Bergaya F. Handbook of Clay Science
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such samples can elicit a mild, dose-dependent fibrogenic response at high exposure
levels. Generally, however, there is a concomitant exposure to other minerals (e.g.,
silica and amphiboles), and the response to these minerals complicates the interpre-
tation of the data. For example, bentonite deposits general ly contain other miner als,
including very fine-grained quartz and amorphous silica. In the case of Wyoming
bentonites, the silica content (which included both quartz and cristobalite) ranges
from 0 to 24% (Ross et al., 1993).
In vivo experiments suggest that samples containing these minerals are slightly
fibrogenic, and in vitro experiments indicate that they may be slightly cytotoxic
(Guthrie, 1992). Gormley and Addison (1983) studied three different samples of
montmorillonite. Although the materials show different cytotoxicities, much of the
variability is apparently due to SiO
2
polymorphs. However, most other montmo-
rillonite samples proved to be very cytotoxic in vitro (Daniel and Le Bouffant, 1980).
Lysis of bovine red blood cells (erythrocytes) by some silicate minerals was stud-
ied by Oscarson et al. (1986). The hemolytic activity of these minerals decreases in
the order smectites>silica>palygorskite E sepiolite>chrysotile>kaolinite. These
in vitro studies showed that the reaction is complete in less than 1 h when the mineral
surfaces became saturated with cellular components and lost their lytic activity.
11.5.3. CONCLUDING REMARKS
In pharmaceutical formulations, spas and beauty therapy, clay minerals are used
for therapeutic purposes and their beneficial effect on human health. In pharma-
ceutical formulations these minerals are used as active principles (gastrointestinal
protectors, antacids antidiarrhoeaics, dermatological protectors, cosmetics) and ex-
cipients (inert bases, delivery systems, lubricants, emulsifiers). In spas and beauty
therapy clay minerals are used in geotherapy, pelotherapy, and paramuds, to treat
dermatological diseases, alleviate the pain of chronic rheumatic inflammations,
moisturise the skin, and combat compact lipodystrophies and cellulite.
However, clay minerals can also have an adverse effect on human health when
they are inhaled over a very long period. In the lung, clay minerals can cause diverse
pathologies such as cancer, mesothelioma, or pneumoconiosis, but the toxicity of
these minerals is generally related to the presence of qua rtz or asbestos from mining
operations. The pathogenicity of fibrous clay minerals (sepiolite and palygor skite) is
related to the geologi cal conditions of formation.
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References 741
Handbook of Clay Science
Edited by F. Bergaya, B.K.G. Theng and G. Lagaly
Developments in Clay Science, Vol. 1
r 2006 Published by Elsevier Ltd.
743
Chapter 11.6
CLAYS AND CLAY MINERALS AS DRUGS
M.T. DROY-LEFAIX
a
AND F. TATEO
b
a
Beaufour-IPSEN, F-75016 Paris, France
b
Istituto di Ricerca sulle Argille, CNR, I-85050 Tito Scalo (PZ), Italy
Clay therapy is based on the ability of clays and clay minerals to adsorb and
retain harmful and toxic substances. The beneficial effects of these materials to
human health, notably in the treatment of gastrointestinal disorders, were recog-
nized. Indeed, the eating of clay (‘geophagy’) was practiced since antiquity in all
parts of the world. Among the variety of clays and clay minerals that were used by
primitive tribes are bentonite, kaolinite, montmorillonite, smectite, and ‘pascalite’
(a Ca
2+
-montmorillonite from Wyo ming, USA) (Eaton and Eaton, 1995).
Examination of the diets of certain tribes in the high Andes of South America and
central Africa, and those of Australian aborigines, showed that these people use clay
to avoid getting stomach-ache, dysentery, and food infections. Indeed, the Quetchus
Indians of South America used to dip their potatoes into an aqu eous suspension of
clay, immediately before eating, in order to prevent the build-up of acidity in the
stomach. This dietetic procedure is still being followed by some tribes of American
Indians. A similar practice was traditionally carried out on board ships where sailors
used clays not only to adsorb odours and moisture but also to treat dysentery, burns,
boils, sore mouths, and other internal and external disorders.
