Symposium no.

24

Paper no. 1499

Presentation: oral

Heavy metals in extracted soil soulutions

DI BONITO M. (1), BREWARD N. (1), SMITH B.M. (1), CROUT N.M.J. (2) and
YOUNG S.D. (2)
(1) British Geological Survey, Kingsley Dunham Centre, Keyworth, Nottingham,
NG12 5GG, UK
(2) School of Life and Environmental Science, University of Nottingham, NG7 2RD,
UK
Abstract
Soil pore water was extracted from a soil treated with sewage sludge using three
different techniques: rhizon samplers, centrifugation and pressure filtering, the latter
two with incremental increases in the applied force. This enabled us to perform
fractionated extraction on the soil, providing soil water originating in different ranges of
pores. Samples collected were analysed for: pH (Automated Titration), TOC, major and
trace cations and anions (ICP-AES, ICP-MS and IC). Results for two trace elements (Cd
and Cu) show that pressure filtering and centrifugation can be used to extract soil pore
water, allowing extraction to be targeted for detailed studies of pore water
contamination. Even though at present data are incomplete, there is evidence that the
chemical composition of the pore water are not homogeneous. Therefore, further study
is required to fully understand these fractionation effects, how the chemical composition
of the extracted pore water relates to in situ conditions and to what extent the different
types of solution are important to environmental and geochemical processes.
Introduction
Heavy metals are of interest due to their abundance in the environment, which has
increased considerably as a result of human activities. Their fate in polluted soils is
subject of study because of direct potential toxicity to biota and indirect threat to human
health from contamination of groundwater and accumulation in food crops (Martinez
and Motto, 2000).
Soil pore water is critical to environmental bioavailability, mobility and
geochemical cycling of chemicals in soil. Its compositional analysis is frequently more
instructive than those of the whole soils or soil extracts (Wolt, 1994). There is a
consensus in the literature that total soil metal content alone is not a good measure of
short-term bioavailability and not a useful tool to determine potential risks from soil
contamination (Tack et al., 1995; Sauv et al., 2000). However, a stable ionic/elemental
equilibrium is not likely to be attained in the entire soil solution of any type of soil
(Tyler, 2000). Pore water contained in micropores, isolated aggregates, within clay
lattices, etc. are only to a limited extent in contact with the solution of the macropores.
Therefore, equating displaced soil pore water composition with in situ pore water
composition is difficult, both from a conceptual point of view (for example, the effect of
an electric double layer may cause differential distribution of anions and cations through
the soil aqueous phase) and from a practical point of view (for example, techniques for
obtaining soil solution commonly recover < 50% of soil water for soils at field moisture
content).

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Of currently available laboratory techniques, direct centrifugation drainage is often

preferred as a simple way of obtaining soil pore water (Edmunds and Bath, 1976;
Zabowsky and Ugolini, 1990); more recently the rhizon soil moisture sampling
technique has gained popularity (Argo and Biernbaum, 1997; Luo et al., 2001). Here we
present a preliminar evaluation of these two pore water extraction techniques and
compare them with the pressure filtering method, used here for the first time on soils.
This technique, in common with high-speed centrifugation, facilitates pore water
fractionation by the application of different applied pressures, although the force exerted
on centrifugation is not sufficient to remove solution associated with charged surfaces
(Jones and Edwards, 1993).
Materials and Methods
Soil Sampling and treatment
Soil was sampled from a sewage re-processing facility (sewage farm), run by a
large water company in Nottinghamshire, UK. The farm is approximately 700 ha, with
about 60 fields and has received sludge for over 100 years. The farm grows mainly
maize and wheat for animal fodder as a dedicated site under the terms of the 1989
Sludge (Use in agriculture) regulations (MAFF, 1998). The area is within the floodplain
of the River Trent, hence the solid geology is obscured by several meters of glacial and
recent sediments. The glacial and older post-glacial deposits within the old river valley
comprise mostly sands and gravels derived from Carboniferous and Triassic rock
material. Overlying the glacial and older-Holocene deposits is a substantial thickness of
river alluvium, mostly consisting of red and brown fine sand, silt and mud derived from
higher in the catchment. These alluvial sediments also contain organic matter and
anthropogenic material derived from the urban and industrial areas within the
catchment.
Following sampling, field-moist soil samples were passed through a polypropylene
sieve (mesh 2 mm), thoroughly mixed and separated into two different portions of 2.5
kg (dry weight basis, DWB) each; these were kept respectively at 5C and 15C.
Moisture content was monitored on a regular basis and maintained by addition of deionized water.
Soil pore water extraction
Samples of soil pore water were extracted from the incubated soil using three
different techniques: 1) rhizon samplers (Soil Moisture Samplers - SMS); 2) drainage
centrifugation; 3) pressure filtering (squeezing).
Rhizon samplers
Rhizon soil moisture samplers (SMS), obtained from Rhizosphere Research
Products (Wageningen, Holland), were used. These consist of a length of porous,
chemically-inert hydrophilic plastic (2.5 mm o.d., 1.4 mm i.d, average pore diameter ca.
0.1 m), capped with nylon at one end, and attached to a 5 cm length of polyethylene
tubing at the other end. For the soil pore water sampling, the procedure described by
Knight et al. (1998) was followed.
Four samplers were insert into the bulk of each of the 2.5 kg (DWB) soils
container. The soil was maintained at field moisture (ca. 53% moisture content, DWB).

