See discussions, stats, and author profiles for this publication at: https://www.researchgate.

net/publication/6412285

Classification of alluvial soils according to their potential environmental risk:

A case study for Belgian catchments

Article  in  Journal of Environmental Monitoring · May 2007

DOI: 10.1039/b616959g · Source: PubMed

CITATIONS READS

15 2,076

2 authors:

Valérie Cappuyns Swennen Rudy

KU Leuven KU Leuven
82 PUBLICATIONS   1,617 CITATIONS    409 PUBLICATIONS   6,988 CITATIONS   

SEE PROFILE SEE PROFILE

Some of the authors of this publication are also working on these related projects:

Fluid flow in sedimentary basins View project

Travertine reservoir systems View project

All content following this page was uploaded by Swennen Rudy on 19 March 2014.

The user has requested enhancement of the downloaded file.

PAPER www.rsc.org/jem | Journal of Environmental Monitoring

Classification of alluvial soils according to their potential environmental

risk: a case study for Belgian catchments
Valérie Cappuyns* and Rudy Swennen
Received 20th November 2006, Accepted 6th February 2007
First published as an Advance Article on the web 23rd February 2007
DOI: 10.1039/b616959g

Alluvial soils may represent important sinks of contaminants as a result of the deposition of
contaminated sediments along the river by overbank flooding or after dredging. Because of the
erosion of alluvial deposits or the release of contaminants from sediments, alluvial soils can also
be a source of contamination. In this paper, a risk assessment for contaminated (alluvial) soils is
presented. The approach, mainly based on physico-chemical soil characteristics, single extractions
and leaching tests, is illustrated by means of a case study from four Belgian catchments. The
extractions and leaching tests that were used have been validated by European testing programs
and can provide valuable information for classifying the potential environmental risks of soils.
Irrespective of the location, pH, organic carbon content and ‘mobilisable’ metal concentrations
were the most important factors explaining ‘mobile’ metal concentrations in the alluvial soils.
Additionally, the data of the physico-chemical soil characterization, extractions and leaching tests
were combined with local and regional factors to classify the alluvial soils in different categories
according to their actual and potential risk for the environment.

Introduction
Heavy metals are brought into river systems by agricultural,
urban1 and industrial2 sources and by mining and smelting
activities.3 The amount of contaminated sediments that is
stored along a river is mainly controlled by the amount of
sediment that is disposed in the floodplain during overbank
flooding and during dredging activities.
In Belgium and Luxembourg, a systematic sampling of
overbank sediments was performed by Swennen et al.4,5 and
Swennen and Van der Sluys.6 The study revealed the existence
of significant different background concentrations between the
northern and the southern part of Belgium in relation to
differences in geological substrate. The most important con-
tamination was found in the northern part of Belgium because
of the high population density and industrial activities in that
region.
To prevent rivers from flooding and to keep waterways
navigable, dredging of sediments is necessary. In the past,
large quantities of dredged sediments have been deposited
along rivers to heighten hydromorphic terrains or disposed
on arable land to improve its productivity,7 without consid-
eration of the environmental impact. In Belgium (Flanders),
the Institute of Forestry and Game Management made an
inventory of dredged sediment-derived soils along the Upper
Scheldt, Sea Scheldt and Leie rivers.8–10 Up to 82% of dredged
sediment disposal sites along the Upper Scheldt river was
contaminated with Cd, Cr, Zn and/or Pb. Along the Sea
Scheldt, up to 96% of sediment-derived soils (ca. 120 ha)
Katholieke Universiteit Leuven, Geo-Instituut, Geologie,
Celestijnenlaan 2003, B-3001 Heverlee, Belgium. E-mail:
Cappuyns@iph.fgov.be. E-mail: Rudy.Swennen@geo.kuleuven.be;
Fax: +3216327981; Tel: +3216327807
was contaminated with Cd, Cr, Zn or Pb, but to a lesser degree
than the Upper Scheldt alluvial plain.
Once a contamination source is removed from a river
system, alluvial soils still act as a secondary source of con-
taminants because flood events can remove contaminated soil
through bank erosion.11,12 Alteration in climate could poten-
tially lead to accelerated erosion and remobilisation of con-
taminants stored along river channels.13 Therefore, it is
important to have an idea of the amount of sediment-asso-
ciated contaminants stored in floodplains and the amount
eroded over time.
Additionally, leaching of heavy metals can affect the quality
of surface waters and groundwater. For example, Kelly et al.14
found vertical movement of Zn and Cd through soils with a
low cation exchange capacity (CEC) into the groundwater.
Most of the release occurred shortly after the disposal of the
dredged sediment because Zn- and Cd-bearing sulfides were
oxidized and complexation of these elements with dissolved
organic carbon (DOC) contributed to their rapid movement
through the soil.
To assess the effect of contaminants in soils on biota, models
for the accumulation of contaminants in biota can also be
useful. Although most of these models use porewater concen-
trations to assess the bio-available contaminant content, for
some organisms the uptake is related to the solid phase of the
substrate.15 For example, soil ingestion can make a significant
contribution to the total amount of metals ingested by grazing
sheep, especially when soil–plant transfer is low.16
The aim of this study was to evaluate the contamination of
alluvial soils (overbank sediment- and dredged sediment-de-
rived soils) along some Belgian rivers and to compare the
actual and potential release (‘mobile’ and ‘mobilisable’ frac-
tions, respectively) of metals (Cd, Zn, Cu, Pb and As) from
these soils. The actual and potential release of metals from

