal mining, metal melting and cokes treatment industries. By comparing the trace element concentrations of
the upper overbank or stream sediment samples with the concentrations detected in the lower overbank samples at each
of the sampling locations, and by evaluating the vertical distribution patterns where available, the degree of pollution
of the alluvial plain and the present-day stream sediments can be assessed. From this exercise, it is clear that highest
pollution occurs in the northern part of Belgium, which relates to its high population density and industrial development.
 1998 Elsevier Science B.V. All rights reserved.

Keywords: heavy metals; overbank sediment; stream sediment; background concentration; Belgium

Ł Corresponding author. E-mail: rudy.swennen@geo.kuleuven.ac.be

0375-6742/98/$ – see front matter
c 1998 Elsevier Science B.V. All rights reserved.
PII: S 0 3 7 5 - 6 7 4 2 ( 9 8 ) 0 0 0 5 7 - 0
28 R. Swennen, J. Van der Sluys / Journal of Geochemical Exploration 65 (1998) 27–45
1. Introduction
In environmental research, reference is often
made to so-called ‘background or reference values’.
These values should correspond to concentrations
in relation to the geological substrates, where no
anthropogenic inputs interfere. Also in exploration
geochemistry, it is attempted to analyse by prefer-
ence samples which display a direct link to the geo-
logical substrate and its hidden mineralisations. It is,
however, clear that in both fields, artificial anomalies
created by human activities (e.g. agriculture, mining
and smelting activities, : : : ) hinder a straightforward
interpretation of the geochemical data.
The aim of this paper is to report on the concen-
trations of Zn, Pb, Cu and As in overbank sediment
profiles from Belgium and Luxembourg and to de-
duce ‘ background’ or at least ‘pre-industrial’ con-
centrations. The latter will then be compared with
the concentrations present in the upper parts of over-
bank profiles and in stream sediments with the aim to
assess pollution. Since in mineralised areas anoma-
lous values already occur in pre-industrial samples,
a discussion on the exploration implications of this
research approach will also be presented.
With the aim to deduce background values, in
many areas such as western Europe, an effort has
been made to sample pristine soils (e.g. Geuzens and
Cornelissen, 1994). However, especially for heavy
metals, an increase in element concentration has
been recognised in most of the top parts of the
studied soil profiles. This is often explained by at-
mospheric deposition related to industrial activities
(e.g. Volden et al., 1997; Pulkkinen and Rissannen,
1997) or to other man-made pollution (e.g. Mack-
lin et al., 1992; Swennen et al., 1994; Belogolova
and Koval, 1995). Furthermore, the intrinsic verti-
cal and lateral heterogeneity of soils especially in
lowland regions like Belgium (Hoogendoorn, 1989)
question the representativity of this sample medium
for regional background concentration calculations
for environmental research purposes, at least if the
number of samples is limited. Stream sediments are
in this respect generally considered to be a better
sampling medium, despite the fact that their repre-
sentativity sometimes can also be questioned on the
base of fluvial erosion processes (Bogen et al., 1992).
Their geochemical signature is generally supposed to
reflect better the geochemical nature of the upstream
drainage geochemistry since input of inorganic flu-
vial particles depends on local bedrock and soil
chemistry. However, heavy metal pollution from con-
temporaneous sources, such as urban centres, agri-
culture, mining and smelting industries are often su-
perimposed on the background compositions. There-
fore in many areas also this sample medium has
been withdrawn as potential medium for deducing
‘background’ concentrations (Bölviken et al., 1990).
Overbank sediments at depth were proposed as an
alternative sampling medium by Ottesen et al. (1989)
and Bölviken et al. (1990, 1996). These consist
of sediments mainly deposited from suspension on
floodplains when water discharge exceeds the capac-
ity of the stream channel or just after water retreat. If
an accommodation potential exists within the flood-
plain a sequence of mainly fine-grained, sometimes
laminated, sediments is accumulated through time
with the oldest sediments occurring in the deepest
parts of such an overbank sequence. The geochem-
istry of one lamina represents the geochemistry of
the fluvial particles transported and deposited dur-
ing one flood. Since during flood discharge many
particles are transported and well mixed, this sam-
ple is highly representative for the geochemistry of
the upstream drainage basin at that time. Geochemi-
cal analysis of superimposed laminae or of intervals
grouping different laminae will at least in undis-
turbed profiles allow reconstruction of the variation
in geochemical signature through time (e.g. Macklin
et al., 1994; Hindel et al., 1996). The fact that in
the lower part of the overbank profiles pre-industrial
and even pristine sediment samples can be collected
may serve to indicate geochemical background val-
ues. To increase representativity, bulk samples, sev-
eral decimetres in thickness grouping several tens
of flood events, have been collected in this study.
