Environ Geochem Health (2008) 30:345353

DOI 10.1007/s10653-008-9167-8
1 3
ORI GI NAL PAPER
Arsenic and Xuoride in the groundwater of Mexico
M. A. Armienta N. Segovia
Received: 1 May 2006 / Accepted: 1 February 2007 / Published online: 12 March 2008
Springer Science+Business Media B.V. 2008
Abstract Concentrations of arsenic and Xuoride
above Mexican drinking water standards have been
detected in aquifers of various areas of Mexico. This
contamination has been found to be mainly caused by
natural sources. However, the speciWc processes
releasing these toxic elements into groundwater have
been determined in a few zones only. Many studies,
focused on arsenic-related health eVects, have been
performed at Comarca Lagunera in northern Mxico.
High concentrations of Xuoride in water were also
found in this area. The origin of the arsenic there is
still controversial. Groundwater in active mining
areas has been polluted by both natural and anthropo-
genic sources. Arsenic-rich minerals contaminate
the fractured limestone aquifer at Zimapn, Central
Mxico. Tailings and deposits smelter-rich fumes
polluted the shallow granular aquifer. Arsenic contami-
nation has also been reported in the San AntonioEl
Triunfo mining zone, southern Baja California, and
Santa Mara de la Paz, in San Luis Potos state. Even
in the absence of mining activities, hydrogeochemistry
and statistical techniques showed that arsenopyrite
oxidation may also contaminate water, as in the case
of the Independencia aquifer in the Mexican Altiplano.
High concentrations of arsenic have also been detected
in geothermal areas like Los Azufres, Los Humeros,
and Acoculco. Prevalence of dental Xuorosis was
revealed by epidemiological studies in Aguascalientes
and San Luis Potos states. Presence of Xuoride in
water results from dissolution of acid-volcanic rocks.
In Mexico, groundwater supplies most drinking
water. Current knowledge and the geology of Mexico
indicate the need to include arsenic and Xuoride
determinations in groundwater on a routine basis,
and to develop interdisciplinary studies to assess
the contaminants sources in all enriched areas.
Keywords Arsenic Chronic arsenicism Fluoride
Fluorosis Groundwater Mexico
Introduction
Groundwater has in Mxico, as in other arid and
semi-arid countries, a signiWcant role on Mexican
welfare and economic development. Potable water
supply for about 75% of the total population relies on
groundwater abstraction. On the other hand, poten-
tially toxic elements may reach hazardous concentra-
tions in groundwater as a result of geochemical
processes. These elements are ubiquitous in certain
geologic environments and may, with time, be released
to groundwater. Exploitation of aquifers naturally
enriched in toxic elements may increase their concen-
tration, and produce adverse health eVects on the
exposed population. Rational use and protection of
aquifers is thus a primary goal of Mexican society.
M. A. Armienta (&) N. Segovia
Instituto de Geofsica, Universidad Nacional Autonoma de
Mexico, UNAM, Mexico, D.F 04510, Mexico
e-mail: victoria@geoWsica.unam.mx
346 Environ Geochem Health (2008) 30:345353
1 3
The complex geology of Mexico with igneous,
sedimentary, and metamorphic rocks and an active
tectonic setting predisposes the environment to natu-
ral groundwater contamination. However, two ele-
ments, arsenic and Xuoride, have been clearly identiWed
as causing adverse eVects on health through ingestion
of contaminated groundwater. Moreover, these two
elements are recognized worldwide as the most serious
inorganic contaminants in drinking water (Smedley
and Kinniburgh 2002; Ng et al. 2003). Abundance of
arsenic and Xuoride in the subsoil has led to Mexico
becoming one of the worlds premier producers of
arsenic and Xuorite. In 2003, Mexico occupied the
fourth place in arsenic production, following China,
Chile, and Peru (COREMI 2004). Fluorite is one of
the main non-metallic minerals exploited in Mexico,
mostly in Coahuila, Durango, and San Luis Potos
states. In 2003 Mexico occupied the worlds second
place in Xuorite production.
In 1958, high levels of arsenic in drinking water
were identiWed for the Wrst time as the cause of
adverse eVects on health at Comarca Lagunera,
North Mexico (Cebrin et al. 1994). Arsenic levels
above the Mexican drinking water standards have
since been detected at other locations also. On the
other hand, the high Xuoride content of groundwater
has caused teeth and bone diseases in some areas, for
example San Luis Potos and Aguascalientes states,
Central Mxico. The aim of this paper is to give an
overview of the reported occurrences, sources and
health eVects of arsenic and Xuoride in the groundwa-
ter of Mexico.
Arsenic and Xuoride in sedimentary basins
and inactive volcanic regions
Comarca Lagunera (Durango and Coahuila states),
located in the central part of North Mexico is one of
the most important agricultural and livestock areas of
the country. Due to its dry weather, groundwater
exploitation was a signiWcant component of its eco-
nomic growth during the 20th Century. In 1958,
Cebrin et al. (1994) reported for the Wrst time occur-
rence of chronic arsenic poisoning in this area. Health
eVects resulting mainly from ingestion of polluted
groundwater included peripheral vascular disease,
keratosis, skin cancer, skin pigmentation changes,
gastrointestinal disturbances and alterations in the
coproporphyrin/uroporphyrin excretion ratio (Cebrin
et al. 1994; Hernndez-Zavala et al. 1998). Various
studies have been developed in this area to assess
speciWc aspects of the eVects of arsenic on the exposed
population. Alteration of bilirubin excretion was stud-
ied in individuals living in three villages exposed to
diVerent As levels in water (0.014, 0.1 and 0.3 mg/l).
