The physicochemical properties of a clay from La Baie, Quebec were found to be typical of Champlain quick clays: very low
plasticity, liquidity index greater than 3, sensitivity greater than 500, and pH of about 9.5. The mineralogy is characterized by the
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abundance of primary or "rock flour" minerals such as feldspar, quartz, amphibole, and calcite, with illite as the principal clay
mineral. The pore water chemistry consists predominantly of sodium bicarbonate. Low concentrations of sulfate, calcium, and
magnesium and high alkalinity and pH are attributed, in part, to anaerobic sulfate-reduction processes taking place in situ.
Quick clay samples stored in the laboratory showed signs of aging regardless of the storage procedure. The remoulded strength
and the liquid limit increased with time, whereas the sensitivity, the liquidity index, and the pH decreased. The water content,
plastic limit, and undisturbed strength remained practically unchanged. The pore water concentrations of calcium, magnesium,
and sulfate increased by severalfold. ,
The aging phenomenon is attributed, for the most part, to the oxidation of iron sulfide, which results in the formation of iron
hydroxide and sulfuric acid. The production of acid causes the dissolution of calcium carbonate, which increases the
concentration of divalent cation in the clay, thereby reducing interparticle repulsion and increasing the remoulded strength. The
oxidation of organic matter, resulting in the formation of carbonic acid, also contributes to the aging by its effect on the solubility
of calcium carbonate.
Key words: aging, chemical reactions, physicochemical phenomena, sensitivity, time effects.
I1 a CtC constate que les propriCtCs physico-chimiques d'une argile de La Baie, QuCbec ktaient typiques des argiles sensibles
For personal use only.
Champlain: trbs faible plasticit&, indice de liquidit6 supkrieure h 3, sensibilitk supkrieure ? 500
i et pH d'environ 9,5. La
miniralogie est caractCriske par l'abondance de "poussibre de roche" ou de minCraux primaires tels que le feldspath, le
quartz, les amphiboles et la calcite. L'illite reprCsente le principal minkral argileux. La chimie de l'eau interstitielle est constituCe
principalement de bicarbonate de sodium. Les faibles concentrations de sulfate, de calcium et de magnksium, de mCme que la
forte alcalinitC et la valeur ClevCe du pH sont attribuees, en partie, aux processus de rkduction anakrobique du sulfate qui se
produit in situ.
Des Cchantillons d'argile sensible entreposks en laboratoire ont montrk des signes de vieillisement indtpendarnrnent de la
procCdure d'entreposage. La resistance remaniCe et la lirnite liquid ont augment6 avec le temps alors que la sensibilitk, I'indice de
liquidit6 et le pH diminuaient. La teneur en eau, la limite plastique et la rksistance intacte sont demeurkes h peu prbs
inchangees. Les concentrations de calcium, de magnesium et de sulfate dans l'eau interstitielle ont augment6 drastiquement.
Le phCnombne de vieillissement est attribuk, en grande partie, h l'oxydation du sulfure de fer qui rCsulte en la formation
d'hydroxide de fer et d'acide sulfurique. La production d'acide cause la dissolution du carbonate de calcium, et augmente la
concentration de cations bivalents dans l'argile, rkduisant ainsi la rCpulsion inter-particule et augmentant la resistance remaniCe.
L'oxydation de matibre organique, rCsultant en la formation d'acide carbonique, contribue aussi au vieillissement par suite de
son effet sur la solubilitC du carbonate de calcium.
Mots clts: vieillissement, rCactions chimiques, phCnombnes physico-chimiques, sensibilitk, effet du temps.
