Ore Geology Reviews 23 (2003) 277 – 297

www.elsevier.com/locate/oregeorev

Environmental geochemistry of the Guanajuato

Mining District, Mexico
A. Carrillo-Chávez a,*, O. Morton-Bermea b, E. González-Partida a, H. Rivas-Solorzano c,
G. Oesler d, V. Garcı́a-Meza e, E. Hernández b, P. Morales f, E. Cienfuegos f
a
Centro de Geociencias, Univ. Nacional Autónoma de México, Campus Juriquilla, Postal 1-742, Querétaro, QRO 76230, Mexico
b
Inst. de Geofı́sica. Univ. Nacional Autónoma de México, Mexico
c
Pos-grado en Ciencias de la Tierra. Univ. Nacional Autónoma de México, Mexico
d
Department of Geology, University of Wyoming, USA
e
Facultad de Quı́mica, Univ. Nacional Autónoma de México, Mexico
f
Inst. de Geologı́a, Univ. Nacional Autónoma de México, Mexico
Received 22 April 2002; received in revised form 8 October 2002; accepted 1 May 2003

Abstract

The Guanajuato Mining District, once one of the major silver producers in the world, has been exploited for silver and
gold from low-sulfidation quartz- and calcite-rich epithermal veins since 1548. Currently, there are some 150 million
tonnes of low-grade ore piles and mine-waste material (mostly tailings) piles, covering a surface area of 15 to 20 km2
scattered in a 100-km2 region around the city of Guanajuato. Most of the historic tailings piles were not deposited as
formal tailings impoundments. They were deposited as simple valley-filling piles without concern for environmental issues.
Most of those historical tailings piles are without any vegetation cover and undergo strong eolian and hydrologic erosion,
besides the natural leaching during the rainy season (which can bring strong thunderstorms and flash flows). There is
public concern about possible contamination of the local aquifer with heavy metals (Fe, Mn, Zn, As and Se) derived from
the mining activities.
Experimental and field data from this research provide strong geochemical evidence that most of the mine-waste materials
derived from the exploitation of the epithermal veins of the region have very low potential for generation of acid mine
drainage due to the high carbonate/sulfide ratio (12:1), and very low potential for leaching of heavy metals into the
groundwater system. Furthermore, geochemical evidence (experimental and modeled) indicates that natural processes, like
metal adsorption onto Fe-oxy-hydroxides surfaces, control the mobility of dissolved metals. Stable isotope data from surface
water, groundwater wells (150-m depth) and mine-water (300- to 500-m depth) define an evaporation line (dD = 5.93
d18O = 13.04), indicating some deep infiltration through a highly anisotropic aquifer with both evaporated water (from the
surface reservoirs) and meteoric water (not evaporated). Zinc concentrations in groundwater (0.03 to 0.5 ppm) of the alluvial
aquifer, some 15 km from the mineralized zone, are generally higher than Zn concentrations in experimental tailings
leachates that average less than 0.1 ppm. Groundwater travel time from the mineralized area to the alluvial valley is
calculated to range from 50 to several hundred years. Thus, although there has been enough time for Zn sourced from the

* Corresponding author.
E-mail address: ambiente@geociencias.unam.mx (A. Carrillo-Chávez).
URL: http://www.geociencias.unam.mx.

0169-1368/$ - see front matter D 2003 Elsevier B.V. All rights reserved.
doi:10.1016/S0169-1368(03)00039-8
278 A. Carrillo-Chávez et al. / Ore Geology Reviews 23 (2003) 277–297
tailings to reach the valley, Zn concentrations in valley groundwater could be due to natural dissolution processes in the deep
portions of the epithermal veins.
D 2003 Elsevier B.V. All rights reserved.
Keywords: Environmental geochemistry; Mine tailings; Groundwater; Heavy metals; Guanajuato; Mexico
1. Introduction
Since early in the history of mankind, metallic ore
deposits have played an important role in the tech-
nologic and economic development of the human
society. The highly industrialized contemporaneous
society requires an increase in metallic mineral
supplies. Thus, it is a priority to increase our activ-
ities of exploration and exploitation of these ore
deposits (Kesler, 1994). However, along with this
priority in exploration comes another basic need of
our society: the preservation of a clean environment
(air – water – soil) (Berner and Berner, 1996; Fyfe,
1998; Hill, 1997; Keller, 1992; Kesler, 1994; Plant
et al., 2001). Regretfully, in most of historical cases
(and some modern cases too), the exploitation of ore
deposits has been accompanied for a negative impact
to the environment (mainly to surface and ground-
water) (Gray et al., 1994; Guogh, 1993; King, 1995).
It is a fundamental task of all of us to find a balance
between exploration and exploitation of metallic ore
deposits with the preservation of a clean environment
for future generations (Hill, 1997; Nriagu, 1990;
Plant et al., 2001). Perhaps the greatest challenge
facing humankind is how to support the growing
population demands, without negatively affecting of
our most basic life-support ecosystems (Fyfe, 1998).
To solve these problems, there is a need for team-
work integrating all the expertise from the natural
sciences and the engineering and economic sciences.
It is also clear that the activities needed for equili-
brated development of ore deposits and the environ-
ment are of multidisciplinary character. However,
punctual actions, like environmental geochemistry
assessments, are basic for future decision-making
activities.
Environmental geochemistry is a relatively new
branch of the natural sciences (geology and chemis-
try) that deals with the analysis of the geologic and
chemical processes that introduce and control the
concentrations of elements or substances potentially
contaminant to the environment (Plant et al., 2001).
The distribution of most of these elements or sub-
stances could be normal in the environment, but when
their concentrations are above certain levels, they
could become toxic to the ecosystem. The main
environmental problems related to ore deposits are
acid mine drainage resulting from the oxidation of
sulfides (mostly pyrite) and hydrolysis of metal
oxides, and high concentrations of heavy metals on
water draining from mining sites (Pb, Zn, Cu, Cd, Cr,
Fe, Mn, As, Se, Sb, etc.).
It is also true that natural processes like the
weathering of metallic ore deposits (mostly sul-
fides), weathering of metal-rich rocks, volcanic
eruptions and mineralized hot springs could produce
naturally acid rock drainage and anomalous amounts
of heavy metals in the environment. But, in most
cases, the activities of the mining industry locally
increase these processes of acid drainage and liber-
ation of heavy metals to the environment (Gray,
1997; Larocque and Rasmussen, 1998; Smith et al.,
1994).
However, during the last two decades, real prob-
lems of high concentration of heavy metals in ground-
water around mining areas have been recognized
(Alpers et al., 1994; Belkin and Spark, 1993; Bowell,
1994; Carrillo and Drever, 1997; Cebrian et al., 1994;
Chavez and Walder, 1995). Since the second half of
the 1980s and during all the 1990s the environmental
research on the impact of mining activities has
increased considerably. Some of this research has
been focused on the effects of acid mine drainage
and high concentrations of heavy metals on surface
and groundwater and soil (Alpers et al., 1994; Bow-
ell, 1994; King, 1995; Haneberg et al., 1993; Fyfe,
1998; Larocque and Rasmussen, 1998; Rösner, 1998).
Other works have focused on the mineralogical and
chemical characterization of metallic ore deposits and
their respective wastes (Carrillo and Drever, 1997;
 A. Carrillo-Chávez et al. / Ore Geology Reviews 23 (2003) 277–297
Chavez and Walder, 1995; Smith et al., 1994; Plumlee
and Severson, 1994). Another research approach has
focused on the characterization of mineral surfaces in
the natural environment and their effects on dissolved
heavy metals (Carrillo and Drever, 1998; Duddley et
al., 1988; Koretsky, 2000; Wuolo, 1986). Other
researches have determined the geochemical baselines
to distinguish between natural and anthropogenic
sources of metals in the environment (Matschullat et
al., 2000; Plant et al., 2001). The use of stable and
radiogenic isotopes also has found a solid place in the
environmental geosciences (Ghomshei and Allen,
2000; Toner et al., 2003). Additional environmental
geochemical research concerning ore deposits
involves geochemical and mathematical modeling,
biogeochemistry, molecular environmental geochem-
istry, laboratory experiments and review on sources,
behavior and distribution of individual elements in the
near-surface environment (Banwart and Malmström,
2001; Bener et al., 2000; Blowes et al., 1998; Brown
et al., 2000; Eary, 1999; Fein et al., 2001; O’Day,
1999; Smedley and Kinniburgh, 2002; Tempel et al.,
2000). All this geochemical information can be com-
bined with hydrogeological data in order to predict
and to model the behavior of heavy metals in ground-
water (geometry of plumes, velocity, residence time,
etc.) (Drever, 1997; Mazor, 1991; Stumm and Mor-
gan, 1996).
The objectives of environmental geochemistry
studies of ore deposits are to provide answers to the
following questions:

What are, and where are, the potential sources of
potential contaminant metal located, and how
much material is exposed?

