3rd AMIREG International Conference (2009): Assessing the Footprint of 249

Resource Utilization and Hazardous Waste Management, Athens, Greece

Leaching of bituminized waste products (BWP) by pure water: the contri-

bution of NMR techniques for the investigation of the porous layer

S. Le feunteun, H. Jaffel and O. Diat

ICSM - UMR 5257 - Bagnols sur Cèze, France

A. Ledieu and A. Poulesquen

DEN/DTCD - CEA Marcoule, France

A. Guillermo
SPrAM - UMR 5219 - Grenoble, France

ABSTRACT techniques allowed to probe mesoscopic length

scales and to highlight the development of a wa-
Aqueous-tight matrixes are used for a great vari-
ter-filled porous network downstream the mac-
ety of hazardous wastes conditioning for long-
roscopic dissolution front.
term disposal or for reprocessing in the frame of
sustainable materials fabrication. Their devel-
opment and industrial applications require a 1. INTRODUCTION
deep knowledge of the interactions between the
In France, bitumen has been used for four dec-
matrix and the constituent leaching. For long
ades as a container material for low/intermediate
lifetime storage, models of the matrix alteration
activity and long lifetime radionuclides. Indus-
and simulations of the leaching mechanisms
trial Bituminized Waste Products (BWP) are
have to be developed to validate the practical
produced by continuous extrusion of 60 %w. of
choices. These theoretical approaches have to be
bitumen and 40%w. of salts (volumetric ratio
built on experimental studies that are often dif-
~3:1), in which a very small fraction is radioac-
ficult to implement because of the slow proc-
tive. The prediction of long term behavior,
esses involved.
needed for a sustainable management of BWP,
We have developed an innovative method of
is usually achieved by studying the leaching of
investigation to probe, in a reasonable period, an
non radioactive-model materials. Previous stud-
ion leaching from a hydrophobic solid matrix
ies have allowed the implementation of models,
resulting from a water lixiviation. This method
able to predict the experimental water uptake
is based on the coupling of NMR and neutron
and ionic releases due to leaching, as a function
scattering studies to cover a large range of time
of inputs such as the proportion of soluble spe-
and length scales that allow a quantitative char-
cies incorporated in BWP and the nature of the
acterization of the leaching process.
leachant (Gwinner et al., 2006; Sercombe et al.,
Our studies were motivated by refining the
2006).
current leaching model (Gwinner et al., 2006) of
In that context, this work is a contribution to
radionuclides (RN) in bituminized waste prod-
the deeper investigation of the leaching phe-
ucts used in France.
nomenology, with a special focus on the role of
Practically, various RN extraction salts (solu-
the insoluble species.
ble and non-soluble) embedded in an asphaltene
matrix were used as samples of interest. 1.1 Materials
Combining 1H-NMR relaxation and self-
Three synthetic and inactive BWP have been
diffusion experiments and 1D-NMR imaging in
studied varying the chemical composition of in-
an elegant way, we succeeded in following the
corporated salts. All have been produced in the
porosity formation and the water diffusion up-
same conditions with respect to the extrusion
stream the dissolution front. Moreover, these
3rd AMIREG International Conference (2009): Assessing the Footprint of
Resource Utilization and Hazardous Waste Management, Athens, Greece
Table 1: Chemical composition of synthesized BWP samples.
Ref of BWP sam- Salts content Volume fraction
ples (%w.) (%)
A 40.3 ± 0.3 23.3
B 40.8 ± 0.1 13.5
C 40.3 ± 0.1 14.3
process (Gwinneret al., 2006), using the same
bitumen composition (Azalt 70/100). Table 1
shows the main parameters related to the chemi-
cal composition of produced materials. A, B and
C-types are simplified model materials.
Figure 1 shows the pristine microstructure of
samples A, B and C as observed with an envi-
ronmental scanning electron microscope, FEI
Quanta 200 ESEM FEG.
From ESEM observations, one gets a qualita-
tive picture of the homogeneity of the incorpo-
ration as well as the granulometry of embedded
particles. Using the laser granulometry techni-
que coupled to an ultrasonic treatment, A-type
samples containing NaNO3 particles show a mo-
nomodal distribution centered at 30 µm, an av-
erage size of crystals observed by SEM. How-
ever, B-type BaSO4 samples shows a monomo-
dal distribution centered at 200 nm, some much
small crystals that are partially and locally ag-
glomerated in the bitumen matrix. C-type is a
mixture of both in which the averaged size of
the NaNO3 crystals is more centered around
10 µm.
Size differences of NaNO3 particles in A-
and C-types are due to the fact that evaporation
flow in the extruding machine was fixed
whereas the ratio soluble to insoluble salts was
varying in the precursory sludges.
1.2 Leaching experiment
Aliquots issued from each BWP type were set-
tled in cylindrical NMR tubes (8 mm in diame-
ter) so that the height of materials was about 15
mm. Pure water, obtained by milli-Q filtration,
A-Type B-Type C-Type
Figure 1: ESEM pictures of sample A, B and C at exit of
extrusion process (scaling bars 100, 100 and 50 μm re-
spectively).
250
Mean diameter of salts (µm) - Incorporated salts
Granulometry data (%w.)
31.5 ± 13.2 100% NaNO3
5±3 100% BaSO4
13.5 ± 7.5 33% NaNO3
2.9 ± 1.2 66% BaSO4
was added and the leaching tests were per-
formed directly in order to follow with time the
progression of the leaching front in the axial di-
rection of the tube. Water uptake kinetics is ob-
tained by using CPMG sequence with a Bruker
45 MHz spectrometer (Carr and Purcell, 1954;
Meiboom and Gill, 1958). In addition to the
CPMG sequence, a new methodology has been
developed based on the determination of the re-
laxation times and the auto-diffusion coeffi-
cients along the tube axis (1H relaxation and dif-
fusion experiments coupled with 1D-NMR im-
aging sequence). This experimental procedure is
carried out on a Bruker 200 MHz spectrometer
using a pulsed field gradient probe. This ap-
proach allows determining the evolution of the
main NMR parameters (1H-T1 relaxation and
diffusion coefficient D) along the progression
front of water into the materials (the NMR tube
axis). Moreover, the reconstitution of the water
profile, the development of porosity (pore size)
and the discrimination of the free or confined
water according to the synthesized BWP type,
as a function of the water penetration depth are
possible. This new procedure will be more de-
tailed in another paper.
2. RESULTS AND DISCUSSION
Using the NMR technique, the water uptake is
extracted from the total magnetization meas-
urement as a function of time. We confirm what
we have already observed using a classical
weighting experiment; the B- and C-type BWP
samples uptake much more water that those
containing only soluble salts in the same time
range.
Figure 2 presents the mapping of the water
quantity as a function of leaching time for the
A-type BWP (100% of soluble salts) and B-type
BWP (100% of insoluble salts). For A-type, the
major part of water is located just below the top
interface (about a millimetre thick layer). These
profiles increase in intensity with the water up-
3rd AMIREG International Conference (2009): Assessing the Footprint of 251
Resource Utilization and Hazardous Waste Management, Athens, Greece