Increased serum alanine aminotransferase activity
and predominantly conjugated hyperbilirubinemia
were related to total arsenic concentration in urine.
Average urine arsenic concentrations increased with
water As content. Results of this study suggested the
presence of cholestasis in As-exposed individuals
(Hernndez-Zavala et al. 1998). A group of 30 indi-
viduals exposed to 0.408 mg/l As in drinking water
showed cytogenetic damage. Total arsenic in urine
was 20 times higher in the exposed population than in
controls in the same area. A signiWcant increase was
observed in the frequency of chromatid and isochro-
matid deletions in lymphocytes, and of micronuclei in
oral and urinary epithelial cells, of exposed individu-
als relative to controls (Gonsebatt et al. 1997).
Del Razo et al. (2002), estimated the levels of
arsenic ingestion through cooked food prepared with
contaminated water (0.410 0.035 mg/l) in a village
of Comarca Lagunera. Results showed average
intakes of 16.6 and 12.3 g/kg body weight/day for
summer and winter, respectively, in the population
exposed to high As drinking water. In contrast, aver-
age As intakes of 0.94 and 0.76 g/kg body weight/
day for summer and winter, respectively, were calcu-
lated in a population consuming water with a lower
As concentration (0.012 0.004 mg/l) in the same
area.
Arsenic is unevenly distributed in the wells of this
region. In 1990, a concentration range from 0.008
to 0.624 mg/l was found in 128 sampled wells. Fifty
percent of the samples had concentrations higher than
0.05 mg/l (the Mexican drinking water standard in
those years). A rural population of 400,000 inhabit-
ants was considered to be exposed to high As levels.
As(V) was the predominant arsenic oxidation state in
93% of the wells (Del Razo et al. 1990). A survey of
58 wells in the year 2000, reported arsenic concentra-
tions up to 0.718 mg/l (Molina 2004). Several studies
have been performed to identify the source of arsenic
in the water. However, the origin of arsenic at
Comarca Lagunera is still controversial. A hydrothermal
system with high contents of lithium, boron, arsenic,
Environ Geochem Health (2008) 30:345353 347
1 3
and Xuoride was proposed as the arsenic source by
Gonzalez-Hita et al. (1991). Ortega-Guerrero (2004),
on the basis of chemical and isotopic composition of
groundwater and regional groundwater Xow modeling,
postulated evaporation as the primary mechanism
of arsenic enrichment in the most southeastern part of
this area.
Molina (2004) proposed several geochemical pro-
cesses in diVerent zones of the aquifer as possible
sources of arsenic contamination. In the granular
aquifer, desorption of arsenic retained on clays may
mobilize arsenic from the aquifer matrix to the
groundwater. Dissolution of iron and manganese
oxides and desorption would also increase the arsenic
water content. Oxidation of sulWdes may also release
arsenic in the limestone aquifer.
Groundwater contamination may produce high lev-
els of arsenic in pasture and contribute to increased
arsenic levels in cattle and their products. This arsenic
transfer is specially relevant since Comarca Lagunera
is one of the main milk producers of Mxico. Rosas
et al. (1999) conducted research in dairy farms of this
area to determine arsenic distribution in the agricul-
tural environment. Arsenic contents in farm wells
ranged from 0.007 to 0.740 mg/l; concentrations in
soil reached 30 g/g, with only 12% of extractable
arsenic. Up to 3.16 g/g arsenic, mostly accumulated
in the roots, were measured in alfalfa. Concentrations
in milk ranged from <0.9 to 27.4 ng/g. Ten percent of
50 samples analyzed were higher than the concentra-
tion level (10 ng/g) suggested as a permitted arsenic
level in milk by the International Dairy Federation
(IDF 1986). Application of a pharmacokinetic approach
showed the value of the milk biotransfer factor was
up to 6 10
4
. Analyses of the results suggested that
arsenic presence in milk was due mainly to consumption
of contaminated water by cattle.
Fluoride is also enriched in groundwater at
Comarca Lagunera. Concentrations from less than 0.5
to 3.7 mg/l Xuoride were reported in 1993. Levels
were higher in wells located in As-polluted areas (Del
Razo et al. 1993).
Arsenic-enriched groundwater was also detected
northwestern Mxico, in Sonora state. Results from
analyses performed in 173 samples from wells during
two sampling periods showed As concentrations were
from 0.002 to 0.305 mg/l. Some of the most polluted
wells were located in the most populated cities of the
state: Hermosillo (610,000 inhabitants), Caborca,
(69,000 inhabitants), and Etchojoa (56,000 inhabit-
ants). Groundwater Xuoride concentrations were also
high, and positively correlated with arsenic at Hermo-
sillo city. The speciWc origin of these elements has
not yet been identiWed. Nevertheless, based on the
geographic distribution of the contaminants, and the
lack of obvious external contamination, the authors
hypothesized a geogenic source (Wyatt et al. 1998a).
Excretion of arsenic in urine by children exposed
to As-containing water was determined in Hermosillo
city by Wyatt et al. (1998b). Arsenic levels of water
supplied to the population had been reduced by dilu-
tion with non-polluted water when the study was per-
formed. Drinking water concentrations in three
studied areas ranged from 0.007 to 0.038 mg/l.