How much metal is being introduced to the
environment and what is its residence time, and
flux-in and flux-out rates?

What are the geochemical processes controlling the
concentration and distribution of the heavy metals
in the natural environment (groundwater-soil)?

What is the distribution of the heavy metals in the
field (potential contamination plumes)?
In the United States alone, between 100,000 and
500,000 mine sites are abandoned or inactive (King,
1995). In Mexico, the number of mining sites is
unknown, but there are estimates of 10,000 to
279
50,000 abandoned or inactive mine sites. Currently,
in the United States there are more than 50 US
Environmental Agency (US-EPA) Superfund restora-
tion sites related to non-fuel mining activity (King,
1995). Currently in Mexico, there are relatively few
environmental studies on mining sites, and no federal
program for restoration of sites exists. One of the
goals of this research is to present pioneering geo-
chemical data on mine tailings and groundwater at a
major mining site in Mexico and to try to motivate the
development of regular environmental geochemical
evaluations in Mexico with the long-term goal of
building a census of mining sites, as a base for future
restoration programs.
In this paper, we present analytical and experimen-
tal geochemical data from several materials of the
Guanajuato mining district (sediments, mine tailings,
natural water, and leachates from column and humid-
ity cell experiments). The purpose of this research is:
(a) to determine, both experimentally and in the field,
the potential for generation of acid mine drainage
and leaching of heavy metals into the aqueous
environment (surface and groundwater) of some
of the historical mine waste materials;
(b) to consider possible natural processes taking place
below the surface to explain the chemical effects
on the groundwater of both the natural material
(ore deposits) and the anthropogenic altered
material (mostly tailings);
(c) to compare experimental and field observations
with analytical data from the groundwater;
(d) to determine processes of the hydrogeochemical
evolution, and
(e) to quantify the natural background values and
anthropogenic pollution in the region.
2. Site description
The Guanajuato Mining District, some 350 km
west – northwest of Mexico City, is located in the core
of the Guanajuato Mountain Range (Fig. 1). This
mining district represents the central zone of a region-
al polymetallic mineralized belt that runs from Taxco
(south central Mexico) to Guanajuato (central Mex-
ico), and to Sta. Barbara, Chihuahua (north-central
Mexico). This regional mineralized belt is related to
280 A. Carrillo-Chávez et al. / Ore Geology Reviews 23 (2003) 277–297

Fig. 1. Regional location of the Guanajuato District in central Mexico and location of four historical tailings sites around the city of Guanajuato
(La Luz, Valenciana, San Nicolas and Noria Alta).

