Environ Geochem Health (2014) 36:517–529
DOI 10.1007/s10653-013-9578-z
ORIGINAL PAPER
Environmental occurrence, origin, physical and geochemical
properties, and carcinogenic potential of erionite near San
Miguel de Allende, Mexico
M. Adrián Ortega-Guerrero •
Gerardo Carrasco-Núñez
Received: 8 May 2013 / Accepted: 29 October 2013 / Published online: 24 November 2013
Ó Springer Science+Business Media Dordrecht 2013
Abstract Detailed geologic surveys and different
microscopic and analytical techniques were conducted
near Tierra Blanca de Abajo where lung cancer and
malignant mesothelioma (MM) are the primary causes of
death. Results show that erionite-K occurs as a diage-
netic product in altered Oligocene–Miocene rhyolitic
tuffs. The microscopic structure of erionite minerals
shows concentrations of individual fibers in the range of
0.14–0.547 lm in diameter and 2.81–50 lm in length,
with a few ‘‘bundles’’ about 0.2–2.5 lm wide by
10–50 lm long. Chemical properties of erionite show
Si/Al in the range of 3.23–3.58 (at.%) and TSi in the range
of 0.76–0.78 (at.%). Potassium is the dominant cation
(K [ Ca [ Mg [ Fe). Associated minerals are heulan-
dite, clinoptilolite, quartz, sanidine, anorthite, smectite
and opal. This mineral assemblage formed in the lower
part of an open catchment, where bicarbonate-rich
(T [ 30 °C, pH [ 8) groundwater discharge conditions
prevailed in the past. The physical and chemical
characteristics of erionite near San Miguel de Allende
are similar to those of erionite from the Cappadocian
region of Turkey where erionite is associated with MM.
The presence of erionite and the type of respiratory
diseases that occur in the village strongly suggest the
need for detailed health-based studies in the region.
M. A. Ortega-Guerrero (&)
G. Carrasco-Núñez
Centro de Geociencias, Universidad Nacional Autónoma
de México, Campus Juriquilla, Querétaro, Boulevard
Juriquilla 3001, CP 76230 Querétaro, Mexico
e-mail: maog@servidor.unam.mx
Pliocene–Holocene fine-grain deposits, used in the past
for the construction of adobe-houses and exposed in
recreational areas, also contain erionite associated with
erosion and alluvial transport from the rhyolitic tuffs,
potentially affecting more than 13 villages located
downstream toward the Allende Dam.
Keywords Erionite
Lung cancer
Malignant
mesothelioma
Zeolitic tuffs
Mexico
San
Miguel de Allende
Tierra Blanca de Abajo
Introduction
Environmental exposure to erionite fibers, an asbes-
tos-like mineral, is gathering importance worldwide
regarding the carcinogenic potential from environ-
mental and occupational exposures. Erionite has been
recognized by the International Agency for Cancer
Research (IARC) as a carcinogen in human and
animals since 1987, and is the most carcinogenic
mineral categorized by the World Health Organization
(WHO) (IARC 2012). Most of the data on the
carcinogenicity of erionite in humans are supported
by the experience of inhabitants exposed to erionite-
contaminated villages in the Cappadocian region of
Turkey. In this area, environmental and medical
studies around three small villages (Karain, Sharihidir
and Turkoy) have shown that environmental exposure
to erionite is the main cause of high rates of mortality
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due to malignant mesothelioma (Baris et al. 1978;
Artvinli and Baris 1979; Baris et al. 1987; Dogan et al.
2008; Carbone et al. 2011).
In the western USA, natural deposits of erionite
have been reported at 95 locations in at least fourteen
states, and numerous concerns have emerged regard-
ing the potential for environmental and occupational
exposures (Fig. 1a); therefore, identifying locations
and geologic environments for erionite formation is
part of a national study of fibrous minerals and their
distribution (Van Gosen et al. 2013). Most of these
diagnostic efforts are concentrated in Dunn County,
North Dakota, where about 500 km of unpaved roads
were surfaced with erionite-bearing gravels (Carbone
et al. 2011).
In Mexico, different natural zeolite locations have
been reported from an economic point of view and due
to their contaminant-absorbing properties (De Pablo-
Galán and Chávez-Garcı́a 1996; Jiménez-Cedillo et al.
2006; Ostrumov 2006; Popov et al. 2006). Of these,
only two reports describe the presence of erionite: one
in Agua Prieta, Sonora, and another between the cities
of Juventino Rosas and Guanajuato. As yet there have
been no reports of any health problems associated with
either one of these erionite-bearing deposits; however,