This journal is

c The Royal Society of Chemistry 2007 J. Environ. Monit., 2007, 9, 319–328 | 319
soils was estimated by means of standardized European
extractions and leaching tests (single extractions with CaCl2
and ammonium-EDTA, and pHstat leaching tests). Together
with information on the total amount of contaminant metals
stored in alluvial soils and on physico-chemical soil properties,
these data were used to divide the alluvial soils into different
categories.
Methodology
Geographical setting and sampling
Between November 2000 and October 2003, alluvial sedi-
ments, consisting of overbank sediment- or dredged sedi-
ment-derived soils were sampled along different rivers in
Belgium (Fig. 1 and Table 1). The influence of substrate
characteristics on soil properties and hence on contaminant
mobility was verified. Therefore, samples were taken in catch-
ments characterized by different substrates, going from glau-
conite-bearing sands, to carbonates, shales and clays.
Fig. 1 Overview of the sampling locations. NL = The Netherlands,
D = Germany, L = Luxemburg, F = France.
320 | J. Environ. Monit., 2007, 9, 319–328
In Flanders, overbank sediment- and dredged sediment-
derived soils were sampled in the catchment of the Scheldt
river (catchment area in Belgium = 13 336 km2), which is
divided into 11 sub-catchments, among which are the
Leie, Zenne and Demer catchments. The Zenne river, located
in Central Belgium (Fig. 1) has a catchment area of 1160 km2
and flows through glauconite-bearing sands (Brusselian
Formation). The Zenne receives water from rain, infiltration,
and wastewater discharge. During centuries, flooding of the
river caused considerable problems in the surroundings of
Brussels. A map from 1863 shows a tributary of the
Zenne, parallel to the Zenne, which was transformed to a
deviation channel in 1863. According to a report of the
Ministry of Public Works,17 the deviation channel was in-
tended to prevent the Zenne river from flooding. The alluvial
soils along this part of the Zenne are currently used for
agriculture and are no longer periodically flooded. The Leie
river (North-West Belgium) is an important tributary of the
river Scheldt and its total catchment area, consisting of
Tertiary sands and clays, is about 3675 km2 (in Belgium).
The Leie river (Fig. 1) is characterized by a regular flooding
regime. In 1976, a part of the river was straightened
and dredged sediments were disposed along the river. Heavy
metals in the dredged sediment-derived soils originate
from industrial activities and agriculture. Most of the dredged
sediment-derived soils are currently used as meadow or
forest. The Grote Beek (Demer catchment, 1272 km2) river
(North Belgium) is underlain by glauconite-rich medium-
grained sands (Diestian Formation). Organic- and iron-rich
wetland soils have developed along this stream. The river
follows a very meandering path and as a consequence several
flooding zones occur along the river, which are flooded a few
times a year during periods of heavy rainfall. The total flood-
ing area is estimated to be at least 142 ha, but this area was
possibly more extended in the past. The industrial activities of
a phosphate ore processing plant, which is classified as the
most important pollution source, go back to 1892. In 1989 the
disposal of dredged sediments on the riverbanks was forbidden
because the sediments were severely polluted and no more
dredging was carried out. As a result, the alluvial soils were
inundated more frequently with polluted riverwater (at least a
few times a year) and more polluted sediment was deposited
on the riverbanks. The majority of the alluvial soils along the
Grote Beek consist of unused land, situated in a natural
reserve.
In East Belgium and in the southern part of the Nether-
lands, overbank sediments were sampled along the Geul river
(Fig. 1). The Geul river, a tributary of the Meuse, flows
through sandstones (Upper Devonian) and carbonates and
shales (Lower and Middle Carbonian.3 The discharge of the
Geul river depends largely on the amount of rainfall and is
characterized by a flashy regime with a sequence of small
floods in autumn and winter and a few major floods in
summer.18 From the Middle Ages until the beginning of the
20th century, extensive Zn–Pb mining and smelting was
carried out in Plombières and La Calamine (eastern Belgium).
Besides the important amount of waste that is stored in the
large mine tailing piles, overbank sediments along the nearby
Geul river are severely contaminated with Zn, Pb and Cd.3
This journal is
c The Royal Society of Chemistry 2007
Table 1 pH, clay, organic carbon (OC) content, cation exchange capacity (CEC) and total concentrations of Zn, Cd, Cu, Pb, As, Fe, Ca, Al and
Mn in alluvial soils along the Leie, Zenne, Grote Beek and Geul rivers. n = Number of samples

Clay OC CEC/ Zn/ Cd/ Pb/ Cu/ As/ Fe Ca Al Mn/

1 1 1 1 1 1 1
River n pH (%) (%) cmol kg mg kg mg kg mg kg mg kg mg kg (%) (%) (%) mg kg
Zenne 50
Mean 7.6 15 0.7 11 55 0.3 33 17 8 1.9 0.5 3.1 662
Stdv 0.6 7 0.5 5 41 0.1 31 15 4 0.5 0.3 0.7 542
Median 7.8 14 0.6 10 42.5 0.22 24 13 8 1.8 0.5 3.2 492
Min 4.9 7 0.2 1.2 16 1.0 4 4 4 1.2 0.1 1.2 60
Max 8.3 27 2.0 26 204 0.1 134 107 32 3.9 1.1 4.9 2730
Leie 39
Mean 7.5 27 5.1 22 956 6.6 217 84 27 2.8 2.9 3.3 459
Stdv 0.4 8 2.4 8 1174 5.3 200 65 26 1.2 1.3 0.7 427
Median 7.6 27 5.0 22 650 6 134 66 15 2.6 3.3 3.4 399
Min 6.4 10 0.9 11 60 1.0 16 7 4 1.3 0.4 1.5 96
Max 8.1 37 10 37 5086 22 756 266 102 7.0 4.6 4.8 2555
Grote Beek 94
Mean 5.6 13 5.5 15 279 13 58 34 107 7.0 0.8 2.0 201
Stdv 0.8 11 6.7 11 713 32 143 96 203 5.4 0.9 1.4 239
Median 5.4 11 6.4 16 50 1.0 14 6 39 5.4 0.4 1.8 75
Min 3.9 3 0.1 0.6 4 0.2 3 1 2 0.5 0.1 0.3 16
Max 7.4 52 35 47 4840 163 864 751 1051 23.5 3.6 7.2 1413
Geul 64
Mean 6.2 22 1.4 7 3557 7.2 1345 23 23 2.0 0.2 4.0 877
Stdv 0.5 4 0.8 1.4 3278 7.7 1779 19 24 0.6 0.1 0.7 457
Median 6.2 21 1.4 7 3508 6.5 895 19 15 2.0 0.2 3.8 1010
Min 4.8 18 0.4 5 279 0.1 38 8 4 0.7 0.1 2.2 74
Max 7.3 42 2.6 10 13 171 28 6530 85 121 4.7 0.6 5.5 1709