subduction processes during the Middle Tertiary and
extensional tectonic stress defined by the NW – SE
orientation of the mineralized veins (Randall et al.,
1994). The geology of the region consists of a
Cretaceous volcano-sedimentary sequence covered
by mafic igneous rocks and intruded by Tertiary
granodiorite batholithic rocks. The older rocks have
been partially covered by volcanic rocks related to a
caldera center, with which the mineralized vein sys-
tems are associated (Randall, 1990; Randall et al.,
1994; Martinez-Reyes, 1992).
Buchanan (1980) described three mineralizing
stages in epithermal veins with abundant quartz,
calcite and adularia. The mineral zoning allowed
Buchanan (1980) to define a mineralization model
and the distribution of an upper zone (precious
metals: Au and Ag), an intermediate zone (transition),
and a deeper zone (base metal: Cu, Zn, Pb). Gold and
 A. Carrillo-Chávez et al. / Ore Geology Reviews 23 (2003) 277–297
silver occur in veins and stockworks (Veta Madre—
‘‘Mother lode’’, Veta La Luz and Veta La Sierra
systems). The gangue minerals are quartz, calcite
and adularia. The hydrothermal wall-rock alteration
consists dominantly of propylitic assemblages and
minor argillic + phyllic assemblages. These alteration
assemblages are overprinted by silicification. This ore
deposit is characteristic of hydrothermal low sulfida-
tion deposits. The mineralized district has been used
as a model of epithermal mineralization due to its
primary mineral alteration assemblages (Buchanan,
1980). In Guanajuato, minerals of tellurium and
selenium associated with gold are not rare. The most
abundant sulfide minerals are: pyrite, marcasite,
acanthite, argentite, polybasite, pearceite, sphalerite,
galena, chalcopyrite, pyrargyrite, tetrahedrite, arseno-
pyrite, pyrrhotite and aguilarite (Querol et al., 1991).
There are two main hypothesis for the source of the
metals in the Guanajuato deposits: (1) magmatic
origin and (2) leaching and remobilization from the
Mesozoic volcano-sedimentary rocks (Taylor, 1972;
Gross, 1975; Mango et al., 1991). The debate con-
tinues, but both parties conclude that the origin of the
sulfur for the metal sulfides is unclear.
Whatever the ultimate source for metals and sulfur
at the mineralized district, one thing is certain;
historically, Guanajuato district has been one of the
major silver producers of the world. The first dis-
covery of silver ore was in 1548 (Wandke and
Martinez, 1928). Veta Madre ( + 20 km in length
and F 8 m wide) was discovered in 1550, and after
451 years of production, this mother lode is still
producing. Since 1550, several other epithermal vein
systems have been intensely exploited for Au, Ag, Pb
and Cu. Currently, three mining companies are active
and are extracting a total of about 300 kg of gold and
50 t of silver monthly. Total metal production of the
Guanajuato mining district is more than 33,000 t of
silver and 170 t of gold (Cardenas, 1992). The
average grade for gold is 4.5 g/t, and for silver is
260 to 450 g/t. Based on this total production, we
estimate that there are more than 150 million tonnes
of waste material scattered in the mining district.
These historic tailings are dispersed around Guana-
juato city. Some tailings areas have been covered and
used as a flat foundation for urban developments.
Other piles are partially covered by vegetation, and
yet others have been partially eroded and remobi-
281
lized. The modern tailings impoundments of the
mining companies are environmentally controlled
and fulfill the current environmental law. We will
focus our analysis and discussion on the historic
tailings.
2.1. Mineral La Luz tailings pile
These tailings are located approximately 8 km
northwest of the city of Guanajuato. This mine-waste
material is derived from the La Luz and other mines
in the La Luz vein system (westernmost mineraliza-
tion in Guanajuato). This locality is not within the
Guanajuato city catchment area, but has environmen-
tal importance because this material is among the
oldest in the region, and was of the first to be treated
with cyanide heap leaching (Martin, 1906). These
tailings are located on the side of one hill covering an
area of some 0.03 km2 with an average thickness of
15 m. The estimated volume of tailings is 1 million
tonnes. The material is quite uniform in texture
(sandy) and highly unconsolidated. The tailings pile
is highly eroded, which has transported approximate-
ly 40% of the material downstream into a creek
draining towards the Silao-León aquifer, located west
of the mining district.
2.2. Monte San Nicolas tailings
The Monte San Nicolas mine and tailings pile is
located north of the city of Guanajuato and within
the Sierra Vein system. This mine operated since the
late 1700s and until the 1920s. The tailings pile
consists of three different layers deposited on the
southeast side of one steep hill. The combined
volume of tailings is about 5 million tonnes. The
oldest and thickest layer is at the bottom, and it is
topped by two thinner and younger layers (Oelsner,
2001). These tailings are heavily eroded, with ap-
proximately 25% of the original material removed
during a heavy rainy season. It is believed that
during a major storm event (some 40 years ago,
based on some anthropogenic material found in the
deposit), the tailings piles were seriously eroded and
a canyon was cut to a depth of 25 m in the tailings
pile. Most of the eroded tailings material was depos-
ited on the alluvial plain of Presa de Mata, a water
reservoir 3 km downstream from the San Nicolas
282 A. Carrillo-Chávez et al. / Ore Geology Reviews 23 (2003) 277–297
area. In the alluvial plain, a more or less continuous
layer of tailings-rich material of 10-cm thickness can
be observed during the dry season (low water ca-
pacity periods of the reservoir). The water from this
reservoir is mostly used for industrial processes
(mineral extraction). But for some years, at the peak
of the dry season (April –May), water in the reservoir
is used for Guanajuato municipal use.
2.3. Valenciana Mine tailings
The Valenciana Mine is perhaps the most famous of
all the Guanajuato mines. The mine started exploitation
in the earliest 1600s, with several ‘‘bonanzas’’ in the
1700s and 1800s (Garcı́a, 1999). The mine tailings were
accumulated on a steep hill along a creek just north of
the city of Guanajuato. There are two tailings impound-
ments located sequentially on the hillside. Their com-
bined volume is around 20 million tonnes of material
covering an area of some 0.5 km2. The mine waste
accumulated in these piles came from several mines
(Valenciana, Rayas, San Vicente), but mostly from the
main Mother Lode (Veta Madre). These tailings piles
have a thickness of 10 to 15 m, and the material is an
inter-layering of sandy and clay horizons. During the
rainy season, a shallow pool forms in the surface of the
upper tailings impoundment. The pool could remain
during several months, indicating the relatively low
vertical permeability of the clay horizons.
2.4. Noria Alta tailings
These tailings are located on the west side of the
city of Guanajuato. During the last 15 to 20 years, the
urban developments have some constructions over the
tailings. This mine-waste material comes mostly from
the mining of the Mother Lode. These deposits are
highly dispersed in an area of more than 0.3 km2, with
a total volume between 5 and 7 million tonnes. The
material is fairly uniform with a sandy texture and is
highly unconsolidated. Locally, some oxidation hori-
zons can be observed in this material.
The Guanajuato mining area is within a mountain-
ous region with local relief of 400 to 500 m with
respect to the regional alluvial valley. Within the
mountains there are some water reservoirs for use as
municipal water along with some groundwater wells.
A high concentration of Zn (0.5 mg/l) has been
detected in groundwater samples from the wells that
supply the city of Guanajuato (some 15 km west of the
mining and mineralized zone). The wells are located in
the same regional basin (Leon-Silao aquifer). The
general public view is that the mining activities (most-
ly the mine tailings) have contributed to the pollution
of the regional aquifer with heavy metals.
3. Sampling and laboratory methods
3.1. Sampling and analytical methods
Samples of tailings material, sediments, surface
water, groundwater and water from the interior of
some mines were taken during a 3-year period from
1998 to 2001. Bulk tailings samples were taken from
historical tailings piles for total digestion and trace
metal analyses. Also, samples were taken for humid-
ity cell test (HCT) and column experiments. The
bulk solid samples for chemical analyses and HCT
were taken in double-sealed plastic bags. The sam-
ples for column experiments were taken in-situ with
25-cm diameter and 1-m long high-density PVC
pipes. Chemical analyses were done with microwave
digestion (method EPA 3051) and multi-elemental
ICP-MS in duplicate at the Analytical Laboratory of
the Institute of Geophysics, UNAM, and the Geo-
chemical Laboratory of the University of Wyoming.
Natural water samples were taken from the wells
(140-m depth average) that supply the city of Guana-
juato, from three different reservoirs (Soledad, Esper-
anza and Purisima) in the region (surface water), and
from runoff water from tailings piles after heavy rains
(natural leaching in the San Nicolas area). All water
samples were filtered in the field (0.45 Am). Samples
for cation analysis were acidified (concentrated HNO3
to pH = 2), whereas non-acidified samples were col-
lected for anion and stable isotope analysis. In the
field, pH, electric conductivity and total alkalinity
were measured. Hydrochemical modeling was done
with PHREEQC (Parkhurst and Appelo, 1999) for
saturation index and advanced modeling.
3.2. Kinetic and static tests
Humidity cell testing is one form of kinetic test.
This testing provides data on the rates of metal leach-
 A. Carrillo-Chávez et al. / Ore Geology Reviews 23 (2003) 277–297
ing, acid generation and acid neutralization for a
selected sample. In turn, these rates provide important
information needed to predict drainage chemistry
(Morin and Hutt, 1997). The humidity cell experi-
ments (HC) used in this work are plastic containers
with tight-fitting lids. Each cell is about 7-cm high and
has about 50-cm2 cross-sectional area. An air inlet
feeds into the center of the top and a drain fitting is
located in the bottom of each cell. Seven individual
cells were connected to a regulated source of com-
pressed air ( f 5 l/min) using 1.3-cm diameter Tygon
tubing. Humidified air was generated using a 20-l glass
carboy that was half-filled with deionized water.
Compressed air was fed directly to the HC (dry-air
cycle for three days) or pumped to the carboy first and
then routed to the HC (humidified-air cycle for 4
days). At the end of the humidified-air cycle, the
sample (200 g of sample) was treated with 200 ml of
double-deionized water passed through a Milli-Q
system and allowed to soak for 1 h (1:1 solid solution
ratio). The leachates were collected using glass
beakers, filtered through 0.45-Am Micro-pore mem-
branes and divided into two subsamples. One was used
for alkalinity titration and anion analysis by anion
chromatography (AC), and the second was acidified to
pH 2 for cation analysis using ICP. The leachates were
stored overnight at 4 jC before analysis. All the
glassware and plasticware were cleaned with deter-
gent, 0.12 M HCl, and rinsed with deionized water.
The humidity cell test is a kinetic method that tries
to simulate the weathering conditions of the tailings
piles in the field, especially heavy metal leaching to
the environment (groundwater and/or soil) and acid-
producing and acid-consuming processes that occur in
the natural environment (Sobbek et al., 1978). At the
Guanajuato quartz and calcite-rich epithermal veins
and corresponding tailings material, far more impor-
tant than the acidity generation and consuming pro-
cesses is the amount of heavy metals that are being
released to the environment.
The most commonly used static test is known as
acid – base accounting (ABA). The ABA test was
originally designed to evaluate acid-producing capa-
bility of coal-mine waters. It is now used to evaluate
both coal- and metal-mine wastes. ABA measures the
balance between the acid-producing potential (AP)
and acid-neutralizing potential (NP) of each mine
(White et al., 1999). For the present research work,
283
three samples from the tailings piles were used for the
ABA test.
3.3. Column experiments
The samples for the column experiments were
taken directly from the tailings piles with 25-cm
diameter and 1-m-long PVC pipes. The pipes were
hammered all the way down into the tailings material,
and then a hole around the pipe was dug to extract the
pipe and avoid loss of material. The columns were
transported to the laboratory where a valve was
installed at the bottom of the column in order to
collect the weekly leachates.
3.4. Adsorption experiments
These experiments were carried out using plastic
containers as batch reactors with 20 ml of double-
deionized MILLI-Q water. Background solutions
with ionic strengths of 0.1 and 0.01 M NaNO3 were
used for different experiments. Different amounts of
natural material from the Mata basin alluvial plain
were used to get total solid-phase iron concentrations
between 0.01 and 0.001 M. The material collected,
and used for these experiments, is considered to be
representative of the alluvial material of the shallow
aquifer of the region, which receives the surface
groundwater and holds the main interaction between
solid-solution (surface complexation reactions). Total
metal (Pb, Zn, Cu, Cd, As) concentrations used
ranged between 3  10 5 and 7  10 5 M. Metal
solutions were prepared from stock standard solution.
HCl or NaOH was added to solutions to adjust the
pH. The experimental solutions were equilibrated for
24 h in the batch reactor with continuous shaking to
maintain a constant solid/liquid ratio. After the equil-
ibration, the final pH was measured and the suspen-
sion was centrifuged for 10 min at 10,000 rpm; 10 ml
of the supernatant was filtered through a 0.45-Am
membrane, transferred to a vial and stored in the dark
at 4 jC overnight for total Pb, Zn, Cu, Cd and As
analysis by atomic absorption spectrometry (AA).
3.5. Surface titration
Four surface titration experiments were performed
on the natural aquifer material of the San Nicolas area
284 A. Carrillo-Chávez et al. / Ore Geology Reviews 23 (2003) 277–297

