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European Journal of Soil Science, October 2008, 59, 855862 doi: 10.1111/j.1365-2389.2008.01045.

Increase in the fracture toughness and bond energy of


clay by a root exudate

B. Z HANG a , P. D. H ALLETT c & G. Z HANG b


a
State Key Laboratory of Soil and Sustainable Agriculture, Institute of Soil Science, Chinese Academy of Science, PO Box 821,
Nanjing 210008, China; bInstitute of Soil Science, Chinese Academy of Sciences, PO Box 821, Nanjing 210008, China, and
c
Scottish Crop Research Institute, Invergowrie, Dundee DD2 5DA, UK

Summary
Root exudates help drive the formation of the rhizosphere by binding soil particles, but the underlying
physical mechanisms have not been quantied. This was addressed by measuring the impact of a major
component of root exudates, polygalacturonic acid (PGA), on the interparticle bond energy and fracture
toughness of clay. Pure kaolinite was mixed with 0, 1.2, 2.4, 4.9 or 12.2 g PGA kg1 to form test speci-
mens. Half of the specimens were washed repeatedly to remove unbound PGA and evaluate the persistence
of the effects, similar to weathering in natural soils. Fracture toughness, KIC, increased exponentially
with added PGA, with washing increasing this trend. In unwashed specimens KIC ranged from
54.3  2.5 kPa m1/2 for 0 g PGA kg1 to 86.9  4.7 kPa m1/2 for 12.2 g PGA kg1. Washing
increased KIC to 61.3  1.2 kPa m1/2 for 0 g PGA kg1 and 132.1  4.9 kPa m1/2 for 12.2 g PGA
kg1. The apparent bond energy, g, of the fracture surface increased from 5.9  0.6 J m2 for 0 g kg1
to 12.0  1.1 J m2 for 12.2 g kg1 PGA in the unwashed specimens. The washed specimens had g of
13.0  1.9 J m2 for 0 g kg1 and 21.3  2.6 J m2 for 12.2 g PGA kg1. Thus PGA, a major compo-
nent of root exudates, has a large impact on the fracture toughness and bond energy of clay, and is
likely to be a major determinant in the formation of the rhizosphere. This quantication of the thermo-
dynamics of fracture will be useful for modelling rhizosphere formation and stability.

Introduction understanding of the underlying mechanical processes has


received much less attention.
Plant roots stabilize soil against physical disruption by en-
Particle binding in soil and its subsequent resistance to
meshing particles (McCully, 1999), altering cycles of wetting
mechanical breakdown can be quantied using approaches from
and drying (Czarnes et al., 2000b), and exuding mucilage that
materials science (Hallett et al., 1998). For instance, Lima &
aggregates and binds soil particles (Tisdall & Oades, 1979).
Grismer (1994) effectively used fracture mechanics to quantify
These processes drive the formation of the rhizosphere, there-
the impact of salinity on crack development and particle bind-
by increasing the functional capacity of soil for plant growth
ing in dry soil. Hallett et al. (1995) quantied the impact of
and environmental buffering (Gregory & Hinsinger, 1999).
soil texture on fracture mechanics. Later work measured the
Considerable research conducted on rhizosphere soil has
fracture mechanics of wet soil, which required an extension to
shown an increased physical stability based on an arbitrary
quantify plastic processes that regulate the thermodynamics of
amount of mechanical stress applied to soil aggregates that
fracture (Hallett & Newson, 2001, 2005). Fracture mechanics
remain adhered to plant roots (Alami et al., 2000; Czarnes
is far more powerful than traditional methods that measure
et al., 2000a; Traore et al., 2000; Caravaca et al., 2002; Kaci
the tensile strength or aggregate stability of soil as physically
et al., 2005). There are clearly increases to particle binding in
meaningful parameters are obtained that can be used to model
the rhizosphere that drive soil stabilization and consequently
structure development (Snyder & Miller, 1985; Lima &
root-soil interactions (Czarnes et al., 2000a). Whilst these stud-
Grismer, 1994). Moreover, the impact of pre-existing cracks
ies have demonstrated that rhizosphere soil is generally far
that dene the soil pore structure can be considered (Ayad
more stable to physical stresses than bulk soil, a quantitative
et al., 1997). Approaches from powder technology that are
based on fracture mechanics could also be employed to
Correspondence: P. D. Hallett. E-mail: paul.hallett@scri.ac.uk describe soil aggregation processes and mechanical stabiliza-
Received 21 May 2007; revised version accepted 3 March 2008 tion (Abdel-Ghani et al., 1991; Birchall et al., 1998).