The Geul drains a predominantly rural catchment with a
relatively low population density.
At each location, vertical profiles were dug and samples
were taken at depth every 5–20 cm, depending on visual
differences in colour, organic matter content and/or texture,
yielding 3–5 samples per horizon. To have an idea of the depth
distribution of texture, organic carbon content and total Zn
concentrations, a schematic representation of three profiles
(see Fig. 1 for the locations) along each river is given in Fig. 2.
The depth of the profiles was limited by the water table. Along
the Leie river, samples were taken in dredged sediment-derived
soils. Along the Zenne and the Geul, profiles were sampled
within overbank sediment-derived soils and along the Grote
Beek both overbank sediment- and dredged sediment-derived
soils were sampled.
Physico-chemical soil characterization
All analyses were performed on oven-dried (30 1C) soil
samples. For the physico-chemical analysis, part of the soil
sample was disaggregated in a porcelain mortar and sieved
(o1 mm). The pH(H2O) was measured in a soil–water suspen-
sion (1 : 2.5). Organic carbon was determined according to the
Walkley and Black method.19 Calcium carbonate content was
measured with the rapid titration method:20 the sample was
treated with 0.2 M HCl, followed by a back-titration of the
unreacted HCl with 0.1 M NaOH. Calcium carbonate content
was only determined for the soils along the Leie, because of
their elevated acid neutralizing capacity (ANC). Texture was
determined by laser diffraction analysis (Malvern Mastersizer
S long bed) and the cation exchange capacity (CEC) was
analyzed using the ‘silver thiourea method’.21
Total element concentrations (Al, As, Cd, Cu, Pb, Zn, Fe,
Mn, and Ca) were determined in all the samples. Ni, Ba, Cr,
Co and K were also determined but will not be discussed. One
gram of sample was dissolved in 4 mL HClconc, 2 mL
HNO3 conc and 2 mL HFconc in a Teflon beaker. The mixture
was gently heated on a hot plate until half dry, subsequently
reattacked with the same amount of the three acids and heated
until completely dry. The residue was redissolved with 20 mL
2.5 M HCl and filtered (Whatman 45). Finally, the solution
was diluted to 50 mL with distilled water. Concentrations of
major elements and trace metals were measured by flame
atomic absorption spectrometry (FAAS, Varian AA6) and
inductively coupled plasma mass spectrometry (ICP-MS, HP
4500 Series). A certified reference material (GBW07411 Soil)
and sample duplicates (of separate subsamples) were used for
quality control. Values (in mg kg 1) obtained were: Cd: 25.9
(certified value 28.2  1.3), Zn: 3630 (certified value 3800 
300), Cu: 62.9 (certified value 65.4  4.7), Pb: 3010 (certified
value 2700  100), and As: 193 (certified value 205  11).
Relative standard deviations on triplicate analysis (three se-
parate subsamples) were below 5% for all elements, except Ca
and Al (below 10%).
Single extractions
Single extractions were performed on 89 samples of alluvial
soils from the Leie, Grote Beek and Geul rivers. For the CaCl2
and ammonium-EDTA extraction the protocol of the SMT
(Standards Measurement and Testing) program22 was fol-
lowed. 20 mL of 0.01 M CaCl2 or 0.05 M ammonium-EDTA,
was added to 2 g of air-dried sediment in a centrifuge tube.
The suspension was shaken for 3 h or 1 h, respectively, in a
reciprocal shaker, centrifuged (3500 rpm, 10 min), decanted
and filtered (0.45 mm). After measurement of the pH, the
CaCl2 extracts were acidified with concentrated HNO3 to
bring the pH to o2. The ammonium-EDTA extracts were

This journal is

c The Royal Society of Chemistry 2007 J. Environ. Monit., 2007, 9, 319–328 | 321
Fig. 2 Depth distribution of Zn concentrations in alluvial soils at three locations along the Leie (L), Zenne (Z), Grote Beek (GB) and Geul (G)
rivers (see also Fig. 1). Texture and organic carbon content are represented schematically.
not acidified prior to analysis to prevent precipitation of
EDTA salts at very low pH. A Reference Material (CRM
483) certified for its ammonium-EDTA- and CaCl2-extracta-
ble content of Cd, Zn, Cu, and Pb was also included. Values
(in mg kg 1) obtained for the ammonium-EDTA extraction
were: Cd: 23.6 (certified value 24.3  1.3), Zn: 607 (certified
value 612  19), Cu: 62.9 (certified value 65.4  4.7), Pb: 202
(certified value 229  8). For the CaCl2 extraction, values (in
mg kg 1) obtained were for Cd: 0.44 (indicative value 0.45 
0.05), Zn: 8.9 (indicative value 8.3  0.7), Cu: 1.3 (indicative
value 1.4  0.4) and Pb: 0.03 (indicative value o0.06). The
standard deviation between triplicate extractions (on separate
subsamples) was less than 5%.
pHstat leaching tests
pHstat leaching tests allow determination of the acid neutraliz-
ing capacity (ANC) of soils, together with the associated
release of heavy metals. The ANC gives the amount of acid
(in mmol kg 1) that is necessary to decrease the pH of a soil to
a certain level.
pHstat leaching tests were performed on a selection of
samples taken along the Leie rivers (ten samples), the Grote
Beek (seven samples) and the Geul river (eight samples). For
the samples taken along the Geul river, only a pHstat titration
at pH 4 was performed since the pH of these samples was
322 | J. Environ. Monit., 2007, 9, 319–328
already close to 6 or below 6. The pHstat test is comparable to
the pH dependence leaching test (PrEN 14429), which is being
developed by the Network for the Harmonisation of Leach-
ing/Extraction Tests (SMT-CT96-2066).23 The pHstat experi-
ments were carried out with an automatic multititration
system (Titro-Wico Multititrators). Soil samples were dried
at 30 1C, homogenized and sieved (o2 mm). 80 g of the
o2 mm fraction was put into an Erlenmeyer flask together
with 800 mL of distilled water and placed on a horizontal
shaking device. A pH-electrode (pH Hamilton single pore
electrode) and an automatic titration dispenser were attached
to each flask. The suspensions were first shaken for 30 min
without addition of acid and then the titration was started.
After 96 h, the suspension was filtered (Acrodisc 0.45 mm) and
acidified to bring the pH below 2 (for more details concerning
pHstat leaching tests, see also Van Herreweghe et al.24).
Analysis of extracts and leachates
Concentrations of Al, Ca, Mn, Fe, Cu, Zn, As, Cd and Pb in
the extracts and pHstat leachates were measured by ICP-MS
(HP 4500 series). Standard series were made up starting from
the ‘10 ppm Multi-Element Calibration Standard 2A in 5%
HNO3’ from Hewlett Packard. The spectroscopic interference
of ArCl, which has the same m/z as As (75) was corrected
according to the recommendations of the EPA.25 All glassware
This journal is
c The Royal Society of Chemistry 2007
was thoroughly cleaned with 0.15 M HNO3. Reagent blanks
were determined for each new batch of reagent.