in order to compare the resulting Point of Zero Charge Table 1

(PZC) with that of the iron oxy-hydroxides (Parks and List of minerals reported in the low sulfidation epithermal vein
mineralization of the Guanajuato District
deBruyn, 1962). The setup for the surface titration
Gold- Silver- Sulfide Silicates Carbonates
was the following: a 200-ml plastic bottle with 20-ml
bearing bearing minerals
double-deionized water and a magnetic stirrer was minerals minerals
used as a batch reactor. Nitrogen gas was bubbled
Native Native Pyrite (+) Quartz (+) Calcite (+)
through Tygon tubing to the solution to exclude CO2 gold silver
from the system. A background electrolyte of NaNO3 Electrum Acanthie Chalcopyrite Adularia Dolomite
at different ionic strengths was used. About 0.04 g of (+)
sediment material was used, which corresponds to a Aguilarite Marcasite Amethyst Siderite
(+)
Fe solid phase concentration of f 2  10 2 M.
Polybasite Sphalerite Chlorite Rhodocrosite
NaOH (0.00125 M) and HCl (0.01 M) solutions were (+)
added to raise or lower the pH at constant intervals of Pyrargyrite Galena Montmorillonite Ankerite
time (5 min); pH readings were made after the 5-min Naumanite Pearceite Nontronite
equilibration time. Tetrahedrite Chalcedony
Arsenopyrite Apophyllite
Pyrrhotite Datolite
Laumonite
4. Results and discussion Stilbite
Saponite
4.1. Mineralogy and geochemistry of tailings (Petruk and Owens, 1974; Oelsner, 2001). (+) Indicates the most
abundant minerals in each group.
Mineralization at the Guanajuato District occurs
mostly in vein structures and minor stockworks. The
mineralogy of the epithermal veins is dominated by calcite and feldspar. Acid – base accounting static
quartz, calcite and adularia (Gross, 1975, Petruk and analysis (ABA) was performed on several tailings
Owens, 1974). Ore minerals (silver and gold) are samples. The results of the ratio (NP/AP) of neutral-
distributed in bands alternating with gangue minerals ization potential (NP) and acidity potential (AP) from
(Table 1). Both Gross (1975) and Buchanan (1980) the ABA tests range between 1.3 and 5.7, which
recognize three mineral assemblages in the mineral- indicate the high neutralization capacity of the mate-
ization of Guanajuato: (a) ‘‘upper’’ (precious metals), rial (White et al., 1999).
‘‘middle’’ (transition zone) and (c) ‘‘lower’’ (base Fig. 2 shows the content of some trace elements in
metals zone). Since early studies (Wandke and Mar- the different tailings materials. Zinc content averages
tinez, 1928), it has been recognized that pyrite occurs 400 mg/kg (ppm), Pb = 100 mg/kg, As = 20 mg/kg
in less than 1% of the ore. Base metals are relatively and Se < 5 mg/kg. The samples were taken from the
low, but in general Cu, Zn and Pb increase in surface of the tailings piles and up to a depth of 1 m,
concentration with depth. These low sulfidation except from San Nicolas area where a profile sam-
deposits are considered to have a relatively low acid pling was taken. However, in the field, it is possible to
mine drainage potential due to their high ratio of observe dramatic variation in coloration (profile in
carbonates/sulfides. some trenches) of some tailings. The upper part of the
X-ray diffraction data indicate that the tailings profiles is highly oxidized (0.25- to 1-m depth). It has
from the different piles consist mostly of quartz, been documented that in the upper part of such
feldspar, calcite, chlorite, kaolin and pyrite (Ramos, tailings (unsaturated zone) highly complex geochem-
1991). Quartz represents 60% of the total; feldspar ical processes take place (dissolution, precipitation of
follows in concentration. Calcite is in 10% and pyrite secondary – tertiary phases, redox, adsorption, etc.;
in less than 1%. This calcite/pyrite ratio in the tailings Alpers and Blowes, 1994; Jambor, 1994).
material (and also in the mineralized veins) indicates Other trace elements are in relatively very low
that any acidity generated by the oxidation of metal concentrations. It can be observed that despite the
sulfides (mostly pyrite) would be neutralized by the different location, the trace element content is essen-
 A. Carrillo-Chávez et al. / Ore Geology Reviews 23 (2003) 277–297
Fig. 2. Content of trace elements in different tailings material from the Guanajuato area. Even though the locations are far apart, the general
concentrations of trace metals are very similar, reflecting the uniform mineralogy of the processed ore.
tially the same. The uniformity in the vein mineralogy
and the mixing of different ores during the extraction
and mineral processing operations could well explain
this similarity in the different tailings.
4.2. Geochemistry of natural water
Fig. 3 shows the trace elements concentration in
water samples from: (a) Valenciana tailings pile pond
(surface water accumulated during the rainy season-
highly evaporated); (b) a water spring from La Luz
zone; (c) La Purisima water reservoir (dam); and (d)
groundwater from municipal water wells. The con-
centration of the different trace elements is generally
low, but the groundwater (samples from municipal
water wells) is higher in Zn (ranging from 0.03 to 0.5
ppm) than in other localities. Water is iron-rich in the
Valenciana pond (up to 2.2 ppm), but Fe concentration
decreases towards the groundwater (less than 0.05
ppm). Saturation index calculation using the code
PHREEQC indicates that ferrihydrite, being saturated
in these waters, is precipitated as mineral surface
coatings, thus creating a potential adsorbing substrate.
Water from a spring at La Luz area is relatively higher
in arsenic (0.01 ppm) than any other locality. All the
other samples are very low in arsenic and selenium
( < 0.01 ppm).
285
Major ion chemistry is dominated by bicarbonate,
sulfate and calcium, which very likely indicate dy-
namic near-surface processes such as dissolution of
calcite, dissolution of metallic sulfides, and dissolu-
tion-precipitation of sulfates. It is true that from the
chemical data available, it is not possible to distin-
guish between sulfate derived from dissolution of
sulfides or sulfates, nor Ca from other sources (alu-
minosilicates reactions). But the X-ray diffraction data
help to confirm that the carbonates, sulfates and minor
sulfides would mostly control the major elements
hydrochemistry. Sulfate precipitation can be observed
on the surface of some of the tailings impoundments
(e.g. Valenciana) as a gypsum ‘‘coating’’ due to
evaporation of rainwater and precipitation of gypsum.
During spring 2001, some other water samples
were taken from water reservoirs (dams), water wells
(groundwater) and mine-water (interior of Valenciana
and Torres mines). The major ions geochemistry is
shown in Fig. 4. The surface water from the reservoirs
(Soledad, Mata and Esperanza) presents the lowest
total dissolved ions (TDS: ranging from 140 to 210
ppm), and plots mostly in the central part and lower
section of the Piper diagram. The evaporation arrow
in Fig. 4 indicates very likely processes in the surface
water. The groundwater (wells 3, 12 and 14) has TDS
ranging from 470 to 560 ppm, very similar to mine-
286 A. Carrillo-Chávez et al. / Ore Geology Reviews 23 (2003) 277–297

water from Las Torres mine. The groundwater and
mine-water plot on the central part of the Piper
diagram with a slightly increases in TDS (with respect
to surface water), indicating the deep infiltration
accompanied of dissolution processes. The highest
TDS is for mine-water from Valenciana mine (range
between 800 to 4500 ppm). This water plots in the
upper corner of the Piper diagram and indicates
gypsum dissolution-dominated processes. The frac-
ture pattern in the area and the similarity between
surface water at Valenciana ponds and Valenciana
mine-water suggest a possible vertical flow from the
surface as a very possible mechanism of groundwater
evolution.
Minor element chemistry indicates low amounts of
Fe, Ni, As, Se and Pb in most of the samples ( < 0.01
ppm). Groundwater (from water wells) is relatively
high in Zn and Cu (up to 1.5 and 0.3 ppm, respec-
tively). This fact could represent zinc derived from the
water pipes in the well or natural Zn in groundwater.
The Zn amount has been constantly high in most of
the groundwater samples for a 3-year period.

