Applied Clay Science 43 (2009) 98102

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Applied Clay Science

j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / c l a y

Modication of clay properties by aging: Role of indigenous microbiota and

implications for ceramic processing
Roberta Gaidzinski a,, Patrcia Osterreicher-Cunha b, Jamil Duailibi Fh. c, Lus Marcelo Tavares a
a
b
c

Department of Metallurgical and Materials Engineering, COPPE, Universidade Federal do Rio de Janeiro, UFRJ. Cx. Postal 68505, CEP 21941-900, Rio de Janeiro, RJ, Brazil
Department of Civil Engineering, Pontifcia Universidade Catlica do Rio de Janeiro, PUC-Rio. Rua Marqus de So Vicente 225-301 L, CEP 22451-900, Rio de Janeiro, RJ, Brazil
Department of Processing and Characterization of Materials, Instituto Nacional de Tecnologia (INT), Av. Venezuela 82, CEP 20081-312, Rio de Janeiro, RJ, Brazil

a r t i c l e

i n f o

Article history:
Received 18 September 2007
Received in revised form 30 June 2008
Accepted 3 July 2008
Available online 15 July 2008
Keywords:
Aging
Clays
Technological properties

a b s t r a c t
Storing clays for a period of time before their use in ceramic processing is recognized to improve their
technological properties as compared with the corresponding freshly-mined materials. Although the
mechanisms underlying this aging process are not well understood, the improvements in quality have often
been attributed to biological factors. The paper investigates the role of indigenous microorganisms and their
activity in clay aging. Two clays from Brazil were sterilized by autoclaving and gamma-ray irradiation, and
their chemical, physical, and technological properties were measured after storing for 6 months. For
comparison, the same measurements were carried out on non-sterilized samples that were subjected to the
same conditions. The clays did not present the same response to sterilization, since aging was benecial for
the ceramic properties of one clay and detrimental to the other. A comparison of data from sterilized and
non-sterilized aged samples showed that the changes in chemical properties could not be directly related to
the presence of microorganisms, since the clays responded to aging independently of sterilization. Further,
the changes in the technological properties of the clays with aging were probably related to their initial
physical properties and not to the presence of microorganisms.
2008 Elsevier B.V. All rights reserved.

1. Introduction
Storing freshly-mined clays in stockpiles and subjecting them to the
action of environmental elements during a reasonable period of time
before entering the production process is a practice often used in the
Ceramic Industry to improve the technological properties of clays (Abajo,
2000). This process, called aging, generally results in the improvement
of the rheological behavior of the clays. The improvement in rheology, in
particular, plasticity, results in better clay workability during ceramic
processing stages, such as drawing and pressing (Abajo, 2000).
Investigations presented in the literature have suggested that the
biological action is the most signicant mechanism responsible for the
improvements during aging (Vaiberg et al., 1980; Groudeva and
Groudev, 1995; Velde, 1995; Abajo, 2000). Organic acids, mainly citric,
gluconic and oxalic acids, released during bacterial growth through
oxidation of inorganic sulfur or nitrogen compounds, are capable of
solubilizing Fe+ 3 and Al+ 3 ions from clay mineral structures (Groudeva
and Groudev, 1995). These modify the clay mineral charge, the specic
surface area, and also the pH of the dispersions, which could contribute
to increased plasticity (Abajo, 2000). Some microorganisms are

Corresponding author. Present address: Centro de Tecnologia Mineral (CETEM) Av.

Pedro Calmon, 900, Cidade Universitria, Rio de Janeiro, Brazil. Tel.: +55 21 38657256;
fax: +55 21 25903047.
E-mail address: gaidzinski@cetem.gov.br (R. Gaidzinski).
0169-1317/$ see front matter 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.clay.2008.07.007