the risk exists. Two cases of mesothelioma attributed to
erionite exposure were reported for Mexico by Ilgren
et al. (2008) and Kliment et al. (2009). Unfortunately,
these authors did not assess the merits of their
hypothesis by confirming the environmental presence
of erionite. About 80.5 % of the cases of mesothelioma
in Mexico are clearly associated with occupational
exposure to asbestos, while the remaining 19.5 % are
of unknown origin (Aguilar-Madrid et al. 2010).
In the village of Tierra Blanca de Abajo, with a
population of 450 inhabitants, located 10 km from San
Miguel de Allende in the State of Guanajuato
(Fig. 1b), high incidence of lung cancer (about 4
deaths/1,000 inhabitants) and malignant mesotheli-
oma (about 1 death/1,000 inhabitants) is occurring
(Ortega-Guerrero and Carrasco-Núñez 2012). This
study also analyzed for nine of the Group 1 lung-
carcinogenic agents listed by IARC (asbestos, arsenic,
cadmium, chromium, erionite, nickel, and dust of
quartz and cristobalite), preliminary findings reported
the presence of erionite near the village. The village is
located in the lower part of the Upper Laja River
Basin, also known as the Independence Basin, which
is mainly delimited by volcanic rock with important
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Environ Geochem Health (2014) 36:517–529
Fig. 1 a Location and geology of the study area. a Distribution c
of erionite sites in 95 erionite locations in USA (Modified from
Van Gosen et al. 2013) and three in Mexico. b Geologic map of
the independence basin (modified from Alanı́s 2002) showing
the location of the study area. This basin is mainly delimited by
rhyolitic and andesitic volcanic rocks. Major cities are SMA San
Miguel de Allende and DH Dolores Hidalgo
outcrops of rhyolites, ignimbrites and andesites in its
interior (Fig. 1b). However, three main types of rock
and sediment exist in the vicinity of Tierra Blanca de
Abajo: (1) Oligocene–Miocene ignimbrites and tuffs
of rhyolitic to rhyodacitic composition; (2) sand-
stones, conglomerates, marls and shales, comprising
the Oligocene to Quaternary basin age constrained by
interbedded volcanic rocks and the presence of fossil
vertebrates; and (3) fluvial deposits. The ignimbrites,
which are by far the most abundant volcanic rocks in
the area, lie unconformably on a marine Mesozoic
basement. The tectonic domain corresponds to an
extension or elongation phase, with simultaneous
normal faulting typical of volcanic activity during
the Oligocene and early Miocene, with Middle
Miocene basalts and Pliocene (SGM 1999).
This work details the environmental occurrence of
erionite in the village of Tierra Blanca de Abajo,
Guanajuato State, central Mexico. The focus of the
research is to present the geologic and mineralogical
environment under which erionite formed, its physical
and geochemical characteristics, and associated pro-
cesses of transport, which provide the basis for epide-
miologic investigations and assessment of lung and
pleural cancer occurrences. These data will permit more
targeted exposure and health assessments that will focus
efforts and resources in specific geographic regions
within the basin. The final goal is to provide the basis for
health and safety protection programs in the region and
the scientific understanding of erionite and its carcino-
genic effects in Mexico, particularly those cases asso-
ciated with genetic susceptibility. We suggest the
hypothesis that most of the 19.5 % of mesotheliomas
in Mexico may be related to exposure of volcanic,
volcano-sedimentary, erionite-bearing deposits, which
have been disturbed and exposed to the environment.
Methodology
Detailed geologic-environmental surveys were con-
ducted in Tertiary volcanic rocks outcropping about
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3–6 km north of Tierra Blanca de Abajo, including the analytical techniques were utilized to identify the
collection of rock samples. More than 50 samples were presence and physical and geochemical characteris-
collected for this purpose. A series of microscopy and tics of erionite and associated minerals: optical
Fig. 2 a Map showing the
fluvial drainage and
observed outcrops of
Oligocene–Miocene
rhyolitic ignimbrites
(Tm Ig) within the El Gato
catchment. The village of
Tierra Blanca is located near
the San Damián river.
b Cross-section showing the
distribution of the zeolitic
tuff between two
Oligocene–Miocene
ignimbrites. The volcanic
rocks are overlyed by a
Pliocene lacustrine
sedimentary sequence.
c Photograph of the zeolitic
tuff with white altered
pumice fragments