Fig. 3. Trace element content of natural water from different location of the Guanajuato area. Iron is the most abundant element. However, Zn
concentrations increase in the groundwater (D).
 A. Carrillo-Chávez et al. / Ore Geology Reviews 23 (2003) 277–297 287

Fig. 3 (continued).

4.3. Isotopic behavior of the water samples
Samples for stable isotopes analysis (dD and d18O)
were taken from a variety of environments: mine-water
from Valenciana and Torres mines; three municipal
water wells (regional groundwater; well nos. 3, 12 and
14); and three water reservoirs (Soledad, Esperanza
and Mata dams). From Esperanza and Mata reservoirs,
water samples were taken from the surface and
depths of 2, 5 and 10 m below the surface. The
results are shown in Fig. 5. In the Torres mine-water,
the values range from d18O =  10.7xto  11.00x
and dD =  78.5xto  74.5x , whereas at the
Esperanza reservoir the values range from d18O =
 7.6xto  8.7xand dD =  56.5xto  62.9x .
The isotopic data at the Esperanza reservoir do not
seem to reflect any evolution or change with depth.
The other samples lie between these two extremes.
According to Craig and Gordon (1965) and Kendall
and Caldwell (2000), the surface evaporation produces
isotopic fractioning, where the remaining water
becomes ‘‘heavier’’, while the rain becomes ‘‘lighter’’.
On ‘‘dry’’ climates, with low vapor content in the
environment, the isotope fractionation processes are
288 A. Carrillo-Chávez et al. / Ore Geology Reviews 23 (2003) 277–297

Fig. 4. Piper diagram for water samples from groundwater (wells 3, 12 and 14), surface water reservoirs (dams: Esperanza, Soledad, Mata),
mine-water (Valenciana and Torres). The water general types fall between bicarbonate- and sulfate-rich type.

controlled mostly by evaporation. On the other hand,
in ‘‘wet’’ environments with high vapor saturation
(close to 100%) the vapor tends to be less fractionated
(Gat and Gonfiantini, 1981; Gat, 1996). It is consid-
ered that the Torres mine environment is close to 100%
of vapor saturation (deep inside the mine), and could
well be considered an ‘‘isotopic closed environment’’.
On the other hand, the Esperanza reservoir is an
‘‘isotopic open system’’ (allowing high evaporation)
with a much higher volume of water being evaporated.
The kinetic isotopic fractionation defines a slope for
the local evaporation curve of dD = 5.93xd18O =
13.04x, determined by the water vapor content in the
environment.
 A. Carrillo-Chávez et al. / Ore Geology Reviews 23 (2003) 277–297 289

Fig. 5. dD vs. d18O plot for some water in the Guanajuato district. Samples were taken from a variety of environments: mine-water from
Valenciana and Torres mines; three municipal water wells (regional groundwater; well nos. 3, 12 and 14); and three water reservoirs (Soledad,
Esperanza and Mata dams); from Esperanza and Mata dams, water samples were taken from the surface and depths of 2, 5 and 10 m below the
surface. Esperanza and Torres water are the end-members of the fractionation processes.

The groundwater flow in the mountainous region
(Valenciana, Torres, Esperanza and Soledad) is along
highly anisotropic, fractured igneous and metamorphic
rocks. It is assumed that the infiltration at Torres mine
is along a high hydraulic conductivity media that does
not allow isotopic fractionation (the closed system
scenario), whereas at Valenciana the infiltration is slow
at the surface, allowing isotopic fractionation and
dissolution of gypsum (high SO4 and Ca content). At
the alluvial valley (groundwater wells) the water is a
mix of quick and slow infiltrated water that plots along
the evaporation line.
4.4. Geochemistry of leachates from humidity cell and
column experiments
Fig. 6 shows the trace element content in leachates
from humidity cell test (HCT) experiments for 10
weeks (after 10 weeks, the general trend of all metals
was to decrease). The filling material for the HCT
was taken from the tailings impoundment of Valenci-
ana (new and old; Fig. 6A and B, respectively),
tailings pile from La Luz (Fig. 6C) and tailings pile
at San Nicolas (Fig. 6D). Trace element content of
these solid materials is shown in Fig. 2 and discussed
in Section 4.1. The key objectives of the humidity
cell tests are: (a) long-term stable reaction under
kinetic conditions and (b) depletion times for acid-
generating, acid-neutralizing and meta-leaching min-
erals (Morin and Hutt, 1997). It is very true that
humidity cell data are not easy to interpret, but also it
is true that these data, when proper handled, give
good estimates of heavy metal leaching potential and
acid mine drainage. Several efforts have been made
to estimates rates of weathering and to scale labora-
tory tests to predict field rates of weathering (Frostad
et al., 2000a,b). The details on the topic of evaluating
weathering rates are beyond the scope of this work,
and the humidity cell test data are used here for a
general comparison with the ABA test and the metal
concentration in surface and groundwater in the study
area. As in most tailings environments, the flow
conditions at the different tailings piles in Guanajuato
are unsaturated. This fact implies that the water/solid
ratios would typically be less than 1:7 or 1:8 by mass
in contact (approximately 20% to 25% porosity, and
grain density of 2.6 g/cm3). Under these weathering
conditions, the general content of trace elements in
the leachates is quite low ( < 0.1 ppm). In general, all
the mine-waste materials decrease their leachate con-
centrations after 3 or 4 weeks, with sporadic spikes of
Zn, As and Se.
290 A. Carrillo-Chávez et al. / Ore Geology Reviews 23 (2003) 277–297

The leachates from Valenciana ‘‘new’’ present the acidity is generated in the leachates by the oxidation of
lowest concentrations of metals from all the material metallic sulfide (Smith et al., 1994):
tested ( < 0.1 ppm for Cu, As, Se and Pb; < 0.001 ppm
Cd). Zinc concentrations present 2 weeks of relatively FeS2 þ 3:5O2 þ H2 O ¼ Fe2þ þ 2SO2
4 þ 2H
þ

high concentration (0.8 ppm), very likely derived from

some Zn within secondary or tertiary phases. The
leachates from Valenciana2 (old material) have a
general trend to decrease in concentrations of metals,
but with some ‘‘peaks’’ of Zn. Interestingly, the As
values have a ‘‘high’’ during week 10, indicating some
potential for arsenic release. Leachates from San
Nicolas present the same general trends of decreasing
concentration with time and some highs on Zn. Las
Luz leachates present the highest concentration of As,
but still this is low (< 0.1 ppm).
The geochemical and mineralogical analyses, along
with results of the humidity cell test results, indicate
that there is a low potential for release of arsenic, zinc
and other heavy metals to the environment. The main
However, the near-neutral pH of the leachates
indicates that the acid-consuming reactions surpass
the acid-producing reactions, which is compatible
with the results of the ABA test (pH of oxidized
tailings between 7 and 9.5; Fig. 7). Other possible
minor acid-generating processes in the area are the
hydrolysis of Fe3 + and Al3 +:
Fe3þ þ 3H2 O ¼ FeðOHÞ3 þ Hþ
Al3þ þ 3H2 O ¼ AlðOHÞ3 þ Hþ
However, in order to have Fe3 + and Al3 + in the
system, the solution must be acidic. Even though
some ‘‘oxide’’ coatings can be observed in the tail-

