Atmospheric Environment 35 (2001) 3539–3542

Short communication
Piezoelectric properties of quartz and cristobalite airborne
particulates as a cause of adverse health effects
B.J. Williamsona,*, S. Pastiroffb, G. Cresseya
a
Department of Mineralogy, The Natural History Museum, Cromwell Road, London SW7 5BD, UK
b
Consultant Chemist, 49 Royal York Crescent, Bristol BS8 4JS, UK
Received 21 June 2000; received in revised form 17 January 2001; accepted 24 January 2001

Abstract

Inhalation of quartz and cristobalite dusts is commonly linked with health effects although the mechanisms involved
are poorly understood. Grinding of these piezoelectric silica polymorphs produces particulates with transient
piezoelectric charges. This is likely to cause vigorous reaction with atmospheric gases and, through interaction with
surface charges and ‘dangling bonds’, may lead to the formation of highly deleterious ozonide, superoxide and hydroxyl
radicals. It is hoped that this study will encourage experimental work to quantify piezoelectric effects in silica dusts and
to develop a method for their neutralisation during cutting and grinding processes. # 2001 Elsevier Science Ltd. All
rights reserved.

Keywords: Silica dusts; Piezoelectricity; Surface radicals; Airborne particulates; Silicosis

1. Introduction Fubini, 1998) but is rare in the natural environment and

It is now widely recognised that adverse health effects
are linked with the inhalation of quartz and cristobalite
dusts (see reviews in Iler, 1979; Fubini, 1998). These
minerals were recently upgraded to Group 1 status
(carcinogenic to humans) in the IARC classification of
carcinogenic materials (IARC, 1997). A recent US
Public Health Report warned of a silicosis epidemic
amongst workers in the United States related to the
inhalation of silica dusts (Markowitz and Rosner, 1998).
Quartz particulates are produced during mining and
quarrying, demolition/construction and manufacturing
or by natural processes, commonly as wind-blown dusts
(Norton and Gunter, 1999). Cristobalite particulates are
produced in foundries, in diatomaceous earth produc-
tion and in the ceramics and pottery industries (see
Hemenway et al., 1990). They also form naturally during
volcanic eruptions, such as in the recent dome collapses
on Montserrat, British West Indies (Baxter et al., 1999).
Tridymite is thought to be more toxic than quartz (see
*Corresponding author. Fax: +44-0-207-942-5537.
E-mail address: bw@nhm.ac.uk (B.J. Williamson).
is therefore of little health concern.
Despite numerous studies, the exact mechanisms that
cause adverse health effects in certain silicas are
unknown (Fubini et al., 1995; Kane, 1996). Early studies
suggested a role for dissolved silica although this is
unlikely as the cytotoxicity of the silica polymorphs is
inversely related to their solubility (Iler, 1979). A variety
of other explanations have therefore been proposed,
including the presence of trace amounts of iron or other
metals on silica surfaces, surface effects controlled by
crystal structure, the presence or absence of an amor-
phous surface layer (often present in quartz) and the
formation of various surface species due to crushing and
subsequent reaction with atmospheric gases (see review
in Fubini, 1998). The last explanation is the most widely
favoured, although not universally so (e.g. Elias et al.,
2000). Here, the breaking of Si–O bonds is thought to
lead to the formation of either homolytic cleavage, with
the production of deleterious Sid and Od radicals
(‘dangling bonds’), or heterolytic cleavage forming Si+
and SiO
electrically charged surface species. Evidence
for the role of these surface species is that freshly ground
silicas are often more reactive than aged or heated