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microscopy (OM), petrographic microscopy (PM), conglomerates. A cross-section toward the ignimbrite
scanning electron microscopy (SEM), energy dis- outcrop located 3 km north of the village is shown in
persive spectroscopy (EDS), X-ray fluorescence Fig. 2b. Rhyolitic zeolitized tuffs are found between
(XRF) and powder X-ray diffraction (XRD). OM was two compacted rhyolitic ignimbrites that will be called
used to observe the presence of fibrous-elongated
minerals, and high resolution SEM was employed to
determine their morphology (size, shape and aspect
ratio). SEM equipped with EDS was used to test the
elemental composition of the minerals, and powder
XRD was utilized to verify the mineralogy of the
fibrous particles at the Centre for Geosciences and
Institute for Geology (LUGIS), both at the National
University of Mexico. The mineralogical content of
the zeolitic tuff was determined through micro-Raman
spectroscopy (MRS) (Almega XR model), equipped
with an Olympus BX 51, at the Materials Laboratory
of the Center of Applied Sciences and Technological
Development, UNAM. Raman spectra were obtained
with a 532 nm laser of Nd: YVO4.
Polarized light microscopy (PLM) determinations
were performed at the International Asbestos Testing
Laboratory (iATL) in the USA for erionite analysis.
This technique is based on the ‘‘Central Stop Disper-
sion Staining’’ method (CSDS), similar to EPA 600 for
identifying asbestos (Solebello and Tomaino 2011).
For positive PLM results, a transmission electron
microscopy (TEM) with chemical analysis by energy
dispersive X-ray spectroscopy (EDS) and crystalline
identification by selected area electron diffraction
(SAED) was used for erionite analysis at the iATL.
About 50 mg of the zeolitic pumice material was
hydrated in fiber-free water, sonicated for 1 min, and
2–3 ml aliquots deposited on 47 mm diameter
0.45 lm mixed cellulose ester. The samples were
scanned at 10009 magnification and examined at
20–60,0009 magnifications.