Arsenic dose values calculated from water intake
(0.253 to 2.995 g/kg/day) exceeded the recom-
mended EPA (Environmental Protection Agency)
reference dose (EPA 1988). A positive correlation was
found between As in water and As in urine. Arsenic in
24-h urine excreted by children 7 to 11 years old
ranged from 5.78 g As/g creatinine (in the control
zone) to 114.29 g As/g creatinine in the zone with
the highest water As content. Concentrations of As
and Xuoride in groundwater samples from drinking
water sources of the studied population had a positive
correlation (r = 0.93), indicating a common source
within the aquifer. The arsenic and Xuoride content of
urine samples from children also correlated (r = 0.47,
P = 0.01) (Wyatt et al. 1998b), reXecting their levels
in water.
Two wells of Meoqui City, Chihuahua, located
1,945 km north of Mexico City, near the USA border,
showed elevated concentrations of Xuoride (5.9 and
4.8 mg/l) and arsenic (0.134 and 0.075 mg/l). Pin-
Miramontes et al. (2003) evaluated a treatment method
to remove Xuoride and arsenic from water of these
wells. The combined use of cake alum (aluminium sul-
fate octadecahydrate) and small amounts of a poly-
meric anionic Xocculant (PAF) reduced arsenic and
Xuoride concentrations by up to 99% and 77%, respec-
tively. EYciency of Xuoride and arsenic removal
depended on the amount of cake alum. On the other
hand, Xuoride removal also varied with pH, being
optimal at pH 7.1 (adjusted with a 8% NaOH solution).
A concentration of 450 mg/l cake alum and 1 mg of
PAF added to 1 l water (containing 5.9 mg/l F

and
348 Environ Geochem Health (2008) 30:345353
1 3
0.134 mg/l As), reduced F

to 1.4 mg/l and As to

<0.001 mg/l.
In the Guadiana valley, Durango state, northern
Mexico, 74 wells used as potable water source for
Durango City (491,000 inhabitants) were sampled
every three months during a year (Alarcn-Herrera
et al. 2001a). About half of the wells exceeded
0.05 mg/l As (59% of wells located in the city and
48% in the rural area). The highest concentration was
0.167 mg/l in the volcanic zone of the valley. Lowest
As contents were found in the recharge zone of the
aquifer. Arsenic presence was related to aquifer
geology. However, the geochemical processes releas-
ing arsenic to the groundwater were not identiWed.
Fluoride concentrations above drinking water stan-
dards (1.55.67 mg/l) have also been measured in the
groundwater of this valley (Alarcn-Herrera et al.
2001b; Ortiz et al. 1998). Approximately 94% of 51
wells sampled in the city of Durango had Xuoride
contents from 1.5 to 5.4 mg/l. About 95% of the pop-
ulation was estimated to be exposed to Xuoride levels
higher than 2.0 mg/l (Ortiz et al. 1998). The propor-
tion of wells exceeding the Mexican drinking water
standard (1.5 mg/l) was lower in the rural area. How-
ever, the highest contamination was found in rural
wellsup to 16.0 mg/l of Xuoride. The exposed pop-
ulation showed dental Xuorosis and increased bone
fractures. Prevalence and severity of dental Xuorosis
in children increased according to the Xuoride con-
centration of their home water supplies (Alarcn-
Herrera et al. 2001b).
Based on geochemical, and statistical interpreta-
tions of chemical, isotopic, hydrogeological, petro-
logical and mineralogical data, Mahlknecht et al.
(2004) explained As and F enrichment in the Indepen-
dence aquifer, Central Mexico. A complex aquifer
system formed mainly by marine sediments, volcanic
rocks, and lacustrine deposits has been identiWed in
this area. Lacustrine deposits, composed of sands int-
erstratiWed by gravels and clay are the most exploited
unit. Concentrations as high as 16 mg/l of Xuoride and
0.12 mg/l of As were measured in wells. Increased
pH, temperature, Na
+
, F

, and SiO
2
occur in the same
geographical zone. Groundwater Xuoride was ascribed
to dissolution of F-rich rhyolite rocks or ash. On the
other hand, oxidation of arsenic-bearing sulWdes may
be releasing As into groundwater.
Concentrations from less than 0.005 to 0.050 mg/l As
were measured in the Rioverde basin, central Mexico
(Planer-Friedrich et al. 2001). Increased groundwater
concentrations were found with lacustrine sediments
and decreased concentrations with Xuvial quaternary
sediments. Arsenic increase is probably due to the
sorption capacity of sediments and slightly reducing
conditions. A correlation of 0.675 (P < 0.001) was
calculated between arsenic and Xuoride. Although a
negative correlation was found between As and Ba,
thermodynamic modeling with PHREEQC indicated
that BaHAsO
4
.H
2
O might be a limiting phase for
arsenic, but at higher concentrations than those found
in the study.
Groundwater contamination by Xuoride has been
reported in San Luis Potos and Aguascalientes states,
central Mexico. Prevalence of dental Xuorosis was
studied in 445 children living in Aguascalientes state
and 201 children living in San Luis Potos (Hernn-
dez-Montoya et al. 2003; Grimaldo et al. 1995). Most
water-supply wells in Aguascalientes state showed
concentrations higher than 1.5 mg/l. Almost 100% of
children exposed to tap water containing more than
5.0 mg/l in Aguascalientes were found to suVer from
dental Xuorosis. Sixty one percent of tap water sam-
ples contained from 0.7 to 1.2 mg/l of Xuoride in four
areas of San Luis Potos City (670,532 inhabitants in
the year 2000) (Grimaldo et al. 1995; INEGI 2000).