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Soil pore water was extracted by connecting a syringe to each sampler and applying a
suction.
Centrifugation
The centrifuge drainage technique as described by Kinniburgh and Miles (1983)
was employed using a Beckman J2-21 high-speed refrigerated centrifuge, with the
modification of fractionating the soil pore water by incremental increases in the
centrifugation speed (Tyler, 2000). This method allows the quick and easy removal of
soil water at precise intervals in time at matric suctions > 100 kPa (Jones and Edwards,
1993). Specially designed Polyoxymethylene (Acetal) tubes provided with 316 stainless
steel, 20 m mesh filters were manufactured in-house to adapt the fixed-angle rotor
available with the centrifuge.
Mineral soil was placed into the top half of the 6 tubes and tamped down. Samples
were centrifuged, for 1 hour at 5C in 5 steps, at Relative Centrifugal Field (RCF g)
values for each pore water fraction of: 110, 439, 1345, 2744 and 5075, respectively. The
driving pressure at the midpoint during centrifugation was calculated using the equation
formulated in Kinniburgh and Miles (1983). As a result of this we had 5 correspondent
pressures: 18, 70, 214, 438 and 809 kPa.
The five water fractions extracted were collected separately, weighed and then
syringe ultrafiltered through a 0.45 m Nylon Acrodisc Syringe Filter (Pall-Gelman HPLC certified) and separated in two aliquots. The fractions of three tubes were
combined to have enough water for the analysis and the whole run repeated twice to
have adequate number of replicates (4) for each sample. pH was determined
electrometrically on an aliquot, whereas the remaining solution was acidified to 1%
HNO3 v/v into 15 mL Nalgene bottles for elemental analysis by ICP-AES or ICP-MS.
When the test was completed, the soil contained in the tubes was weighed and oven
dried at 105C for determination of moisture content.
Squeezing
The pressure filtering technique (or soil squeezing) was undertaken at the British
Geological Survey (Keyworth, Nottingham, UK). This method has been proved to be
effective with various materials, including peat, clay, till sand, silt, chalk, sea sediments
(Entwisle and Reeder, 1983) but had never previously been used on soils. The stress
applied can be controlled and increased as the test requires. The methodology enabled
us to perform fractionated extraction on the soil, providing soil water possibly
originating in different ranges of pores.
The squeezing apparatus in use at BGS utilises a hydraulic pump (Wykeham
Farrance Engineering Ltd., Slough), which has a maximum output stress of 70,000 kPa.
The main body of the cell and other metal parts in contact with the sample or pore water
are manufactured from Type 316 stainless steel.
For soft and disaggregated material the procedure suggested (Entwisle and Reeder,
1983) to pour or place the material into the cell, which has been previously washed and
dried. A separate sub-sample was also taken for moisture content determination.
Temperature of the cell is thermostatically controlled, in order to match the incubation
temperature of the soil.