Results and discussion

Geologic setting

Two outcrops of rhyolitic ignimbrites (Tm Ig) exist

upstream from the village within the El Gato
watershed (Fig. 2a), which is a tributary of the San
Damián River that feeds into the main La Laja River.
The village is built along the left margin of the river
on old alluvial terraces and lacustrine sedimen-
tary rocks, basically low-cemented sandstones and
Fig. 3 Representative microstructures and minerals identified
through petrographic microscopy. a Banded pumice (Pz) with
glass shards (Gs), zeolite (Z) and quartz (Qtz) (5x, NII);
b plagioclase (Pl), feldspar (Sanidine) (Sa), zeolite (Z), FI-
sanidine and glass shard (Gs) (5x, NX); c zeolite partial
pseudomorph of glass shard (20x, NII)

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the upper and lower ignimbrite units. In the cross-
section, the thickness of the zeolitic tuff is 30 m, but
toward the north, it increases to over 50 m. The
zeolitic tuff also presents vertical variation in its
physical properties (color, texture and degree of
alteration) and surely in its geochemistry. The volca-
nic rocks are covered by Pliocene lacustrine rocks,
which have been eroded for thousands of years,
exposing them to the environment. The upper part of
the zeolitic tuffs presents white altered pumice
fragments where microscopic fibrous-elongate min-
eral particles are barely visible in the field (Fig. 2c).
Mineralogy
Different aspects of the zeolitic tuff are observed in
microphotographs of thin films analyzed through a
petrographic microscope (Fig. 3a–c). Some observed
minerals are as follows: subhedral to anhedral and
subangular to subrounded quartz crystals (Qtz) of
0.1–0.7 mm; feldspar (FI-sanidine) of 0.1–2 mm,
slightly fractured by the matrix and replaced with
corrosion gulfs; and plagioclase of 0.2–0.5 mm.
Accessory minerals are biotite, pyroxene, zircon,
hematite and other, opaque minerals. Secondary
minerals are sericite and altered glass to clay. Glass
shards are (45 %) of shredded fragments (Gs); banded
pumice (Pz) up to 9.5 mm; zeolites (Z) of 0.2 mm.
Glass shards showing fiamee textures, flow-banding
and elongated shapes forming the matrix represent
broken fragments of pumice produced by highly
explosive eruptions that flowed in pyroclastic density
currents (high temperatures and high speed) deposit-
ing ignimbrite units.
Chemical results and ratios among the major
components of the three ignimbrites and the zeolitic
tuff, through XRF, are presented in Table 1. The
ignimbrites contain between 73.576 and 79.79 %
SiO2, contrasting with a lower SiO2 of 67.037 % in
the zeolitic tuff. The Al2O3 content is higher in the
zeolitic tuff at 14.84 % and lower in the ignimbrites,
between 9.77 and 11.80 %, whereas MgO and CaO
show higher contents in the zeolitic tuff. The SiO2/
Al2O3 and (K2O ? Na2O)/(CaO ? MgO) ratios are
higher in the ignimbrites compared to the zeolitic tuff.
Note the higher amount of loss of ignition (LOI) in the
zeolitic tuff (8.5 %). The above concentrations and
ratios are in the same range as that reported by De
Pablo-Galán and Chávez-Garcı́a (1996) for two of the
equivalent members of the Chichindaro Formation,
described by the authors about 20 km to the west of the
study area, suggesting that erionite deposits in the
altered zeolitic tuffs may extend to other areas within
the basin due to its geologic evolution.
Figure 4a shows a sample selected from the altered
pumice fragment observed through OM, where a
banded structure is visible. A concentration of bundles
of an acicular mineral grew parallel to the pumice
banding. Samples from this altered pumice that
concentrated the fibrous-elongate minerals were
selected for further microscopic identification of
erionite.

Table 1 Chemical composition of rhyolitic rocks

Sample SiO2 TiO2 AI2O3 Fe2O3t MnO MgO CaO Na2O K2O P2O5 LOI Total
(%) (%) (%) (%) (%) (%) (%) (%) (%) (%) (%) (%)

Ignimbrite 1 79.786 0.12 9.768 1.87 0.022 0.002 0.237 2.969 4.392 0.017 0.94 100.123
Ignimbrite 2 74.935 0.33 11.799 2.468 0.037 0.753 2.251 0.579 1.489 0.044 5.32 100.005
Ignimbrite 3 73.576 0.436 11.482 3.512 0.065 1.19 2.062 1.048 2.02 0.269 4.26 99.92
Rhyolitic tuff 67.036 0.163 14.837 2.595 0.017 1.271 3.16 0.881 2.069 0.027 8.48 100.536
SiO2 Fe2O3t MgO CaO K2O Na2O (K2O ? Na2O)
AI2O3 AI2O3 AI2O3 AI2O3 AI2O3 AI2O3 (MgO ? CaO)

8.17 0.19 0.00 0.02 0.45 0.30 30.80

6.35 0.21 0.06 0.19 0.13 0.05 0.69
6.41 0.31 0.10 0.18 0.18 0.09 0.94
4.52 0.17 0.09 0.21 0.14 0.06 0.67
Analysis by X-ray fluorescence

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b Fig. 4 Identification of the erionite mineral. a Micrograph

showing the banded pumice structure, where microscopic
acicular crystals grow parallel to the banding (35x). PLM
identification of erionite by: b sign of elongation (100x),
c birefringence (100x) and d central stop dispersion staining
(CSDS) (100x)