Results
General soil characteristics
Zenne. The Zenne is one of the most severely contaminated
rivers in Belgium.26 However, samples were taken from over-
bank sediment-derived soils along a section of the Zenne that
is almost never flooded. This was reflected in the weakly
contaminated nature of the soils along this part of the Zenne:
heavy metal concentrations are below intervention values for
soil contaminations.27 Slightly increased As concentrations
(up to 32 mg kg 1, Table 1), but still below intervention values
for soil contamination (Table 2), are found at a depth of 200
cm. Increased As concentrations in the Zenne occur as a result
of pollution from industrial and sewage effluents. Andreae and
Andreae 28 found As concentrations up to 30 mg L 1 in water
from the Zenne river. However, the As concentrations in most
of the Scheldt catchment were in the range 0.75–3.8 mg L 1
and were not significantly different from baseline concen-
trations.
Leie. Dredged sediment-derived soils along the Leie river
are characterized by an elevated clay, organic carbon and
CaCO3 content (up to 7.7%; not given in the table) and a
neutral to slightly alkaline pH.
The study area is situated in the Loess Belt, which explains
the rather high CaCO3 content of the sediment samples and
which contributes to the neutral to slightly alkaline pH. The
elevated organic carbon (around 5%) and clay content
(around 30%) of the sediments result in a considerable cation
exchange capacity (up to 38 cmol kg 1). Generally, the sedi-
ments are contaminated with Pb, Zn (Fig. 2), Cr and Cd.
Based on the favorable physico-chemical properties (i.e. high
pH, elevated CaCO3 and organic carbon content) of the soils,
a low mobility of heavy metals is expected. However, com-
plexation by dissolved organic matter may enhance the mobi-
lity of metals, especially Pb and Cu.29
Grote Beek. The alluvial soils of the Grote Beek are con-
taminated with As, Cd, Cu, Zn and Pb and contain elevated
Fe concentrations. The pH ranges from 3.9 to 7.4 (Table 1)
and the clay and organic carbon content are very variable. The
Fig. 3 Mean CaCl2-extractable Zn, Cu, As, Cd and Pb concentra-
tions in alluvial soils of the Leie (n = 33), Grote Beek (n = 26) and
Geul (n = 30) rivers.
elevated Cd and As concentrations are above intervention
values for soil contamination (Table 2) in the majority of the
samples. The degree of contamination of overbank sediment-
derived soils varies from one location to another: the regularly
flooded peat soils and clay-like soils at locations GB1 and GB3
are seriously contaminated (e.g. for Zn in Fig. 2), whereas the
sandy soils at location GB2 are hardly contaminated.
Geul. Overbank sediment-derived soils along the Geul river
are mainly contaminated with Zn, Pb and Cd (Table 1). Total
Zn, Pb and Cd concentrations decrease with increasing dis-
tance from the mine tailings (Fig. 2), which are respectively
located 1 km (G2) and 7 km (G3) downstream from location
G1 (Fig. 1). As and Cu are around background concentrations
in the majority of the samples. The soils have a loamy-sand
texture, a low organic carbon content and a pH between 4.8
and 7.3. As a consequence, the CEC is also low (in the range
5–10 cmol kg 1), suggesting a relatively low retention of heavy
metals. In general, pH decreases in the downstream direction
[i.e. from Plombières (G1) to Epen (G3)], which is related to
the transition from a carbonate (Lower and Middle Carbo-
nian) substrate to a sandy (Upper Devonian) substrate.
Single extractions
A CaCl2 extract was used to simulate porewater composition.
A 0.01 M CaCl2 solution, with a pH of 4.57  0.20 has a low
effect on soil pH. As a consequence, the pH of the extract is
mainly determined by the soil and is very close to the soil pH
(generally within 0.5 units). Average Zn, Cu, As, Cd and Pb
concentrations in the CaCl2 extracts are given in Fig. 3 for the
Leie, Grote Beek and Geul rivers. The concentrations are
expressed in mg L 1 to facilitate the comparison with back-
ground and intervention values for groundwater (Table 2).
For the Zenne, CaCl2 extractions were only performed for a
selection of samples. Extracted Zn concentrations were in the

Table 2 Background values (B.V.) and intervention values (I.V.) for soil contamination for nature areas and agricultural areas, calculated for a
clay content of 10, 20 or 30% and an organic carbon (OC) content of 2 or 5%.27 The last column contains B.V. and I.V. for groundwater (gw)
1
Clay (%) 10 20 30 10 20 30 gw/mg L
OC (%) 2 2 2 5 5 5
Background values (B.V.)/mg kg 1
As 19 24 29 19 24 29 5
Cd 0.8 1.1 1.4 1.0 1.3 1.6 1
Cu 17 20 23 17 20 23 20
Pb 40 43 46 47 50 53 5
Zn 62 73 84 69 80 91 60
Intervention values (I.V.)/mg kg 1
As 45 57 69 45 57 69 20
Cd 2.2 2.9 3.7 2.8 3.6 4.3 5
Cu 200 235 271 200 235 271 100
Pb 216 231 246 275 290 304 20
Zn 632 739 847 748 855 962 500

This journal is
c The Royal Society of Chemistry 2007 J. Environ. Monit., 2007, 9, 319–328 | 323
Table 3 Linear relation between total and ammonium-EDTA-ex-
tractable concentrations of Zn, Cd, Pb and Cu in alluvial sediments
from the Leie, Grote Beek and Geul rivers

Leie (n = 33) Grote Beek (n = 26) Geul (n = 30)

Zn y = 0.34x + 5.8 y = 0.79x 33.5 y = 0.22x + 28.6
R2 = 0.90 R2 = 0.97 R2 = 0.80
Cd y = 0.64x + 0.29 No linear correlation y = 0.77x 0.20
R2 = 0.98 R2 = 0.91
Pb y = 0.48x 31.63 y = 0.27x 0.38 y = 0.62x 93.2
R2 = 0.84 R2 = 0.83 R2 = 0.96
Cu y = 0.50x 2.66 y = 0.44x 1.32 y = 0.66x 5.0
R2 = 0.84 R2 = 0.98 R2 = 0.95