Bottled water was also found to contain 0.33
6.97 mg/l Xuoride. Severity and prevalence of dental
Xuorosis increased with water Xuoride content. Each
mg/l increase in Xuoride water produced an increment
of 0.54 mg/l (P < 0.0001) of Xuoride in urine. Preva-
lence of dental Xuorosis was higher in San Luis Potos
than in cities in the United States consuming tap
water with similar Xuoride concentrations. Results
showed that ambient temperature, direct consumption
of boiled water, and consumption of food prepared
with boiled water, explain the prevalence of dental
Xuorosis in the area (Grimaldo et al. 1995).
The aquifer system of San Luis Potos valley is
formed by a shallow unconWned aquifer that overlies
a clay lens and a deep fractured volcanic aquifer.
Three Xow systems were identiWed in the aquifer: a
local Xow controlled by the clay layer, an intermedi-
ate system in which water inWltrates beyond the
boundary of the clay layer, and a regional system
originating outside the surface catchment. Groundwa-
ter chemistry in the regional Xow path is dominated
by natural water-rock reactions (Carrillo-Rivera
et al. 1996). Fluoride concentrations correlated with
Environ Geochem Health (2008) 30:345353 349
1 3
temperature in this valley. Leaching of rhyolitic rocks
was postulated as the Xuoride source in the deep
aquifer (Carrillo and Armienta 1989; Cardona et al.
1993). Increased pumping from the upper part of the
deep aquifer has induced an upward regional Xow,
rising temperatures and increasing water-rock
reactions, especially those related with Xuoride. The
deep waters containing high Xuoride concentrations
contaminated the shallower waters (Carrillo-Rivera
et al. 1996). Saturation indices suggested that Xuorite
solubility controls Xuoride concentrations in regional
waters. The appropriate mixture of cold and thermal
Xows may be used to decrease Xuoride concentrations
in abstracted groundwater (Carrillo-Rivera et al.
2002).
Arsenic in mining zones
Arsenic minerals occur in association with ores in
several mining areas of Mxico. Notable occurrences
of arsenic-bearing minerals like arsenopyrite, scoro-
dite, mimetite, adamite, tennantite, and nickeline
have been reported in various locations. Extraction
and processing of ores in these zones may be a source
of arsenic pollution. Besides, high arsenic levels
may also be naturally present in these environ-
ments. Few studies have been developed in Mxico to
identify each source and its environmental arsenic
contribution.
A multidisciplinary approach was developed in the
mining area of Zimapn, located in central Mexico, to
characterize the arsenic contamination problem, and
develop feasible solutions. Mining is the most impor-
tant economic activity in Zimapn. Silver extraction
has been performed since the 16th Century. Extrac-
tion and processing of silver, zinc, and lead ores is
currently going on. Wastes from the selective Xotation
process have accumulated near the town for more than
50 years and are now within its limits. Various arsenic
minerals occur in the Zimapn area. Arsenopyrite
(FeAsS) is widely distributed in the mineralized areas,
but scorodite, lolingite, tennantite, adamite, mimetite,
geochronite, and hidalgoite (PbAl
3
(AsO
4
)(SO
4
)(OH)
6
)
have also been recognized (Simons and Mapes-
Vzquez 1956; Garca and Querol 1988; Villaseor
et al. 1996).
Water is a scarce resource in the area. Potable
water relies totally on groundwater. Arsenic was Wrst
identiWed in the water by the National Commission
of Water while looking for cholera bacteria in
1992. A series of studies was subsequently started by
the National Autonomous University of Mxico
(UNAM). Concentrations up to 1.1 mg/l were deter-
mined in deep wells used for potable water supply.
About 34% of samples from shallow and deep wells
had As contents over 0.05 mg/l. As(V) is the predom-
inant form of arsenic. Presence of arsenic is due to
multiple sources, both natural and anthropogenic.
Hydrogeological, geological, and chemical studies
allowed their identiWcation.
The Zimapn aquifer system is formed mainly by
fractured limestone overlain by fanglomerate and
alluvial deposits. Geochemical and hydrogeological
evidence showed that oxidation of arsenopyrite and
dissolution of scorodite naturally present in the aquifer
release arsenic and contaminate the limestone aquifer
(Armienta et al. 1997a, 2001; Rodrguez et al. 2004).
Exploitation of deep wells promotes this process by
allowing oxygen interaction with minerals. SulWde
minerals oxidize during the dry season and the rise in
the water table mobilizes arsenic during the rainy
season (Rodrguez et al. 2004). Tailings constitute
another pollution source, with As concentrations up to
8.25%. Complex chemical processes occur within tail-
ings, releasing and retaining arsenic (Mndez and
Armienta 2003; Romero et al. 2006). Although most
arsenic occurs in a low-available form, it has reached
the shallow aquifer that is exploited mainly for non-
drinking water uses (Armienta et al. 1997a). Arsenic-
rich fumes from smelters operating until the mid 20th
Century were another source of arsenic in shallow
groundwater. Fumes settled on the soil and increased
its As content (Ongley et al. 2003), and by the action
of rain and irrigation the As was transported to the
shallow aquifers.
Zimapn town is a low-income community of
nearly 15,000 inhabitants. Arsenic-related health
eVects caused by consumption of polluted water have
been shown by various studies. Armienta et al.
(1997b) determined hair arsenic concentrations and
conducted a poll to identify possible health problems
linked with arsenic exposure. Of 120 sampled inhabit-
ants, 97 showed some degree of eVect on the skin.
SigniWcant diVerences in hair contents were obtained
among people with some degree of skin disease and
individuals with no visible health eVect. Skin diseases
such as light and dark skin spots and thickening of the
350 Environ Geochem Health (2008) 30:345353
1 3
outer layer of palms and soles were related with the
continuous consumption of water containing more
than 0.3 mg/l of arsenic. Sister chromatid exchanges
(SCE) in the broad bean Vicia faba were used to
examine contaminated water at Zimapn. SigniWcant
increases of SCE were observed compared with con-
trols; a concentrationresponse relationship was also
determined (Gmez-Arroyo et al. 1997).