Fibrous-elongate mineral particles were isolated for

characterization by PLM. Figure 4b–d shows the PLM
examination: Refractive indices, sign of elongation
(Fig. 4b), and birefringence (Fig. 4c) are consistent
with erionite. Central stop dispersion staining (CSDS)
was used for refractive index matching (at 1.470), and
the blue color produced is consistent with erionite
identification (Fig. 4d).
Erionite was identified through SEM/EDS. Differ-
ent aspects of the microscopic structure are presented
in Fig. 5a–d. Porous channels apparently develop
during the growth of the heulandite-clinoptilolite
mineral series, where both individual fibers and
bundles of erionite crystallized later (Fig. 5a).
Another structure of the heulandite-clinoptilolite
mineral series in the form of spherical aggregates is
shown in Fig. 5b, with an intergrowth of erionite
fibers. An isolated erionite fiber is observed in Fig. 5c,
with a size of 1 lm in diameter and 70 lm in length.
Figure 5d shows erionite crystals with small spheres
around them. The composition of this mineral is Si/
Al = 1 and TSi = 0.5.
Heulandite and clinoptilolite are other zeolites
associated with erionite. Both heulandite and clinop-
tilolite possess the same tetrahedral framework (HEU)
and form a continuous compositional series sometimes
referred to as heulandite group zeolites. Figure 6a
shows a micrograph of heulandite and Fig. 6b a
micrograph of clinoptilolite. The heulandite series
pertains to all those samples with Si/Al \4
(TSi \ 0.80), and the clinoptilolite series includes all
compositions with Si/Al [4, as suggested by the
International Zeolite Association (IZA 2013). The
presence of both mineral series—heulandite and
clinoptilolite—may indicate different stages of growth
associated with differing amounts of water as a
function of their non-framework cation chemistry
and hydration state (Bish and Boak 2001; IZA 2013).
The position of the erionite-bearing tuffs in the
basin corresponds to the end of the hydrologic basin
(Fig. 1b) and to a groundwater discharge area that was
important in the past (Ortega-Guerrero 2009). The
groundwater flow regime and associated chemistry