range 3–56 mg L 1, indicating a very low actual Zn mobility in

these soils. For Cd, Pb and Cu, ‘mobile concentrations’ were
often below 1 mg L 1. The results of the Zenne will not be Fig. 4 Release of Zn, Cd, Cu, Pb, Ca and acid neutralizing capacity
included in the discussion. (ANC) of alluvial soils from the different rivers.
In the three other river catchments, Zn generally displays
the highest soluble concentrations (up to 41 817 mg L 1),
leached and less than 1% of the total amount of Pb, Cu
followed by Cd (up to 456 mg L 1) and Pb (up to 429 mg L 1).
and As.
Ammonium-EDTA was used to estimate the ‘mobilisable’
metal concentrations. EDTA is a non-selective reagent that
exhibits a strong capacity to complex metals. The affinity of Discussion
EDTA for heavy metals decreases according to: Cu 4 Ni 4
The possible associations between variables was investigated
Pb 4 Zn c Cd.30 EDTA was shown to dissolve carbonates,
by Varimax-rotated principal component analysis (PCA).
thereby mobilising occluded elements.31 Borggaard32 showed
PCA was first applied to all the data concerning physico-
that EDTA extracts amorphous Fe-oxides, but this dissolution
chemical sample properties (pH, clay content, organic carbon
is very slow in the presence of other metal–chelate com-
content, CEC) and total element concentrations. The variables
plexes.33 It is also able to form organo–metal complexes,
that showed deviation from normality were log-transformed.
which compete with organic matter in soil.
76% of the total variance in the dataset was explained by four
A significant linear correlation was found between total and
principal components: the first component included organic
ammonium-EDTA-extractable Zn, Cd, Pb and Cu concentra-
carbon content and cation exchange capacity; the second
tions in all the alluvial sediments, except for Cd in the
component included Zn and Pb; Fe was associated with the
sediments from the Grote Beek river (Table 3). A much lower
third component; and the fourth component included pH, Cr,
amount of Zn is extracted with ammonium-EDTA from the
Cu, Al and clay content.
sediments originating from the Geul and the Leie (22% of
PCA was carried out separately for the 89 samples for which
total concentration) compared with the Grote Beek river (79%
data were also available concerning EDTA- and CaCl2-ex-
of total concentration, Table 3). This is most likely due to the
tractable metal concentrations. In this second PCA analysis,
fact that, in the alluvial soils of the Geul, Zn partly occurs as
EDTA- and CaCl2-extractable metal concentrations were also
mineral phases such as smithsonite (ZnCO3), hemimorphite
included. The most significant result was obtained for Cd and
[Zn4Si2O7(OH)2
H2O] and sphalerite (ZnS).34 The low extrac-
Zn. Respectively, 98 and 96% of the variability in CaCl2-
tability of Zn in the CaCO3-rich dredged sediments from the
extractable Zn or Cd concentrations could be explained by
Leie can also be related to the saturation of the ammonium-
three components: the first one including EDTA-extractable
EDTA solution with Ca.
Zn or Cd concentrations; the second one including the organic
carbon content, and the third including pH.
pHstat leaching tests Because of the very low CaCl2-extractable metal concentra-
The acid neutralizing capacity (ANC) and release of Zn, Cd, tions in the samples from the Zenne, and because of the
Cu, Pb and As at pH 4 and pH 6 is presented in Fig. 4. The relatively unpolluted nature of the samples from the Zenne,
sediments of the Leie are characterized by an elevated acid the discussion concerning the prediction of ‘mobile metal
neutralizing capacity, whereas the alluvial soils from the Geul concentrations’ and the potential mobilisation of contami-
are only weakly buffered against acidification. At pH 4, a nants will be focussed on alluvial soils along the Leie, Grote
linear correlation can be seen between the release of Ca and Beek and Geul rivers.
the ANC (Fig. 4). In general, at pH 4, Zn and Cd are released
Prediction of ‘mobile’ metal concentrations
in higher amounts than Cu and Pb, and the amount of Cd
released is proportional to Zn. Between 8 and 70% of total Zn The composition of soil porewater is important from an
and Cd concentrations are released at pH 4, while a maximum environmental point of view because it gives an indication of
4% of total Pb concentrations, 13% of total Cu concentra- the ‘actual mobility’ of heavy metals and because the uptake of
tions and 2% of total As concentrations are released at pH 4. trace elements by plants occurs via the porewater. Moreover,
At pH 6, less than 12% of the total amount of Zn and Cd is porewater is also the carrier for elements to the groundwater.

324 | J. Environ. Monit., 2007, 9, 319–328 This journal is

c The Royal Society of Chemistry 2007
Leaching is the process by which inorganic or organic con- centrations, indicating that the available pool of Cd is not
taminants in the porewater are moved to deeper soil layers or proportional to total Cd concentrations.2 In this case, ‘total’
to the groundwater by infiltrating water. The composition of metal concentrations would not have been adequate to predict
the CaCl2 extract is often considered representative for pore- ‘soluble’ metals concentrations with eqn (1). Therefore, am-
water composition.35 Degryse et al.36 found that an extraction monium-EDTA-extractable metal concentrations are a more
with a 0.01 M CaCl2 solution gives a good estimate of the useful parameter than ‘total metal concentrations’. Moreover,
concentration of Cd and Zn in the porewater of field-con- the determination of ‘ammonium-EDTA-extractable metal
taminated soils. concentrations’ is less laborious and time-consuming than
Metal partitioning in soils can be quantified by models in the determination of ‘total metal concentrations’.
which metal concentrations in the porewater are described as a For the carbonate-containing soils of the Leie, the relation-
function of the metal binding solid phases such as Fe- and Al- ship of ‘soluble’ Cd and Zn concentrations with pH and
(hydr)oxides, organic matter and clay and as a function of soil EDTA-extractable Zn and Cd was less significant than for
characteristics that influence heavy metal partitioning, such the soils from the Grote Beek and the Geul. De Groot et al.39
as pH. mentioned that metal partitioning in soils containing carbo-
The ratio between total metal content bound to a soil nate differs significantly from metal partitioning in soils that
relative to its concentration in the soil solution is often do not contain detectable carbonate levels. This may be a
represented by Kd coefficients. However, such a model assumes consequence of precipitation processes, which can result in
that the sorption capacity of a material is independent of the relatively high metal levels in the solid phase which are not
soil properties (organic matter content, pH, clay content, . . .) related to any of the soil constituents.39 Cu concentrations
and therefore, single Kd values are not appropriate to predict could also be described with eqn (1), but the correlation was
metal solubility in soil. Therefore, several authors indicated not very significant (R2 = 0.51).
that metal solubility could be predicted from soil properties. When the soils of the Geul and the Grote Beek are con-
For example, Houba et al.35 observed a significant relationship sidered together, the contribution of the organic matter con-
between the distribution coefficient (Kd) of Cd in soils and the tent [‘d’ in eqn (1)] and the EDTA-extractable Cd content [‘c’
pH of the CaCl2 extract. According to McBride et al.,37 most in eqn (1)] in explaining soluble Cd concentrations increases
of the variability of metal solubility in soil is explained by pH, considerably. Soils of the Geul are characterized by a much
organic matter content and total metal concentrations. higher potentially available pool of Cd (in absolute concentra-
A semi-mechanistic approach was developed by Sauvé tions), but have a lower organic carbon content than the soils
et al.,38 which is based on the assumption that exchangeable from the Grote Beek.
metals and protons compete for adsorption on soil-exchange For Zn, the correlation between ‘soluble’ and EDTA-ex-
sites. In this model, pH, total metal concentrations and soil tractable concentrations, pH and organic carbon of sediments
organic matter are used to predict dissolved metal concentra- from the Geul and Grote Beek is less significant than for Cd
tions. In the present study, a modified version of this compe- (Table 4). For the Geul river, EDTA-extractable Zn concen-
titive adsorption model was applied, since ammonium-EDTA- trations are much more important in explaining Zn solubility
extractable metal concentrations were used instead of total than for the Grote Beek. Zn-containing mineral phases most
metal concentrations. EDTA extractions are often used to likely contribute to the solubility of Zn in the soils from the
estimate the potentially ‘available pool’ of metals (i.e. the pool Geul.
that can deliver metals from the solid phase of the soil to the
soil solution in a relatively short time period).
Acid neutralizing capacity (ANC) and potential mobilisation of
PCA analysis showed that, for Cd and Zn, 96–98% of the
contaminants
variability in the CaCl2-extractable Zn or Cd concentrations
could be explained by EDTA-extractable Zn and Cd concen- The ANC can be used to estimate the probability that the pH
trations, organic carbon content and pH. The datasets were of a soil will drop to a certain level.40 The ratio between the
subjected to multiple linear regression, using the following
fitting equation: Table 4 Fitting parameters from eqn (1) for alluvial soilsa from the
Leie, Grote Beek and Geul catchments. n = number of samples
log[M]s = a + b pH + c log[M]a + d logOC (1) a b c d R2 n
Cd
with [M]s = the metal concentration in the CaCl2 extract Leie (L) 0.59NS 0.22* 0.79*** 0.006NS 0.77 36
(mg L 1), [M]a = the ‘available pool’ of the metal (mg kg 1), Grote Beek (GB) 2.45** 0.15NS 1.17*** 0.36*** 0.94 26
OC = the organic carbon content (%). Geul (G) 1.13** 0.53*** 1.18*** 0.93*** 0.95 33
Because of the linear correlation between total and ammo- G + GB 2.32*** 0.39*** 1.83*** 1.43*** 0.92 59
nium-EDTA-extractable Zn and Cd concentrations in the Zn
alluvial sediments from the Leie and Geul catchments, the Leie (L) 0.93NS 0.70* 1.01*** 0.62NS 0.51 36
use of total metal concentrations in eqn (1), instead of Grote Beek (GB) 0.86NS 0.67*** 0.94*** 0.03NS 0.83 26
Geul (G) 2.83*** 0.95*** 1.70*** 1.07*** 0.87 33
ammonium-EDTA-extractable metal concentrations, will re-
G + GB 0.68* 0.42*** 0.50*** 0.91*** 0.74 59
sult in an equally good fit for the predictive model. However, a
Level of significance: * for p o 0.1; ** for p o 0.01; *** for
for the Grote Beek river there was no linear correlation
p o 0.001; NS = not significant.
between total and ammonium-EDTA-extractable metal con-