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Journal compilation # 2008 British Society of Soil Science 855
856 B. Zhang et al.

No study has evaluated the impact of biological exudates like Two paste batches were formed for each concentration:
root exudates on particle binding and fracture mechanics. Pre- (i) unwashed batches were formed into test specimens with no
vious studies have used polygalacturonic acid, PGA, as an ana- further treatment; and (ii) washed batches were mixed with deion-
logue of root mucilage, to evaluate its impact on soil stability, ised water and centrifuged to remove non-absorbed or non-
with positive correlations found between the amount of added reversibly adsorbed PGA. Washing involved diluting the paste
PGA and soil tensile strength (Czarnes et al., 2000b) or water to 50 g kg1 solids, mixing thoroughly with a spatula to obtain
stability (Traore et al., 2000). The long-term persistence of a suspension, waiting 2 days for the suspension to settle, remov-
biological exudates on soil tensile strength was investigated ing the supernatant above the settled soil by decanting, centri-
by Chenu & Guerif (1991), who applied scleroglucan as an fuging at 12000 g for 10 minutes and adding deionised water to
analogue of fungal exudates to soil and simulated wetting return to the initial water content. This was repeated twice.
cycles by washing the soil-exudate mix to remove the fraction The pastes were formed into deep-notch bend specimens
that was not bound to particles. by remoulding into rectangular moulds with a dimension of
In this study we quantied the impact of PGA, as a model root 140 mm long, L, 31 mm thick, B, and 34 mm wide, W. The
exudate, on soil fracture mechanics. The parameters quantied moulds were built of aluminium and lined with cut acetate
were, fracture toughness, KIC, which is a measure of the resis- sheet folded on the inside to allow for easy removal of the
tance to crack growth, elastic modulus, E, which denes the specimen with minimal damage. Remoulding involved smear-
relationship between stress and strain, and apparent bond ing the specimen along the longest axis in depth increments of
energy, g, which is the energy required to create a new surface 23 mm, with care taken to avoid bubbles. The specimen was
by cracking. Different concentrations of PGA were mixed with removed in the acetate sheet liner and dried rst at room tem-
kaolinite to form test specimens for fracture testing. Kaolinite perature (20C) for 24 hours and then at 40C until water loss
was chosen for this initial study to improve homogeneity be- ceased. Ten replicates were formed for each treatment.
tween specimens and to remove the impact of natural organic
compounds in soil that may inuence mechanical behaviour.
Fracture testing
One batch of specimens was washed repeatedly to evaluate the
effect of wetting cycles on the persistence and redistribution of Figure 1 illustrates the fracture specimen, the symbols used to
root exudates on fracture mechanics. We hypothesized that describe specimen dimensions and the test conguration. To
particle binding and fracture toughness would be positively overcome the effect of the crack-tip process zone size on fracture
correlated with the amount of root exudate. Washing of the toughness that Hallett et al. (1995) identied, a large crack
soil was hypothesized to remove unbound PGA, but the more length, a, to width, W, ratio was used. A crack, a, 12 mm long
homogeneous distribution and adsorption of PGA after wash- (0.35 a/W), was cut into the centre of the dry specimen with
ing should increase KIC and g. The work will help unravel the a hacksaw blade that was restrained from lateral movement in
complex processes involved in the formation of the rhizo- a mitre block. The crack tip was sharpened by running a razor
sphere and provide quantitative data that could be used in blade across its surface several times. Special care was taken to
future models of soil structure genesis. impose minimal compressive stress during cutting, as this
could pre-strain the specimen and induce microcracking.
The specimen was fractured using the three-point bend
Material and methods test, which is commonly used for engineering materials ranging
from steel to concrete (British Standards Institution, 1991).
Preparation of specimens
It was supported at the base using two rollers, with a span
Test specimens were formed by mixing dry pure kaolinite
(Supreme Powder, English China Clay, St Austell, UK) with
polygalacturonic acid (PGA;(C6H8O6)n; Fluka BioChemika
81325, EC No. 2116826, Gillingham, UK) solution. Other
studies have identied PGA as a model root exudate (Gessa
et al., 1997; Grimal et al., 2001). PGA was made soluble by the
addition of 0.46 ml 1M KOH per 100 mg of PGA (Czarnes
et al., 2000b). The solution was diluted with deionised water
so that PGA concentrations of 0, 1.2, 2.4, 4.9 and 12.2 g PGA
kg1 soil would be obtained in dried specimens. Clay pastes
were formed at 90% liquid limit (640 g kg1) of pure kaolin-
ite. Sodium azide (50 mg kg1) was added to minimize micro- Figure 1 Deep notch three-point bend test used for fracture mecha-
bial growth. The pastes were mixed with a heavy duty kitchen nics testing. The specimen is exed between a top roller and two
mixer for 10 minutes and then sealed in plastic bags for 2 days bottom rollers separated by distance S. The width, W, thickness, b,
and stored at 20  1C. and crack length, a, are shown.

