Clay mineral encapsulation of
silica minerals in bentonites and
some other clays
I.E. Odom
Abstract - An electron optical and microprobe study
was made to determine the physical and chemical nature of
the silica minerals that occur as natural impurities in bento-
nite and montmorilloniticfuller's earth clay products (both
granular and powder) and that occur in <IO-,um dusts from
plants that process these products. The purpose of the study
was to determine if discrete 'yree" silica minerals, such as
quartz, could be observed using SEM and EDS methods.
No "free" silica minerals could be observed in the SEM
images of the granular andpowderedproducts, either among
or on the surfaces of theparticles.Also, no 'yree" silica could
be identified by either SEM or EDS analyses of the dusts. even
though quantitative X-ray diflraction analysis indicated that
trace amounts of quartz occurred in all samples. It was
determined that these quartz and other silica minerals were
encapsulated or coated by montmorillonite. V~gorouswash-
ing, however, removed some of the clay coatings, so that
small amounts of silica minerals could be seen by SEM and
EDS analysis.
It was found that all primary crystalline quartz grains in
the bentonites have diagenetic overgrowths consisting (?fa
mixture of montmorillonite, opaline silica and possibly mi-
crocrystalline quartz. Detrital quartz grains in the fuller's
earth have thin diagenetic overgrowths of opaline silica, also
containing montmorillonite.
The clay encapsulation of the silica minerals in the prod-
ucts studied, as well as in the potentially respirable ( < l o - p )
dust produced during manufacturing of bentonite and mont-
morillonitic fuller's earth clay products, is considered to he
an important factor influencing the potential health efleects
(e.g.. silicosis) of the contained silica. Even if clay dust
containing silica should be inhaled, the montmorillonite
encapsulating the quartz and other silica minerals would
prevent direct contact of the silica with lung tissue. The clay
encapsulation of quartz, as well as the highly hydroscopic
nature of montmorillonite, may explain why not a single
confirmed case of silicosis has ever been reported among
plant workers in more than 65 years of production.
Introduction
A comprehensive electron optical and microprobe study
was made of the physical and chemical nature of the silica
1.t.Odom is consultantwithAmerican Colloid Co., Arlington Heights,
IL. Preprint 96-1 59, presented at the SME Annual Meeting, March
1 1-14. 1996, Phoenix, AZ. Revised manuscript received for publica-
tion September, 1997. Discussion of this peer-reviewed and ap-
proved paper is invited and must be submitted to SME prior to Sept.
30, 1998.
(SO2) minerals found in several bentonite samples and a
fuller's earth sample. Included in the study were granular and
powder products and potentially respirable ( < l o - p ) dusts
from plants that process these products. The objective of the
study was to determine if discrete crystals of "free" quartz or
other silica minerals, which constitute only a small percent-
age of these clays, could actually be observed in SEM images.
The information presented on the nature of the silica minerals
in the clays studied is believed to be extremely important
relative to health-related diseases attributed to quartz.
It has been known for many years that exposure to respi-
rable crystalline silica can produce silicosis, a nonmalignant
lung disease. The possibility that certain silica minerals
might be carcinogenic to humans was postulated in 1987 by
the International Agency for Research on Cancer (IARC).
This possibility was based on the results of a study on the
effects of injecting <2 pMin-U-Sil quartz into the lungs of
mice and hamsters. ~ e c a u s ~e i n - u - ~isfproduced
i by crush-
ing high-purity quartz sand, followed by air classification,
the particles have very angular and fresh surfaces.
Based on the animal study, IARC classified quartz and
cristobalite as probable (Group 2A) carcinogens. In the
United States, the Occupational Safety and Health Adminis-
tration (OSHA) automatically adopted the IARC classifica-
tion without public comment and later issued a rule requiring
that a warning of the possible health risks of quartz and/or
cristobalite be included in an MSDS and printed on the
containers of all industrial products containing 0.1 % or more
of either quartz or cristobalite.
In October 1996, a second IARC Working Group reevalu-