responsible for secretion of polysaccharides, which can bridge the

particles in aggregates and promote an increase in plasticity and a
reduction in drying shrinkage (Abajo, 2000).
Investigations to assess the inuence of microorganisms in the
process of clay aging (Vaiberg et al., 1980; Baranov et al., 1985)
demonstrated that processing clays using bacteria increased both
plasticity and strength after drying and sintering and reduced water
absorption. Besides improving the ceramics technological and physicochemical properties, the treatment also reduced the required time for
aging. Work from Groudeva and Groudev (1995) demonstrated the
contribution of extra-cellular polysaccharides in this process. They
showed that silicate bacteria cultures were the most effective to improve
the ceramic properties of kaolins from Bulgaria. The improvement by
these bacteria was attributed mainly to the mucilaginous exopolysaccharides produced during their growth. Organic acids produced by
bacteria were considered to be responsible for the reduction in the size
of kaolin particles, which increased plasticity. Another key factor
identied to be responsible for the increase in plasticity was the
formation of colloidal particles as a result of the partial degradation of
the structure of clay minerals, mainly aluminum and iron hydr(oxides)
and silica.
The present work aims to assess the role of indigenous soil
microorganisms in clay aging, when isolated or bioaugmented microorganisms and/or populations have not been introduced in the clays.
The role of these microorganisms was investigated by comparing the

R. Gaidzinski et al. / Applied Clay Science 43 (2009) 98102

characteristics of clays that were sterilized using different techniques to

those of non-sterilized clays both before and after storage for 6 months.
2. Materials and methods
2.1. Clay samples
Samples from Itabora (State of Rio de Janeiro) and from Santa
Gertrudes (State of So Paulo) were collected for the study. The freshly
collected samples were placed in sealed plastic bags, the samples were
air-dried, crushed in a laboratory smooth double roll crusher, mixed
and then coned and quartered using a conical heap (Herbst and
Sepulveda, 1985) to guarantee that the samples were as representative
as possible. Each lot of clay was then split into four representative
samples for testing: one sample was used for initial material
characterization, two were sterilized using irradiation and autoclaving, respectively, and the last was left non-sterilized and used as a
control sample.
2.2. Characterization
Mineralogical analyses were carried out by X-ray diffraction. These
analyses were conducted with samples of the clay fraction (natural,
heated and intercalated with ethylene glycol) of each raw material, in
pulverized form, using CuK radiation with sweeping angles 2
varying from 3 to 60 (Jackson, 2005). The chemical composition of
the raw materials was determined by X-ray uorescence spectrometry. The loss on ignition and the moisture content were determined
by gravimetric methods. The plasticity of the clays was determined
according to Associao Brasileira de Normas Tcnicas (1984a,b) from
calculation of Atterberg indices: lower plasticity limit (LPL), upper
plasticity limit (UPL) and plasticity index (PI).
2.3. Sterilization
Sterilization consisted of rst conditioning a representative sample
of each clay in an Erlenmeyer ask. Autoclaving was carried out using
an autoclave, set at 121 C and 1 kgf/cm2 (1 atm). Following
recommendations from Wolf and Skipper (1994), samples were
subjected to three consecutive 1-hour sessions of autoclaving with 2day incubation periods in-between sessions.
Selected samples were irradiated using gamma radiation with a
60
Co isotope source, in a Gammacell irradiator (MDS Nordion, model
GC220E). The radiation dosage used was 28 kGy, with 4.0 kGy/h for a
total time of 7 h. This dosage was chosen following the literature
(Brown, 1981; Lessard and Mitchell, 1985), which suggests that a
dosage in the range from 20 to 40 kGy would be sufcient for the
inhibition of bacterial activity in soils and clays.
After three autoclaving sessions and one 28 kGy-irradiation
session with samples of the two different clays, the effectiveness of
the sterilization process was assessed by analyzing the survival of
culturable bacterial populations. Pour-plating was used as described
by Lorch et al. (1995). Briey, 1 g of clay was used for successive
dilutions down to a concentration of 10 4, and 1 mL of this diluted
sample was added to the culture medium (Tryptone Soy Broth 1:10
with 1.8% of agar) in Petri dishes (plates). Triplicate samples were then
incubated at 30 C for a period of 10 days, at the end of which, it was