The most polluted wells tapping the limestone
deep aquifer also have the highest yield of the valley,
and until early 2004 were the main potable water
source. Currently, a new well drilled in other valley
supplies non-polluted water to Zimapn. Neverthe-
less, its low production does not fulWll the town
requirements, and groundwater from a contaminated
well is still mixed with non-polluted water. Arsenic
concentration of 0.15 mg/l was measured by UNAM
in the potable water supply in February 2005.
A mining area dominated by epithermal veins with
the important presence of arsenopyrite is located in
Southern Baja California (Carrillo-Chvez et al.
2000). Silver and gold ores have been mined since the
late 1700s. A shallow unconWned aquifer in highly
fractured igneous rocks and patches of alluvial mate-
rial constitutes the local aquifer. Groundwater near the
mineralized zone showed high concentrations of total
dissolved solids, sulfate, bicarbonate, and arsenic. The
highest As values (0.41 mg/l) were found in this area,
near mine waste piles, and decreased with distance
along the groundwater Xow. Geochemical modeling
indicated that dilution, precipitation of calcite, and
arsenic sorption on to iron hydroxide surfaces are the
most likely processes occurring along the Xow-path
(Carrillo-Chvez et al. 2000).
Mining has been carried out at Santa Mara De la
Paz (approximately 500 km NNW of Mexico City) in
the state of San Luis Potos, for more than 200 years.
Ore deposits consist of a PbZnAg ore body and a
CuAu (Zn) ore body. Mineralogy of the PbZnAg
ore body is constituted by galena, arsenopyrite, pyrite,
sphalerite, and Cu-Sb sulfosalts (Megaw 1999; Razo
et al. 2004). Wastes produced from ore processing
have accumulated in Wve tailing impoundments
around the town of Villa de la Paz (5,120 inhabitants).
Water samples from mine channels and storage ponds
in the mining district ranged from 0.059 to more than
0.400 mg/l of arsenic. Mine water is directly used for
irrigation. One sample contained more than 5.900 mg/
l. Oxidation of sulWde minerals contained in mine
wastes, arsenopyrite oxidation in the aquifer, and natu-
ral release of As by dissolution of sulWdes present in
the aquifer under high alkalinity and anaerobic condi-
tions may be causing the groundwater arsenic increase
(Razo et al. 2004). Irrigation with mine water has also
contaminated agricultural soils with arsenic and toxic
metals (Castro-Larragoitia et al. 1997). Children
exposed to arsenic and lead in surface soil at Villa de la
Paz, showed DNA damage in blood cells (Yez et al.
2003).
Arsenic and Xuoride in geothermal areas near
active volcanic zones
Los Azufres in Michoacn state West Mexico, in the
Mexican Volcanic Belt, is one of the main geothermal
Welds of the country. It has been exploited since 1982.
A study carried out from November 1994 to May 1996
showed contamination of shallow aquifers and surface
waters. Arsenic and Xuoride reached maximum values
of 24 and 17 mg/l, respectively, in geothermal wells,
and of 8 and 16.3 mg/l, respectively, in surface waters.
The concentration increase in surface waters was pro-
duced by inadequate exploitation of deep brines,
mainly from leakage of evaporation ponds. Leaking of
pipelines, occasional overXowing of reinjection wells
and pond rims, and out-Xowing of brines during reha-
bilitation or drilling operations have also contributed to
water pollution. River pollution decreased down-
stream of contamination sources. However, concentra-
tions above background levels were found as far as
10 km outside the geothermal Weld (Birkle and Merkel
2000). Arsenic enrichment of water from geothermal
exploitation wells (up to 73.6 mg/l) was also measured
at Los Humeros geothermal Weld in Puebla state, Cen-
tral Mexico (Gonzlez-Partida et al. 2001). The geo-
thermal area of Acoculco, Puebla, is a volcanic caldera
with rhyolitic domes, scoria, and andesitic Xows. High
arsenic contents of calcic-sulfate type spring waters
located inside the caldera were reported in this zone
also (Quinto et al. 1995).
Groundwater arsenic and Xuoride in areas from
undetermined sources
In Acmbaro, Guanajuato state, Central Mxico,
Gutierrez-Pizano et al. (1996) reported arsenic
Environ Geochem Health (2008) 30:345353 351
1 3
concentrations up to 16 times the Mexican drinking
water standard in 1996 (0.05 mg/l) in well water. The
authors also refer the existence of cutaneous diseases
linked with arsenic consumption in that area.
The Salamanca aquifer system (central Mexico)
has been aVected by As, Pb, and benzene from diVer-
ent pollution sources (Rodrguez et al. 2005). Salam-
anca City is an important industrial center. An oil
reWnery, pesticides manufacturing industries, and a
thermoelectric plant are located in the city. An active
fault associated with an intense groundwater abstrac-
tion regime, crosses the urban area and the reWnery
lands. Three units compose the local aquifer system
a shallow non-exploited granular with a predomi-
nance of clay and clay-sand layers, an intermediate
exploited region including granular material, and a
deep formation formed mainly of fractured volcanic
rocks exploited only by the thermoelectric power
plant. Groundwater is the only drinking water sup-
ply of the population. Most urban wells contained
over 0.025 mg/l (the Mexican drinking water stan-
dard in 2005) of arsenic. A maximum concentration
of 0.28 mg/l was measured in a well near a fault area
(Rodrguez et al. 2005). The presence of As in ground-
water could be associated with a hydrocarbon spill
which occurred in 1992, with leakages from industrial
wastes, or with As-bearing rocks (Rodrguez et al.