ated the animal and human data published since 1987 on the
health aspects of silica minerals. As a consequence of this
reevaluation, quartz and-cristobalitewere reclassified from a
Group 2A to a Group 1 human carcinogen. The language used
in the 1987 IARC classification did not restrict the particle
size of quartz or cristobalite that was considered to be a
possible health hazard. In contrast, the 1996 Working Group
evaluation states specifically that only inhaled crystalline
quartz or cristobalite from occupational sources are carcino-
genic to humans. In the United states, only particles <10 p
are considered to be potentially respirable, but some Euro-
pean countries regard only particles <5 p as potentially
respirable. No explanation is given in the 1996 IARC re-
evaluation as to why just occupational sources and not all
sources of inhaled quartz and cristobalite are carcinogenic to
humans.
Included in the 1996 IARC Working Group overall re-
evaluation are the following two qualifications that may have
considerable importance in some mineral industries:
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 carcinogenicity was not detected in all industrial cir-
cumstances studied, and
carcinogenicity may depend on inherent characteris-
tics of crystalline silica or on external factors affecting
its biological activity or distribution of its polymorphs.
These qualifications open the possibility that the silica in
some industrial mineral products, such as clays, may not be
carcinogenic due to its inherent characteristics. For example,
clay encapsulation may be an inherent characteristic that
could have an important bearing on the potential carcinoge-
nicity of respirable silica found in bentonites and some other
clays.
The author is aware of only one reference to the possible
mitigating effect of clay on the health risks of silica minerals.
Le Bouffant et al. (1982) reported that, based on studies in
rats by inhalation and intratracheal injection, other minerals
in some coal-mine dusts appeared to reduce the carcinogenic
effect of quartz. They postulated that the presence of the clay
mineral illite in the coal dust might provide a protective
effect. The author is not aware of other studies that focused
specifically on the physical nature of silica minerals in clays.
Recently, it was suggested that the age of the surface of
inhaled crystalline silica particles may have an important
bearing on possible health effects. Castronova et al. (1996)
reported that freshly fractured silica was considerably more
toxic and inflammatory in vivo than silica of the same
composition and particle size after being aged in the labora-
tory for just two months. The interpretation of these results is
that freshly fractured silica has chemically active
silicon-oxygen radicals; but these radicals decay rapidly with
age. This relationship may. explain the high incidence of
-
silicosis in occupations such as sand blasting, rock cutting
and polishing, concrete sawing and metal casting cleaning,
where dust containing freshly fractured silica is generated
and immediately inhaled.
The silica minerals in the bentonites and fuller's earth
studied are millions of years old. In addition, no evidence was
found in this study that the original particle size or the surface
properties of the small amounts of quartz in these clays were
changed in the granulation of products such as cat litter or in
the grinding of powder products. Statistically, only a very
small amount of the silica minerals that occur in bentonites
have a natural particle size that is potentially respirable (< 10
pn). The standard methods used today to process bentonites
and fuller's earths into a variety of industrial and consumers
products do not appear to change the natural particle size or
to remove clay coatings from the silica minerals. For these
reasons, it is believed that surface chemical activity of silica
minerals in bentonites and other clays studied are not changed
during standard forms of processing.
Among the many industries that use bentonite, foundries
are the only industry were bentonite has been implicated in
silicosis. Foundries use silica sand to create economical
casting forms. To bind the sand into the desired forms,
pulverized bentonite in amounts of 6% to 9%, along with 2%
to 3% water, are commonly mixed with the sand. In a study
of several hundred silicosis claims involving foundry work-