Fig. 6. Trace elements in leachates of the humidity cell experiments (10 weeks). The concentrations of metal in the leachates from these
experiments are relatively low. The general trend is to decrease with time.
 A. Carrillo-Chávez et al. / Ore Geology Reviews 23 (2003) 277–297
Fig. 6 (continued).
ings, the contribution to acidity of these reactions is
considered to be negligible.
On the other hand, the acidity generated by sulfide
oxidation would be neutralized by the following major
acid-consuming processes:
CaCO3 þ 2Hþ ¼ Ca2þ þ H2 O þ CO2
ðdissolution of calciteÞ
KAlSi3 O8 þ Hþ þ 7H2 O ¼ Kþ þ 3H4 SiO4 þ AlðOHÞ3
ðdissolution of feldsparÞ
The kinetics of the weathering of feldspar is very
slow compared with the rest of the reactions, so its
contribution to the consuming acidity process is
neglected. An acidity-budget calculation shows that,
at pH values between 3 and 5, for every mole of FeS2
dissolved, 2 mol H+ is released. On the other hand, for
every mole of calcite dissolved, 2 mol H+ is consumed.
A simple estimation on the amount of sulfides, calcite
291
and ‘‘oxide’’ coatings present in the tailings indicates
that the acid-consuming processes surpass the acid-
generating processes by a factor of 12.
Zinc is a minor element in the system. X-ray
diffraction data do not show any zinc mineral phases.
But the chemical analyses indicate an average of 400
mg/kg Zn in the tailings material (see Section 4.1).
Zinc could be present in different secondary and/or
tertiary solid phases, besides the primary mineral
sphalerite. Even though a minor phase in the system,
Zn is important because groundwater increases its
content with respect to the leaching experiments.
But the low Zn content of the leachates indicates
that: (a) a small amount of Zn phases is present in the
tailings material; and/or (b) a slow dissolution rate of
the Zn phases present, so there is insufficient time for
dissolution.
The concentration of trace elements in the leach-
ates is relatively low when compared with leachates
from other type of sulfide-rich ore deposits. Fiklin
292 A. Carrillo-Chávez et al. / Ore Geology Reviews 23 (2003) 277–297
Fig. 7. Diagram indicating the pH variations during the humidity cell experiments. The pH remains near neutral due to the high acid-consuming
capacity of the material in the tailings (high ratio calcite/sulfides; see text for details).
diagrams (sum of Zn, Cu, Cd, Pb, Co and Ni vs. pH)
of the leachates show the low concentrations and
near-neutral pH characteristic of quartz– calcite vein
ore deposits (Plumlee, 1999). Column experiments
described in Section 3 indicate that the results are
similar to the HCT leachates for all the material
tested.
4.5. Natural leaching from the tailings
Water samples at San Nicolas area were taken
directly from the base of the tailings piles, from a
creek flowing directly from the tailings pile, and
from a creek formed by the mixing of upstream,
unpolluted waters, and the creek from the tailings, as
it flowed to Mata reservoir. The sampling was done
after several heavy rainstorms (natural leaching). The
samples were taken at the beginning and the peak of
the rainy season (April –August). Fig. 8 shows the
analytical data from this water samples. It was
determined that water downstream of the tailings
pile does not contain significant concentrations of
heavy metals. All the samples have a similar com-
position in major and minor elements, with Fe and
Mn being the trace elements with the highest con-
centration (1 to 2 ppm). Manganese is ubiquitous in
most of mineralized terrains. But also, it is known
that Mn balls were used to crush the ore, so it is
assumed that Mn in sediments and leachates could
be derived from both natural and anthropogenic
sources. Iron seems to be derived from a natural
source, probably iron sulfide. The variation between
the two sampling seasons is very small and only Fe
and Mn show significant concentrations in both
sampling.
Major ion chemistry indicates that dissolution of
calcite and minor sulfides and gypsum (gypsum is
present mostly as hardpans on the tailings impound-
ments and it is not rare to find gypsum in fractures
in tunnels in the mines) controls the hydrochemistry
of the region. Modeling with PHREEQC shows that
the stream water is never saturated with respect to
gypsum or calcite. Total dissolved solids is higher
in samples near the tailings pile, whereas pH is
neutral and remains between 7.1 and 8.3 in all the
samplings.
The low concentrations in trace metals can be
attributed to several factors: low concentration of
metal in solid tailings; not enough time for dissolution;
metal fixed to insoluble phases; pH of the water near
neutral, which is high enough for most metals to be
insoluble. Iron is high enough to precipitate ferrihy-
drite (PHREEQC modeling), which in turn becomes a
good adsorbing surface for many metals.
4.6. Adsorption of heavy metals by natural material
Fig. 9 shows the results of the different adsorp-
tion experiments. Fig. 9A shows the percent
adsorbed by the natural material vs. pH on Cd.
The topology of the curves is appropriate for cation
adsorption (higher adsorption at high pH and lower
 A. Carrillo-Chávez et al. / Ore Geology Reviews 23 (2003) 277–297 293

Fig. 8. Trace metals content in natural leachates. The samples were taken directly at the base of the tailings piles after heavy rain to assure
natural leaching from the tailings. The concentrations are lower than the experiments of the humidity cell, indicating quick infiltration with no
time for dissolution of metal phases contained in the tailings material.

adsorption at low pH). The material is relatively
rich in Fe2O3 content (f 10%). The high adsorp-
tion (f 100%) even at pH 7 is probably due to the
highest solid/solution ratio used (total Fe = 0.01 M).
This experiment was in NaNO3 0.1 M background
electrolyte. Fig. 9B shows the adsorption of Pb by
the natural material. A slight decrease is observed.
This experiment used the same amount of solid
total Fe phase (0.01 M) as the first set of experi-
ments for Cd. Fig. 9C and D shows the same
experiment but for Cu and Zn, but a lower ionic
strength was used (I = 0.01). The four experiments
look very similar even though they were conducted
in solutions with different ionic strengths.
Arsenic adsorption experiments were also con-
ducted (not shown in Fig. 9), but in this case, the
highest percent of adsorption obtained was about also
100%, but the lowest adsorption dropped to near 60%.
This is probably due to the presence of arsenite
(H3AsO3) besides arsenate (H3AsO4) in the solution.
It has been shown that arsenite is less adsorbed onto
iron oxy-hydroxide surfaces than arsenate under sim-
ilar conditions (Dzombak and Morel, 1990), but the
natural environment in Guanajuato is highly oxidized,

Fig. 9. Experimental results from the adsorption experiments of Cd, Cu, Pb and Zn onto natural material from the Guanajuato mining area. The
natural material is relatively rich in iron and has very high capacity for adsorbing dissolved metals. Experiments were carried out with a NaNO3
background electrolyte (I = 0.1 and I = 0.01). See text for details.
294 A. Carrillo-Chávez et al. / Ore Geology Reviews 23 (2003) 277–297
so it is assumed that most of the arsenic must be
arsenate (higher adsorption).
Even though these experiments have relatively few
points, the results show the expected topology for
cations and for total As (arsenate + arsenite) adsorption
curves and show consistency in the maximum and
minimum adsorption ends. A final experiment was the
surface titration of the natural aquifer material. A blank
titration was used to correct suspension titrations for
supernatant effects (Machesjy and Anderson, 1986).
The results for the surface titration indicate that iron
oxy-hydroxides are the most likely adsorbing surface
in the environment. However, the relatively abundance
of calcite and clays indicates that some of the adsorb-
ing processes are controlled by the surface complex-
ation reactions.
In summary, experiments for adsorption of differ-
ent metals onto natural sediments of the Mata basin
alluvial plain indicate the high adsorbing capacity of
the sediments at near-neutral pH. These adsorbing
processes, along with the low metal concentration of
heavy metals in the natural leachates, explain the very
low concentrations in the natural waters.
5. Discussion and conclusions
The chemistry and mineralogy of the different
tailings piles at Guanajuato reflect the vein mineral-
ogy of the mining district. The tailings material is
composed mostly of quartz, feldspar and calcite.
Pyrite is the most common sulfide, but represents
less than 0.1%, and the base metals are present in
very low concentrations. The combination of all the
analytical and experimental results indicates that the
mine-waste material has very low potential for gen-
eration of acidity (AMD) and leaching of heavy
metals to the environment. The ratio of carbonates
to sulfides is 12:1, indicating that acidity generated
by sulfides oxidation would be buffered by dissolu-
tion of calcite. The humidity cell experiments, even
though they increase the amount of water and O2
through the material by a factor of 8 with respect to
the natural environment of the tailings material,
indicate very low potential for leaching metals. Nat-
ural leaching is also very low for most trace metals,
and the chemistry of the natural waters is controlled
by dissolution of calcite and gypsum. Previous local
environmental studies conducted by Blumberg (1992)
and Oelsner (2001) in Las Torres mine and San
Nicolas area concluded that acidity and leaching of
heavy metals are not problems of concern. Further-
more, the work by Rivas-Solorzanao (2001) demon-
strated that the natural sediments in the Mata basin
alluvial plain have a high capacity for adsorbing the
low metal concentrations of Zn, Pb, Cu, Cd and As in
solution. However, trace elements chemistry of
groundwater some 15 to 20 km southwest of the
mining area and tailings piles indicate relatively high
Zn concentrations (up to 1 ppm). This ‘‘high Zn’’
area is located on a continuous groundwater flow path
from the mineralized area. But so far, there is not data
on the groundwater velocity in the system. The
possibility of a long travel time (longer than 200
years, which is the average time for the most impor-
tant tailings piles in the area) for the groundwater
from the mineralized area towards the ‘‘high Zn’’ area
was explored with a rough calculation for the velocity
of the groundwater (Table 2). This calculation could
be improved with field data for different water-wells,
which currently are not available. Because the lowest
and highest values of hydraulic conductivity (K) and
porosity (n) used in the calculation (Table 2) are the
extreme cases, a good estimate for the total time for
the groundwater to reach the ‘‘high Zn’’ area would
be in the range of 50 to several hundred years. These
velocities indicate that there has been enough time for
Zn to reach the area for the groundwater wells. But, if
not high Zn comes from the tailings piles, the
possibility that Zn concentrations in groundwater
are due to natural processes still remains. So, the
key issue remaining is to explain Zn concentrations in
Table 2
Estimated travel time for groundwater flowing from the mineralized
area in the Guanajuato mountains (Mines zone) towards the alluvial
valley where the groundwater wells are located (Valley zone)
Mines zone, dh/ds = 0.02 Valley zone, dh/ds = 0.01 Total time
K (m/s) n Time K (m/s) n Time
(year)
(%) (year) (%) (year)
1e  08 2 27,059 1e  06 15 19,422 46,481
1e  06 4 541 1e  04 25 324 865
1e  04 10 14 1e  02 40 5 19
K = hydraulic conductivity; dh/ds = hydraulic head gradient; n
(%) = percent porosity.
 A. Carrillo-Chávez et al. / Ore Geology Reviews 23 (2003) 277–297 295

