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AB ST R ACT : Natural zeolites have traditionally been used as supplements in animal nutrition with
positive effects in terms of either faster growth or reduced incidence of diseases and death. The
discovery that natural zeolites may act as drugs or coadjutants in pharmaceutical preparations has
greatly enlarged the field of their applications in many sectors of biology and medicine, opening
unexpected horizons for either basic or applied research. This review updates the state of the art of
research in this sector, focusing on clinoptilolite-rich materials, with two main purposes: (1) trying to
rationalize this subject, which is extremely variable and heterogeneous, and (2) raising doubts about
unsuitable uses of natural zeolites in the light of their known properties and expected behaviour.
KEYWORDS: natural zeolites, clinoptilolite, animal feeding, veterinary science, biomedicine, pharmacology,
health care.
The first experiments on surface-active materials
for biomedical uses concerned animal nutrition.
Several publications, from the early 1950s, reported
that dietary clay supplements (bentonite and
kaolin), used as binding and lubricating agents in
the production of pelleted feeds for poultry, resulted
in evident improvements in animals performance.
Later studies demonstrated that improvements did
not depend on the way feed was administered, but
just on the presence of clay, resulting in a
slowdown of feed passage rate through the
intestinal tract and therefore in better nutrient
assimilation and calorific efficiency (Quisenberry,
1968).
The use of natural zeolites, namely clinoptiloliteand mordenite-rich tuffs, for animal nutrition began
in Japan in the mid 1960s in imitation of the
* E-mail: carmine.colella@unina.it
DOI: 10.1180/claymin.2011.046.2.295
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Alkaline nature
Depending on their structure and chemistry, the
zeolites are subjected to hydrolysis, which can be
regarded also as a cation exchange reaction with the
hydronium ion, giving rise to alkaline pHs,
according to the following main equilibrium:
MZ + n H2O > HnZ + Mn+ + n OH
n+
(1)
Cation exchange
Zeolites are the most important inorganic cation
exchangers. Ion exchange arises from the presence
of extraframework cations located in the regular
array of channels and cages of the rigid anionic
framework. Cations are bound to the lattice and to
water molecules, which normally fill the zeolite
micropores. When a zeolite is put into contact with
an electrolyte solution, the extraframework cations
are removed from their sites and replaced by other
cations from the solution, according to the
following equilibrium reaction:
AnZ + m Bn+(s) > BmZ + n Am+(s)
(2)
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(4)
Physical sorption
This is a key property of zeolites, which enables
functionality in operations of great industrial
relevance, such as molecular sieving and catalysis.
The interaction of molecules with the extended
internal surface of zeolites (several hundred m2g 1)
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TABLE 1. Quantitative X-ray analysis of three clinoptilolite-bearing rocks (wt.%).
Sample
PEN1
SCL2
MIC3
CLI
O-CT
QTZ
FEL
BIO
SME
92
66
71
2
5
4
5
19
16
1
2
1
4
8
From de Gennaro et al., 2005. 2 From de Gennaro et al., 2010. 3 This study.
Legends: PEN = Pentalofos (Thrace, Greece); SCL = St. Cloud (NM, USA); MIC = Michoacan (SW Mexico).
CLI = clinoptilolite; O-CT = Opal-CT; QTZ = quartz; FEL = feldspar; BIO = biotite; SME = smectite.
Porosity (%)
13.0
33.2
28.4
0.04
0.25
0.21
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BIOMEDICAL ZEOLITE
APPLICATIONS
With reference to the properties described above,
natural zeolites present a wide spectrum of possible
applications in bio-medicine. Zeolite application as
a drug, coadjutant in medicine or supplement in
animal feeding is, however, subjected to preliminary assessments of its toxicological effects.
Many studies can be found in the literature
demonstrating that zeolite (mainly CPT) administration, even for several months, to animals or
humans showed no evidence of harmful reaction or
adverse change of their biochemical and haematological profiles (see, e.g. Martin-Kleiner et al., 2001
[and references therein]; Anonymous, 2003,
ESA (m2g 1)
ECEC (meq kg 1)
ESCD (e nm 2)
ESCD (C m 2)
14.0
11.4
18.3
149
102
135
6.4
5.4
4.6
1.0
0.9
0.7
1
See Table 1 for sample identification. ESA = External surface area; ECEC = External cation exchange capacity;
ESCD = external surface charge density. e = elementary charge; C = Coulomb.
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ZEOLITES IN ANTICANCER
THERAPY
This is the most recent field of potential application
of natural zeolites: research started in fact at the
end of the 1990s. The subject is treated separately
because of the complexity of the biological
processes involved. At present, the action mechanisms of zeolites are unknown and only hypotheses
have been made. It is recognized, however, that
zeolites must be considered only as adjuvants in a
possible anticancer therapy.
Most research on the use of clinoptilolite in
oncology has been carried out in the laboratories of
the Division of Molecular Medicine, Ruer Boskovic
Institute, Zagreb (Croatia) (Poljak-Blazi et al.,
2001; Pavelic et al., 2001b, 2002; Zarkovic et al.,
2003; Katic et al., 2006). The CPT sample used in
all the studies was a Slovakian material, finely
powdered by tribomechanical micronization. Either
in vitro or in vivo experiments were carried out.
Experiments in vivo on mice and dogs, suffering
from a variety of tumour types, resulted in
improvement of the overall health status, prolonged
life-span, and decrease in tumour size. In addition,
local application of CPT to skin cancers in dogs
effectively reduced tumour formation and growth.
Experiments in vitro on tissue cultures helped to
interpret these results through the analysis of
various medical and biochemical parameters.
These appeared to be distinct in the cancer
evolution with and without CPT treatment.
Initially, the positive results were explained in
terms of attenuation of survival signals and
induction of tumour suppressor genes in the
treated cells (Pavelic et al., 2001b). Further
research in vivo demonstrated antimetastatic and
immunodepressive effects of clinoptilolite (Pavelic
et al., 2002). Treatment of animals with CPT in
combined cancer therapy (specifically with an
antibiotic used in chemotherapy) resulted in strong
reduction of the pulmonary metastasis count, giving
indications in terms of interference of CPT with
lipid peroxidation (Zarkovic et al., 2003). In
contrast to the previous papers, which did not
mention the effective role of clinoptilolite, in the
most recent paper of the group (Katic et al., 2006),
the positive results of CPT is credited, at least
partially, to adsorption of growth factors from
serum (with the presumable involvement of external
surface activity of the zeolite) and to modification
of ion concentrations in the cellular microenviron-
ment, which may affect Ca2+ levels and calciumdependence, signalling pathways through ion
exchange. Results coherent with those of the latter
paper have been obtained more recently with a
Cuban CPT (Martn et al., 2010).
In summary, this field of investigation needs
further research to find more strict connections
between the results obtained and the action actually
played by the zeolite.
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