ers, the author found that all workers diagnosed as having
silicosis worked for many years in the "cleaning room,"
where sand that adheres to metal castings is removed using
grinding abrasives. In this work activity, the workers prob-
ably were exposed to dust containing large amounts of
freshly fractured quartz. No foundry silicosis claimant has
proven that bentonite clay is implicated in silicosis. The
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results of this study suggest that bentonite clay is not impli-
cated in silicosis etiology, because the small amounts of silica
minerals present are encapsulated by a clay coating. Al-
though small amounts of quartz may be present in potentially
respirable dust that might be generated in bentonite usage and
production, these silica particles also are coated by montmo-
rillonite clay.
The term "free silica" has been defined in the literature in
the following two ways:
to identify minerals containing Si combined with 0
(SiO,) and
to more generally indicate the presence of discrete
silica minerals (i.e., quartz grains) that can be observed
by visual or microscopic means.
As previously stated, the purpose of this paper is to show
that, in bentonite and at least some fuller's earth granular and
powder clay products and in <lo-pn dust generated in the
processing of these products, discrete silica (SiO,) minerals
cannot be directly observed by SEM microscopic methods
due the clay coatings.
Abundance of silica minerals
There are many forms of both crystalline and amorphous
Si02. In most industrial mineral materials, quartz is the only
significant crystalline silica mineral present. Less abundant
are several types of hydrated amorphous forms of Si0, called
opaline silica. Although most industrial specialty clays such
a bentonites, kaolins, attapulgites and ball clays are of high
purity, they all contain small amounts of quartz, and some of
these clays may also contain trace amounts of opaline silica.
Cristobalite is a much discussed but very rare form of
silica. In numerous studies of the mineralogy of clays, opa-
line silica has been incorrectly identified as cristobalite. For
example, in the 1950s, US Geological Survey (USGS) per-
sonnel reported that some Wyoming bentonites contained
trace amounts of cristobalite.
Subsequent studies of Wyoming and other bentonites
(Elzea, Odom and Miles, 1994) have shown that the silica
mineral previously called cristobalite is actually hydrated
opaline silica of diagenetic origin.
Next to the feldspars, quartz is the most abundant mineral
composing the earth's continental crust. Because quartz is
much more resistant to weathering than feldspars, it is by far
the most abundant mineral in earth surface materials -many
soils contain over 50% quartz. The sand composing many of
the worlds beaches consists of nearly 100% quartz. Recent
studies show that dust derived from earth surface materials
contains a significant percentage of quartz, some of which is
potentially respirable (<lo pn).
Due to the ubiquity of quartz in nature, humans are
constantly exposed to both respirable and nonrespirable
silica. The household environment is an excellent example of
the ubiquitous abundance and of the constant human expo-
sure to quartz.
The author has found that, in many households, quartz is
very abundant in <64-pn dust collected from vacuum cleaner
bags and furnace filters. To illustrate that some of the silica
found in household environments is potentially respirable,
Fig. 1is an XRD pattern showing crystalline quartz in the dust
removed from the filter of an air cleaner used in a midwest
household. Because this quartz was airborne, its particle size
probably is in the respirable range (<lo pn). The origin of
TRANSACTIONS VOL. 302 119
 bentonites is believed to form from excess
silica that often exists after or during the
alteration of the glassy materials to mont-
morillonite. As previously indicated, opa-
line silica in some bentonites was mistak-
enly identifiedas cristobalite. Opaline silica
has not been associated with any known
health-related problems.
The fuller's earth studied is a montmo-
rillonitic claystone of sedimentary origin.
This claystone, identified as the Porters
Creek claystone, was deposited in the Mis-
sissippi embayment during the Upper Cre-
laceous. The clay and nonclay sediments
composing the claystone were transported
, .
! ~ r i ] ' , TmTpr:IIIiII
l l y T
to the embayment by rivers. It is likely that
"15
~ y r