This type of research was for example carried out
in Fennoscandia, Hungary and China (Edén, 1994;
Odor et al., 1997; Xie et al., 1997). In some of
these countries it was shown that this low-density
sampling of overbank sediments yields maps which
correlate well with data gathered from higher-density
sampling of other media such as stream sediments
(Demetriades et al., 1990; Edén, 1994; Edén and
Björklund, 1994; Shen and Yan, 1995; Demetriades
and Volden, 1996).
 R. Swennen, J. Van der Sluys / Journal of Geochemical Exploration 65 (1998) 27–45
It is appropriate here to mention that the sampling
of lower and upper overbank and floodplain mate-
rials was incorporated (with other sampling medi-
ums) into the UNESCO report’s recommendations
for worldwide geochemical mapping (Darnley et
al., 1995). Also in the recently published FOREGS
(Forum of European Geological Surveys) geochem-
ical mapping field manual (Salminen et al., 1998),
overbank sediments are considered as an optional
sampling medium.
Some authors, however, have expressed their con-
cerns about the suitability of overbank sediments
as sampling medium to infer pristine geochemi-
cal signatures. Macklin et al. (1994) and Ridgway
et al. (1995) questioned the possibility of obtain-
ing pre-industrial overbank sediments, especially if
no dating control is available. It furthermore can-
not be excluded that vertical element migrations
may disturb the original concentration levels in un-
derlying layers (Edén, 1994; Edén and Björklund,
1994; Swennen et al., 1994). Finally, it is now well
known that important lateral variations occur in over-
bank systems (Leenaers, 1989; Swennen et al., 1994;
Ridgway et al., 1995). Therefore, to avoid arbitrary
results, especially in cases of widespread sampling,
one should at least check whether variability between
overbank profiles on the same floodplain or on flood-
plains with a similar substrate are significantly lower
than the geochemical variability between overbank
profiles belonging to geologically different catch-
ments.
Finally, if we consider that in many parts of the
world more than 50% of the population is living
on alluvial plains and that agricultural as well as
industrial activities are concentrated in these areas, it
is justified to pay special attention to the degree of
pollution of these often active sedimentation areas.
2. Geology and environmental framework
Based on geomorphological and geological crite-
ria it is possible to split Belgium up into two major
parts (Fig. 1). The flat northern and middle part
of Belgium (north of the rivers Meuse and Sam-
bre; Fig. 1) developed mainly on non-lithified sands,
marls and clays of Quaternary to Tertiary age. The
sands are relatively less resistant to weathering and
29
form some low-relief expressions in the landscape.
Grain size analysis shows that stream and overbank
sediment samples here are commonly sandy. In the
southern part of Belgium and parts of the Grand
Duchy of Luxembourg faulted and folded Palaeozoic
sandstones, shales and carbonate rocks dominate. In
this region some base metal mineral deposits are
present. Furthermore some Caledonian massifs coin-
cide with the topographically highest-relief areas. In
this southern region the most eroded and weathered
areas correspond with shale-dominated lithologies.
This is also reflected in the stream and overbank
lithologies where grain size analysis shows the dom-
inance of clay- to silt-particles.
From an environmental point of view there ex-
ists also a difference between northern, middle and
southern Belgium (Fig. 1). With the exception of the
industrial axes along the rivers Meuse and Sambre
where underground coal mining and steel industries
were very important in the beginning of this century,
in middle and southern Belgium the impact of large
industrial plants was and still is limited. In the Grand
Duchy of Luxembourg only the major steel industry
in the southern part of the country and the metal-
related and chemical industries around Luxembourg
city should be mentioned. However, industrial activ-
ities are widespread in northern Belgium and do not
only occur along the major river systems. Notice the
presence of cokes treatment plants along the most
important industrial axes.
An important remark is that in this project
medium river systems were studied. Therefore, the
pollution impact within the alluvial plain deposits of
the larger river systems such as the Meuse, Sambre
and the Scheldt are not detected.
3. Methodology
Following the recommendations of the Working
Group on regional geochemical mapping of west-
ern Europe (Bölviken et al., 1990) 66 sampling
sites were sampled on the territory of Belgium and
Luxembourg (Fig. 1; area of about 33,000 km2 ).
Consequently, one representative site for a catch-
ment area of about 500 km2 was selected. However,
catchment areas in reality ranged between 60 and
600 km2 . To assure representativity of the sampling
 30
R. Swennen, J. Van der Sluys / Journal of Geochemical Exploration 65 (1998) 27–45
Fig. 1. Geographical location map of sampling sites with division in northern and southern sub-province and mean .X / and standard deviation .¦ / data of some major (in
wt%) and trace elements (in ppm) of L-samples illustrating the difference between both areas.