99

veried if any growth of microorganism cultures occurred in the

plates.
For autoclaved samples, no growth of microorganisms was
observed in the plates. However, for irradiated samples growth of
microorganisms in the plates was observed for both clays studied.
Therefore, an additional irradiation session at a dosage of 28 kGy was
carried out for each clay. The additional irradiation session was
conducted 3 days after the last irradiation, during which period the
samples were kept at 30 C. A subsequent new plating of the samples
demonstrated no growth of microorganisms. The overall dosage of
irradiation for each sample was equal to 56 kGy (two 28 kGy sessions).
2.4. Experiments after sterilization
After sterilization, samples were kept at room temperature for
6 months in sealed containers to simulate the process of aging. In
addition, clay samples that were not subject to sterilization were also
stored for the same period under the same conditions. After the end of
this storage period, chemical, biological and technological characterization tests were carried out. Chemical characterization consisted of
pH measures in water (Thomas, 1996), of redox potential using
potentiometric methods (Patrick et al., 1996) and measurement of
the amount of organic matter with the Walkley and Black method
(Embrapa, 1997). The cation exchange capacity was determined by
adsorption of methylene blue (American Standard for Testing and
Materials, 1999). The specic surface area of particles was determined
by adsorption of N2 gas at 195 C, and applying the BET equation using
a Quantachrome instrument.
Biological characterization was conducted by measuring the total
degrading enzymatic activity of the clays (Adam and Duncan, 2001).
This consisted of adding 2 g of clay to 15 mL of potassium phosphate
buffer and incubating the suspension with 200 L of uorescein
diacetate (FDA) for 20 min at 30 C using an orbital shaker at 100 rpm.
After incubation, the samples were centrifuged during 3 min at
2000 rpm, ltered and the amount of uorescein formed by microbial
activity was determined in the ltrate with a Gensis 2 spectrophotometer (Spectronics Instruments) at 490 nm. For each analyzed
sample, a blank with no FDA and eight replicates were prepared. The
statistical treatment used for these results was the test Q with
reliability level at 90% condence (Ohlweiler, 1984).
Technological characterization of the samples consisted of rst
preparing test bodies measuring 11.4 2.5 1.0 cm by applying a 30MPa uniaxial pressure. After drying at 110 C, the test bodies were then
sintered in the laboratory at 1050 C, with a heating/cooling ramp of
10 C/min and maintaining at the set temperature for 1 h. The following
parameters were then measured: apparent density, linear retraction,
exural strength (American Association of Testing Materials, 1988b),
water absorption (American Association of Testing Materials, 1988a)
and loss on ignition.
3. Results and discussion
3.1. Clays characterization
Table 1 summarizes data on the particle size distributions and
measurements of plasticity of the two clay samples. Itabora clay
presented the largest proportion of material b2 m and was classied

Table 1
Physical properties of the clays
Clay

Itabora
Santa Gertrudes

Mass (%)

Plasticity (%)

Coarse sand (20.2 mm)

Fine sand (0.20.05 mm)

Silt (0.050.002 mm)

Clay (b0.002 mm)

LPL

UPL

PI

8.0
30.6

4.6
21.8

21.4
25.6

66.0
22.0

36.24
22.30

69.00
34.20

32.8
11.9

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R. Gaidzinski et al. / Applied Clay Science 43 (2009) 98102

Table 2
Chemical composition of the clays (mass %)
Clay

Al2O3

SiO2

TiO2

Fe2O3

CaO

Na2O

MgO

K2O

P2O5

Mn2O3

Itabora
Santa Gertrudes

25.46
15.05

47.87
69.62

1.11
0.70

7.62
5.28

0.06
0.81

0.13
1.98

1.25
2.55

1.92
3.78

0.08
0.19

0.04
0.04

14.46
8.20

LOI

Loss on ignition.