10 20 much of the montmorillonite in the Porters

2 8 DEGREES Creek claystone was derived from the
weathering of volcanics that were abun-
Fig. 1 - X-ray diffraction pattern showing the presence of quartz in dust from a home air- dant in the western United States during
cleaner filter.
the Upper Cretaceous. Although the
claystone has a high montmorillonite con-
Table 1 - Plants studied and sampled and analyses of particulates and quartz in plant tent, it is not a bentonite. Sedimentary
dusts. structures, the presence of several types of
4 0 prn particulate 4 0 p m quartz clay minerals,-a high organic matte; con-
tent and a marine fossil content together
Results9 'One' indicate that the claystone consists of flu-
Date Plant mgIrn3 rngIm3 rngIrn3 rngIrn3 rngIrn3
vial sediments deposited in a restricted
22/Nov/94 Illinois 0.12' 10.0 marine embaymen(.
01/Dec/94 South Dakota 0.31 10.0 Opaline silica is abundant in the Porters
02/Dec/94 Wyoming #1 0.29 10.0
Creek fuller's earth. In fact, the commer-
cial value of the clay is enhanced by its
05/Dec/94 Wyoming #2 0.64 10.0
high opaline silica content. The highly
08/Dec/94 Wyoming #3 0.15 10.0
porous opaline silica particles reduce the
13/Dec/94 Alabama 0.12' 10.0 bulk density and increases the absorption.
15/Dec/94 Mississippi 0.72 10.0 The opaline silica in the claystone is be-
10/Jan/95 Tennessee 0.27 10.0 lieved to be both organic (diatoms) and
'Permissible exposure limit = 10.0 mg/m3. diagenetic in origin.
'Permissible exposure limit = 10.0 mg/m3/0/oSi0,+2
Samples a n d methods of analyses
-
"Designates that levels were less than the accurate detectable amount.
Granular and powder samples were
Note: These data show that the exposures to silica at the locations sampled to be very obtained from seven bentonite and fuller's
minimal. The highest concentration is only about 35% of the allowable amount. Two of
the samples contained less than the accurate detectable amount for total respirable earth production plants. Dust samples were
dust. Four of the samples contained less than the accurate detectable amount for collected in eight plants. The particle size
of the granular samples ranged from 5 to
0.25 mm. The powder samples consist of
bentonites pulverized to from 70% to 90%
quartz in households is from soil and other grime being -200 mesh (-75 p ) in Raymond-type roller mills. The
deposited from shoes onto carpets and floors. particle size of the dust samples is <10 p . The dust samples
were collected in the plants using standard MSHA approved
Origin of the bentonites and fuller's earths studied dust-collection equipment. The dust samples were collected
in duplicate over an 8-hr work day. One set of the dust
The sodium and calcium bentonites studied are volcanic in samples was analyzed for quartz by an approved laboratory
origin, and all are Upper Cretaceous in age. They are a using NIOSH analytical method 7601.
diagenetic rock formed from volcanic glass (ash) or tuff The locations of the plants studied are shown in Table 1 .
transported by air and deposited in marine water. After The plants, located in southern Illinois and Tennessee, pro-
deposition, the glassy volcanics were altered in situ to the duce primarily granular cat litter and Ag-carriers from the
clay mineral called montmorillonite. All of the bentonites Porters Creek claystone. The plants in Mississippi and Ala-
studied contain small amounts of quartz, feldspar and mica bama produce powdered and dried and crushed Ca bento-
(<lo% of the total) that were present in the volcanics at the n i t e ~The
. three Wyoming plants produce a variety of granu-
time of deposition. Some of the bentonites studied contain lar and powdered Na bentonite products. The plant in South
trace amounts of hydrous opaline silica, probably in the form Dakota (dust only) produces water-purified Na bentonite.
of opal C T (Elzea, Odom and Miles, 1994). This form of The granular. powder and dust samples were studied by
silica is believed to be diagenetic in origin. Opaline silica in scanning electron microscopy (SEM) and energy dispersive

SOCIETY FOR MINING, METALLURGY. AND EXPLORATION, INC.

120 TRANSACTIONS VOL. 302
X-ray microprobe (EDS) analysis at the University of Ne-
vada, Reno, NV, and the Illinois State Geological Survey,
Urbana, IL. Microscopic examination of granular samples
was also performed in a private laboratory. Details on sample
preparation for SEM and EDS analyses are given in the
section on Na and Ca bentonite powders.

Results

Due to publication page limitations, only a limited number

of the SEM photomicrographs and EDS analyses are pre-
sented. Special emphasis is given to the dust samples studied
because of the health issues associated with potentially
respirable dust-containing quartz. The author has tried to
present visual and analytical data that are representative of
the results obtained on the variety of samples studied.

Granular products. No "free" silica minerals could be

directly observed by microscopic or SEM examination in any Fig. 2 -SEM photomicrograph of the bentonite particles composing
of the granular bentonite or fuller's earth samples. All silica one of the powder samples from Wyoming Plant No. 1 .
minerals are entirely encapsulated by clay (montmorillo-
nite). These granular products were prepared with roll-type
crushers. There does not appear to be any breaking or libera-
tion of the clay encapsulating silica minerals present in the
Wyoming DC 1
granular products during processing. The breakage of the Vert= 2087 counts
granules occurs only through the soft clay matrix. It is shown Quantex) I
later in this paper that the silica minerals present in bentonite
and fuller's earth dust generated in the processing of granular
products also are encapsulated by clay. For this reason, it is
believed that no "free" silica minerals would be present in
dust that might be generated in the handling or pouring of
granular bentonite or montmorillonitic fuller's earth prod-
ucts such as cat litter.