This journal is

c The Royal Society of Chemistry 2007 J. Environ. Monit., 2007, 9, 319–328 | 325
amount of an element released during pHstat titration and the
ANC gives a ‘normalised’ idea of the extent of metal release
upon input of acidifying substances. For the Geul river, the
ratio Zn/ANCpH4 is between 0.1 and 0.3, indicating that up to
60% of the protons introduced during the titration are re-
placed by Zn, which is released into the pHstat suspension. For
the Grote Beek and Leie rivers this ratio is much lower
(o0.01). First of all, these soils are characterized by an
elevated CEC (Table 1). Additionally, much more Ca was
released from these soils. The ANC is proportional to the
amount of Ca released (Fig. 4), indicating that the exchange
reactions with Ca and dissolution of CaCO3 are important
acid neutralizing reactions. Especially in the CaCO3-rich soils
from the Leie, a considerable amount of protons is consumed
by the dissolution of CaCO3, which buffers the added acidity.
In the Fe-rich soils from the Grote Beek, the (partial) dissolu-
tion of Fe-(hydr)oxides provides a certain acid neutralizing
capacity.
Classification of alluvial soils according to environmental risk
According to the Flemish Environmental legislation,26 con-
taminated soils are classified according to their total heavy
metal concentrations, taking into account clay and organic
carbon content and land-use. Therefore, two types of guideline
values were defined, namely background values and interven-
tion values. Table 2 presents the background and intervention
values for agricultural soils and nature areas for a range of
organic matter concentrations and clay contents. The heavy
metal content of alluvial soils along the Zenne (locations Z1,
Z2 and Z3) are below intervention values for soil contamina-
tion and no further action (restriction of land-use, soil reme-
diation) has to be undertaken. At the other locations,
intervention values are exceeded for one or more heavy metals
and further investigation is required. Given the considerable
amount of contaminated soils in Flanders (since 1996, the
Flemish Waste Agency has made an inventory of more than
20 000 contaminated spots), additional criteria would be help-
ful to set up a list of soils with high risk for the environment
and thus with higher priority for investigation.
Besides ‘total’ metal concentrations, other factors can be
taken into account to classify alluvial soils and sediments
according to the environmental risk, such as soil type, pH,
permeability (as inferred by grain size), and ANC. Gäbler and
Schneider40 presented an alternative classification system for
contaminated soils, based on soil type, sequence of horizons,
the permeability of the saturated soil to water and the results
of pHstat leaching tests. This classification system was further
developed for the soils investigated in the present study, taking
into account the actual and potential mobility of heavy metals.
‘Mobile’ contaminant concentrations can be determined by
the porewater composition, an extract with a diluted salt
solution (e.g. CaCl2 0.01 M) or derived from soil properties
such as pH, CEC, organic matter content, clay content and
‘mobilisable’ metal concentrations (determined with ammo-
nium-EDTA). In this study, we compared the ‘mobile’ metal
concentrations with intervention values for groundwater.26
(Table 2) (Fig. 5). However, more specific threshold values
could be determined, which can, for example, depend on the
326 | J. Environ. Monit., 2007, 9, 319–328
Fig. 5 Classification of alluvials soils according to their risk to the
environment. I.V. = intervention values for soil contamination. See
text for more details.
type of vegetation (some plant species are more tolerant to
heavy metals than other species). The estimation of potential
mobility upon acidification was based on the results of pHstat
leaching tests.
Other relevant factors that are to be considered are land-
use, the probability of flooding, the depth of the groundwater
table and seasonal fluctuations of the groundwater table,
especially when contaminated soil is situated close to or below
the groundwater table. The consideration of geomorphologi-
cal and/or sedimentological controls on metal dispersion
would allow a more detailed assessment of dispersal patterns
of heavy metals in different river catchments, but this was not
within the scope of the present study.
Class 1: locations without hazard to the environment. Total
heavy metal concentrations are below intervention values for
soil contamination (I.V.).
Although ‘total’ metal concentrations cannot be directly
related to the environmental risk, ‘intervention values’ allow
us to make a selection of soils with a higher probability to be
harmful for the environment.
Whereas the Zenne river is polluted by industrial activities
and urban effluents, the section analysed in this study is not
contaminated. Total metal concentrations in alluvial soils are
far below intervention values for soil contamination and the
sediments have a slightly alkaline pH (Table 2). As a conse-
quence, mobile metal fractions are low. The alluvial soils
studied along the section of the Zenne are currently used for
agriculture and are no longer periodically flooded. Addition-
ally, the groundwater table is at a depth of approximately 2 m
and no migration of heavy metals is expected.
Class 2: locations with a relatively low risk for the environ-
ment on the long term. Total metal concentrations are above
I.V. for one or more heavy metals, but ‘actual’ and ‘potential’
heavy metal mobility are low. CaCl2-extractable heavy metal
concentrations are low (below treshold values for groundwater