 R. Swennen, J. Van der Sluys / Journal of Geochemical Exploration 65 (1998) 27–45
location and to exclude locations with canalised beds
or artificial banks a brief geographical, hydrological
and historical research was carried out for each of
the potential locations. Sampling was carried out in
the summer and early autumn season when the water
level was low (in July=August 1991 for the pilot
study area in E Belgium, De Vos et al. (1996); in
July till the beginning of November 1992 and 1994,
respectively, for northern=middle and for southern
Belgium). In the field, in general, at least two stream
bank exposure surfaces, separated over a distance of
some hundreds of metres, were cleared and inspected
with regard to sedimentological profile characteris-
tics and the presence of datable peat layers and
anthropogenic particles (slags, brick and charcoal
fragments, plastics). All studied profiles were situ-
ated in the immediate vicinity of the actual stream
channel, most often in the cut bank of meander bends
(Fig. 2). Experience shows that at these locations, if
polluted, it is likely to find the highest metal con-
centrations (Swennen et al., 1994; Langedal, 1996).
This most likely relates to the fact that particulate
pollutants are most easily deposited next to the river
channel, and also that here the sediment sequence
is thickest. Finally, the most representative and sedi-
mentological continuous profile was selected. Based
mainly on colour and grain size variations as well
as other sedimentological criteria, it was possible to
differentiate lithological units several tens of cen-
timetres in thickness within most profiles. But in
general such variations in one individual profile
are minor, with the exception of profiles in east
Belgium where gravel interlayers commonly occur
between clay=silt-rich overbank sediments. Biotur-
bation commonly obliterates sedimentary structures
such as laminations within lithological units. At each
selected site, after removing the outer 10 to 20 cm
exposure surface, a vertical section was dug as deep
as possible, often several tens of centimetres be-
low groundwater level. At each sampling location
two sampling approaches were followed (Fig. 2). In
this paper data reflecting the broad regional geo-
chemical patterns using three types of bulk samples
(the so-called L-U-S-approach) are reported. De-
tailed variations in geochemical distribution patterns
(the so-called geohistory approach) determined by
taking a continuous vertical sequence of samples re-
flecting variation through time are also discussed. A
31
full description of the sampling strategy is given in
Swennen et al. (1998a). A description of the L-U-S-
samples follows below.
(1) A bulk (commonly 20–40 cm thick) lower (L-)
overbank sediment sample taken at depth (where
possible ½1.5 m). This sample is assumed to re-
flect pre-industrial and often pre-anthropogenic, i.e.
pristine sedimentation and thus also background geo-
chemical characteristics of the catchment area. Age
dating by 14 C in about 15% of the profiles as well as
the presence=absence of anthropogenic particles sup-
ports the validity of the just mentioned assumption.
Additionally, statistical geochemical criteria were
used, as will be illustrated below. In about 15% of
the studied cases it was, however, not possible to
confirm with certainty the pre-industrial nature of
the lower overbank sample. 5% of the cases provided
clear evidence of the absence of pristine sediment in
the collected lower overbank sample.
(2) A bulk (20 cm thick) upper (U-) overbank sed-
iment sample, normally taken within the upper 5 to
25 cm, reflecting background signatures with super-
imposed anthropogenic influences. This U-sample
can therefore serve to assess the actual degree of pol-
lution of the floodplain. As far as can be judged from
locations where several profiles were sampled within
the floodplain over short distances, this U-sample
reflects the general characteristics of the upper flood-
plain (e.g. Swennen et al., 1994).
(3) A bulk (about 5 kg) active stream (S-) sed-
iment which should indicate present-day degree of
pollution in the Belgian–Luxembourg stream sys-
tem.
In the geohistory sampling approach, representa-
tive sediment samples were taken over 10 to 20 cm
depth intervals along the vertical profiles (Fig. 2).
Only profiles with major differences in geochemi-
cal characteristics based on the analytical results of
the L-, U- and S-mapping exercise, in addition to
well dated profiles (by means of 14 C), have been
selected (in total 35 profiles) for further research.
This means that there is an overrepresentation of
anomalous locations. This sampling approach was
added to investigate the vertical extent and transi-
tion between polluted and unpolluted sediments and
to detect whether vertical downward migration of
elements occurred or not. Based on a thorough eval-
uation of these profiles Swennen et al. (1997) came
32 R. Swennen, J. Van der Sluys / Journal of Geochemical Exploration 65 (1998) 27–45

Fig. 2. Schematic overview of the two sampling approaches.

to the conclusion that the basic assumption, namely
that pre-industrial or even pre-anthropogenic sam-
ples can be collected in the bottom part of most of
the profiles, is valid.