2001, 2005).
Final remarks
Arsenic and Xuoride concentrations above drinking
water standards have been detected in various Mexican
aquifers. Both elements coexist at hazardous levels in
some areas. Arsenic enrichment has been caused by
geogenic processes in most of the studied sites. Water
rock interaction with volcanic rocks and As-rich ores
had released arsenic in fractured aquifers. Desorption
from clays and Fe and Mn oxides, and evaporation,
may account for arsenic in granular aquifers. Fluoride
contamination is related mainly to dissolution of acid
volcanic rocks. On the other hand, the aquifers com-
plexity has made it diYcult to identify the speciWc
source of these elements in all known polluted areas.
Interdisciplinary studies including geology, hydrogeol-
ogy, and geochemistry should be done to constrain
arsenic and Xuoride sources in the majority of contami-
nated aquifers. Most research in Mxico has been
focused on biomarkers and health eVects caused by
intake of contaminated drinking water. Epidemiologi-
cal studies have shown the link between adverse health
consequences and ingestion of water containing high
levels of arsenic and Xuoride. Results of these investi-
gations prompted the authorities to supply water from
other non-polluted sources in some of the polluted
areas. However, these studies were conducted in some
zones only. There is a need to conduct similar studies
in all polluted areas. Six-hundred and Wfty-three aqui-
fers exist in the Mexican territory (CNA 2004). A
global evaluation of the concentration of these and
other, minor, toxic elements should be conducted in all
Mexican territory. IdentiWcation of the oxidation state
of arsenic would also be advisable, because of the
higher toxicity of As(III) than As(V).
The geological characteristics of the Mexican terri-
tory indicate that As and F may be above drinking
water standards in many areas of the country. The
exposed population may be larger than that already
identiWed. Therefore, arsenic and Xuoride must be
determined in all groundwater sources in Mexico on a
regular basis. Much research is needed to ascertain
the actual levels, causes, and mobilization of these
elements in aquifers. These studies will give options
for delivering good-quality water based on abstrac-
tion regimes or treatment procedures. Meanwhile,
however, an eVort must be made to supply good
drinking quality water to the inhabitants.
References
Alarcn-Herrera, M. T., Flores-Montenegro, I., Romero-Navar, P.,
Martn-Domnguez, I. R., & Trejo-Vzquez, R. (2001a).
Contenido de arsnico en el agua potable del valle del Guadi-
ana, Mxico. Ingeniera Hidrulica en Mxico, XVI, 6370.
Alarcn-Herrera, M. T., Martn-Domnguez, I. R., Trejo-
Vzquez, R., & Rodrguez-Dosal, S. (2001b). Well water
Xuoride, dental Xuorosis, bone fractures in the Guadiana
Valley of Mexico. Fluoride, 34, 139149.
Armienta, M. A., Rodriguez, R., Aguayo, A., Ceniceros, N.,
Villaseor, G., & Cruz, O. (1997a). Arsenic contamination
of groundwater at Zimapn, Mxico. Hydrogeology Jour-
nal, 5, 3946.
Armienta, M. A., Rodriguez, R., & Cruz, O. (1997b). Arsenic
content in hair of people exposed to natural arsenic pol-
luted groundwater at Zimapn, Mxico. Bulletin of Envi-
ronmental Contamination and Toxicology, 59, 583589.
Armienta, M. A., Villaseor, G., Rodrguez, R., Ongley, L. K.,
& Mango, H. (2001). The role of arsenic-bearing rocks in
groundwater pollution at Zimapn Valley, Mxico. Envi-
ronmental Geology, 40, 571581.
352 Environ Geochem Health (2008) 30:345353
1 3
Birkle, P., & Merkel, B. (2000). Environmental impact by spill
of geothermal Xuids at the geothermal Weld of Los Azufres,
Michoacn, Mexico. Water, Air, and Soil Pollution, 124,
371410.
Cardona, B. A., Carrillo R. J. J., & Armienta, H. M. A. (1993).
Elemento traza: contaminacin y valores de fondo en aguas
subterrneas de San Luis Potos, SLP, Mxico. Geofsica
Internacional, 32, 277286.
Carrillo, J. J., & Armienta, M. A. (1989). Diferenciacin de la
contaminacin inorgnica en las aguas subterrneas del
Valle de la ciudad de San Luis Potos, S.L.P., Mxico.
Geofsica Internacional, 28, 763783.
Carrillo-Chvez, A., Drever, J. I., & Martnez, M. (2000).
Arsenic content and groundwater geochemistry of the San
Antonio-El Triunfo, Carrizal and Los Planes aquifers in
southernmost Baja California, Mexico. Environmental
Geology, 39, 12951303.
Carrillo-Rivera, J. J., Cardona, A., & Moss, D. (1996). Impor-
tance of the vertical component of groundwater Xow: A hy-
drogeochemical approach in the valley of San Luis Potos,
Mexico. Journal of Hydrology, 23, 2344.
Carrillo-Rivera, J. J., Cardona, A., & Edmunds, W. M. (2002).
Use of abstraction regime and knowledge of hydrogeolog-
ical conditions to control high-Xuoride concentration in ab-
stracted groundwater: San Luis Potos Basin, Mexico.
Journal of Hydrology, 261, 2447.
Castro-Larragoitia, J., Krama, U., & Puchelt, H. (1997).