Can. Geotech. J. 22, 335-346 (1985)
Introduction Samples of Swedish clays taken from the Gota River valley
Soil engineering studies often include laboratory tests aimed lost their original quickness after being stored for 2-4 years.
at predicting the behaviour of the in situ soil. Generally, Similar sensitivity reduction was observed in situ, as a clay
undisturbed samples are taken from the site and transported to sampled in 1967 at a depth of 1 m below an exposed slide bottom
the laboratory, where they are stored at room temperature and of the 1960 slide at Veston had lost its quickness in the
100% relative humidity to prevent water losses. Whether the meantime (Soderblom 1969). Quantitative analyses by standard
properties measured by laboratory tests carried out weeks to paper chromatography showed that before aging, the quick clay
months after sampling are representative of the in situ character- contained mainly Naf and ~ 0in its~pore~water. - After aging,
istics of the soil is questionable. Many cases have been reported there was a significant amount of Mg2+ and Ca2+ and a marked
where significant changes in sensitivity, Atterberg limits, and increase of ~ 0(Soderblom
~ ~ 1974). - According to Soderblom
pore water chemistry occurred during storage. The process (1969), "the change from anaerobic to aerobic state and the
responsible for these changes, generally referred to as aging, accompanying changes in the microbial activity may be the
has been observed in Scandinavian as well as Canadian clays. most important factor in the aging process."
Bjermm and Rosenqvist (1956) observed an increase in the Torrance (1976) reported the effects, on the pore water
Atterberg limits of a marine clay from Asrum, Norway, that was chemistry, of 3 months' storage under a wide variety of standard
a result of aging. The plasticity index of a sample rose from 21 % and modified storage procedures. The material was a soft
to 27% over a 2 year period and was accompanied by an increase Champlain clay with a low salinity and a sensitivity of 10-20.
in potassium ion concentration in the pore water, which was Irrespective of the storage method, the salinity and the percent-
attributed to the weathering of the clay minerals. age of divalent cations in the pore water had increased. The most
CAN. GEOTECH. J. VOL. 22, 1985
STORAGE PROCEDURE
A: Shelby tube, ends waxed ( 4 samples
from t u b e )
0: Aluminum f o l d , waxed ( d u p l i c a t e
samples)
C: P l a s t i c wrap waxed ( d u p l i c a t e
samples)
D: Waxed
E: C o n t a i n e r NZ
F: C o n t a i n e r , p l a s t i c wrap N
G: C o n t a i n e r , a i r
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Na KMg Ca Na K Mg Ca
El#!
Na K MgCa
ORIGIIIAL AVERAGE
STORED
FIG.1. Effect of 3 months' storage upon the cation distributionin the pore water under various storage procedures (adaptedfrom Torrance 1976).
conspicuous changes were observed for the clay stored in plastic Experimental methods and material characteristics
containers without the protective seal of the wax (Fig. 1). Upon reception of the samples in the laboratory, about 1
According to Torrance, the increase in the concentration of month after sampling, an extensive analysis of the geotechnical
calcium and magnesium in the pore water during aging is and physicochemical properties of the quick clay was under-
probably related to attack on carbonates present in the soil. taken. The purposes of the analysis were firstly to evaluate
In order to better understand the geotechnical and chemical whether any change had occurred in the geotechnical properties
changes occurring in a quick clay during storage, an extensive of the material since sampling and secondly to establish the in
testing program was carried out on a Champlain quick clay
For personal use only.
d
H • A 6.2
H
H
0
:
fr.
. 4.4
6.5
0
6.0 o
H .O
H 0 . 3.1
H 0 : 4.4 0
Can. Geotech. J. Downloaded from www.nrcresearchpress.com by University of Regina on 05/02/13
H C, 6.0
d
H 4.6 o
.
0'
H a ' 4.0
H
- .
a
'
'0
. 7.0
3.4 0
PL LL WC
FIG.2. Geotechnical and compositional characteristics of La Baie clay measured 1 week (A) and 1 month (0)
after sampling.
Most values fall between 50 and 70 kPa with a very slight of acid that is left after reaction with the carbonate is determined
increase with depth. The undisturbed strength measured at 1 by NaOH titration.
month is essentially the same as at 1 week after sampling. The tests indicated carbonate contents varying between 7%
The remoulded strength was determined by the fall-cone test and 9%, with an average value of 8%. No particular trend with
For personal use only.
from at least five measurements. Before each test, the soil was depth was observed. Such high values of carbonate content are
thoroughly remoulded in order to minimize thixotropic effects. common for the LaFlamme Sea clays.