Within the first sampling approach, bulk samples
of 5 to 15 kg were taken, but with growing field
experience, quantities of 1 to 5 kg turned out to
be sufficient to yield representative material of the
<125 µm fraction to be analysed. Samples collected
for the second approach were in the order of 1 to
2.5 kg. L-U-S-samples were dried at 80ºC and the
‘geohistory’ samples were dried at 40ºC (to allow
 R. Swennen, J. Van der Sluys / Journal of Geochemical Exploration 65 (1998) 27–45 33

clay mineralogy determinations), disaggregated and Table 1

sieved. The L-U-S-samples were exclusively anal- Mean values .X / and standard deviations .¦ / of L-U-S samples
ysed by XRF. The ‘geohistory’ samples were anal- Subprovince a L-sample U-sample S-sample
ysed by XRF for the major elements and by ICP–
X ¦ X ¦ X ¦
AES (aqua regia digestion) for the trace elements (in
total 25). Flame-AAS was used for the determina- (A) With outliers
As N 12 (8) 22 (14) 14 (9)
tion of Cd (HClconc C HNO3 conc C HFconc digestion)
S 15 (11) 15 (9) 13 (10)
and As (K2 S2 O7 melting C HCl (1 N) digestion). Cd N 0.7 (0.4) 1.9 (2.3) 1.9 (1.8)
Concentrations below detection limits were set at 0.5 S 2.1 (1.7) 2.1 (1.1) 2.7 (1.7)
of the detection limit. Replicate analysis was carried Cu N 10 (17) 43 (65) 50 (90)
out on 5% of the samples and showed no variations S 22 (42) 28 (34) 38 (59)
Pb N 37 (111) 90 (158) 95 (116)
at a significance level of 5%, at least for the data
S 54 (120) 71 (84) 77 (103)
with concentrations 2 times the detection limit. This Zn N 62 (152) 216 (422) 334 (370)
paper focuses on the results of Zn, Pb, Cu and As. S 124 (157) 209 (319) 311 (359)
Detection limits for the latter elements are set at 1 (B) Without outliers
ppm. The entire data set has been published in report As N 12 (8) 22 (14) 14 (9)
283 of the Belgian Geological Survey (Van der Sluys S 13 (6) 15 (9) 13 (10)
et al., 1997) and thus can be requested from the Cd N 0.7 (0.4) 1.9 (2.3) 1.9 (1.8)
authors. S 2.1 (1.1) 2.1 (1.1) 2.7 (1.7)
Cu N 7 (4) 43 (65) 50 (90)
S 16 (7) 18 (34) 38 (59)
Pb N 16 (11) 49 (38) 66 (50)
4. Results and discussion S 26 (17) 55 (48) 49 (31)
Zn N 33 (18) 136 (134) 334 (370)
Based on the distribution maps of major, and to S 82 (34) 159 (90) 311 (359)
some extent, trace elements, Swennen et al. (1997) a N D northern sub-province; S D southern sub-province.
concluded that two geochemical sub-provinces
should be differentiated in the study area (Fig. 1).
Notice that the term ‘sub-province’ is used here elements with Rb, Sc and V. The latter correlate neg-
to describe a rather large area with rather uniform atively with SiO2 accentuating the contrast between
geological=geochemical characteristics, which might both sub-provinces (Swennen et al., 1997).
belong to a geochemical province used in the sense This difference in geological substrate also exerts
as defined by Bradshaw et al. (1972). In the north- an influence on the heavy metal contents of the
ern sub-province high SiO2 and low Al2 O3 , Fe2 O3 , overbank and stream sediment samples. However, as
MgO, K2 O values occur (Fig. 1), which is explained will be shown below this effect is largely masked by
by the weathering characteristics of the Tertiary and man-made pollution in the upper overbank sediment
Quaternary formations. The vertical distribution pat- and stream sediment samples. The regional contrast
terns of SiO2 and Al2 O3 in the profiles Rivierbeek between north and south for heavy metals is best
and the non-polluted lower part of the Dijle and Leie expressed in the lower overbank samples (Table 1,
(respectively, Fig. 5A, Fig. 5C and Fig. 6A) reflect Figs. 7 and 8). Notice that especially for some heavy
this pattern. Notice that here only minor vertical vari- metals, values below detection limit may affect the
ations occur. In contrast, the southern sub-province data set distribution.
displays an opposite geochemical behaviour (Fig. 1) In Figs. 3 and 4 an overview of the vertical dis-
pinpointing to the fact that here Palaeozoic shaley tribution patterns of, respectively, Zn and Pb of all
formations are more affected by weathering. As an investigated profiles is given. Some of the Zn, Pb,
example the SiO2 –Al2 O3 content of the lower non- Cu and As profiles are shown in more detail in
polluted part of the Salm and Haine overbank profile Figs. 5 and 6. Selection of the latter profiles was
is given (Fig. 5B, Fig. 6B). Factor analysis also based on representativity to illustrate vertical ele-
showed a covariant behaviour of clay-related major ment patterns discussed below. All patterns will be
 34
R. Swennen, J. Van der Sluys / Journal of Geochemical Exploration 65 (1998) 27–45
Fig. 3. Vertical distribution patterns in overbank profiles for Zn (note the difference in concentration scale between the different profiles). At each of the sample locations
the Zn content of the stream sediment is given graphically.