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A small nominal stress (<1,000 kPa) was then applied to remove most of the air
from the cell and to allow the sample and the components to bed in. When the selected
temperature was attained, the pressure was increased and water collected.
Pore fluid was collected directly into disposable polypropylene syringes. Two
syringe taps were pushed onto the pore water pipe allowing flexibility of pore water
collection. In general the test may produce either a single bulk sample or a number of
fractionated water samples. For the soil tested it was decided to run fractionated
extractions, which allowed us to analyse the samples separately to study the change in
composition with progressive pore water extraction. When the soil sample stopped
releasing pore water at a certain pressure (< 1 mL collected in 18-24 h), the syringe was
removed and the sample filtered as soon as collected through a 0.45 m Nylon Acrodisc
Syringe Filter. The samples were poured into 30 mL Nalgene bottles from which a subsample of each syringe was acidified to 1% v/v (Aristar HNO3) for ICP analysis.
Further fractions of sample were collected, using a new syringe assembly, until no
further pore water could be obtained (Cave et al., 1998). The pressures applied to the
soil samples were: 200, 500, 1000, 1500, 3000, 9000 and ca. 50,000 kPa.
When the test was completed, the test soil was weighed and oven dried at 105C for
density and determination of moisture content.
Chemical analysis
pH was determined on all samples as soon as possible after collection using a
Standard pH meter provided with a 4 mm leadless micro electrode. Major cations (Ca,
K, Mg, Na,), trace cations (B, Ba, Be, Cu, Fe, Mn, Ni, Si, Sr, Zn) and total P and S were
determined by ICP-AES. Trace elements (Al, As, Li, Cd, Co, Cr, Cs, Cu, Mo, Ni, Pb,
Sb, Sn, U, V and Zn) were also determined using ICP-MS. Analysis were carried out on
5 mL of sample acidified to 1% v/v with respect to Aristar HNO3. Major anions (Cl,
NO3, SO4) were determined by ion chromatography. A Shimadzu TOC-5000 total
organic analyser fitted with ASI-5000 autosampler was used to determine (5 mL of unacidified sample) Total Organic and Inorganic Carbon.
Results and Discussions
Pore water collection
Soil pore water was collected using three different techniques and, where possible,
applying a variable force of extraction. According to Cabrera (1998), 10 mL plastic
syringes applied to soil moisture rhizon samplers are likely to generate an average
suction of -48.1 0.5 kPa. Nevertheless, the volume of pore water extracted depends
upon soil conditions and characteristics, unsaturated hydraulic conductivity and
moisture content. Soil moisture samplers will only function when the soil is not too dry.
When the matric potential is greater than 50 kPa, the potential gradient and the
hydraulic conductivity are too low to obtain a sample.
Centrifugation achieved an efficiency of 28% (measured on a single tube), and very
little pore water was collected at the lower speeds used (1,000 and 2,000 rpm = 18 and
70 kPa). This is due to the moisture content of the soil used, below field capacity, and
the low pressure differential between these steps. A significant amount of water (40%)
remained in the samples at the end of the 5-step centrifugation (Figure 1). The
extraction efficiency was calculated as

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% extraction efficiency (% E ) =

M p 100
M0 Md

where: Mp is the weight of pore water extracted (g), M0 the weight of pre-squeezed
sample (g) and Md the weight of oven-dried sample (g).

Gravimetric Water content (g)

90
80
70
60
50
40
30
0

200

400

600

800

1000

Pressure (kPa)

Figure 1 Water remaining in each soil sample during centrifugation at 15C.

Centrifugation was performed in 5 steps: 18, 70, 214, 438 and 809 kPa
(converted to pressures from rpm: 1000, 2000, 3500, 5000 and 6800). Initial
water content: 84.7 g (56% moisture content, DWB). Water extracted: 62.4
% of total content. Moisture content at the end of the run: ca. 40 % (DWB).
The squeezing technique showed an extraction efficiency of 68%. This is due to the
higher maximum pressure that can be exerted during the test, allowing extraction of
pore water that cannot be accessed using centrifugation. Although further evidence is
required, squeezing may access not just free and capillary water, but also hygroscopic
water, defined to be at potentials higher than 3,100 kPa.
Nevertheless the time needed for the extraction and the poor control over the low
pressure range are negative aspects of this technique. Squeezing requires more time than
the other two techniques to extract water at a given pressure. Unfortunately, this might
produce pore water that has been subject to different chemical conditions and kinetic
processes. For example, the development of anaerobism may affect metal solubility and
speciation. We controlled the temperature at 5C for one set of tests, in order to
diminish microbial reduction processes. However, these tests are at present still in
progress and results will be available later. By comparison, centrifugation and rhizon
samplers can produce multiple water samples in a few hours. We compared soil
incubated at 5C and 15C.
Solute concentration
Solute concentrations in soil water may depend on a number of factors, including:
the method of extraction, imposed tension, flow rate to the sampler, relation of the soil
volume sampled versus the scale of heterogeneity in solute concentration, complexation
and sorption reactions that may take place and time.