as highly plastic (PI N 15%). Santa Gertrudes clay contained lower

proportion of material b2 m and intermediate plasticity (7% b
PI b 15%).
The mineralogical characterization of the b2 m material by means
of X-ray diffraction and semiquantitative analyzes (Santos, 1998)
showed the presence of 24% illite and smaller amounts of kaolinite
and smectite for the Itabora clay; and illite (47%), and smaller
amounts of kaolinite, quartz and interstratied smectitevermiculite
for the Santa Gertrudes clay.
Table 2 summarizes the chemical composition of the two clays.
Itabora clay presented low silica (SiO2) and high alumina (Al2O3)
content, which are indicative of the high content of clay minerals
present. In the case of Santa Gertrudes clay the opposite occurred,
with a high content of silica and low alumina content, which are
indicative of the low proportion of clay minerals and large amounts of
free quartz in the sample. Santa Gertrudes clay showed a high
potassium oxide content, which is probably due to the presence of
illite, already identied by X-ray diffraction. The alkaline earth oxide
(CaO and MgO) contents are also higher, which may be an indication of
the presence of carbonates.
Itabora clay presented a higher moisture content and specic
surface area than Santa Gertrudes clay (Table 3). Santa Gertrudes clay
was mildly alkaline (pH in H2O), whereas Itabora clay was acid.
Negative pH (Table 3) indicates that both samples are cationretaining clays. They present redox potentials in the interval of 100 to
+100 mV, which characterizes them as reducing clays (Patrick et al.,
1996). The lower absolute value for Santa Gertrudes clay indicated
predominance of metabolism of strictly anaerobic microorganisms.
The redox potential for Itabora clay is characteristic of metabolism of
strictly aerobic microorganisms. Further, Itabora clay presented a
higher cation exchange capacity than Santa Gertrudes clay due to the
presence of smectite. The enzymatic activity of Itabora clay was
higher than that of Santa Gertrudes clay.

the enzymatic activity for Itabora clay, compared to a modest

reduction for Santa Gertrudes clay. Particularly for Itabora clay,
aging was detrimental to the microbiota.
3.3. Aging of sterilized samples
For the autoclaved sample of Santa Gertrudes clay, the enzymatic
activity was zero (Table 3) indicating that no microorganisms survived
in the sample, at least in active state, or evolved during aging. The
irradiated sample showed an 86% reduction in the enzymatic activity
in comparison to the initial sample. As in this case the culture of clays
samples was negative immediately after sterilization (Section 2.3),
non-culturable microorganisms and/or exoenzymes probably survived, resisting the irradiation treatment. Exoenzymes, released by
microorganisms to act outside the cells, do not survive autoclaving, but
are able to resist irradiation. Therefore, in the irradiated samples, active
enzymes present in the clay can exist and hydrolyze FDA, while whole
bacterial cells that form colonies on the culture media have been
eliminated. This does not occur with autoclaving. The positive
enzymatic activity observed is only related to the non-culturable
microorganisms that resisted sterilization. This is in accordance with
the activity results of all sterilized samples, with the activity in
autoclaved samples being lower than those of irradiated ones (Table 3).
In the case of Itabora clay neither autoclaving nor irradiation resulted
in an enzymatic activity of zero after aging, which indicated the
survival of microorganisms in these samples. These microorganisms
that resisted sterilization were also non-culturable, since they did not
appear active upon plating conducted immediately after sterilization
(Section 2.3). Still, signicant reduction in the enzymatic activity in
relation to the non-sterilized samples was observed.
Larger amounts of organic carbon and ner soil particles can
protect the microbiota from harsh environmental conditions as well as
from predation. Finer materials that create smaller pores also promote
the formation of aggregates that provide deep protection for microbial
cells. However, a less efcient circulation of air and water inside these
pores and aggregates depletes those populations of appropriate
amounts of oxygen and nutrients for intensive activity. Also, the
higher specic surface area of ner soils provides better support for
the adhesion of microorganisms (Ladd et al., 1996; Krumholz, 2000;

3.2. Aging on non-sterilized samples

No signicant change in moisture content and organic matter
occurred, whereas a reduction was observed in cation exchange
capacity (Table 3). Aging at the conditions studied strongly reduced

Table 3
Changes of the chemical and biological properties of the clays after sterilization and aging
Clay

Itabora

Santa
Gertrudes

Aging

None
Yes
Yes
Yes
None
Yes
Yes
Yes

Sterilization

None
None
Autoclaving
Irradiation
None
None
Autoclaving
Irradiation

Moisture
(%)

E.A.
(g/min g)

b
Eh
(mV)

7.12 (0.4)
7.14 (0.8)
4.43 (Na)
7.09 (Na)
3.70 (1.5)
3.53 (0.9)
2.81 (Na)
3.35 (Na)

0.0744 (30.9)
0.0012 (27.2)
0.0023 (2.9)
0.0177 (12.9)
0.0378 (10.5)
0.0232 (22.8)
0.0000 (0.0)
0.0053 (0.0)

98.9
90.7
86.3
143.3
43.2
85.0
35.6
66.6

Coefcients of variation in parentheses. Na: Measurement not available.