1352-2310/01/$ - see front matter # 2001 Elsevier Science Ltd. All rights reserved.
PII: S 1 3 5 2 - 2 3 1 0 ( 0 1 ) 0 0 1 2 1 - 2
3540 B.J. Williamson et al. / Atmospheric Environment 35 (2001) 3539–3542
samples (Fubini et al., 1999). This explanation, however,
cannot account for the much greater toxicity of quartz
and cristobalite compared with other silica polymorphs
(see Section 3.2).
The possible health effects relating to the piezoelectric
properties of some silica polymorphs have been largely
overlooked. The piezoelectric properties of quartz, and
its effect on fibrogenic activity, were considered in a
review paper by Pecherskii (1989). This was, however,
mainly with regard to the mechanisms of production of
quartz particulates, the general effects on surface charge
and the slightly increased ability of piezoelectric
particulates to penetrate into the deepest regions of the
lung. Piezoelectric effects have not been considered in
the light of extensive subsequent experimental and
toxicological studies, the evidence from which is
discussed in Section 3.
2. Piezoelectricity
Piezoelectricity is a property shown by certain crystals
whereby the application of pressure causes opposite
electric charges to appear on opposite sides of the
crystal. This remarkable effect is used in a wide variety
of devices such as quartz watches and electric lighters. In
the latter, a visible spark is produced by the compression
of a quartz single crystal.
Piezoelectric properties are confined to crystalline
substances belonging to non-centrosymmetric crystal
classes, which include materials in 20 of the 32 crystal
point groups (Burns, 1985). Most common natural or
anthropogenically produced minerals at the earth’s
surface have centrosymmetric crystal structures and
are therefore non-piezoelectric (e.g., calcite, gypsum,
halite, feldspar, hematite, rutile). Quartz, cristobalite
and some forms of tridymite are piezoelectric because
their structures do not possess a centre of inversion
symmetry and their opposite sides have structurally
dissimilar surfaces and carry opposite electric charges.
In nature, these charges would have been usually
neutralised by adsorbed ions. However, due to the
piezoelectric properties of these materials, if the
equilibrium polar charges are disturbed by distorting
the electron clouds, either by heating or by applying
mechanical stress, then net charges will momentarily
appear at opposite ends of the crystal, until other ions
are attracted to restore surface neutrality.
3. Discussion
3.1. Mechanisms for radical generation due to
piezoelectric effects
The production of airborne particulate quartz and
cristobalite by crushing, grinding and cutting will result
in many particulates possessing a piezoelectric dipole
moment. Laboratory experiments have shown that
unloading stress on granite induces a pulsed electric
potential variation which decays exponentially with a
time constant ranging from 1.5 to 4.0 s (Sasaoka et al.,
1998). Epidemiological studies indicate that workers in
the granite cutting/grinding industry have increased
occupational health risks associated with the inhalation
of silicas (see Goldsmith, 1994).
Absorption of gases on the surfaces of silicas is
highest for H2, followed by CO2 and O2 (Steinike and
Hennig, 1992). However, the most abundant atmo-
spheric molecule available for surface reaction is O2
(20.95%) with CO2 (0.03%), H2 and H2O (commonly
51%) being much less abundant. Table 1 shows
possible reactions at each pole of freshly produced silica
particulates, between atmospheric O2 and ‘dangling
bonds’ (Sid and Od ) and surface charged species (Si+
and O
), the ‘dangling bonds’ and surfaces charges
having formed as a result of grinding and the production
of fresh mineral surfaces (e.g., Fubini et al., 1999).
The overall positive charge at the positive pole of the
particulate, due to piezoelectric effects, will induce rapid
adsorption of atmospheric components in order to re-
establish local electrical neutrality. Reaction of O2 with
the Sid and Od ‘dangling bonds’, electrically favourable
at the positive pole as a result of piezoelectric effects, is
especially likely to lead to the production of highly
deleterious radicals including Od3 and SiOOd (silylper-
oxide radical). The detachment of Od3 in solution, most
importantly within the lung, will cause the production of
the highly reactive Od
3 ozonide free radical. The
presence of ozonide and silylperoxide radicals in ground
quartz samples has been suggested from electron spin
resonance (ESR) studies (Costa et al., 1991), with their
existence thought by Costa et al. to be due to the release
of electrons from defect structures during grinding.
If electrical neutrality is readily established at the
positive pole between the surface and air (oxygen), then
because the air surrounding the particulate is an
excellent electrical insulator, excess electrons may build
up at the negative pole surface. These may interact with
‘dangling bonds’, surface charges, atmospheric compo-
nents or any molecules on the lining of the lung with
which they are in contact. From Table 1, the range of
deleterious radicals produced at the negative pole is
likely to be limited, perhaps only involving the forma-
tion of silylperoxide radicals. There is, however, the
possibility of direct interaction of surface electrons with
O2, which may produce the Od
2 superoxide radical.
Reaction with atmospheric water molecules is also
likely to generate surface radicals at each pole. These
will be mainly SiOHd , hydroxyl radicals identified in a
number of ESR studies (see Fubini, 1998), formed as a
result of protonation of Si2Od species and hydroxila-
tion of Sid . Hydroxyl radicals are thought to cause DNA
 B.J. Williamson et al. / Atmospheric Environment 35 (2001) 3539–3542 3541