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Journal compilation # 2008 British Society of Soil Science, European Journal of Soil Science, 59, 855862
Root exudate impact on soil fracture 857

distance, S, of 70 mm (i.e. 50% of the specimen length) so that a material with considerable strength but very poor fracture
self-weight was balanced. Testing was conducted using an toughness.
INSTRON mechanical test frame (Model 5544; INSTRON, Another important parameter to quantify is the elastic mod-
Canton, MA). During testing, the upper load-point illustrated ulus, E. It describes the rigidity of a material through the rela-
in Figure 1 was lowered, causing the specimen to ex and tionship E r/e, where strain, e, is the change in specimen
eventually fracture. The cross-head displacement and force, length versus its original length. We estimated E from the
P, was recorded using Merlin software (INSTRON, Canton, slope of the force-displacement curve in the three-point bend
MA). The cross-head speed was set to 1 mm minute1 for all tests using the relationship
specimens (Hallett et al., 1998). The load cell had a range of
50 N and was accurate to 1% at 1/250 maximum load. @P S3
E  ; 4
@q 4BW a3
Soil analysis
where q is the cross-head displacement. Instron Merlin soft-
The amount of the model root exudate, PGA, in the specimens ware calculated the slope @P=@q automatically for the linear
was estimated from a direct measurement of carbon. Each PGA portion of the force-displacement curve.
and washing treatment and all replicates were measured for car- Knowledge of both KIC and E provides powerful informa-
bon with a continuous ow mass spectrometer consisting of an tion for assessing the energetics behind fracture. The critical
ANCA SL sample converter attached to a 20/20 isotope ratio- strain energy release rate at fracture, Gc, denes the energy
mass spectrometer (Europa Scientic, Crewe, UK). pH was required to propagate a crack and can be approximated from
determined using a 1:5 ratio mixture of soil and water. Linear
shrinkage, liquid limit and plastic limit were determined accord- KIC 2
Gc : 5
ing to the British Standards Institution (1975). E
From this the bond energy, g, can be determined as
Fracture mechanics
Gc 2g: 6
A thorough description of the fracture mechanics of dry soil can
be found in Lima & Grismer (1994) and Hallett et al. (1995). The
failure stress, rF, was determined by Scanning electron microscope images
3PMAX S Soil was taken from the fracture surface and coated with gold so
rF 2
; 1 that particle packing and aggregation could be assessed using
2BW a
a Sirion scanning electron microscope (Sirion, Tampa, FL).
with a taken as the value at the onset of testing and PMAX the Gold coating involved a 70-second treatment in a SCD 005
maximum applied force recorded from the load cell (Lima & Sputter Coater (Bal-Tec GmbH, Balzers, Germany) at a current
Grismer, 1994). Failure stress is inuenced by both particle of 40 mA, followed by ushing the working chamber with argon
bonding and pre-existing cracks in soil. The impact of these two gas several times. This provided a qualitative assessment of
properties can be separated by analysing data from the three- the extreme treatments, i.e. 0, 1.2 and 12.2 g PGA kg1 for
point bend tests with fracture mechanics, as described below. unwashed and washed specimens.
Fracture mechanics parameters were quantied using
approaches described in BS 74481: 1991 (British Standards
Institution, 1991). Fracture toughness, KIC, is related to rF by Results
p
the simple relationship KIC rF Y a, where Y accounts for
Specimen properties
specimen geometry. The geometry of a three-point bend speci-
men can be accounted for using the equations Experimental error between the desired and actual amount of
PMAX S a PGA added to the kaolinite was minimal as determined from the
KIC 1:5
f ; 2 carbon content (P > 0.05; Figure 2). The kaolinite without
BW W
added PGA contained carbon that was accounted for in the
where calculations of total carbon in the amended specimens. Wash-
 a 0:5 h  a  a  3:93a 2:7a2 i ing the kaolinite removed a considerable amount of carbon
a 3 1:99  1 2:15 
f W W