 R. Swennen, J. Van der Sluys / Journal of Geochemical Exploration 65 (1998) 27–45
35
Fig. 4. Vertical distribution patterns in overbank profiles for Pb (note the difference in concentration scale between the different profiles). At each of the sample locations
the Pb content of the stream sediment is given graphically.
36 R. Swennen, J. Van der Sluys / Journal of Geochemical Exploration 65 (1998) 27–45

Fig. 5. Detailed view on the vertical distribution patterns of Zn, Pb, Cu and As of (A) the Rivierbeek (location 37), (B) the Salm (location
70) and (C) the Dijle (location 17). The dashed lines represent the XRF data of the L- and U-overbank sediment samples for comparison.
14 C dates are given where available.
 R. Swennen, J. Van der Sluys / Journal of Geochemical Exploration 65 (1998) 27–45 37

Fig. 6. Detailed view on the vertical distribution patterns of Zn, Pb, Cu and As of (A) the Leie (location 39), (B) the Haine (location 45)
and (C) the Zenne (location 25). The hashed lines represent the XRF data of the L- and U-overbank sediment samples for comparison.
14 C dates are given where available.
38 R. Swennen, J. Van der Sluys / Journal of Geochemical Exploration 65 (1998) 27–45
published in report 290 of the Geological Survey
of Belgium (Swennen et al., 1998b). In most pro-
files where a pristine origin of the lower overbank
sediment samples can be assumed, the lower profile
section is characterised by low to moderate concen-
trations. SiO2 and Al2 O3 contents do not vary much,
illustrating that variations in the quartz=clay content
are minor. A gradual slight to important increase in
heavy metal concentration can often be recognised
in the upper part of the profiles (Figs. 3 and 4). In
Fig. 5A,B representative examples are given, respec-
tively, from the northern and southern part of the
investigated area. This behaviour is more character-
istic in profiles from the northern part of the study
area, while in the southern part different profiles
display a rather uniform vertical distribution pattern.
Here the minor variations in element concentration,
which sometimes occur, relate to minor differences
in lithology (clay and organic matter content).
The mild gradual increase in heavy metal and
As concentrations also occurs in catchments where
no important industrial activities have been reported.
Apart from local pollution sources, which always
have to be taken into account, the overregional in-
crease relates to atmospheric deposition of metal
bearing aerosol particles. A limited downward trans-
port possibly also occurs.
Other profiles display in their upper part more
important increases of most heavy metals (espe-
cially Zn and Pb), leading to concentrations 2–5
times higher than in the lower profile part. This
phenomenon is related to the deposition of water or
suspension transported metal-bearing particles. An
example is location 17 (Dijle catchment; Fig. 5C)
where a clear increase of Pb (from <25 ppm be-
low 70 cm and >80 ppm in the upper 40 cm) and
Zn (from <30 ppm below 70 cm and >200 ppm
in the upper 40 cm with one spike value at about
70 cm depth of 924 ppm) occurs. This increase in
Pb and Zn is probably caused by a battery factory
25 km upstream of the sample site. More dramatic
shifts in element concentration occur at locations 71
and 39 (respectively, Alzette and Leie catchments;
Figs. 3 and 4). Details of the latter profile are illus-
trated in Fig. 6A. Here the presence of steel and re-
lated industries (e.g. Zn coating industries) explains
the sudden increase in heavy metal and As content
(Figs. 3–6) in the upper profile parts. A similar shift
in the Alzette overbank profile at location 71 (Figs. 3
and 4) is marked by an increase in P2 O5 , while
the clay-related elements (Al2 O3 , K2 O, Sc, Rb, : : : )
decrease in concentration and SiO2 increases ac-
cordingly (Swennen and Van der Sluys, 1998). It is
explained here by the use of the phosphate-rich iron
ore, the so-called ‘Minette’ (Thein, 1975), which
was intensively mined during the last century. Min-
ing and ore processing raised groundwater extraction
and discharge into the Alzette, which caused fine
sediment particles to be preferentially transported
further downstream, explaining the change in major
element content (Swennen et al., 1997).
It is only within these heavily polluted profiles
that vertical downward migration of heavy metals
can be fully evaluated. In most profiles the important
Zn, Pb, Cu and As increase occurs at the same profile
depth position (Fig. 6A, B), suggesting that down-
ward migration of some of these pollutants is minor.