a
Enzymatic activity.
b
Redox potential.
c
Organic matter.
d
Cation exchange capacity.
e
Specic surface area.

pH
H2O

KCl

pH

4.8
4.4
4.3
4.7
7.8
8.9
6.9
7.3

3.3
3.1
2.9
3.2
5.9
7.3
4.9
5.4

1.5
1.3
1.4
1.5
1.9
1.6
2.0
1.9

c
O.M.
(g/kg)

d
CEC
(meq/100g)

1.7
1.5
1.7
1.7
1.9
1.9
1.8
1.5

9.0
6.8
4.8
7.0
5.5
3.0
2.3
1.8

30.7
Na
25.8
33.6
10.9
Na
9.7
12.3

SSA
(m2/g)

R. Gaidzinski et al. / Applied Clay Science 43 (2009) 98102

Ranjard and Richaume, 2001; Holden and Fierer, 2005). Sandy media
present higher porosity and therefore better air, water and nutrients
circulation and input, favoring microbial growth to some extent. On
the other hand, in such soils humid heat from autoclaving has greater
penetration capacity thus providing a more efcient sterilization, as
seen in the case of the Santa Gertrudes clay. As for irradiation, soils
with a large proportion of material b2 m (such as Itabora clay)
present better protection for microorganisms, hindering and/or
obstructing the efciency of sterilization.
A reduction in the amount of organic matter was observed for
irradiated samples of Santa Gertrudes clays samples. This may be
related to the consumption by remaining microorganisms during the
long time (6 months) of incubation after sterilization with no increase
in biomass and also to organic matter denaturation after sterilization
(McNamara et al., 2003). As the organic matter includes biomass, this
reduction also could have occurred as a result of the death of the
microorganisms. The measurement of organic matter carried out in
the present study gives the total carbon content. However, the organic
carbon can be present in the biomass and/or the clay. Since for the
aged non-sterilized sample no consumption of organic matter was
observed, it is likely that the reduction is associated to denaturation of
organic matter.
No changes in the organic matter were observed after sterilization
for the Itabora clay sample. The ner particle size could be, at least in
part, responsible for these results. The organic matter could also be
conned in the small pores of the clay, being thus protected against
denaturation or consumption by microorganisms that survived
sterilization. It is still possible that the biomass associated with the
organic substance was not totally eliminated by sterilization, since
some activity was detected. Since no change in organic matter was
observed for the non-sterilized sample, it may be concluded that no
consumption of organic matter was produced by the microorganisms
present in the sample during aging.
Some variations have been observed in the redox potential, both
for sterilized and non-sterilized samples, but they remained within
the expected range of redox reactions of all clays (Table 3).
The pH values of both clays in water changed after sterilization by
autoclaving. Salonius et al. (1967), Brown (1981), Shaw et al. (1999)
and Gaidzinski (2006) observed a decrease in pH of soil samples after
autoclaving. This reduction was attributed to the solubilization of
organic acids during autoclaving. However, Wolf et al. (1989) did not
observe changes in the pH of soil samples after three autoclaving
sessions. Thus, different soils may behave differently, demonstrating
the importance of the specic properties of each soil.
Sterilization reduced the cation exchange capacity. One of the most
likely factors is the reduction in negative charge density in the surface of
clay minerals as a result of the dead population of microorganisms after
sterilization. Another factor would be the dead biomass associated to
organic matter.