Figure 2: 1D profile as a function of leaching time for A- and B-type BWP - 2, 4, 6 and 8 months of leaching.
The upper part of the tube in contact with water is close 0 for the depth axis, the right part of the profile being close to the
bottom of the tube (15 mm max).
take whereas the water penetration depth creasing much more smoothly than for the solu-
evolves very little (the water progression front is ble samples.
well determined). The kinetic of water progres- Finally the T1 variation for the C-type sam-
sion is approximately (2 mm/year). On the other ple looks as a combination of the two previous
hand, for B-type, the water penetrated on the en- T1 behaviours namely a fast decay starting at
tire tube in eight months with a progression about 2.5 s (as for the soluble salt samples) and
front of water much more spread out. The ki- then a plateau at about 1.5 s as for the insoluble
netic of progression of water along the tube is samples. It appears also from the spectrum
much more rapid than for soluble salts sample analysis a shorter component (below 500 ms) in
and may be estimated of the order of the longitudinal relaxation that could be attrib-
10 mm/year. uted to a stronger confinement of the water
Due to the chemical composition of each molecules in very small pores, a hypothesis
BWP type, these results clearly show that the 3 2
soluble salts dissolve in contact with water and
T1 (s) & Profil 1D

therefore delay the progression of water whereas 1,5

T1 (s) & Profil 1D

the unsoluble salts play the role of guide for the 1

water transport. 1
0,5
To investigate accurately these effects and in 0
particular the role of the insoluble salts, global -1 0 1 2 3
Profondeur (mm)
4 5
0
0 2 4 6
Profondeur (mm)
8 10

1
H relaxation time experiments and 1D-NMR (a) (b)
4000
imaging sequence has been used.
Figure 3 show the superposition of the longi- 3500
T1 en ms, Porportion a/b & Profile 1D

tudinal water profile with the variation of the 3000

1
H-T1 relaxation time. For the A-type BWP
2500
sample, the T1 is about 2.5 s, a value which is
close to those that can be measured for water 2000

saturated with NaNO3. Then as we probe the 1500

depth of the sample, this value is decreasing
1000
rapidly. On the other end, for the case of the B-
type samples, the 1H-T1 relaxation time is about 500

1.5 s close to the outer surface, a value which is 0

lower than those of bulk water but slightly be- 0 2 4 6 8 10

low, a value that can be explained taking into
account some confinement effect between salt
grains or between the salt and the bitumen ma-
trix. As a function of depth, this value is de-
(c)
Figure 3: Superposition of water profile and variation of
the T1 relaxation time for sample A (a), B (b) and C (c)
with for this latter, 2 relaxation time. Graphs determined
after 6 months of leaching.
3rd AMIREG International Conference (2009): Assessing the Footprint of 252
Resource Utilization and Hazardous Waste Management, Athens, Greece

which has to be checked using scattering tech-

niques.

3. CONCLUSIONS
Global 1H relaxation time experiments and 1D-
NMR imaging sequence have been used to in-
vestigate the water progression in a hydrophobic
material such as bituminized waste products.
These new results make it possible to partly ex-
plain the surprising results of water uptake on
the macroscopic leaching experiments and espe-
cially to show that the chemical composition of
the salts dissolved in the bituminous matrix has
an essential role. Indeed, upstream to the disso-
lution front, mainly due to the dissolution of
NaNO3 salts, the development of porous layer
takes place and downstream the water pro-
gresses very rapidly in a more restricted poros-
ity by means of insoluble salts network
(BaSO4). The rate of the dissolution front is ap-
proximately 1-2 mm/year whereas the water
progresses 5-10 times faster downstream this
front. In addition, the swelling of the BWP were
also noted principally on the samples containing
soluble salts.

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Meiboom S. and D. Gill., 1958. Rev. Sci. Instrum. 29,
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