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Figures 2 and 3 show the variation in concentrations of Cd and Cu in extracted soil

pore water with increasing centrifugal force. The general trends showed a slight
decrease in concentrations during centrifugation. Cadmium concentrations apparently
decreased with temperature. Pore water collected by rhizon samplers had a similar range
of concentrations to the centrifugation samples but there were some significant
differences. It has been suggested that successive increments of extracted pore water
may be sampled from regions close to soil particle surfaces, which may differ in
chemical composition. Thus, the uniformity of composition of these extracted solution
increments cannot be used as a means to verify that the true soil solution has been
sampled (Sposito, 1989).
300

Rhizon 5C

Concentration (g/L)

Cu 5C

250

Cu 15C
Rhizon 15C

200

189

150

141

100
0

100

200

300

400

500

600

700

800

900

Load (kPa)

Figure 2 Concentrations of Cu in pore water using centrifugation and rhizon samplers.

Centrifugation was performed at two temperatures (5C and 15C) in 5 steps:
18, 70, 214, 438 and 809 kPa; y-bars indicate the range of values.
Rhizon 5C

Concentration (g/L)

17

16.6

Cd 5C
Cd 15C

15

Rhizon 15C

13
11
9.5

9
7
0

100

200

300

400

500

600

700

800

900

Load (kPa)

Figure 3 Concentrations of Cd in pore water using centrifugation and rhizon samplers.

Centrifugation was performed at two temperatures (5C and 15C) in 5 steps:
18, 70, 214, 438 and 809 kPa; y-bars indicate the range of values.
Figures 4 and 5 show Cd and Cu concentrations of the samples collected with the
two incremental methods (centrifugation and squeezing): Cd shows a general decrease
of concentrations whereas Cu presents a different pattern. Both results seem to agree
qualitatively with a general decrease in ionic strength found in previous studies (Cave et
al., 1998), although these effects can be highly variable depending on the type of soil;
moreover, there are few prior reports on trace metals to provide comparisons. Reeder et

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al. (1998) reported that the solute concentration of the extracted pore water, with
successive increments of extraction pressure, tends to decrease, although for some
elements (e.g., monovalent cations) an increase in concentration was observed. Some of
the factors that could contribute include mineral dissolution and re-equilibration, cation
exchange and ion exclusion or filtration.

Cd Concentration (g/L)

13
11
9
7
Centrifugation

Squeezing

3
1
10

100

1000

10000

100000

log pressure (kPa)

Figure 4 Concentrations of Cd in pore water using centrifugation and squeezing at 15

C; y-bars indicate the range of values. Centrifugation was performed in 5
steps: 18, 70, 214, 438 and 809 kPa, squeezing was performed in 7 steps:
200, 500, 1,000, 1,500, 3,000, 9,000 and ca. 50,000 kPa.
270

Cu Concentration (g/L)

220
170
120
Centrifugation

Squeezing

70
20
10

100

1000

10000

100000

log pressure (kPa)

Figure 5 Concentrations of Cu in pore water using centrifugation and squeezing at 15

C; y-bars indicate the range of values. Centrifugation was performed in 5
steps: 18, 70, 214, 438 and 809 kPa, squeezing was performed in 7 steps:
200, 500, 1,000, 1,500, 3,000, 9,000 and ca. 50,000 kPa.
Other authors (Essert and Hopmans, 1998) have noted that pore water concentration
is greater in the smaller solution-filled pores, explaining that this is due to anion
exclusion, as the relative exclusion volume increases with decreasing soil water content.
Similar results (Harvey, 1993) have been attributed to the delayed diffusion of solute
from macropores to the finer pores of the soil matrix.

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Conclusions
Final conclusions will emerge following full analysis of the samples described in
this paper. Initial results show that pressure filtering and centrifugation can be used to
extract soil pore water efficiently and their flexibility may allow extraction to be
employed for detailed studies of pore water composition. Although data are partial,
there is evidence that the chemical compositions of pore water fractions are not
homogeneous. Therefore, further study is required to fully understand these apparent
fractionation effects, how the chemical composition of the extracted pore water relates
to in situ conditions and to what extent the different types of solution are important to
environmental and geochemical processes.
Acknowledgements
A special thanks to Declan Brady, John Corrie, Dave Entwisle, Humphrey Wallis,
Linda Ault, Mark Cave, Jon Robinson and Jo Wragg, for their technical help, Rachel
Heaven and Barry Rawlins for the patient revision of my English and their support.
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