Table 1 (1) Particulates produced from different silica

Possible surface reactions occurring at the positive and negative polymorphs show extremely varied health effects
poles of a piezoelectric silica particulate (Hemenway et al., 1986). Stishovite is considered to be
Positive pole non-pathogenic whilst coesite is thought to be patho-
genic, but less so than quartz (see review in Fubini,
Silica surface species Surface reaction with atmospheric
1998). Amorphous silicas, although varied in their origin
O2 attracted to positive end
and type, are generally non-toxic or show a much
O
No reaction reduced biological response (e.g., Czernikowski et al.,
Heterolytic cleavage 1991). From ESR studies, the production of surface
Si+ Siþ þ O2 , SiOþ radicals due to grinding decreases in the sequence:
2
Heterolytic cleavage cristobalite, quartz, coesite, stishovite, which has been
suggested to be caused by increasing density (Fubini
Od Od þ O2 , Od3 possibly detaching
et al., 1995). However, this does not explain the lack of
Homolytic cleavage in solution to form Od

3 (ozonide
radical) substantive health effects related to amorphous silica,
the least dense of the polymorphs. With an identical
Sid Sid þ O2 , SiOOd (silylperoxide chemistry and with very little difference in surface
Homolytic cleavage radical) properties, the only major factor which differentiates
quartz and cristobalite (and some forms of tridymite)
Negative pole from the other silica polymorphs, including amorphous
silica, is that they are piezoelectric.
Silica surface species Surface reaction with excess
electrons (2) The production of deleterious surface species such
as the peroxy radical SiOOd and the superoxide radical
O
No reaction ion O
2 by reaction between atmospheric components
Heterolytic cleavage and surface ‘dangling bonds’ was previously considered
Si+ Siþ þ e
! Sid Sid þ O2 , SiOOd to be the main mechanism causing adverse health effects.
Heterolytic cleavage Their formation, however, also occurs on the surfaces of
Od Od þ e
! O
ground amorphous silica and other more chemically
Homolytic cleavage complex substances (Giamello et al., 1990), which have
not been shown to produce adverse health effects. This
Sid Sid þ e
! Si
may indicate the involvement of more reactive radical
Homolytic cleavage
species in silica toxicity such as superoxides or ozonides.
e
e
þ O2ðatmosÞ , Od

2 (superoxide The production of ozonide (Table 1) may preferentially
excess at (
) end radical) occur in piezoelectric particulates due to the increased
likelihood at the positive pole, compared with non-
charged surfaces, of reactions between O2 and ‘dangling
bonds’. Superoxide and silylperoxide radicals may form
at the negative pole due to the interaction of atmo-
damage, protein oxidation and lipid peroxidation and spheric O2 with surface piezoelectric charges.
may therefore be more harmful than superoxide radicals (3) The grinding of material in a wet environment
which can be neutralised by cell antioxidants (Fubini inhibits the formation of radicals compared with
and Otero Are!an, 1999). The occurrence of excess grinding the same material when dry. The presence of
electrons at the negative pole may also lead to the water was previously thought to assist in surface
reduction of Fe3+, which may be present as a surface reconstruction (Volante et al., 1993), although how
contaminant. A variety of subsequent oxidative surface this occurs is not known. A compelling explanation
reactions between Fe2+ and atmospheric O2 could occur for this is the rapid neutralisation of surface charges
(e.g., Fe2þ þ O2 ! Fe3þ þ Od
2 ) leading to the genera- due to the adsorption of water molecules and the
tion of hydroxyl radicals, superoxides or peroxide (see stripping of surface electrons from negative poles due
Fubini and Otero Are!an, 1999). to the more conductive properties of water compared
with air.
3.2. Evidence for the role of piezoelectricity in silica (4) Ground quartz and cristobalite show varying
toxicity degrees of radical production which is vaguely explained
by environmental differences (e.g., humidity, grinding
Many poorly understood aspects of the surface rate/time/energy) or, for cristobalite, due to the presence
properties and health effects of silicas from previous of metal oxide contaminants (Fubini et al., 1990). From
studies are more reasonably attributed to piezoelectric epidemiological studies, dust produced in different
effects than previously proposed mechanisms: industries also show varying health effects (Fubini,
3542 B.J. Williamson et al. / Atmospheric Environment 35 (2001) 3539–3542
1998). Apart from environmental factors, this could also
be explained by differences in induced piezo-
electric charge as a result of variations in applied
pressures during grinding or different methods of
particle generation.
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