200 years of mining activity at La Paz/San Luis Potos/
Mexico-Consequences for environment and geochemical
exploration. Journal of Geochemical Exploration, 58,
8191.
Cebrin, M. E., Albores, A., Garca-Vergas, G., & Del Razo, L.
M. (1994). Chronic arsenic poisoning in humans: The case
of Mexico. In: J. O. Nriagu (Ed.), Arsenic in the environ-
ment Part II (pp. 93107). New York: Wiley.
COREMI. (2004). Anuario Estadstico de la Minera Mexicana
2003. Pachuca: Consejo de Recursos Minerales, 252 pp.
CNA, Comisin Nacional del Agua. (2004). Statistics on water
in Mexico 2004. Mxico, D.F.: Comisin Nacional del
Agua, 141 pp.
Del Razo, L. M., Arellano, M. A., & Cebrin, M. E. (1990). The
oxidation states of arsenic in well-water from a chronic ar-
senicism area of northern Mexico. Environmental Pollu-
tion, 64, 143153.
Del Razo, L. M., Corona, J. C., Garca-Vargas, G., Albores, A.,
& Cebrin, M. E. (1993). Fluoride levels in well-water
from a chronic arsenicism area of northern Mexico. Envi-
ronmental Pollution, 80, 9194.
Del Razo L. M., Garcia-Vargas G. G., Garca-Salcedo J.,
Sanmiguel M. F., Rivera M., Hernandez M. C., & Cebrian
M. E. (2002). Arsenic levels in cooked food and assessment
of adult dietary intake of arsenic in the Region Lagunera,
Mexico. Food and Chemical Toxicology, 40, 14231431.
EPA, Environmental Protection Agency. (1988). Risk Assess-
ment Forum, Special Report on Ingested Inorganic
Arsenic: Skin Cancer Nutritional Essentiality. EPA/625/3-87/
013.
Garca, S., & Querol, S. F. (1988). Descripcin de algunos
yacimientos del distrito de Zimapn, Hidalgo. In: G. P.
Salas (Ed.), Geologa econmica de Mxico (pp. 383400).
Mxico, D.F.: Fondo de Cultura Econmica.
Gmez-Arroyo, S., Armienta, M. A., Corts-Eslava, J., &
Villalobos-Pietrini, R. (1997). Sister chromatid exchanges
in Vicia faba induced by arsenic-contaminated drinking
water from Zimapan, Hidalgo, Mexico. Mutation Research,
394, 17.
Gonsebatt, M. E., Vega, L., Salazar, A. M., Montero, R., Guz-
mn P., Blas, J., Del Razo, L. M., Garca-Vargas, G., Alb-
ores, A., Cebrin, M. E., Kelsh, M., & Ostrosky-Wegman,
P. (1997). Cytogenetic eVects in human exposure to ar-
senic. Mutation Research, 386, 219228.
Gonzlez-Hita, L., Snchez, L., & Mata, I. (1991). Estudio hid-
rogeoqumico e isotpico del acufero granular de la
Comarca Lagunera. Morelos: Instituto Mexicano de Tec-
nologa del Agua.
Gonzlez-Partida, E., Hinojosa, T. E., & Verma, M. P. (2001).
Interaccin agua geotrmica-manantiales en el campo geo-
trmico de Los Humeros, Puebla, Mxico. Ingeniera Hid-
rulica en Mxico, XVI, 185194.
Grimaldo, M., Borja-Aburto, V. H., Ramrez, A. L., Ponce, M., Ro-
sas, M., & Daz-Barriga, F. (1995). Endemic Xuorosis in San
Luis Potos, Mexico. Environmental Research, 68, 2530.
Gutirrez-Pizano, A., Rodrguez, R. E., Romero, G. J., & Velz-
quez, G. A. (1996). Eliminacin del arsnico en agua pota-
ble de pozos. Actas INAGEQ, 2, 319322.
Hernndez-Montoya, V., Bueno-Lpez, J. I., Snchez-Ruelas,
A. M., Garca-Servn, J., Trejo-Vzquez, R., Bonilla-Pe-
triciolet, A., & Mrquez-Algara, C. (2003). Fluorosis y car-
ies dental en nios de 9 a 11 aos del estado de
Aguascalientes, Mxico. Revista Internacional de Con-
taminacion Ambiental, 19, 197204.
Hernndez-Zavala, A., Del Razo, L. M., Aguilar, C., Garca-Var-
gas, G. G., Borja, V. H., & Cebrin, M. E. (1998). Alteration
in bilirubin excretion in individuals chronically exposed to
arsenic in Mexico. Toxicology Letters, 99, 7984.
IDF, Internacional Dairy Federation. (1986). Levels of trace
elements in milk and milk products. Questionnaire 2386/E.
Brussels.
INEGI, Instituto Nacional de Estadstica, Geografa e Inform-
tica. (2000). XII Censo General de Poblacin y Vivienda.
Retrieved February 15, 2006, from: http://www.inegi.
gob.mx.
Mahlknecht, J., Steinich, B., & Navarro de Len, I. (2004).
Groundwater chemistry and mass transfers in the Indepen-
dence aquifer, central Mexico, by using multivariate statis-
tics and mass-balance models. Environmental Geology, 45,
781795.
Megaw, P. (1999). The high temperature Ag-Pb-Zn-(Cu) Car-
bonate-replacement deposits of Central Mexico. In: J. L.
Jambor (Ed.), VMS and carbonate-Hosted polymetallic
deposits of Central Mexico (pp. 2540). Vancouver: Brit-
ish Columbia and Yukon Chamber of Miner.