The test was repeated until a constant reading was obtained, thus
indicating a complete remoulding and homogenization of the Soil pH
material. For all the tests performed, the clay samples became The soil pH was measured in a 1: 1 (by weight) mixture of soil
so liquid upon remoulding that the penetration of the 10 g cone and distilled water. Five grams (dry weight) of wet soil of
was greater than 20 mm, which corresponds to a remoulded known water content was used for the test. Distilled water was
strength lower than 0.07 kPa and a sensitivity greater than 500. added to the soil to obtain a total weight of 10 g. The slurry was
mixed thoroughly and then allowed to stand undisturbed for 1 h,
SpeciJicgravity and grain-size distribution after which the pH was measured by means of a combination
The specific gravity of the soil solids measured on six samples electrode and a Beckrnan pH-meter positioned in near-contact
varied only from 2.75 to 2.78, which reflects a homogeneous with the bottom of the container. Typically, the reading
mineralogical composition of the material. decreased rapidly to reach a stable value within 2-3 min.
The results of grain-size analyses performed on six samples The soil pH measured in the clay samples decreases with
are shown in Fig. 2. The clay-size fraction (-2 pm) varies from depth, with values ranging from 9.6 in the upper part of the
40% to 62%, with the smaller values at mid-depth. Not boring to 9.3 in the lower part.
surprisingly, the grain-size distribution correlates well with the
water content of the material and plastic limit profile. Mineralogy
The mineralogical analysis of the clay was performed by the
Organic matter
X-ray diffraction method using a RIGAKU diffractometer and
The organic matter content of the clay was measured by redox
titration (Rankin 1970). The method is based on the oxidation of Cu K, radiation. Six samples from various depths were air-dried
carbon by potassium dichromate. The procedure consists of and reduced to powder. The material passing the #200 mesh
adding concentrated sulfuric acid and a known amount of sieve was packed into the sample holder and the surface struck
off smooth and level. The X-ray patterns obtained for the six
potassium dichromate to 5.0g of dry soil. The amount of
powder samples indicate that the mineralogical composition of
dichromate that does not react with the oxidizable carbon is
the material is virtually the same throughout the profile. As
determined by titration.
shown in Fig. 3 a , the material contains a substantial amount of
The results showed no particular trend with depth. The
organic matter content varied between 0.4% and 0.6%, with an rock flour minerals such as quartz, feldspar, amphibole, and
calcite. Illite is the main phyllosilicate mineral. Chlorite and
average of 0.5%, which corresponds to 0.3% of oxidizable
kaolinite are also present in traces.
carbon.
A semiquantitative X-ray analysis was performed on one
Carbonate sample. Approximately 2 0 g of air-dried soil was ground for
The total insoluble carbonate content was determined using 2 min in a rotative grinder. The powder obtained was packed in
the rapid titration method (Hesse 1971). The procedure consists the sample holder, smoothed off, and pressed with fine-grained
of adding 50 mL of 1 N HC1 to 5 g of air-dried soil. The amount sandpaper to minimize the preferential orientation of platy mica
CAN. GEOTECH. J. VOL. 22, 1985
Cu Ka R A D I A T I O N , = 1.54 i
Q: quartz
F: feldspar
A : amphibole
C: calcite
I: illite
K: kaolinite
Ch: chlorite
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1 1 1 1 1 1 1 1 1 , 1 1 1 1 , 1 , 1 , , 1 , , , , 1 , , 1 , 1
5 10 15 20 25 29 30
35
(b) Clay-size fraction ( c2um )
FIG.3. X-ray diffraction powder patterns of fraction passing #200 sieve ( a ) and oriented <2 Fm fraction (b) of sample from La Baie.