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Fig. 5 Scanning electron microscope (SEM) images of erionite
(the fibrous-elongate minerals). Erionite fibers are observed to
growth in different zeolite (heulandite-clinoptilolite) structures
may have played an important role in the zeolitization
process, as discussed below.
A 1009 objective was used to focus the laser on the
sample in the MRS. A charge-coupled device (CCD),
cooled thermoelectrically to -50 °C, collected the
signal detector in a 180° geometry. Data acquisition
time was 50 s (10 acquisitions of 5 s each) for each
grain. Analysis of different powder samples from the
zeolitic tuff through MRS identified the mineral
heulandite. Other zeolites were not identified through
this technique.
Erionite ([30 lm, 5:1 aspect ratio) was detected
by TEM/EDS/SAED as \1 % of the total particle
examined from the altered pumice; the balance of
particles were of the same chemical fingerprint as
erionite by EDS but were not fibrous. In contrast, in the
tuff matrix, erionite (1–5 lm, [5:1 aspect ratio) was
detected as\0.1 % of the total particle examined; the
balance of the particles were of the same chemical
fingerprint as erionite by EDS but were not fibrous.
Different aspects of the TEM results are presented in
Fig. 7a–d. Erionite fibers end in the TEM diffraction
mode (Fig. 7a) and imaging mode (Fig. 7b). The sizes
of individual fibers are as follows: 0.547 lm in diameter
by 4.06 lm in length (Fig. 7c) and 0.203 lm in
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Environ Geochem Health (2014) 36:517–529
a and b. c An isolated erionite fiber. d Group of erionite fibers
with a grow of an spherical in shape mineral
diameter by 3.68 lm in length (Fig. 7d). Table 2 shows
the diameter and length in microns of five selected
samples of erionite, where the mean is 0.327 lm in
diameter by 6.93 lm in length.
The Si/Al ratio of erionite fibers ranges from 3.231
to 3.577 (at.%), with a mean of 3.345 (at.%) and a
standard deviation of 0.13. The Si/(Si ? Al) ratio is
between 0.764 and 0.782 (at.%), with a mean of 0.770
(at.%) and a standard deviation of 0.01 (Table 2).
These values are also in the range of the chemical
values of the erionite reported for Cappadocia in
Turkey and North Dakota in the USA (Dogan et al.
2008; Lowers et al. 2010; Carbone et al. 2011).
The results of the elemental distribution in crystal
chemistry of erionite-K (n = 6) are also shown in
Table 2. Si, Al, K and Ca present a narrow range of
variation, whereas Mg is absent in two of the samples.
Sodium was not detected, and iron is present in only
one sample. The Tierra Blanca erionite presents a
lower concentration of magnesium than the erionite
from Turkey and North Dakota, and plots slightly to
the right in a ternary diagram (Fig. 8).
Representative XRD patterns for two samples from
the altered pumice fragments and from the bulk rock
sample identified heulandite, clinoptilolite, quartz,
Environ Geochem Health (2014) 36:517–529
Fig. 6 Scanning electron microscope (SEM) images of a heu-
landite and b clinoptilolite
anorthite and smectite (probably montmorillonite)
(Fig. 9). This method confirms the presence of both
zeolites heulandite and clinoptilolite identified above
using SEM/EDS techniques. De Pablo-Galán and
Chávez-Garcı́a (1996) reported clinoptilolite, morde-
nite and traces of erionite between Juventino Rosas
and the city of Guanajuato. Mordenite was not found
in the zeolitic tuff from Tierra Blanca.
Origin of erionite
Erionite-K is found in altered rhyolitic tuffs in both
banded pumice fragments (*1 %) and the rock matrix
(*0.1 %). It is not yet clear if the tuffs were deposited
in lacustrine conditions within the lacustrine sequence
or were covered after aerial deposition. The Upper
Laja River Basin region, where the zeolitic tuff is
located, is conformed mainly by volcanic rocks of
rhyolitic and andesitic composition, with isolated
outcrops of Mesozoic marine rocks. The Pliocene–
Holocene fine-grain lacustrine deposits also contain
525
erionite associated with erosion and alluvial transport
from the rhyolitic tuffs and Quaternary fluvial and
alluvium deposits (Fig. 1b).
Diagenetic facies in the zeolitic tuff may result from
the reactions between the rhyolitic glass, heulandite–
clinoptilolite and erionite. The Upper Laja River Basin
(or Independence Basin) has been hydraulically open,
due to the fact that the Pliocene sedimentary sequences
that cover the Miocene-Oligocene volcanic rocks do
not present evaporitic mineral deposits, neither evi-
dence of saline groundwater. However, discharge
groundwater flow conditions prevailed in the part of
the basin where the zeolitic tuff outcrops, and it is
assumed that the main mechanism for zeolitization was
the flow of bicarbonate-rich groundwater at tempera-
tures [30 °C and pH [ 8. Groundwater flow through
the porous tuff dissolved unstable glassy components.
Partial replacement of glass by smectite and the
simultaneous precipitation of heulandite and clinop-
tilolite were associated with differing amounts of H2O
as a function of their non-framework cation chemistry.
Precipitation of erionite crystals is mainly parallel to
the pumice banding and apparently later than the
precipitation of heulandite and clinoptilolite. The
estimated depth to which zeolitization occurred is
*1,000 m under upward groundwater flow condi-
tions, basically through fracture ignimbrites and
porous tuffs. The estimated temperature of diagenesis
is unknown at this stage of the research. These geologic
conditions are similar to those reported by Shepard
(1996) for the western region of the USA.
Erionite deposits are found worldwide: in Antarc-
tica, Austria, Canada, the Czech Republic, Slovakia,
France, Georgia, Germany, Iceland, Italy, Japan,
Kenya, Korea, New Zealand Russia, Scotland, Tanza-
nia and Turkey (Dogan and Dogan 2008). Sheppard
(1996) describes different occurrences of erionite in
the western USA that had a similar geologic evolution
to that of western Mexico. He reports the presence of
erionite in continental tuffaceous rocks that are essen-
tially lacustrine. The host rocks range in age from the
Eocene to the Pleistocene, with variable erionite
content in the range of trace to 100 %, and thicknesses
in the range of centimeters to several meters. Coexis-
ting diagenetic minerals are other zeolites (chabazite,
clinoptilolite [most common], mordenite, phillipsite
and analcime), smectite, opal CT, quartz, potassium
feldspar, calcite, searlesite and fluorite. Other geologic
environments for erionite in the USA include erionite-
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Fig. 7 Transmission electron microscope (TEM) images showing a and b characteristics of individual fiber ends; and c and d sizes of
two individual fibers
filling fractures in silica-rich volcanic rocks affected by
hydrothermal groundwater and erionite as a lining in
vesicles and cavities mainly in basaltic rocks as
compiled by Van Gosen et al. (2013).
Erosion and alluvial transport of erionite
to populated areas
The erionite-bearing rock, a zeolitic rhyolitic tuff, has
been exposed to wind and water erosion agents for
thousands of years, and this has carried microscopic
erionite fibers to downstream areas, transported by surface
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water runoff and deposited with alluvial sediments of
different granulometric size (coarse boulders, gravel,
sand, silt and clay). Lower concentrations of erionite fibers
were identified in silt-clayey alluvial deposits near the
village of Tierra Blanca on the left margin of the San
Damián River (Ortega-Guerrero and Carrasco-Núñez
2012). The erionite-bearing alluvial sediments may extend
to the main Laja River and perhaps to the Allende Dam.
This transport process provides the basis for
epidemiologic investigations and assessment of lung
cancer occurrences, and allows for more targeted
exposure and health assessments that will focus efforts
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Table 2 Diameter and