W W W2 : (P < 0.001), causing the specimens with 4.9 g PGA kg1 or less
W 2a  a 1:5
2 1 1 to drop to almost the amount in the 0 g PGA kg1 specimens.
W W
3 In both the unwashed and washed specimens, carbon content
increased with added PGA (P < 0.05).
The fracture toughness indicates the capacity of a material Table 1 lists other physical properties of the specimens. The
to resist the growth of a crack. Diamonds are an example of water content of the specimens at testing was 6 g kg1, with no

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Journal compilation # 2008 British Society of Soil Science, European Journal of Soil Science, 59, 855862
858 B. Zhang et al.

7 Fracture toughness, KIC

6 Adding PGA to kaolinite increased KIC (Figure 4). The addi-


tion of 12.2 g PGA kg1 almost doubled the fracture tough-
5 ness of kaolinite before washing. For any amount of added
Carbon /g kg1

PGA, washing increased the fracture toughness further. The


4 KIC followed the same relationship that Birchall et al. (1987)
found for a particulate system mixed with a binder,
3
 
2
KIC;PGA KIC;Soil c 1  dPGA ; 7

1 where c and d are tting parameters, and [PGA] is the concen-


tration of added PGA to soil (g kg1). Table 2 lists the tted
0 values for these parameters.
0 1.2 2.4 4.9 12.2
Added PGA /g kg1 Soil
Elastic modulus, E
Figure 2 The desired (black), actual (grey) and post-washing (white)
carbon content on the kaolinite amended with polygalacturonic acid, A clear trend between the amount of added PGA and the
PGA. The background carbon content of the kaolinite was accounted elastic modulus, E, was not found for the unwashed specimens
for, as shown by the bars for the 0 g kg1 treatment. Each bar is the (Figure 5). For unwashed specimens the addition of 1.2 g
mean of 10 replicates (1 SE). PGA kg1 resulted in the greatest increase in E, with further
addition of PGA diminishing E. There was a clearer trend for
the washed specimens, where E generally increased with the
difference between treatments. Liquid limits were not inu- amount of added PGA.
enced by PGA or washing and although statistical differences
were found for the plastic limit (P < 0.01), the water content
Apparent bond energy, g
difference was less than 3% between the extremes. Linear
shrinkage was inuenced signicantly by both the amount of The apparent bond energy, g, generally increased with added
PGA and washing, with signicant interaction (P < 0.001). PGA but the results for 1.2 g PGA kg1 for both washing
However, the amount of linear shrinkage in all specimens was treatments obscured any trend (Figure 6). Washing the clay
small, with a maximum difference of 0.37 m 100 m1. A small and adding 12.2 g PGA kg1 more than tripled the bond
number of specimens cracked during drying and these were energy compared with the unwashed control specimen.
excluded from testing.
Scanning electron micrographs
Failure stress, rF
A visual assessment of SEM images showed that the unwashed
The failure stress of pure kaolinite was about 720 kPa for both specimen with 0 g kg1 added PGA had a dispersed structure
washed and unwashed specimens (Figure 3). It increased mark- with little aggregation (Figure 7). The addition of the smallest
edly by adding PGA, with an overall greater increase following and largest amounts of PGA, 1.2 g kg1 and 12.2 g kg1,
washing the kaolinite. The specimens with 12.2 g kg1 added respectively, enhanced aggregation, although differences be-