clay. Biotite was used to estimate the illite content, since the two
have similar structures. The percentages of the various minerals %
in the clay were estimated by comparing the intensity of Mineral by weight
characteristic peaks with the peak intensity of standard miner-
als. The results are presented in Table 1. Primary minerals
The mineralogy of the clay-size fraction was examined by Plagioclase
running an X-ray analysis on samples made of the -2 Fm clay K-feldspar
suspension allowed to air-dry slowly on glass slides for at least Quartz
Amphibole
24 h. The X-ray diffraction pattern of an oriented air-dried Calcite
sample of the clay-size material is shown in Fig. 3b. As
expected, the proportion of phyllosilicate minerals is more Clay minerals
Illite
important in the clay-size fraction. Rock flour minerals, how- Chlorite
ever, remain present in significant quantities. On the pattern of a Kaolinite
heat-treated sample (500°C), the peaks at 7 A and 3.5 A had
disappeared, thus confirming the presence of a small amount of
kaolinite which becomes amorphous at 500°C. The oriented and
glycolated samples showed no trace of montmorillonite or other method whereby the sulfate ion is precipitated with barium
smectites. chloride to form barium sulfate crystals. Chloride was measured
by potentiometry, i.e. by means of a chloride-sensing electrode
Pore water chemistry coupled with a reference electrode and a pH-meter. The
The pore water used for the soluble salt determination was bicarbonate ion was determined by potentiometric alkalinity
obtained by squeezing the soil in a modified consolidation titration with 0.01 N HCI. In all the pore water samples tested,
apparatus. The upper porous stone was covered with plastic and the concentration of C032- was small (less than 5% of the total
the lower porous stone was replaced by a perforated plastic disc. alkalinity) and, therefore, its value was included in the
The water was collected from the base of the sample. A slow concentration of HC03-. All the above tests, with the exception
loading rate had to be used at the beginning of consolidation to of the chloride analysis, have an accuracy better than *5%. For
avoid the squeezing out of liquefied soil between the piston and the potentiometric measurement of chloride, the accuracy is
the consolidation ring. Overnight, about 6-10 g of water could about '- 10%.
be obtained from the squeezing of some 80 g of clay at its initial The results of the pore water chemistry analyses are shown in
water content. The ion concentration in the squeezed pore water Fig. 4. Sodium and bicarbonate are the predominant species in
was not found to be pressure dependent for the range of the pore water of La Baie clay. Their concentrations generally
consolidation pressure used. increase with depth. In all the samples examined, the chloride
The concentrations of various ions were determined using concentration was less than 0.5 meq/L, with no particular trend
standard procedures. Dissolved sodium, potassium, magnes- with depth. The concentrations of dissolved potassium, mag-
ium, and calcium were measured by atomic absorption spec- nesium, and calcium are also very low, showing a slight
trophotometry. Sulfate was determined by the turbidimetric increase with depth.
LESSARD AND MITCHELL
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FIG.4. Pore water and adsorbed layer characteristics of La Baie clay measured 1 month after sampling.
The pore water chemistry analysis shows evidence of TABLE2. Comparison between the composition of seawater and the
leaching and sulfate reduction, two conditions apparently composition of the pore water of the La Baie clay
necessary to the development of quickness. The composition of
the clay pore water is compared with the average composition of Seawater* Pore water Ratio
For personal use only.
.--- -
sodium, potassium, and magnesium with depth follow the same
trend as the variation of the CEC (Fig. 4). Sodium makes up 4 2.0 - [I'
&-
-
=a
SO -
I o<--31------:g:
,,,- --- ------
a-
up about 30% of the total exchangeable cations, is very high 0.5: 'o ,,"";'
-
compared with the amount of magnesium in the free pore water. fi 1 5 ,,' *, ,, 2.0-
, , a - - - - --
--
Although the double-layer theory predicts a larger proportion of 2 o,2-
x
;,, ,, -
divalent cations in the adsorbed system than in the equilibrium 2 ;o,l a
solution, it is probable that at least a portion of the measured O.l:
;1', _ -
0
I 0 I
I 2 2.5- 1 ,-b 0
Can. Geotech. J. Downloaded from www.nrcresearchpress.com by University of Regina on 05/02/13
I I ,:8;-~-6--------A~
Storage procedures 6 -
I
0 -
u
E o n
-0'-
'
,a U N W A X E D SAMPLES:
g0
Upon reception, the samples, which had been waxed with ,I I
-.