Powder products. Powder samples from five bentonite

production plants were studied in two ways. First, a sample
of each powder was shaken for a few seconds on a 200-mesh
(74-pm) screen. Care was taken to not abrade the particles by
the wire mesh. This was done to remove some of the ex-
tremely small particles that cause conductive coating prob-
lems in SEM sample preparation. Second, nonclay minerals
were separated for examination by dispersing a 25-g sample
of each of the as-received powdered bentonites in 400 mL of
distilled water, followed by stirring the slurry with a Waring
blender for 5 min. The slurry was then washed with tap water
on a 325-mesh ( 4 4 - p ) screen. Washing removed the mont-
morillonite coatings as much as possible from the quartz and
the other nonclay minerals, so that these minerals could be
observed by SEM and chemically analyzed by EDS methods.
Both the crude powder and the washed grain (grit) samples
were prepared in the same way for SEM and EDS analysis. Fig. 3 - EDS spectra of an Na-bentonite grain shown in Fig. 2.
The clay coatings were found to be more difficult to remove
from quartz and other nonclay minerals in the fuller's earth
than in the Ca and Na bentonites. bentonite mined from the famous Clay Spur bed specifically
for use in US foundries. The trade name of the product is
Sodium bentonites powders. Sodium bentonite powder DC-I.
products from three plants in Wyoming were studied. Not a single nonclay-coated quartz grain can be seen in
Wyoming Plant No. 1: This plant is near Colony, WY, Fig. 2, and no nonclay-coated quartz grains were found in
which is located north of the Black Hills. Several dozen other DC- I samples studied. Also, no nonclay coated quartz
powder product samples of Na bentonite processed at the grains were observable in another foundry product (DC-2)
plant were analyzed. Figure 2 shbws an SEM micrograph of prepared at this plant from bentonite mined from Bed F.
the bentonite particles composing one of the powder samples. These results are confirmed by EDS analysis of individual
This sample is representative of many types of pulverized particles. Figure 3 is an EDS spectra of one of the bentonite
bentonite products prepared by Raymond mill grinding. The grains in Fig. 2. This spectra is typical of all bentonite grains
sample shown in Fig. 2 is a product prepared entirely from in Fig. 2.

SOCIETY FOR MINING, METALLURGY, AND EXPLORATION. INC TRANSACTIONS VOL. 302 121
Fig. 4 - SEM photomicrograph of mineral particles recovered from
a washed sample of the powder shown in Fig. 2. Shown is the nature
of the quartz grains present.
4-Jan-1996 15: S R : 16
Wyoming DC 1 Washed
Vert= 2842 c o u n t s
Quantex> I of the quartz grain shown in the center of Fig. 4. Note that Mg
Fig. 5- EDS spectra showing composition of overgrowth on quartz
grain shown in Fig. 4.
Figure 4 shows mineral particles recovered from a washed
sample of the powder shown in Fig. 2 and shows the nature
of several quartz grains present, none of which were observ-
able before the sample was washed. Note that the surface of
the quartz grains is very irregular and porous. This is the
physical form of all quartz grains found in Wyoming Na
bentonites, regardless of their location or bed of origin. The
surface texture is a product of diagenetic addition of Si02 to
a primary quartz grain. The primary quartz grains that form
the center of most of these grains can be seen in polarized
light. The overgrowths consist primarily of a mixture of
122 TRANSACTIONS VOL. 302
Fig. 6 - SEM of particles from foundry-grade bentonite product
(DC-3), Wyoming Plant No. 2.
montmorillonite and opaline silica, but some may also con-
tain microcrystaline quartz. The presence of montmorillonite
in the overgrowths indicates that the clay formed before or
during the precipitation of Si02. Figure 5 is an EDS spectra
and A1 are prominent components of the spectra, indicating
the presence of rnontmorillonite in the overgrowth. he
and irregularities in the overgrowth surface were filled with
montmorillonite prior to washing. This covering or encapsu-
lation by montmorillonite is the reason that the silica grains
cannot be seen in the powder samples.
A feldspar grain is shown in the lower left comer of Fig.
4. Feldspar
. grains
. are characterized by a smooth surface
texture. Mica grains also have a smooth surface. No
overgrowths were observed on feldspar or mica. The
overgrowths occurring on quartz are believed to be a product
of the bentonite origin. Most volcanic glasses have an excess
of silica over that required for the crystallization of montmo-
rillonite. Some of the excess silica was precipitated on the
surface of the primary quartz grains.
Wyoming Plant 2: This plant is located at Upton, WY.,
which is west of the Black Hills. Figure 6 shows particles
from another foundry grade bentonite product (DC-3) also
produced by Raymond mill processing. No "free" silica
grains were found at the surface of the bentonite particles
shown in this micrograph. Figure 7 shows grains from the
DC-3 product after washing. Note that the quartz grains,
which were totally encapsulated by clay before washing,
have the same porous and irregular surfaces as occur in
Wyoming Plant 1 bentonite. The composition of these
overgrowths is identical to those occurring on quartz in
Wyoming Plant 1 bentonite. The smooth grains shown in Fig.
7 are feldspars. The white areas are caused by electron
buildup due to insufficient conductive coating.
Wyoming Plant3: This plant islocatedeastofYellowstone
National Park near Lovell, WY. Several samples, before and
after washing, of a well-drilling-grade bentonite powder
product were studied. No "free" silica minerals were observ-
able in SEM micrographs of the power samples. The quartz
grains that occur in the washed samples of the Lovell Na
bentonite have overgrowths identical in composition and
surface texture to the overgrowths on quartz occurring in the
bentonites produced at Wyoming Plants No. 1 and No. 2.
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 Fig. 9 - SEM photomicrograph showing the irregular and porous
Fig. 7 - SEM of DC-3 product grains after washing. overgrowths that occur on quartz grains In the Ca bentonites.