Hudson-Edwards et al. (1998) came to a similar con-
clusion in their study of the overbank deposits in the
Yorkshire Ouse Basin. However, in coarser-grained
sediment layers at depth (which occur at some places
in the mineralised eastern part of Belgium), an in-
crease in concentration is sometimes observed in
deeper parts of the profiles especially for mobile ele-
ments such as Cd and As (e.g. Swennen et al., 1994).
Based on our data set this suggests that within such
permeable layers some caution should be paid to
treat these systems as fixed. Downward percolation
of mobile elements can occur. This effect, however,
is limited and manifests itself by elevated concen-
trations in discrete high-permeability horizons in
profiles with low retardation factors (e.g. clay and
organic poor lithologies). It is also recognisable by
the fact that within layers which from a sedimen-
tological point of view are likely to be pristine, a
larger depth extension of anomalous concentrations
of mobile elements with respect to less mobile heavy
metals occurs (Swennen and Van der Sluys, 1998).
Some profiles display also high to very high Zn
and Pb concentrations in the lower profile part. In
the case of the Viroin, Vesdre and Geul (respectively,
sample locations 47, 6 and 14), this pattern is related
to the presence of base metal mineral deposits in
the catchment. Where they have been mined in the
past, very high concentrations are characteristic for
the upper profile intervals. In some other profiles,
 R. Swennen, J. Van der Sluys / Journal of Geochemical Exploration 65 (1998) 27–45
especially in the northern part of Belgium, high
heavy metal concentrations occur all over the profile.
Since anthropogenic particles were found all over the
profile, the assumption that pre-industrial samples
can be collected in the lower parts of the profiles is
not valid here. A clear example is sample location
25 (Zenne catchment; Fig. 6C) where up to a depth
of >2 m concentrations above 1500 ppm Zn, 500
ppm Pb, 150 ppm Cu and 75 ppm As occur. This
catchment was one of the most heavily industrialised
parts of Belgium in the last 150 years.
Histograms of Zn and Pb, and Cu and As of
the lower (L), upper (U) overbank and stream sedi-
ment (S) samples are given, respectively, in Figs. 7
and 8. In the histograms, data are shown for the
entire population (66 sites) and for the northern (No)
and southern (So) sub-provinces separately. At first
glance one can see that the lower overbank sedi-
ment samples possess the lowest concentrations for
each of the elements. However, in the latter data
set clear outliers are also present. An outlier in the
northern sub-province for Zn, Pb (Fig. 7) and Cu
(Fig. 8b) corresponds to a sample taken in the Zenne
catchment (sample location 25). Here also other el-
ements such as As (see Fig. 6C), Cd (up to 6.6
ppm) and Ba (>600 ppm) are anomalous over the
entire profile depth. The profile also exhibits very
high Al2 O3 (10.1%), K2 O (2.07%), and low SiO2
(60.6%) contents in the L-sample which contrasts
to the general pattern of the northern sub-province
(see values given in Fig. 1 and Van der Sluys et al.,
1997). Based on the many outliers within this profile
it was also possible to exclude this sample site from
the pristine or pre-industrial data set on a statistical
base. As mentioned above this river drains part of
the heavy industrialised area next to the cities of
Brussels and Vilvoorde (Fig. 1). The lower sample
does not fulfil the criteria to be pre-anthropogenic.
Therefore, this sample was rejected when calculat-
ing the univariant statistics (Table 1B). The three
anomalous Zn and Pb values in the southern sub-
province of the L-sample data set (Fig. 7) all belong
to stream systems where base metal mineral deposits
have been reported and locally even mined (e.g.
Swennen et al., 1994). Whether these elevated ‘lo-
cal’ background concentrations are in every location
pre-anthropogenic or influenced by small-scale min-
ing activities during the Middle Ages is not always
39
known. For the Geul catchment (sample location 14)
14
C dating showed that the lower overbank sediments
are deposited around 1630. Hence its anomalous
contents most likely relate to the small-scale min-
ing activities during that period. For the calculation
of ‘background’ concentrations this type of sample
will clearly affect the values of mean concentrations
and standard deviations. Consequently, they were not
used for calculating the univariant statistics given in
Table 1B. This also accounts for the outliers for Cu
and Cd (266 and 9.9 ppm, respectively), which occur
in the mineralised Wiltz catchment (sample location
67) and the As outlier (67 ppm) which could relate
to a polymetallic disseminated type of mineralisation
in the Helle catchment (sample location 75) (Fig. 8).