PGA were 1.7 and 2.4 times stronger than the pure kaolinite tween them were not evident. Washing promoted aggregation,
for the unwashed and washed treatments, respectively. even for 0 g kg1, with increased PGA concentration leading

Table 1 Properties of kaolinite amended with different amounts of polygalacturonic acid, PGA

Linear shrinkage/m 100 m1 pH


Added PGA Liquid limit Plastic limit
/g kg1 /g kg1 /g kg1 Unwashed Washed Unwashed Washed

0 733  22a 367  1 3.20  0.02 3.44  0.03 8.0 7.5


1.2 707  56 344  4 3.19  0.01 3.40  0.02 7.3 7.5
2.4 696  33 341  33 3.24  0.02 3.36  0.04 7.0 7.6
4.9 722  54 345  2 3.38  0.01 3.47  0.03 5.8 7.8
12.2 790  82 361  3 3.38  0.03 3.10  0.02 4.6 7.9
a
The standard error of the mean is shown.

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Journal compilation # 2008 British Society of Soil Science, European Journal of Soil Science, 59, 855862
Root exudate impact on soil fracture 859

2000 Table 2 Fitted parameters relating added PGA to KIC for washed and
unwashed specimens (Equation 7)
1800
Treatment c D KIC, Soil R2
1600
Unwashed 69.2 0.92 53.3 0.99
1400
Washed 95.9 0.92 69.4 0.84
F /kPa

1200

1000
exudate contents in the rhizosphere. Cycles of wetting, which
800 were simulated by washing the clay repeatedly, enhanced the
600
impact of PGA concentration on fracture toughness, despite
the leaching of some PGA (Figure 2; Table 2).
400 The impact of PGA on fracture toughness was a result of
0 2 4 6 8 10 12 14
interactions with clay particles. PGA made pH more acidic in
Added PGA /g kg1
the unwashed samples, which may have caused a shift from
Figure 3 Failure stress, rF, of the unwashed (black) and washed negative to positive net total particle surface charge (Kretzschmar
(white) kaolinite specimens with different amounts of added poly- et al., 1997). As this would increase edge-face bonding, the
galacturonic acid, PGA. Bars over the symbols are the standard error contact area between clay particles and hence bond energy
of the means (n 10). would be expected to decrease by the action of pH alone.
Wang & Xu (2007) reported greater compressibility of kaolin-
to further increases in aggregation. The washed 12.2 g kg1 ite with decreasing pH. Shrinkage on drying and compressibil-
appeared to have the greatest aggregation of all the treatments. ity are analogous (Vogel et al., 2005) and our linear shrinkage
results showed greater shrinkage with increasing PGA for the
unwashed specimens. Although this may counteract the effects
Discussion of increased edge-face bonding, the difference in shrinkage
The large increase in fracture toughness caused by the addition from 0 g PGA kg1 to 12.2 g PGA kg1 samples was only
of PGA demonstrated the potential of root exudates to change 0.19 m 100 m1 and the trend was not observed for the
the mechanical behaviour of dry kaolinite. Based on Equations washed specimens, so the impact of shrinkage on porosity and
5 and 6, almost three times the energy was needed to rupture hence mechanical behaviour was likely to be negligible.
unwashed specimens with 12.2 g PGA kg1 than for pure It was likely that the polymer structure of PGA acted as
kaolinite. Based on measurements of root exudates from Zea a glue between clay particles, as the fracture tests showed a
mays into soil by Kuzyakov et al. (2003), the range of PGA positive impact of PGA concentration on fracture toughness.
added to soil in the current study was 1 to 10 times the root Mikutta et al. (2004) observed that PGA clogged pores in