4-Jan-1996 16: 12: 4 2

Mississippi Washed
Vertp 536 c o u n t s

Fig. 8 - SEM photomicrograph of Ca bentonite powder product.

Ca bentonites. Ca bentonites from Mississippi and Ala-

bama were studied. As in the Na bentonite, no nonclay
minerals are visible in SEM images of the -200-mesh (-74-
pn) powder products of either the Alabama or Mississippi
bentonites (Fig. 8). Quartz and other nonclay minerals can be
seen only in the washed +325-mesh (+44-pn) grit samples.
Irregular and porous overgrowths, similar in texture and
composition to those in Na bentonites, occur on the quartz
grains in both Ca bentonites (Fig. 9). Figure 10 is an EDS
spectra showing the chemical composition of an overgrowth Fig. 10- EDS spectra of overgrowth on quartzgrain from Mississippi
Ca bentonite.
on quartz in the Mississippi bentonite. The Mg and Al in this
spectra are due to the presence of montmorillonite within the
overgrowth. The quartz grains in both Ca bentonites have and agricultural carriers. The important economic properties
more porous and thicker overgrowths than occur in the Na of the Porters Creek clay are high adsorption, high granule
bentonites. The overgrowths are believed to primarily consist hardness, and low bulk density. All products are +50-mesh
opaline silica, because trace amounts occur in XRD patterns ( + 3 0 0 - p ) granules. Less than 50-mesh fines are discarded
of both the bentonites and the washed grits. Feldspar in both or recompacted by extrusion.
bentonites has a smooth surface texture. A feldspar grain can Figures 11 and 12 show crude and washed samples of
be seen in the lower right corner of Fig. 9. Porters Creek fuller's earths from southern Illinois. There are
no silica minerals visible in the crude sample. Only in the
Fuller's earth. Fuller's earth samples from two locations, washed sample can quartz be identified by SEM and EDS
Tennessee and Illinois, were studied. At both locations, the methods. As in the bentonites, silica minerals in the Porters
Porters Creek clay is being produced for traditional cat litter Creek fuller's earth are encapsulated by montmorillonite.