For the latter two sample locations a pre-industrial
origin of the overbank sediment samples is, how-
ever, very likely considering sedimentological crite-
ria and the absence of anthropogenic particles in the
lower parts of the profiles. The presence of anoma-
lous values in the lower overbank sediment samples,
possibly pristine but at least pre-industrial in ori-
gin, provides a possible alternative for exploration
for base metal mineralisations in polluted regions
like in the area studied (see also De Vos et al.,
1996). Finally, the overall higher contents in heavy
metals (except As) in L-samples occurring in non-
mineralised catchments in the southern sub-province
in comparison to the L-overbank samples in the
northern sub-province (Table 1, Figs. 7 and 8) are
mainly interpreted in terms of weathering of clay-
rich lithologies and the adsorptive characteristics of
the clays.
Comparison of the heavy metal concentrations
of the upper with the lower overbank or stream
sediment samples shows for Zn, Pb and Cu an im-
portant increase, while for As from the southern sub-
province this increase in concentration is less obvi-
ous (Figs. 7 and 8, Table 1). This shift towards higher
Zn and Pb concentrations is also visible in Figs. 3–
6. Within the histograms this increase is in general
characterised by a larger spread in concentration of
the main population with the development of a larger
number of outliers. These characteristics are best
developed for Zn. Within both the northern and the
southern sub-provinces, a clear shift towards higher
concentrations is recognisable with the development
of a complex population pattern. Since within both
40 R. Swennen, J. Van der Sluys / Journal of Geochemical Exploration 65 (1998) 27–45
 R. Swennen, J. Van der Sluys / Journal of Geochemical Exploration 65 (1998) 27–45 41

sub-provinces no increase in Al2 O3 and K2 O occurs
in the overbank sediments (Swennen et al., 1997)
and no systematic shift in clay or organic matter con-
tent has been recognised, this shift in Zn (and also
Pb and Cu) is not related to a change in lithology.
It is explained by the effect of man-made pollution
as discussed before. The outliers of the Geul in the
Zn-histogram (sample location 14; see also for Pb,
Cu, As in Figs. 7 and 8) are connected to former
mining activities in the catchment (Swennen et al.,
1994). The other outliers either relate to the presence
of steel and metal processing industries in the catch-
ment (Alzette and Leie, respectively, locations 71
and 39) or the (former) existence of intensive indus-
trial activities which often developed along streams
(Groot Schijn and Zenne, respectively, sample loca-
tions 23 and 25). This Zn increase becomes even
more expressed in the stream sediment geochemistry
and can be explained in a similar way. For Pb and
Cu a similar evolution is present (Figs. 7 and 8, Ta-
ble 1). Many of the catchments, which displayed an
anomalous behaviour for Zn, are also anomalous for
the latter elements. Some of the anomalies relate to
former mining activities of Pb–Zn ore (Geul, Viroin
and Vesdre, respectively, sample locations 14, 47 and
5, and 6). The fact that the stream sediments are
still heavily polluted, even after mining and smelt-
ing activity has ceased for more than 50 years in
certain areas possibly relates to the reworking of
polluted overbank sediments which were temporar-
ily stored in the alluvial plain. Similar features have
been reported by Macklin (1996). However, this also
might relate to new pollution sources which became
recently active. Influence of such pollution sources
can in general terms be attested by the fact that
the concentration increase between lower and upper
overbank sediments is well developed in the northern
sub-province but less expressed in the southern sub-
province. This clearly relates to the lower degree of
industrial activities in the southern part of Belgium
and many parts of Luxembourg. In contrast to the
heavy metals discussed, the As concentration even
falls back towards its background concentrations in
the studied stream sediments. This is most probably
caused by the lowered use of As in agriculture and
industry over the last years.
5. Conclusions
Geochemical baseline data become more and
more relevant within environmental research. Over-
bank samples taken at depth form a suitable sampling
medium to infer background concentrations as long
as pristine or at least pre-industrial samples can be
collected. In this paper results of a two-step approach
are given. The first so-called L-U-S approach (L D
lower overbank sediment sample, normally taken at
½1.5 m depth; U D upper overbank sediment sam-
ple, normally 5–25 cm depth from soil surface; S
D stream sediment sample) allowed to infer regional
data suitable for geochemical mapping. The second
so-called geohistory approach enabled to study some
of the vertical distribution patterns in more detail.
Based on the variable nature of the geological
substrate, different geochemical background signals
were calculated in the study area. In the northern
part of the study area fluvial particulate material
dominantly is sand-rich while in the southern part
more clay- to silt-rich particulate material occurs.
The latter originates from weathered shale strata.
Background concentrations deduced from the lower
overbank sediments for heavy metals including As
are lowest in the sand-rich northern area. In absolute
values this contrast between north and south is best
expressed for Zn.
Within the study area only few of the lower
overbank samples are clearly influenced by man.
The latter are clearly not suitable for deduction of
background values. In general the lower overbank
sediment samples show the lowest heavy metal and
As concentrations within each of the catchments.