contamination) and the ratio of heavy metal release/ANC is
below 0.01.
This journal is
c The Royal Society of Chemistry 2007
 Although sampling location GB2 (Fig. 1 and 2) is situated
along a river that carries severely polluted sediments, alluvial
soils are only slightly contaminated and intervention values for
soil contamination are only exceeded for Cd in the upper
20 cm of the soils nearby the river.
Total metal concentrations in the dredged sediment-derived
soils along the Leie are above intervention values for soil
contamination for one or more metals. However, the soils
have a high pH, a high CEC and an elevated ANC (ANCpH6
between 150 and 1111 mmol kg 1, ANCpH 4 between 432 and
2521 mmol kg 1), so the ‘mobile fractions’ of metals are low.
In general, the groundwater table fluctuates between 1 and 2 m
depth. Because of the elevated clay content of the soils,
migration of metals to the underlying soil is of little concern.
Class 3: locations with an apparent limited actual risk of
heavy metal contamination, but under changing environmental
conditions (pH, redox conditions, salinity), mobilisation of heavy
metals might occur. Alluvial soils along the Grote Beek (GB1
and GB3) are severely contaminated with Zn, Cd and As.
However, the mobility of Cd and Zn is rather limited under
‘normal’ present-day environmental conditions because the
soils are characterized by a near-neutral pH and an elevated
Fe content, which is related to the occurrence of glauconite in
the subsoil. ANC is rather variable at different locations, but
the release of metals upon acidification is comparable to the
release from the highly buffered soils from the Leie (Fig. 4). If
soil properties are influenced by the geological substrate, this
can be helpful to derive information on soil properties on
other locations underlain by the same substrate.
The majority of the alluvial soils along the Grote Beek
consist of unused land situated in a natural reserve. Uptake of
heavy metals by human beings is of little concern.
Nevertheless, some precautions should be taken to limit the
future dispersion of heavy metals. For example, the impor-
tance of chloride salts towards the mobility of Cd in overbank
sediments was demonstrated with batch tests.2 An obvious
recommendation would be to stop the emission of chloride
salts into the river and to remove the contaminated riverbed
sediments, since they still represent a pollution source for the
alluvial plain. At some locations, the groundwater occurs at
shallow depth.
Class 4: alluvial soils with a considerable risk for the environ-
ment. Total concentrations of Zn, Pb and Cd in the alluvial
soils of the Geul are extremely high. Because alluvial soils
along the Geul are used for pasture, there is a risk of ingestion
of contaminants by cattle. Therefore, farmers are advised to
keep the cattle inside after a flooding event until sediment
particles are removed from the vegetation by rainfall. Since
playgrounds are located in the floodplain, ingestion of soil by
playing children must also be considered as a possible pathway
for the uptake of contaminants.
Moreover, the ‘mobile fraction’ of Cd and Zn is very high,
since Zn concentrations up to 42 mg L 1 and Cd concentra-
tions up to 456 mg L 1 are encountered in the CaCl2 extracts.
Elevated Zn and Cd concentrations in the CaCl2 extracts
indicate a considerable availability of these metals for leaching
and uptake by living organisms. This is also reflected in
This journal is
c The Royal Society of Chemistry 2007
elevated Zn and Cd concentrations in plants growing on the
alluvial plain. For example, in the above ground parts of
stinging nettle (Urtica dioica L.), Zn and Cd concentrations of
around 2000 mg kg 1 and 1 mg kg 1, respectively, were
encountered.41 The alluvial soils along the Geul river also
represent a considerable risk for the environment in the long
term because of the very high load of Cd, Zn and Pb, the
limited retention capacity for heavy metals and the low ANC.
Despite the occurrence of carbonates in the substrate in
Plombières, alluvial sediments display a very low acid neutra-
lizing capacity. The ANCpH4 values in the top layers (0–30 cm)
are in the range 104–261 mmol kg 1, which is low compared to
the ANC values in other regions. Although the soil pH is
currently neutral to slightly alkaline, acidification can result in
a substantial release of Zn and Cd. In Plombiéres, very high
metal concentrations (Fig. 2 for Zn) occur up to a depth of
240 cm. The risk for groundwater contamination has to be taken
into account since the groundwater table fluctuates around the
2 m depth. Klok42 analysed groundwater samples from aqui-
fers located in the catchment of the Geul. The groundwater
samples contained between 13 and 138 mg L 1 Zn, which is
much lower than the Zn concentrations found in the CaCl2
extracts of the soils (37–42 817 mg L 1). This may indicate that
the translocation of Zn into the groundwater is rather limited.
Moreover, Zn in the groundwater can also originate from
Pb–Zn mineralisations.
Conclusions
Legal limits on soil contamination with heavy metals often
mainly based on total concentrations. However, towards the
management of contaminated sediments, it is more important
to know the risk associated with a contamination and the
factors that influence the release of contaminants from these
soils.
In this paper, a risk assessment for contaminated soils,
based on physico-chemical soil properties and on the results
of extractions and leaching tests is presented. CaCl2 and
EDTA extractions and pHstat leaching tests, which have been
tested by European research programs, can provide valuable
information that can be used in the framework of a risk