SOCIETY FOR MINING, METALLURGY, AND EXPLORATION, INC TRANSACTIONS VOL. 302 123

Fig. 1 1 - SEM of crude Porters Creek fullers earth.
Fig. 12 - SEM of washed Porters Creek fuller's earth.
Fig. 13 - SEM photomicrograph showing dust particles collected
from Wyoming Na-bentonite Plant 1 .
The clay coatings are not removed in the production, han-
dling or pouring of products made from the Porters Creek
clay. Silica minerals present in dust generated in the produc-
tion of Porters Creek products also are encapsulated by
124 TRANSACTIONS VOL. 302
Fig. 14 - SEM photomicrograph showing dust particles collected
from Wyoming Na-bentonite Plant 2.
Fig. 15 - SEM photomicrograph showing dust particles collected
from Wyoming Na-bentonite Plant 3.
montmorillonite (see discussion of dusts). The clay encapsu-
lation of silica minerals observed in fuller's earth and bento-
nite is an inherent property and is believed to be important
relative to possible health problems that have been associated
with silica minerals.
Health aspects in the usage of granular and powder
products
Relative to health aspects in the production and use of Na
and Ca bentonites and montmorillonitic fuller's earths, silica
mineral grains are encased or encapsulated in clay (montmo-
rillonite). Granulation and grinding Ca or Na bentonites to
approximately -200 mesh (74 pn) or the granulation of
fuller's earths does not expose the nonclay minerals or reduce
their size, because particle breakage occurs through the soft
clay.
Even quartz particles larger than 200 mesh (74 ,m)are not
reduced in size. All quartz in these clays have a coating of
diagenetic silica added during the formation of the montmo-
rillonite from the volcanic ash or from other silica sources.
Due to the clay encapsulation, it is believed that the quartz
present in these clays would not come into direct contact with
lung tissue, even if inhaled. Inhalation seems unlikely be-
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Fig. 16 - SEM photomicrograph showing dusts collected at the Fig. 18 - SEM photomicrograph showing dusts collected at the
Mississippi Ca-bentonite plant. Illinois fuller's earth plant.

Fig. 17- SEM photomicrograph showing the dusts collected at the Fig. 19 - SEM photomicrograph showing dusts collected at the
Alabama Ca-bentonite plant. Tennessee fuller's earth plants.

cause dried bentonite and other clay powders are extremely

hydroscopic.
This decreases the possibility that even <lo-pm clay
encapsulated silica or montmorillonite particles could pass
through the mouth and throat or through nasal passages to
reach the lungs. Natural moisture is nasal and throat passages
would, from empirical observation, engage the hydroscopic
properties of bentonite, making significant particle respira-
tion improbable.

Dust analyses. As previously indicated, dust samples

were collected from six bentonite and two fuller's earth
production plants (Table 1). The dust samples studied were
obtained at the same time that a duplicate sample was col-
lected for MSHA safety requirements. One set of the dust
samples was quantitatively analyzed for silica mineral con-
tent by X-ray diffraction (Table 1).
Figures l 3 20 are micrcOgra~hs Fig. 20 - SEM photomicrograph showing dust collected near a
the nature of the dust particles collected and analyzed by micronizing mill used to grind a water-purified Na bentonite.
SEM and EDS. Quartz is the only silica mineral that was
identified in the dust samples (Table 1). All of the dust Figures 13 through 15 show the dust particles collected
samples contain small amounts of quartz. The quartz content from Wyoming Na bentonite Plants 1.2 and 3, respectively.
of the dust samples is at least three times below the permis- No discrete "free" silica minerals could be identified in these
sible TLV values required by MSHA (Table I). dusts. All of the particles have a morphology and chemical