400
160

140
Elastic Modulus /MPa

300

120
KIC /kPa m1/2

200
100

80
100

60

40 0
0 2 4 6 8 10 12 14 0 2 4 6 8 10 12 14
Added PGA /g kg1 Added PGA /g kg1

Figure 4 Fracture toughness, KIC, of the unwashed (black) and Figure 5 Elastic modulus, E, of the unwashed (black) and washed
washed (white) kaolinite specimens with different amounts of added (white) kaolinite specimens with different amounts of added poly-
polygalaturonic acid, PGA. Bars over the symbols are the standard galacturonic acid, PGA. Bars over the symbols are the standard error
error of the means (n 10). of the means (n 10).

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Journal compilation # 2008 British Society of Soil Science, European Journal of Soil Science, 59, 855862
860 B. Zhang et al.

35 et al., 1997). Moreover, after washing PGA may be more


homogeneously distributed in the clay, with the removal of
Apparent Bond Energy, /J m2

30 excess PGA from between clay particles. Thinner layers of


PGA would provide the same adhesion, with the decreased
25
particle separation distance increasing the contribution from
20 Van der Waals forces.
Research by Czarnes et al. (2000b) showed that 1.2 g PGA
15 kg1 caused a much greater increase in the failure stress of
a natural sandy loam than our study found for kaolinite. This
10
difference is probably due to the presence of 2:1 clay minerals,
where overlap between the quasicrystals is greater than for 1:1
5
kaolinite (Tessier et al., 1990). Research by Chenu & Guerif
0 (1991) supports this argument, as they found the impact of
0 2 4 6 8 10 12 14 organic compounds on failure stress to be much greater for
Added PGA /g kg1 montmorillonite than for kaolinite.
For kaolinite, Chenu & Guerif (1991) showed that the fungal
Figure 6 Apparent bond energy, g, of the unwashed (black) and
exudate scleroglucan, at similar concentrations to the PGA
washed (white) kaolinite specimens with different amounts of added
polygalacturonic acid, PGA. Bars over the symbols are the standard
tested here, had a much greater impact on failure stress (reported
error of the means (n 10). as modulus of rupture). Secondary microbial metabolites pro-
duced in the rhizosphere may therefore be more important for
structural stabilization than root exudates. This was demon-
AlOOH, thus producing bridges between particles. This strated by Alami et al. (2000) and Kaci et al. (2005), who both
would increase the contact surface area and thus the fracture found more rhizosphere aggregation in a sterile soil amended
toughness through PGA adhesion (Johnson et al., 1971). with Rhizobium than in the control. However, the impact of
With washing, fracture toughness increased further for kao- microbial polysaccharides requires greater investigation as
linite amended with PGA. The physical process of washing Czarnes et al. (2000a) found dextran to reduce failure stress
provided a dispersed liquid environment that could have and xanthan to have a lesser effect than PGA on failure stress
increased the potential for clay occulation (Tarchitzky & at similar concentrations. One reason for this difference could
Chen, 2002). Increased pH with washing may have increased be the ionic structure of PGA versus the non-ionic structure of
face-face bonding and hence the bond energy (Kretzschmar both xanthan and dextran.

Figure 7 SEM images of the test specimens. The scale is marked on each image.