Fig. 10. Schematic representation of the general geochemical processes taking place in the surface and near-surface environment in the
Guanajuato area. Rainwater infiltration into the tailings dissolves relatively few metals because: (a) rapid infiltration or (b) low rate of
dissolution. Some As and Se is dissolved from secondary phases within the tailings material. Surface runoff is iron-rich and other-metal-poor.
Iron precipitates as Fe-oxy-hydroxides to enhance adsorption processes. Deep infiltration allows dissolution of primary phases of Zn, which
increases concentration in the deep groundwater flow. Groundwater extracted at the wells has more Zn than the surface runoff because of slow
groundwater flow and more time for dissolution processes.

Guanajuato groundwater despite the low leaching of
Zn from tailings.
Isotopic data (dD and d18O) of water samples from
different environments in the area indicate infiltration
of meteoric water into a highly anisotropic, fractured
media in igneous and metamorphic rocks before reach-
ing the granular aquifer in the alluvial valley. The
meteoric water that infiltrates can be evaporated (high-
ly fractionated) as is the water from the Esperanza
dam, or quickly infiltrated (non-fractionated) as the
case of the Torres mine-water. This variation in time of
infiltration could cause dissolution of Zn sulfides at
depth. Buchanan’s (1980) mineralization model pre-
dicts an increase in base metals at depth in the district.
So, it is reasonable to assume that Zn sulfides increase
below the current mining operations. The Zn concen-
trations in groundwater from municipal wells thus can
be interpreted as being derived from Zn-rich natural
sources rather than from Zn-poor mine-waste material.
Fig. 10 shows an schematic representation of the main
environmental geochemistry processes taking place in
the Guanajuato mining district. Infiltration of meteoric
water through the Zn-poor tailings dissolves some As
and Se phases. The surface runoff is relatively poor in
trace elements (base metals). Surface complexation of
Fe oxy-hydroxides, calcite and clays and base metal
(including As) adsorption onto these adsorbing surfa-
ces control the mobility of trace elements in the near-
surface environment. However, slow and deep infil-
tration of water into a relatively Zn-rich environment
leads to dissolution of Zn phases and consequent
increases of Zn in groundwater extracted in municipal
water wells.
Acknowledgements
This work was supported by grant no. 27821-T
from CONACyT-Mexico. The authors wish to thank
the detailed and helpful reviews by Drs. Mark J.
Logsdon and Richard Kyle. The authors also thank the
enthusiastic assistance of Jorge Servin and Carolina
Muñoz in the field and laboratory works, and Eloisa
Dominguez-Mariani for her skillful hand in drawing.
References
Alpers, C.N., Blowes, D. (Eds.), 1994. Environmental geochemis-
try of sulfide oxidation. ACS Symposium, p. 550.
Banwart, S.A., Malmström, M.E., 2001. Hydrochemical modelling
for preliminary assessment of minewater pollution. J. Geochem.
Explor. 74, 73 – 97.
296 A. Carrillo-Chávez et al. / Ore Geology Reviews 23 (2003) 277–297
Belkin, H.E., Spark, H.M., 1993. Mercury, arsenic, antimony and
selenium contents of sediment from the Kuskokwin river, Be-
thel, Alaska, USA. Environ. Geol. 22, 106 – 110.
Berner, E.K., Berner, R.A., 1996. Global Environment: Water, Air
and Geochemical Cycles. Prentice Hall, New Jersey. 376 pp.
Bener, S.G., Gould, W.D., Blowes, D.W., 2000. Microbial popula-
tions associated with the generation and treatment of acid mine
drainage. Chem. Geol. 169, 435 – 448.
Blowes, D.W., Jambor, J.L., Hanton-Fong, C.J., 1998. Geochemi-
cal, mineralogical and microbiological characterization of a sul-
phide-bearing carbonate-rich gold-mine tailings impoundment.
Appl. Geochem. 13 (6), 687 – 705.
Blumberg, J., 1992. The environmental impact of the Torres tailing
pond in Guanajuato, Mexico: an assessment of possible heavy
metals contamination. Unpublished senior honor thesis. Dart-
mouth College, New Hamphisere.
Bowell, R.J., 1994. Sorption of arsenic by iron oxides and oxy-
hydroxides in soils. Appl. Geochem. 9, 279 – 286.
Brown, J.G., Bassett, R.L., Glynn, P.D., 2000. Reactive transport of
metal contaminants in alluvium- model comparison and column
simulation. Appl. Geochem. 15, 35 – 49.
Buchanan, L.J., 1980. Ore controls of vertically stacked deposits,
Guanajuato, Mexico. AIME, 80 – 82.
Cardenas, V.J., 1992. Gelogical and Mining Monograph of the State
of Guanajuato. CRM, Mexico.
Carrillo, A., Drever, J.I., 1997. Environmental assessment of the
potential for arsenic leaching into groundwater from mine waste
in Baja California Sur, Mexico. Geofı́s. Int. 37 (1), 35 – 39.
Carrillo, A., Drever, J.I., 1998. Adsorption of arsenic by natural
aquifer material in the San Antonio – El Triunfo mining area,
Baja California. Environ. Geol. 35 (4), 251 – 257.
Cebrian, M.E., Albores, G.A., Garcı́a-Vargas, G., Del razo, L.M.,
Ostrosky-Wegman, P., 1994. Chronic arsenic poisoning in hu-
mans: the case of Mexico. In: Nriagu, J.O. (Ed.), Arsenic in the
Environment: Part II. Human Health and Ecosysytems Effects.
Wiley, New York, pp. 93 – 107.
Chavez, W., Walder, I., 1995. Mineralogical and geochemical behav-
ior of mine tailing produced from lead and zinc skarn mineraliza-
tion, Hanover, Grant County, New Mexico, USA. Environ. Geol.
26, 1 – 18.
Craig, H., Gordon, L., 1965. Deuterium and oxygen-18 in the ocean
and the marine atmosphere. In: Tongiogi, E. (Ed.), Stable Iso-
topes in Oceanographic Studies and Paleotemperatures, Spoleto,
p. 130.
Drever, J.I., 1997. The Geochemistry of Natural Waters, 3rd ed.
Prentice Hall, New Jersey. 437 pp.
Duddley, L., McLean, J., Sims, R., Jurinak, J., 1988. Sorption of
copper and cadmium from the water-soluble fraction of an
acid mine waste by two calcareous soils. Soil Sci. 145 (3),
207 – 214.
Dzombak, D.A., Morel, F.M., 1990. Surface Complexation Model-
ing (Hydrous Ferric Oxide). Wiley, New York 392 pp.