0 AIR 'a
- 5.0-
several layers of paraffin, were stored in a wet room at 20°C and I I O OXYGEN '
Z
/
I
I
I
I
A NITROGEN
-
g
p 2.5-
I - 0
-
,'
,
0 _
most frequently used in soil laboratories. For that reason it will C -
I
1
)
1 - 5:
-I
-&--+
-/o;---Q--
>-
- - - - - - - O
I
be referred to as "standard" procedure. Two months after $ I
I
'
'\
3
0
sampling, several samples were removed from the wet room and 2 - 1
o'. ..- , 20
stored under "special" storage conditions. bx...~o A-s ---____ cjD---~.
.',.
1 - -----a- ---_..-.- 101- -
In order to better understand the role of oxidation in the aging --
.-.4:-------.
phenomenon, several samples were unwaxed and stored at 20°C o I I o I
g,o
..
containers filled with air, nitrogen, and oxygen. The nitrogen
and oxygen atmospheres were obtained by flushing the con-
tainer with the appropriate gas for about 5 min. The degree of 8.0
\
, - LO
20 2 5 - I,:.-
&
,
A,---
Bb-;gn--------d--
_ _ ---a-
-
-
oxygen depletion was not assessed. A bottle of water was placed a
in each of the containers to maintain 100% relative humidity. 7.5
0 5 10 15
-O
0 5 10 15
In order to study the effect of temperature on aging, six TIME AFTER SAMPLING -MONTHS TIME AFTER SAMPLING - MONTHS
200 g were at 40C' After months of FIG. 5. Effect of time on the properties of samples unwaxed 2 months
the wax on two of the samples was removed, in order to after sampling and stored in air, 02,and N2 at 2Oof'.
accelerate the rate of aging.
In an attempt to measure the influence of bacterial activity on
aging, four 400 g samples were sterilized using X-rays frdm a brownish. The samples had fissured and seemed stronger and
60Co source. The waxed undisturbed samples were irradiated stiffer as if they had dried, but measurement of the water content
for 24 h, receiving a total dose of 0.2 MGy (20 Mrad).' A dose showed no significant change during the storage period. The
of 0.02-0.04 MGy (2-4 Mrad) is generally recommended for undisturbed strength increased by 10-20% during aging.
100% sterilization (McLaren et al. 1957, 1962; McLaren However, this might be due to the loss of sensitivity, which
increases the adhesion along the fall-cone.
1969). The effect of irradiation on the geotechnical and
chemical properties of the clay is minimal. A visual examina- The remoulded strength increased markedly with time,
tion of one sample immediately after sterilization showed the whereas the liquidity index and the pH decreased, as shown in
same extreme quickness as before. The sterilized samples were Fig. 5. The concentration of all ions in the pore water increased
stored in standard conditions, i.e., waxed, at 20°C, and 100% with time, with the exception of bicarbonate, which shows a
relative humidity. downward trend beginning some 3 months after removal of the
The changes in properties of all the samples stored under wax coating. The chloride concentration was found to remain
"standard" or "special" conditions were measured by periodic very low during aging and for that reason has not been plotted. It
tests carried out over a 12 month period. At the end of the testing is noteworthy that the use of nitrogen did not slow down the
program on aging, one sample that had been left in the original aging process. It appears that the amount of residual air in the
Shelby tube for a period of 14 months was also tested. container or possibly seeping through the "airtight" seal is
quite sufficient to achieve considerable oxidation of the sam-
Results pies. In this regard, it should be pointed out that the greatest
Unwaxed samples scattering in the results was obtained between two samples from
After 3 months' storage in airtight plastic containers, in the about the same depth, stored 114 months in the same N2-filled
presence of air, oxygen, and nitrogen, all samples were partially plastic container.