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Journal compilation # 2008 British Society of Soil Science, European Journal of Soil Science, 59, 855862
Root exudate impact on soil fracture 861

An energetic analysis of the fracture data based on KIC valuable data for aggregation and cracking models (Vogel et al.,
requires knowledge of E (Equation 4). As E depends on the 2005). Such model tests allow for better control and replica-
relationship between the applied stress and the deformation of tion of the specimens, but the practical signicance of the
the specimen, specimen microstructure should have a greater work would improve by testing the impact of roots and micro-
impact on E than KIC. The combination of microaggregation organisms on the fracture mechanics of natural soils. This
and particle binding in the unwashed specimens could explain might be possible using an experimental set-up similar to
the sharp rise in E for 1.2 g kg1 PGA followed by subsequent Alami et al. (2000) and harvesting rhizosphere soil to form into
decline as the amount of added PGA increased. Although fracture specimens (Figure 1). The impact of water potential
microaggregation and particle bonding are linked, micro- on fracture behaviour also needs to be considered. Consolidating
aggregation results in more densely packed structural singular- the soil under a compressive load rather than letting it air-dry
ities (aggregates) separated by microcracks. Microaggregation might help alleviate problems encountered with microaggrega-
should decrease E as microcracks will deform under stress. On tion inuencing E.
the other hand, particle bonding in the absence of micro-
aggregation should increase E. However, microaggregation
Conclusions
observed from the SEM images did not support this argument
as it did not appear to change between 1.2 g kg1 and 12.2 g Our experiments demonstrated that PGA, a major component
kg1 added PGA. For the washed specimens aggregation was of root exudates, has a great capacity to increase bond energy
evident even in the controls and adding PGA probably further and fracture toughness of clay. Weathering of soil, simulated by
increased E through interaggregate and particle bonding. washing the clay repeatedly, increased fracture toughness and
The reliability of the apparent bond energy data will be af- bond energy further, suggesting that the changes were persistent.
fected by E (Equations 5, 6). Nevertheless, a trend of increasing The ultimate outcome of this type of research is the capacity to
g with increasing PGA was found for all but 1.2 g PGA kg1 quantify bonding by exudates in soil and the subsequent
specimens. Knowing g would be extremely valuable in soil impact on fragmentation. These data are useful for understand-
science as it is a basic thermodynamic property that is commonly ing the formation of soil structure from its basic thermodynamic
used in aggregation models of other materials (Haw et al., properties.
1995). In particle agglomerates like soil, g determined from
fracture tests is different from the actual bond energy because
Acknowledgements
energy is wasted through plastic processes such as friction and
microcracking (Johnson et al., 1971; Hallett et al., 1995). The authors gratefully acknowledge the Royal Society and
Attempts to upscale g that operates between particles to the Chinese Academy of Sciences as well as the National Natural
behaviour of particle agglomerates have therefore given poor Science Foundation of China (40520130223), who funded the
estimates, so the actual testing of agglomerates is required. academic exchange between our institutions. We are extremely
The fracture test employed here evaluated KIC effectively. grateful to Pierre Barre, who provided valuable comments when
Specimen size can inuence results because of the impact of revising the manuscript. Dennis Gordon is thanked for his help
boundary conditions. Compliance testing using the relation- in developing the fracture test equipment. The Scottish Crop
ship a, b, W > 2.5 (KIC/rF)2 (British Standards Institution, Research Institute is grant-aided by the Scottish Government
1991) showed that the specimens were compliant but on the Rural and Environment Research and Analysis Directerate.
boundary of being too small, so the testing of larger specimens
is recommended. An important property of the specimens
tested was the large a/W. This minimizes the impact of the pro- References
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different organic compounds and soil minerals would provide 14561458.

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Journal compilation # 2008 British Society of Soil Science, European Journal of Soil Science, 59, 855862
862 B. Zhang et al.

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# 2008 The Authors


Journal compilation # 2008 British Society of Soil Science, European Journal of Soil Science, 59, 855862

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