Fig. 7. Histograms of L-, U- and S-samples for Zn (a) and Pb (b) in northern (No), southern (So) and total (T) population. Sample site
numbers for Zn: L-67 D Wiltz; L-25 D Zenne; L-47 D Viroin; L-5 D Vesdre; L-14 D Geul; U-23 D Groot Schijn; U-25 D Zenne; U-39
D Leie; U-14 D Geul; U-71 D Alzette; S-23 D Groot Schijn; S-25 D Zenne; S-28 D Durme; S-29 D Dender; S-30 D Dender; S-16 D
Demer; S-71 D Alzette; S-65 D Attert; S-72 D Hoegne; S-5 D Vesdre; S-6 D Vesdre; S-45 D Haine. For Pb: L-25 D Zenne; L-5 D
Vesdre; L-47 D Viroin; L-14 D Geul; U-25 D Zenne; U-39 D Leie; U-5 D Vesdre; U-6 D Vesdre; U-14 D Geul; S-72 D Hoegne; S-25
D Zenne; S-23 D Groot Schijn; S-5 D Vesdre; S-6 D Vesdre.
42 R. Swennen, J. Van der Sluys / Journal of Geochemical Exploration 65 (1998) 27–45
 R. Swennen, J. Van der Sluys / Journal of Geochemical Exploration 65 (1998) 27–45
Some of the locations display anomalous values,
which either relate to the downward migration of
pollutants in permeable layers or to the pre-indus-
trial or pristine signature of mineralised catchment
areas. Especially the former is not straightforward to
recognise, illustrating that sampling overbank sedi-
ment samples for environmental purposes should not
be carried out blindly. The second type of anoma-
lous samples enables to set up a exploration strategy
for searching base metal mineralisations in heavily
polluted areas. Sampling lower overbank sediment
samples thus allows to look through the pollution
window and thus is recommended for calculating
geochemical background concentrations.
Several overbank profiles (about 40 to 50%) dis-
play rather uniform low heavy metal and As vertical
distributions with concentrations gradually doubling
and sometimes tripling in the upper 0.5–1 m of
the profile. In most of these locations the stream
sediment sample displays similar concentrations as
recorded in the upper profile parts. The majority of
these locations are situated in the middle and south-
ern part of the research area. The increase in the
upper profile part also occurs in areas without impor-
tant industrial activity in the catchment so that the
pattern most likely relates to atmospheric deposition
of pollutants. In the northern part of the study area
as well as in other locations which are characterised
by important industrial activities in the catchment,
such as steel and metal processing industries (e.g.
southern Luxembourg), an abrupt sudden increase
in heavy metal and As concentration in the upper
part of the overbank profiles is recognisable. Con-
centrations commonly increase by a factor 10 for
Zn, and about 5 for the other heavy metals and As.
The presence of several types of anthropogenic par-
ticles (e.g. slag, charcoal, brick, plastics) within the
heavy metal-enriched overbank sediment indicates
man-related influences.
Fig. 8. Histograms of L-, U- and S-samples for As (a) and Cu (b)
in northern (No), southern (So) and total (T) population. Sample
site numbers for As: L-75 D Helle; U-25 D Zenne; U-39 D
Leie; S-28 D Durme; S-71 D Alzette; S-75 D Helle. For Cu:
L-25 D Zenne; L-67 D Wiltz; U-25 D Zenne; U-23 D Groot
Schijn; U-10 D Kleine Nete; U-39 D Leie; U-6 D Vesdre; U-74
D Warche; S-25 D Zenne; S-23 D Groot Schijn; S-28 D Durme;
S-16 D Demer; S-5 D Vesdre; S-6 D Vesdre.
43
In general, absolute concentrations for Zn, Pb
and Cu increase from lower to upper overbank
and stream sediment samples reflecting the effect
of pollution. For As, the present-day stream sedi-
ment concentrations are in many areas comparable
to the background values deduced from the lower
overbank sediment samples. The comparison of the
concentrations of lower versus upper overbank or
stream sediment samples allows assessment of the
catchment-specific degree of pollution. In the stud-
ied catchments this comparison can be done without
grain size correction since grain size effects are mi-
nor.
Acknowledgements
The authors wish to thank R. Hindel and U. Siew-
ers from the ‘Bundesanstalt für Geowissenschaften
und Rohstoffe’ and W. De Vos from the Geologi-
cal Survey of Belgium for stimulating discussions
and analysis. D. Coetermans made the Cd and As
analyses. I. Van Keer and E. De Coene helped in
the survey preparation, field work and sample prepa-
ration. P. Vervaeke helped in making some of the
drawings. A. Darnley and A. Bockstam helped by
reviewing to improve the manuscript. The editorial
handling by L. Gough is highly appreciated.
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