covered with white and orange mold and with brown to black Waxed samples
spores. The clay, originally bluish gray in colour, had turned As shown in Fig. 6, the changes in geotechnical properties
and pore water chemistry of waxed samples stored at 20°C were
h he gray (Gy) is the absorbed dose that is equal to one joule per less pronounced than in unwaxed clay (Fig. 5). The wax slowed
kilogram (J/kg) . down the aging process but did not prevent it. With time, more
LNDMITCHELL 34 1
5.0
SAMPLE
- 8~ ZOOC
WAXED m 0
22'0- UNWAXED 0 0 ,"-
,
Can. Geotech. J. Downloaded from www.nrcresearchpress.com by University of Regina on 05/02/13
7.51 I I I I I
5 10 15 0 5 10 15 LOO
TIME AFTER SAMPLING - MONTHS TIME AFTER SAMPLING - MONTHS
50
FIG. 7. Effect of time on the properties of waxed and unwaxed
samples stored in air, at 4OC, and 20°C. The arrows indicate when the
wax was removed from the samples.
20
;
A
no brownish ring of oxidation was found on the periphery of the STORAGE CONDITIONS
sample. The steel itself did not show any sign of oxidation inside 2
SAMPLE 4'C 20DC
the tube. Apparently, the thick wax caps are less susceptible to WAXED •
the formation of small fissures (possibly caused by handling or I
UNWAXED O 0
,,I WAXED m
0.05
..
r e o .cr C: .-2
0 UNWAXED O 0
Can. Geotech. J. Downloaded from www.nrcresearchpress.com by University of Regina on 05/02/13
0.1 0.2 0.5 1.0 2.0 5.0 10 20 50 LOO 200 500 1000
CONCENTRATION - msq/L
FIG. 13. Relationship between remoulded strength and the con-
centrations of divalent cations and divaient plus monovalent cations in
samples stored under various conditions.
QUIGLEY,R. M. 1980. Geology, mineralogy, and geochemistry of TAVENAS, F., CHAGNON, J.-Y., and LA ROCHELLE, P. 1971. The
Canadian soft soils: a geotechnical perspective. Canadian Geotech- Saint-Jean-Vianney landslide: observations and eyewitnesses ac-
nical Journal, 17, pp. 261-285. counts. Canadian Geotechnical Journal, 8, pp. 463-478.
RANKIN,W. L. 1970. Suggested method of test for organic matter TORRANCE, J. K. 1976. Pore water extraction and the effect of sample
content of soils by redox titration. American Society for Testing and storage on the pore water chemistry of Leda clay. Soil Specimen
Materials, Special Technical Publication, No. 479, pp. 286-287. Preparation for Laboratory Testing, American Society for Testing
SNOEYINK,V. L., and JENKINS,D. 1980. Water chemistry. John and Materials, Special Technical Publication, No. 599, pp. 147-
Wiley & Sons, New York, NY, 463 p. 157.
S~DERBLOM, R. 1969. Salt in Swedish clays and its importance for YONG,R. N., SETHI,A. J., and LA ROCHELLE, P. 1979. Significance
quick-clay formation. Results from some field and laboratory of amorphous material relative to sensitivity in some Champlain
studies. Swedish Geotechnical Institute, Proceedings, No. 22,63 p. clays. Canadian Geotechnical Journal, 16, pp. 51 1-520.
1974. Aspects on some problems of geotechnical chemistry, YONG,R. N., SETHI, A. J., and SUZUKI,A. 1980. Contribution of
Part 111. Swedish Geotechnical Institute, Proceedings, No. 55, pp. amorphous material to properties of a laboratory-prepared soil.
452-468. Canadian Geotechnical Journal, 17, pp. 440-446.
Can. Geotech. J. Downloaded from www.nrcresearchpress.com by University of Regina on 05/02/13
STUMM,W., and MORGAN,J. J. 1970. Aquatic chemistry, Wiley ZAJIC,J. E. 1969. Microbial biogeochernistry . Academic Press, New
Interscience, New York, NY. York, NY, 345 p.
SVERDRUP, H. U., JOHNSON, M. W., and FLEMING, R. H. 1942. The
oceans, their physics, chemistry and general biology, Prentice-Hall
Inc., New York, NY.
For personal use only.