Sample Diameter Length Si Al Mg K Ca Fe Si/Al Si/(Si ? Al)
length of erionite fibers, Si/ (lm) (lm) (at.%) (at.%) (at.%) (at.%) (at.%) (at.%) (at.%) (at.%)
Al and Si(Si ? Al) ratios
(at.%) and results of 1 0.547 4.06 66.69 20.42 0.98 6.09 5.15 0.67 3.266 0.766
elemental distribution in
2 0.289 17.1 66.57 20.08 0.52 8.77 4.06 0 3.315 0.768
crystal chemistry of
erionite-K 3 0.3 7 68.33 19.1 1.09 8.03 3.45 0 3.577 0.782
4 64.49 19.96 0 8.75 6.8 0 3.231 0.764
5 0.298 2.81 67.06 20.55 0.55 7.48 4.36 0 3.263 0.765
6 0.203 3.68 67.24 19.67 0 9.05 4.03 0 3.418 0.774
Mean 0.327 6.930 66.730 19.963 0.523 8.030 4.642 0.112 3.345 0.770
Std D 0.13 5.90 1.26 0.53 0.46 1.11 1.19 0.27 0.13 0.01

agricultural land. Potential villages located down-

stream toward the San Damián River and respective
populations are as follows: Cruz del Palmar (903),
Oaxaca (31), Ojo de Agua (6), San Isidro de Bandita
(122), Banda (394), Bandita (93), Rancho Nuevo
(209), Presita de Santa Rosa (84), Artesano (84),
Lindero Taboada (59), Xote (54), Cieneguita (*400)
and Vivienda de Abajo (145).

Carcinogenic potential of erionite from Tierra

Blanca

The physical and chemical characteristics of erionite

Fig. 8 Triangular diagram showing the compositional com-
parison of Tierra Blanca erionite (inverted triangles) with
respect to those of Turkey (empty circles) and North Dakota
(filled circles) (Modified from Carbone et al. 2011)
and resources on specific geographic regions down-
stream from the San Damian River, where alluvial
deposits bearing erionite have been used in the
construction of houses or in the development of
in San Miguel de Allende are also consistent with
those from Turkey and North Dakota. Erionite is
associated with MM in Turkey, but no specific cases of
this disease have been correlated so far in North
Dakota in the USA; however, the presence of erionite
and the type of respiratory diseases that occur in the
village strongly suggest the need for detailed health-
based studies in the region of the independence basin

Fig. 9 X-ray diffraction

(XRD) patterns from
powder of the zeolitic tuff,
indicating the presence of
heulandite, clinoptilolite,
quartz, anorthite and
smectite