101

On the other hand, the reduction in cation exchange capacity of

both non-sterilized clays could be related to the reduction in their
enzymatic activity and the detrimental effect of aging. As the result of
the death of microorganisms by the reduction of oxygen intake, water
and nutrients to the clays (the samples were stored in sealed plastic
bags during aging) there was a reduction in negative charge density in
the surface of clay minerals as a result of the dead population of
microorganisms.
Only a marginal change of specic surface area was observed after
sterilization and aging, with a reduction in the case of autoclaved and
an increase in the case of irradiated samples (Table 3). The reduction in
the specic surface area during autoclaving is consistent with results
by Jenneman et al. (1986), who observed the same trend for
autoclaved soil samples. Based on results of scanning electronic
microscopy after autoclaving the authors demonstrated that the clay
mineral particles were changed into rounded-off shapes with the
increase in the amount of aggregates. These aggregates then
presented a lower surface area for adhesion of bacterial cells in
comparison to the original untreated clay. On the other hand, the
increase in specic surface area in comparison to the initial sample for
the irradiated samples is consistent with results from Pushkareva et al.
(2002). These researchers concluded that the increase in radiation
dosage caused an increase in the amount of centers of radiation within
the sample. An increase in the amount of different types of induced
radiation defects can result in the observed increase in the specic
surface area and, consequently, a higher protection against
sterilization.
3.4. Inuence of aging and sterilization on technological properties
Aging of non-sterilized samples did not signicantly inuence
neither the density of the green body or the sintered product nor the
linear retraction (Table 4). An improvement in some technological
properties was observed for Itabora clay: increase in exural strength
in both green and sintered test pieces and the reduction in water
absorption. The opposite response was found for Santa Gertrudes clay.
The different responses of the two clays to aging may be explained on
the basis of their distinct initial physical and chemical characteristics.
Aging under the conditions studied, that is, with no intake of air or
moisture, was favorable for some ceramic properties of Itabora clay. This
may be attributed to the comparatively higher initial plasticity, moisture
content and clay mineral content. The higher water-retention capacity
may have helped in wetting the clay mineral particles, as well as
hydrating the interlayer cations during the period of 6 months of storage.
This may have been responsible for improvement in clay rheology and,
in turn, exural strength of the test piece before sintering, as well as after
sintering. The opposite response of Santa Gertrudes clay to aging could
be associated to its comparatively lower initial moisture content and
plasticity, and coarser particle size, which resulted in an unfavorable

Table 4
Technological properties of the clays after sterilization and aging
Clay

Itabora

Santa Gertrudes

Aging

None
Yes
Yes
Yes
None
Yes
Yes
Yes

Sterilization

None
None
Autoclaved
Irradiated
None
None
Autoclaved
Irradiated

Coefcients of variation in parenthesis.

a
Loss on ignition.

LOI (%)

Unsintered
Density
(g/cm3)

Flexural strength
(MPa)

2.19 (3.1)
2.19 (1.0)
2.12 (2.9)
2.10 (1.5)
2.07 (2.5)
1.99 (2.2)
2.05 (1.5)
2.04 (1.7)

2.24 (23.0)
2.72 (8.4)
2.66 (10.0)
3.00 (12.5)
3.15 (13.3)
1.86 (3.0)
2.00 (5.0)
1.88 (4.6)

14.73 (0.4)
16.88 (0.3)
15.04 (1.3)
15.56 (1.5)
8.76 (3.8)
7.62 (1.1)
6.84 (1.1)
7.02 (0.6)

Sintered
Density
(g/cm3)

Flexural strength
(MPa)

Water absorption
(%)

Linear retraction
(%)

2.22 (3.0)
2.24 (0.01)
2.08 (2.5)
2.06 (2.2)
2.33 (1.5)
2.25 (1.1)
2.30 (2.1)
2.29 (2.6)

6.52 (23.1)
7.89 (14.8)
7.02 (6.0)
9.04 (8.8)
28.03 (7.1)
25.45 (1.2)
23.16 (0.7)
21.86 (3.0)

9.93 (1.1)
8.94 (5.0)
10.67 (4.8)
10.01 (4.2)
0.35 (12.7)
1.86 (13.8)
2.15 (4.3)
2.13 (0.6)

5.42 (1.9)
5.50 (1.9)
5.13 (1.8)
5.05 (3.6)
6.75 (1.1)
6.53 (0.3)
6.79 (1.0)
6.64 (1.7)