Although recent research confirmed that clays and clay minerals possess general
curative properties, it is the treatment of disorders that remains the focus of atten -
tion. By adsorbing ‘aggressors’ (infectious factors) of the gastrointestinal mucosa
barrier, these materials can serve as both prophylactic and therapeutic agents.
11.6.1. INTERACTIONS OF CLAY MINERALS WITH
GASTROINTESTINAL MUCUS
At the surface of the gut, a mucus gel adheres to the epithelial cells of the mucosa.
This adherent mucus is dynamic, being continuously secreted by the cali ciform cells
and regularly eroded by environmental ‘aggressors’ present in the gut lumen.
The mucus gel is large ly composed of glycoprotein polymers, lipids, and proteins,
linked together by covalent bonds. As such, it acts as a physical barrier protecting
DOI: 10.1016/S1572-4352(05)01025-1
the mucosa agains t penetration by extraneous molecules and mechani cal injury.
By maintaining a pH gradient and competing with the epithelial surface for micro-
organisms, the mucus gel also acts as a chemical barrier.
Thus, a weakening of the mucus gel barrier may be at the origin of disorders such
as gastritis and colitis (Droy-Lefaix, 1987). Short-term treatment with clay minerals,
such as smectites (More
´
et al., 1987) and attapulgite (More
´
et al., 1992) increases the
thickness of the adherent mucus. This may be ascribed to interactions of mineral
particles with mucus components (Leonard et al., 1994) by which the gastrointes-
tinal glycoproteins are modified, and their polymerization is enhanced (Droy-Lefaix
et al., 1986). Similarly, aluminium (hydr)oxides (e.g., boehmite) can reduce mucus
degradation (Bouyssou et al., 1990). The beneficial effects of minerals are also as-
sociated with improvements in the rheological properties of the mucus gel, such as
spinability. This reflects the increased extent of polymerization, and the improve-
ment in quality, of the adherent mucus (Droy-Lefaix et al., 1985). Changes in the
physico-chemical properties of the mucus, induced by the action of clay minerals,
were confirmed by electron paramagnetic resonance and fluorescence spectroscopy.
The results indicate that clay mineral ingestion decreases mucus solubility. At the
same time, the viscosity and hydrophobicity of the mucus increases, enhancing its
adhesion to epithelial cells.
11.6.2. CLAY MINERALS, MUCOSAL BARRIER, AND
GASTROINTESTINAL ‘AGGRESSORS’
By acting directly on the mucus gel, clays and clay minerals exert a stabilizing
effect on the mucosal barrier (Gwozdzinski et al., 1997), providing protection against
different ‘aggressors’ of the gastrointestinal mucosa.
Pepsin, a substa nce necessary for digestion, is a typical ‘aggressor’. Experiments
with rats showed that if pepsin secretion at the surface of the gastric mucosa is
strongly increased (due to pathological disregulation), the adherent mucus layer is
progressively disrupted. At the same time haemorrhagic mucosal lesions appear, and
significant bleeding occurs in the lumen as well as localized ulceration in an other-
wise intact epithelium. By binding to the mucus components, smectite can com-
pletely inhibit the damage induced by pepsin (Leonard et al., 1994).
Samson et al. (1995), for example, showed that patients with ulcerative colitis
show a six-fold greater mean total faecal proteinase activity (expressed in mmol
terminal NH
2
/min/g dry weight of faeces) than the control. Smectite totally inhibits
this enzyme activity. The effects of smectite on mucus proteolysis are assessed using a
model of mucolytic activity, assayed by the release of degraded colonic mucin
from the adherent mucus gel of freshly prepared pig colonic bags in vitro. Similarly,
trypsin (2 mg/mL) releases three times more soluble mucin per bag than the
control. Smectite (100 mg/mL) inhibits trypsin activity, causing the level of degraded
mucin to fall below the normal value. This is ascribed to the interaction of smectite
Chapter 11.6: Clays and Clay Minerals as Drugs744