assessment. The approach is illustrated by means of a case
study from four Belgian catchments. Therefore, the data of the
physico-chemical soil characterization, extractions and leach-
ing tests were combined with local and regional factors to
classify the alluvial soils in different categories according to
their actual and potential risk for the environment.
Acknowledgements
Grateful acknowledgements are made to Danny Coutermans
and Martijn Goffings for their skilful assistance with the
experiments and to Professor Dr N. Vandenberghe for the
use of the Malvern Mastersizer. This research was financed by
the Flemish Institute for the promotion of Scientific-Techno-
logical research in the Industry (IWT) and the Research
Foundation of the K. U. Leuven.
J. Environ. Monit., 2007, 9, 319–328 | 327
 References
1 H. W. Mielke, C. R. Gonzales, M. K. Smith and P. W. Mielke, Sci.
Total Environ., 2000, 246, 249.
2 V. Cappuyns and R. Swennen, J. Environ. Monit., 2004, 6(5), 343.
3 R. Swennen, I. Van Keer and W. De Vos, Environ. Geol., 1994, 24,
12.
4 R. Swennen, J. Van der Sluys and R. Hindel, Zbl. Geol. Paläont.,
1996, 1, 925.
5 R. Swennen, J. Van der Sluys, R. Hindel and A. Brusselmans, J.
Geochem. Explor., 1998, 62, 67.
6 R. Swennen and J. Van der Sluys, J. Geochem. Explor., 2002,
75(1–3), 93.
7 R. G. Darmody and J. C. Marlin, Environ. Monit. Assess., 2002,
77(2), 209.
8 B. Vandecasteele, B. De Vos and F. M. G. Tack, J. Environ.
Monit., 2002, 4, 306.
9 B. Vandecasteele, B. De Vos and F. M. G. Tack, Sci. Total
Environ., 2002, 290(1–3), 1.
10 B. Vandecasteele, B. De Vos and F. M. G. Tack, Environ. Pollut.,
2003, 122, 7.
11 R. H. Kesel, K. C. Dunne, R. C. McDonald, K. R. Allison and B.
E. Spicer, Geology, 1973, 2(9), 461.
12 W. A. Marcus, G. A. Meyer and N. R. DelWayne, Geology, 2001,
29(4), 355.
13 W. M. Stigliani, P. Doelman, W. Salomons, R. Schulin, G. R. B.
Smidt and S. E. A. T. M. Van der Zee, Environment, 1991, 33(4),
5–9; 26–30.
14 W. R. Kelly, H. A. Wehrmann, T. R. Holm, J. L. Talbott and L.
M. Skowron, Environ. Geol., 2003, 45, 23.
15 W. Peijnenburg, A. de Groot, T. Jager and L. Posthuma, Eco-
toxicol. Environ. Saf., 2005, 60, 1.
16 P. W. Abrahams and J. Steigmacher, Environ. Geochem. Health,
2003, 25, 17.
17 N. Dufourny and L. De Rote, Senne: Projet des travaux d’améli-
oration a exécuter a la deuxième section de cette rivière. Ministère
de l’Agriculture et des Travaux publics, 13 février 1896.
18 H. Lenaers, Hydrol. Processes, 1989, 3, 325.
19 D. W. Nelson and L. E. Sommers, in Methods of soil analysis, part
2: Chemical and biological properties, ed. C. A. Black, Agronomy
Monograph 9, American Society of Agronomy, Madison, Wiscon-
sin, 2nd edn, 1982, pp. 516–593.
20 L. E. Allison and C. D. Moodie, in Methods of soil analysis. Part 2:
Chemical and microbiological properties, ed. C. A. Black, Agron-
omy Monograph 9, American Society of Agronomy, Madison,
Wisconsin, 2nd edn, 1965, pp. 1379–1396.
21 R. Chhabra, J. Pleysier and A. Cremers, in Proceedings of the
International Clay Conference, ed. S. W. Bailey, Applied Publishing
Ltd, Wilmette, IL, 1975, pp. 439–449.
328 | J. Environ. Monit., 2007, 9, 319–328
View publication stats
22 Ph. Quevauviller, Trends Anal. Chem., 1998, 17(5), 289.
23 CEN (Comité Européen de Standardisation), pHstat test, draft 7,
‘Basic characterization test for Leaching Behavior, ’ doc no. CEN/
TC292/WG6 N213, August 2000. .
24 S. Van Herreweghe, R. Swennen, V. Cappuyns and C. Vandecas-
teele, J. Geochem. Explor., 2002, 76, 113.
25 C. A. Brockhoff, J. T. Creed, T. D. Martin, E. R. Martin and S. E.
Long, EPA Method 200.8, Revision 5.5, ‘Determination of trace
metals in waters and wastes by inductively coupled plasma-mass
spectrometry, ’ EPA-821R-99-017, October 1999, p. 61.
26 OVAM, Vlaams reglement betreffende de bodemsanering-VLAR-
EBO, ‘Openbare afvalstoffen-maatschappij voor het Vlaamse
Gewest., ’ Publicatienummer D/1995/5024/5, 1995, p. 63.
27 Vlaamse Milieumaatschappij, ‘Waterbodemkwaliteit 2002, ’ VMM,
Aalst, 2003.
28 M. O. Andreae and T. W. Andreae, Estuarine, Coastal Shelf Sci.,
1989, 29(5), 421.
29 L. Weng, E. J. Temminghoff, S. Lofts, E. Tipping and W. H. Van
Riemsdijk, Environ. Sci. Technol., 2002, 36(22), 4804.
30 W. A. Norvell, in Microelements in Agriculture, ed. J. J. Mortvedt,
F. R. Cox, L. M. Shuman and R. M. Welch, Soil Science Society of
America, Madison, Wiscosin, 2nd edn, 1991, pp. 187–227.
31 W. P. Miller, D. C. Martens, L. W. Zelazny and E. T. Kornegay, J.
Environ. Qual., 1986, 15, 69.
32 O. K. Borggaard, J. Soil Sci., 1979, 30, 727.
33 B. Nowack and L. Sigg, Geochim. Cosmochim. Acta, 1997, 61,
951.
34 Y. Gao, unpublished Master thesis, Katholieke Universiteit
Leuven, 1995.
35 V. J. G. Houba, Th. M. Lexmond, I. Novozamsky and J. J. van der
Lee, Sci. Total Environ., 1996, 2, 21.
36 F. Degryse, K. Broos, E. Smolders and R. Merckx, Eur. J. Soil
Sci., 2003, 54(1), 149.
37 M. McBride, S. Sauvé and W. Hendershot, Eur. J. Soil Sci., 1997,
48, 337.
38 S. Sauvé, W. Hendershot and H. E. Allen, Environ. Sci. Technol.,
2000, 34(7), 1125.
39 A. C. De Groot, W. J. G. M. Peijenburg, M. A. G. T. van den
Hoop, R. Ritsema and R. P. M. van Veen, Report no. 607220001,
National Institute of Public Health and the Envirionment,
The Netherlands, 1998.
40 H.-E. Gäbler and J. Schneider, Environ. Geol., 2000, 39(7), 774.
41 V. Cappuyns, A. Van Damme, M. Niclaes, R. Swennen and
O. Vanpeetegem, in Proceedings of the 1st International Symposium
on Wetland Pollutant Dynamics and Control, ed. F. Tack and
N. De Pauw, Ghent University Press, Ghent, Belgium, 2005, pp.
26–27.
42 M. Klok, unpublished Master thesis, Katholieke Universiteit
Leuven, 1983.
This journal is
c The Royal Society of Chemistry 2007