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R. Gaidzinski et al. / Applied Clay Science 43 (2009) 98102

effect of aging under the conditions of little oxygen intake and water
availability.
Essentially the same response to aging has been found for samples
that were subject to sterilization, in spite of the signicantly lower
enzymatic activity and cation exchange capacity of the clays subjected
to autoclaving and irradiation. This suggests that, under the aging
conditions studied, the change in ceramic properties observed may
not be attributed to the microbiology.
4. Conclusions
Three sessions of autoclaving at 121 C and 1 atm were capable of
sterilizing the clays, as measured from the lack of activity in bacterial
cultures in plates. Sterilization by irradiation was only successful with
a gamma irradiation dosage of 56 kGy, which is well above 40 kGy as
suggested in the literature (Brown, 1981; Lessard and Mitchell, 1985).
Measurement of enzymatic activity after storage for a period of
6 months demonstrated that complete sterilization was probably only
achieved for Santa Gertrudes clay subjected to autoclaving. The
differences observed in the behavior of the clays after sterilization may
be an indication of the role of mineralogy and diversity of microorganisms present.
Besides a reduction in enzymatic activity, aging and sterilization
also reduced the cation exchange capacity.
In respect to the technological ceramic properties, the samples
studied presented opposite responses to aging: while an improvement
in some properties was observed for Itabora clay, aging for 6 months
was detrimental to some ceramic properties, such as exural strength
and water absorption, of Santa Gertrudes clay. These changes were
observed for both sterilized and non-sterilized samples after aging for
6 months without direct contact with the environmental elements,
and are not likely to be related to microbiology. Indeed, the distinct
response of the clays to aging may be associated to the different initial
properties of the clays, including plasticity, particle size and moisture
content. The higher plasticity and moisture content, and ner size
distribution of Itabora clay make it amenable to aging even without
direct contact with fresh air or additional moisture. On the other hand,
the lower plasticity and moisture content and coarser size distribution
of Santa Gertrudes clay, coupled to exposure to conditions of poor
oxygen and no water intake studied resulted in a detrimental effect of
aging.
Acknowledgment
The authors would like to thank the nancial support from the
Conselho Nacional de Desenvolvimento Cientco e Tecnolgico.
References
Abajo, M.F., 2000. Manual sobre fabricacin de baldosas, tejas y ladrillos. Beralmar,
Colombia, 360 pp.
Adam, G., Duncan, H., 2001. Development of a sensitive and rapid method for the
measurement of total microbial activity using uorescein diacetate (FDA) in a range
of soils. Soil Biology and Biochemistry 33, 943951.
American Standard for Testing and Materials, 1988a. Standard Test Method for Water
Absorption, Bulk Density, Apparent Porosity, and Apparent Specic Gravity of Fired
Whiteware Products. ASTM C 37272, 2 pp.
American Standard for Testing and Materials, 1988b. Standard Test Methods for Flexural
Properties of Ceramic Whiteware Materials. ASTM C 674677, 4 pp.
American Standard for Testing and Materials, 1999. Standard Test Method for
Methylene Blue Index of Clay. ASTM C 837881, 2 pp.