123
528
and in the northwestern portion of Mexico. There is a
common geologic influence for natural erionite depos-
its that may exist through the evolution of the Mexico-
US Cordilleran, as reported in 95 documented natural
occurrences of erionite in the USA (Van Gosen et al.
2013) and three documented sites in Mexico: Agua
Prieta, Sonora, Juventino Rosas-Guanajuato, state of
Guanajuato (De Pablo-Galán and Chávez-Garcı́a
1996), and Tierra Blanca, state of Guanajuato
(Ortega-Guerrero and Carrasco-Núñez 2012), (Fig. 1a).
Conclusions
Erionite-K is hosted in a zeolitized rhyolitic tuff
confined between two rhyolitic ignimbrites (Oligo-
cene–Miocene), which are overlaid by a Pliocene
lacustrine sedimentary sequence. Erionite, heulandite
and clinoptilolite occur as diagenetic products in the
rhyolitic tuffs, associated with quartz, anorthite,
smectite (probably montmorillonite) and opal. The
microscopic structure of erionite, through TEM,
shows individual fibers that range from 0.14 to
0.547 lm in diameter and 2.81 to 17.1 lm in length,
while the observed bundles of fibers are in the range of
1–5 lm in width and 10–50 lm in length. Identifica-
tion of erionite requires a combination of adequate
microscopic and analytical methods due to the size and
limited abundance of these fibrous-elongate mineral
particles. In general, similar physical characteristics of
erionite from San Miguel de Allende exist with respect
to erionite from Cappadocia and North Dakota; the
main difference detected so far is the absence of
‘‘bundles’’ and ‘‘fibrils’’ of erionite.
The geochemical properties of erionite show low
concentrations of Mg and Si/Al ratios in the range of
3.23–3.58 (at.%) and Si/(Si ? Al) ratios in the range
of 0.76–0.78 (at.%), through TEM. These ranges of
values are similar to those reported for erionite in
Cappadocia, Turkey and North Dakota in the USA.
Potassium is the dominant cation and calcium occurs
occasionally, generally speaking K [ Ca [ Mg [ Fe.
Other minerals associated with erionite are heulandite
(Si/Al 2.5–3.7), clinoptilolite (Si/Al 4.3–5.3), quartz,
sanidine, anorthite and smectite. The origin of erionite
is associated with the reactions that occurred under
bicarbonate, slightly thermal, basic groundwater con-
ditions between the rhyolitic glass that formed the
123
Environ Geochem Health (2014) 36:517–529
zeolites series heulandite-clinoptilolite and then erio-
nite-K, in an open hydrologic basin that represents a
geologic environment ideal for the formation of other
erionite deposits.
The presence of erionite fibers of breathable size in
both the environment and housing construction mate-
rials in Tierra Blanca and a high incidence of lung
cancer and MM strongly suggest the hypothesis of
airborne exposure; however, as the various aspects of
exposure are not yet fully understood, they are the
focus of ongoing research. The physical and chemical
properties of erionite in Tierra Blanca are similar to
those of erionite in Turkey, where a clear association
between erionite and MM has been reported; however,
in North Dakota, no specific cases of MM have been
correlated so far, yet the risk exists. These results
provide the basis for epidemiologic investigations and
assessment of lung cancer occurrences, allowing for
more targeted exposure and health assessments that
will focus efforts and resources in specific geographic
regions. Around 13 small villages were identified
downstream along the San Damián River, near the
confluence with the main La Laja River, where a
potential risk of alluvial-bearing erionite exposure
may exist due to the interaction between alluvial
sediments and the activities of villagers. These results
also provide the basis for health and safety protection
programs in the lower region of San Damián River and
for a better scientific understanding of erionite and its
carcinogenic effects.
Acknowledgments We are grateful to people from the Tierra
Blanca de Abajo Village for their collaboration during different
stages of the research, in particular to the Community Health
Committee. Thanks to R.G.N. and other people who died before
the first stage of the research was completed. We also thank
Marı́a de la Luz Núñez, former major of the San Miguel de
Allende Municipality and Silvia Patricia Valdez Haro, former
director at the Second Sanitary Jurisdiction of the Health
Secretary at the State of Guanajuato (SSG), who provided the
EEMSG and the medical background information. The
Municipality of San Miguel Allende provided financial support
through the agreement: CV-COSJ-CGEO-009-V/2012. Thanks
to CEDESA a non-for-profit organization for logistic support
with the community. We also thank Marina Vega and Carolina
Muñoz at the Centre for Geoscience for chemical and
mineralogical determinations and the students Vanessa
Martı́nez and Erika Olivares who helped in the organization of
samples. Thanks to Dr. De Pablo at the Institute for Geology
(UNAM) for assisting part of the mineralogical studies. Thanks
to Lorena de León for petrographic analysis. Margarita Reyes,
Patricia Girón and Leticia De Alba provided additional SEM,
XDR and Raman analysis for some samples.
Environ Geochem Health (2014) 36:517–529
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