Mndez, M., & Armienta, M. A. (2003). Arsenic phase distribu-
tion in Zimapn mine tailings, Mexico. Geofsica Internac-
ional, 42, 131140.
Molina, M. A. (2004). Estudio hidrogeoqumico en la Comarca
Lagunera, Mxico. M.Sc. Thesis, Posgrado en Ciencias de
la Tierra, National Autonomous University of Mexico,
UNAM, Mxico D.F.
Ng, J. C., Wang, J., & Shraim, A. (2003). A global health prob-
lem caused by arsenic from natural sources. Chemosphere,
52, 13531359.
Environ Geochem Health (2008) 30:345353 353
1 3
Ongley, L. K., Armienta, A., & Mango, H. (2003). Concentra-
tions of heavy metals in soil, Zimapan, Mxico. Journal de
Physique IV, 107, 983986.
Ortega-Guerrero, M. A. (2004). Origin of high concentrations of
arsenic in groundwater at the La Laguna Region, northern
Mexico, and implications on aquifer management. In Work-
shops: Program with Abstracts, 32nd IGC Florence, p. 1486.
Ortiz, D., Castro, L., Turrubiartes, F., Milan, J., & Diaz-Barriga,
F. (1998). Assessment of the exposure to Xuoride from
drinking water in Durango, Mexico, using a geographic
information system. Fluoride, 31, 183187.
Pin-Miramontes, M., Bautista-Margulis, R. G., & Prez-Her-
nndez, A. (2003). Removal of arsenic and Xuoride from
drinking water with cake alum and a polymeric anionic
Xocculent. Fluoride, 36, 122128.
Planer-Friedrich, B., Armienta, M. A., & Merkel, B. J. (2001).
Origin of arsenic in the groundwater of the Rioverde basin,
Mexico. Environmental Geology, 40, 12901298.
Quinto, A., Santoyo, E., Torres, V., Gonzlez, E., & Castillo, D.
(1995). Estudio geoqumico-ambiental de los eXuentes
naturales producidos en la zona geotrmica de Acoculco,
Puebla. Ingeniera Hidrulica en Mxico X, 2127.
Razo, I., Carrizales, L., Castro, J., Daz-Barriga, F., & Monroy,
M. (2004). Arsenic and heavy metal pollution of soil, water
and sediments in a semi-arid climate mining area in
Mexico. Water, Air, and Soil Pollution, 152, 129152.
Rodrguez, R., Armienta, A., Berln, J., & Meja, J. A. (2001).
Arsenic and lead pollution of the Salamanca aquifer, Mex-
ico: Origin, mobilization and restoration alternatives. In: S.
F. Thornton & S. E. Oswald (Eds.), Groundwater quality:
Natural and enhanced restoration of groundwater
pollution (pp. 561565). Proceedings of the Groundwater
Quality 2001, SheYeld U.K., IAHS Publ 275, Walling-
ford, Oxfordshire.
Rodrguez, R., Ramos, J. A., & Armienta, M. A. (2004).
Groundwater arsenic variations: The role of local geology
and rainfall. Applied Geochemistry, 19, 245250.
Rodrguez, R., Armienta, M. A., & Meja Gmez, J. A. (2005).
Arsenic contamination of the Salamanca aquifer system in
Mexico: A risk analysis. In: J. Bunduschuh, P. Bhattach-
arya, & D. Chandrasekharam (Eds.), Natural arsenic in
groundwater: Occurrence, remediation and management
(pp. 7783). London: Taylor & Francis Group.
Romero, F. M., Armienta, M. A., Villaseor, G., & Gonzlez, J.
L. (2006). Mineralogical constraints on the mobility of
arsenic in tailings from Zimapn, Hidalgo, Mexico. Inter-
national Journal of Environment and Pollution, 26, 2340.
Rosas, I., Belmont, R., Armienta, A., & Baez, A. (1999).
Arsenic concentrations in water, soil, milk and forage in
Comarca Lagunera, Mexico. Water, Air, and Soil Pollution,
112, 133149.
Simons, S. F., & Mapes-Vazquez, V. E. (1956). Geology and
ore deposits of the Zimapn Mining District, State of
Hidalgo, Mexico. US Geological Survey Professional
Paper 284.
Smedley, P. L., & Kinniburgh, D. G. (2002). A review of the
source, behaviour and distribution of arsenic in natural
waters. Applied Geochemistry, 17, 517568.
Villaseor, C. M. G., Petersen, E. U., Avendao-Cano, S., Go-
mez-Caballero, J. A., Sousa, J., & Reyes-Salas, A. M.
(1996). Minerales del grupo de la tetrahedrita en las minas
de Lomo de Toro y Las Animas, Zimapn, Hidalgo. Actas
INAGEQ, 2, 129134.
Wyatt, C. J., Fimbres, C., Romo, L., Mndez, R. O., & Grijalva,
M. (1998a). Incidence of heavy metal contamination in
water supplies in Northern Mexico. Environmental Research
A, 76, 114119.
Wyatt, C. J., Lopez, Q. V., Olivas, A. R. T., & Mndez, R. O.
(1998b). Excretion of arsenic (As) in urine of children, 7
11 years, exposed to elevated levels of As in the City water
supply in Hermosillo, Sonora, Mxico. Environmental Re-
search A, 78, 1924.
Yez, L., Garca-Nieto, E., Roas, E., Carrizales, L., Meja, J.,
Caldern, J., Razo, I., & Daz-Barriga, F. (2003). DNA
damage in blood cells from children exposed to arsenic and
lead in a mining area. Environmental Research, 93, 231240.