Associao Brasileira de Normas Tcnicas, 1984a. Solo - Determinao do Limite de

Plasticidade. NBR 64596484 Rio de Janeiro, 3 pp.
Associao Brasileira de Normas Tcnicas, 1984b. Solo - Determinao do Limite de
Liquidez. NBR 71807184 Rio de Janeiro, 6 pp.
Baranov, V.V., Vainberg, S.N., Vlasov, A.S., Yashchenko, O.I., Sidorova, V.A., Skripnik, V.P.,
Solnyshkina, T.N., Nozhnikova, Yu.V., 1985. Effect of biological treatment of the ceramic
mass on the drying and ring of facing tiles. Glass and Ceramics 42, 239241.
Brown, K.A., 1981. Biochemical activities in peat sterilized by gamma-irradiation. Soil
Biology and Biochemistry 13, 469474.
Embrapa, 1997. Manual de mtodos de anlise de solo, 2 ed. Centro Nacional de Pesquisa
de Solos, Rio de Janeiro. 212 pp.
Gaidzinski, R., 2006. Fatores envolvidos no sazonamento e suas implicaes nas propriedades
de argilas para a indstria cermica. Ph.D. Thesis, Department of Metallurgical and
Materials Engineering, COPPE-UFRJ, Rio de Janeiro, 179p. (in Portuguese).
Groudeva, V.I., Groudev, S.N., 1995. Microrganisms improve kaolin properties. American
Ceramic Society Bulletin 74 (6), 8589.
Herbst, J.A., Sepulveda, J.L., 1985. Particle size analysis. In: SME Mineral Processing
Handbook (N.L Weiss, ed), vol. 2, Section 30, pp. 2043.
Holden, P.A., Fierer, N., 2005. Microbial processes in the vadose zone. Vadose Zone Journal
4, 121.
Jackson, M.L., 2005. Soil chemical analyses: advanced course. A manual of methods
useful for instruction and research in soil chemistry, physical chemistry of soils, soil
fertility, and soil genesis. UW-Madison Libraries Parallel Press, pp. 169251.
Jenneman, G.E., McInerney, M.J., Crocker, M.E., Knapp, R.M., 1986. Effect of sterilization
by dry heat or autoclaving on bacterial penetration through Berea sandstone.
Applied and Environmental Microbiology 51 (1), 3943.
Krumholz, L.R., 2000. Microbial communities in the deep subsurface. Hydrogeology
Journal 8, 410.
Ladd, J.N., Foster, R.C., Nannipieri, P., Oades, J.M., 1996. Soil structure and biological
activity. In: Stotzky, G., Bollag, J.M. (Eds.), Soil Biochemistry, 9. Marcel Dekker, New
York, pp. 2378.
Lessard, G., Mitchell, J.K., 1985. The causes and effects of aging in quick clays. Canadian
Geotechnical Journal 22, 335346.
Lorch, H.J., Benckieser, G., Ottow, J.C.G., 1995. Basic methods for counting microorganisms in soil water. Methods of Applied Soil Microbiology and Biochemistry, ch.4:
Enrichment, isolation and counting of soil microorganisms. Academic Press, San
Diego, pp. 146161.
McNamara, N.P., Black, H.I.J., Beresford, N.A., Parekh, N.R., 2003. Effects of acute gamma
irradiation on chemical, physical and biological properties of soils. Applied Soil
Ecology 24 (2), 117132.
Ohlweiler, O.A., 1984. Qumica Analtica Quantitativa, v. 1., 3rd ed. Livros Tcnicos e
Cientcos, Rio de Janeiro, Brasil. 365 pp.
Patrick, W.H., Gambrell, R.P., Faulkner, S.P., 1996. Redox measurements of soils. Methods
of Soil Analysis. Part 3: Chemical Methods. Soil Science Society of America,
Madison, WI, pp. 12551273. Book Series n.5.
Pushkareva, R., Kalinichenko, E., Lytovchenko, A., Pushkarev, A., Kadochnikov, V.,
Plastynina, M., 2002. Irradiation effect on physico-chemical properties of clay
minerals. Applied Clay Science 21, 117123.
Ranjard, L., Richaume, A., 2001. Quantitative and qualitative microscale distribution of
bacteria in soil. Research in Microbiology 152, 707716.
Salonius, P.O., Johnson, J.B., Chase, F.E., 1967. A comparison of autoclaved and gammairradiated soils as media for microbial colonization experiments. Plant and Soil 27,
239248.
Santos, J.P., 1998. Determinao do teor de ilita em argilominerais interestraticados a
partir da anlise do potssio total. Sitientibus - Revista da Universidade Estadual de
Feira de Santana, vol. 18, pp. 127141.
Shaw, L.J., Beaton, Y., Glover, L.A., Kilham, K., Meharg, A.A., 1999. Re-inoculation of
autoclaved soils as a non-sterile treatment for xenobiotic sorption and biodegradation studies. Applied Soil Ecology 11, 217226.
Thomas, G.W., 1996. Soil pH and soil acidity. Methods of Soil Analysis. Part 3: Chemical
Methods. Soil Science Society of America, Madison, WI, pp. 475490. Book Series
n.5.
Vaiberg, S.N., Vlasov, A.S., Skripnik, V.P., 1980. Treating clays with silicate bacteria. Glass
and Ceramics 37 (78), 387389.
Velde, B., 1995. Origin and Mineralogy of Clays: Clays and the Environment. Springer,
New York. 358 pp.
Wolf, D.C., Dao, T.H., Scott, H.D., Lavy, T.L., 1989. Inuence of sterilization methods on
selected microbiological, physical and chemical properties. Journal of Environmental Quality 18, 3944.
Wolf, D.C., Skipper, H.D., 1994. Soil sterilization. Methods of Soil Analysis. Part 2:
Microbiological and Biochemical Properties. Soil Science Society of America, Madison,
WI, pp. 4151. Book series n.5.