SOCIETY FOR MINING. METALLURGY, A N D EXPLORATION. INC. TRANSACTIONS VOL 302 125

Wyoming Dust No. 1
Vert= 509 c o ~ ~ r ~ t s
>
Quantex
I si
t- keV
Fig. 21 - EDS spectra of dust particle from Wyoming Na-bentonite
Plant (Fig. 2).
composition characteristic of Na montmorillonite. Figure 2 1
is an EDS spectra of a typical bentonite dust particle in Fig.
13. The C1 in this spectra is from the filter.
Figures 16 and 17 show the dusts collected at the Missis-
sippi and Alabama Ca bentonite plants, respectively. As in
the Na bentonites, all of the particles have a morphology and
chemical composition characteristic of montmorillonite, and
the quartz present in these dusts is totally encapsulated by
montmorillonite.
The round objects present in the Mississippi plant sample
(Fig. 16) are filter material, due to a defect. Figure 22 is an
EDS spectra of a dust particle collected from Mississippi Ca
bentonite plant (Fig. 16).
Figures 18 and 19 show the dusts collected at the Illinois
and Tennessee fuller's earth plants, respectively. As in the
bentonite dusts, no discrete silica minerals are identifiable
among the dust particles collected from these plants.
Figure 20 shows dust collected near a micronizing mill
used to grind a water-purified Na bentonite. After purifica-
tion, the Na bentonite is dried in a drum dryer. Although
water purification was used in the processing of this bento-
nite, after drying, the quartz in the dust was also totally
encapsulated by montmorillonite. Figure 23 is an EDS spec-
tra of a dust particle from South Dakota water-purified Na
bentonite plant (Fig. 20).
In summary, in the SME and EDS analyses of the eight
dust samples, no "free" silica particles could be identified.
The coatings of montmorillonite made it impossible to iden-
tify dust particles that may contain a silica. Dust particles are
4-Jan-1996 13:25: 19
Mississippi Dust
Verte 3190 counts
-
Fig. 22 EDS spectra of a dust particle collected near a micronizer
used to grind water-purified Na bentonite (Fig. 20).
so thin that chlorine present in the filters appear in almost all
EDS chemical spectra due to electron beam penetration. All
of the dust particles show the morphology of montmorillo-
nite. This characteristic also confirms that the silica present
in these dusts are totally clay encapsulated.
Summary
Silica (Si02) minerals, sometimes called "free silica", in
bentonites, montmorillonitic fuller's earths and some other
clays are entirely encapsulated by clay, even when particles
are <10 p.
Grinding of bentonites, fuller's earths, etc. to standard
commercial sizes does not remove the clay coatings. In
addition, quartz in bentonites and fuller's earths has a diage-
netic coating consisting of a mixture of opaline silica, clay
and possibly microcrystalline quartz.
The morphology and clay content of the diagenetic
overgrowths indicate that they are not crystalline quartz. The
low bulk density Porters Creek fuller's earth contains several
percent opaline silica, some of which may be of organic
brigin (diatoms).
No silica minerals in the < l o - p dusts collected in eight
bentonite and fuller's earth producing plants could be di-
rectly observed in SEM micrographs or analyzed by EDS
methods. Analysis of these dusts by NIOSH procedure 7601
confirmed the presence of quartz in all samples. The dusts
from plants were well below MSHA approved PEL values for
crystalline quartz.
SOCIETY FOR MINING, METALLURGY, AND EXPLORATION, INC.
 There have been reports of bentonite workers afflicted
with silicosis. It is the author's opinion that these reports may
South Dakota Dust not be medically accurate. Experience demonstrates that
Vert= 829 c o u n t s silicosis is very difficult to diagnose. Only specially trained
Quantex)
I Ru
physicians are competent to diagnose silicosis from radio-
graphs alone.
Multiple diagnoses are recommended where silicosis is
suggested. It is the author's experience that silicosis diag-
noses may actually relate to other causes, such as pneumoco-
niosis, bacterial or viral infections, or neoplasm. Other causes
are described by Guthrie and Mossman (1993).

Acknowledgments

Lee Grasseschi, University of Nevada, Reno, NV, assisted

the author in all phases of the SEM and EDS analyses. Anita
Heuer is also thanked for her assistance in the preparation of
this manuscript.

References

Castronova, V., et al., 1996, 'Enhanced pulmonary response to the inhalation of freshly
fractured silica as compared with aged dust exposure."AppliedOccupationaland Environ-
mental Hygiene, Voi. 11, No. 7, pp. 937-941.

Elzea, J.M.. Odom, I.E., and Miles. W.J., 1994, Distinguishingwell ordered opal-CT and
Opal-C from high temperature cristobalite by X-ray diffraction." Analytica Chimica Acta.
286. pp. 107-116.

Guthrie, G.D., Jr., and Mossman, B.T., 1993, "Health effects of mineral dusts." Reviewsin
Mineralogy, MineralogicalSociety of America, Voi. 26.

InternationalAgency for Research on Cancer, 1967, "Monographson the Evaluationof the

Carcinogenic Risk of Chemicals to Humans, Silica and Some Silicates," World Health
Organization, Vol. 42.
Fig. 23- EDS spectra of dust particlecollectedfrom Mississippi Ca- Le Bouffant, L., Daniel. H., Martin, J.C., and Bruyere, S.. 1962. "Effect of impurities and
bentonite plant (Fig. 16). associated minerals on quartz toxicity," Ann. Occup. Hyg, Vol. 26, pp. 625-634