Eary, L.E., 1999. Geochemical and equilibrium trends in mine pit
lakes. Appl. Geochem. 14, 963 – 987.
Fein, J.B., Martin, A.M., Wighitman, P.G., 2001. Metal adsorption
onto bacterial surfaces: development of a predictive approach.
Geochim. Cosmochim. Acta 65 (23), 4267 – 4273.
Frostad, S., Klein, B., Lawrence, R.W., 2000a. Kinetic testing: 1.
Effects of protocol variable on rates of weathering. Proceedings
from the Fifth International Conference on Acid Rock Drainage,
Denver, CO, May 2000, vol. 1, pp. 641 – 649.
Frostad, S., Klein, B., Lawrence, R.W., 2000b. Kinetic testing:
2. Scaling up laboratory data to predict field rates of weath-
ering. Proceedings from the Fifth International Conference on
Acid Rock Drainage, Denver, CO, May 2000, vol. 1. Society
for Mining, Metallurgy and Exploration, Littleton, Colorado,
pp. 651 – 659.
Fyfe, W.S., 1998. Toward 2050: the past is not the key to the
future—challenges for the science of geochemistry. Environ.
Geol. 33 (2/3), 92 – 95.
Garcı́a, M.J.V., 1999. Algas de desecho mineros. Unpublished MSc
Thesis. Facultad de Ciencias, UNAM.
Gat, J.R., 1996. Oxygen and hydrogen isotopes in the hydrologic
cycle. Annu. Rev. Earth Planet. Sci. 24, 225 – 262.
Gat, J.R., Gonfiantini, R., 1981. Stable Isotope Hydrology: Deu-
terium and Oxygen-18 in the Water Cycle. IAEA Technical Re-
port Series #210. International Atomic Energy Agency, Vienna,
p. 337.
Ghomshei, M.M., Allen, D.M., 2000. Potential application of oxy-
gen-18 and deuterium in mining effluent and acid rock drainage
studies. Environ. Geol. 39 (7), 767 – 773.
Gray, N.F., 1997. Environmental impact of acid mine drainage: a
management problem. Environ. Geol. 30 (1/2), 62 – 71.
Gray, J.E., Coolbaugh, M.F., Plumlee, G.S., Atkinson, W.W., 1994.
Environmental geology of the Summitville mine, Colorado.
Econ. Geol. 89, 2006 – 2014.
Gross, W.H., 1975. New ore discovery and source of silver-gold
veins, Guanajuato, Mexico. Econ. Geol. 70, 1175 – 1189.
Guogh, L.P., 1993. Understanding our fragile environment. Lessons
from geochemical studies. USGS Circ., 1105.
Haneberg, W.C., Auston, G.S., Brabvold, L.A., 1993. Soil lead
distribution at an abandoned smalter in Socorro, New Mexico.
Environ. Geol. 2, 90 – 95.
Hill, M.K., 1997. Understanding Environmental Pollution. Cam-
bridge Univ. Press, Cambridge. 316 pp.
Jambor, J.L., 1994. Mineralogy of sulfide-rich tailing and their ox-
idation products. In: Jambor, J.L., Blowes, D.W. (Eds.), The
Environmental Geochemistry of Sulfide Mine Wastes. Min. As-
soc. of Canada, Vancouver Short Course Handbook, pp. 59 – 102.
Keller, E.A., 1992. Environmental Geology, 6th ed. MacMillan,
New York. 521 pp.
Kendall, C., Caldwell, E.A., 2000. Fundamentals of isotope geo-
chemistry. In: Kendall, C., McDonnell, J.J. (Eds.), Isotope Trac-
ers in Catchment Hydrology. Elsevier, Amsterdam. Second
impression, Chap. 2.
Kesler, S.E., 1994. Mineral Resources, Economics and the Environ-
ment. MacMillan Collegue Pub., New York. 391 pp.
King, T.V., 1995. Environmental considerations of active and aban-
doned mine lands: lessons from Summitville, Colorado. USGS
Bull., 2220.
Koretsky, C., 2000. The significance of surface complexation reac-
tions in hydrologic systems: a geochemist’s perspective. J. Hy-
drol. 230, 127 – 171.
Larocque, A.C.L., Rasmussen, P.E., 1998. An overview of trace
 A. Carrillo-Chávez et al. / Ore Geology Reviews 23 (2003) 277–297
metals in the environment, from mobilization to remediation.
Environ. Geol. 33 (2/3), 85 – 91.
Machesjy, L.M., Anderson, M.A., 1986. Calorimetric acid – base
titrations of aqueous goethite and rutile suspensions. Langmuir
(America Chemical Society) 2, 582 – 587.
Mango, H.N., Zantop, H., Oreskes, N., 1991. A fluid inclusions and
isotope study of the Rayas Ag-Au-Cu-Pb-Zn mine, Guanajuato,
México. Econ. Geol. 86, 1554 – 1561.
Martin, F.P., 1906. Mexico’s Treasure-Huose (Guanajuato): An Il-
lustrated and Descriptive Account of the Mines and their Oper-
ations in 1906. Wiley, New York. 259 pp.
Martinez-Reyes, J., 1992. Mapa Geológico de la Sierra de Guana-
juato con Resumen de la Geologı́a de la Sierra de Guanajuato.
Cartas Geologicas y Mineras, vol. 8. UNAM, Instituto de Geo-
logı́a, Mexico.
Matschullat, R., Ottenstein, R., Reimann, C., 2000. Geochemical
background—can we calculate it? Environ. Geol. 39 (9),
990 – 1000.
Mazor, E., 1991. Applied Chemical and Isotopic Groundwater Hy-
drology. Wiley, New York. 274 pp.
Nriagu, J.O., 1990. Global metal pollution ‘‘poisoning the bio-
sphere’’. Environment 32, 7 – 11, 28 – 33.
Oelsner, G.P., 2001. The impact of abandoned mine tailing on sur-
face water: Monte de San Nicolas, Guanajuato, Mexico. MS
Thesis, unpublished. Department of Geology and Geophysics,
University of Wyoming. 71 pp.
O’Day, P.A., 1999. Molecular environmental geochemistry. Rev.
Geophys. 37 (2), 249 – 274.
Parks, G.A., deBruyn, P.L., 1962. The zero point of charge of
oxides. J. Phys. Chem. 66 (6), 967 – 973.
Parkhurst, D.L., Appelo, C.A.J., 1999. User’s guide to PHREEQC
(Version 2)—a computer program for speciation, batch-reaction,
one-dimensional transport, and inverse geochemical calcula-
tions. USGS Water-Resour. Invest. 99-4259. 312 pp.
Petruk, P., Owens, D., 1974. Some mineralogical characterisitcs of
the silver deposits in the Guanajuato Mining District, Mexico.
Econ. Geol. 69, 1078 – 1085.
Plant, J., Smith, D., Smith, B., Williams, L., 2001. Environmen-
tal geochemistry at the global scale. Appl. Geochem. 16,
1291 – 1308.
Plumlee, G.S., 1999. The environmental geology of mineral deposits.
In: Plumlee, G.S., Logsdon, M.J. (Eds.), The environmental geo-
chemistry of mineral deposits. Rev. Econ. Geol., SEG, vol. 6, pp.
71 – 113.
Plumlee, G.S., Severson, R.C., 1994. USGS Environmental geo-
science studies on the Summitville mine and its effects on the
agriculture and wildlife ecosystems in the San Luis Valley, Col-
orado—Project Review. USGS Circ. 1103-A, 78 – 80.
Querol, S.F., Lowther, G.K., Navarro, E., 1991. Mineral deposits of
the Guanajuato Mining District, Guanajuato. In: Salas, G.P.
(Ed.), Econ. Geol. Mex., GSA, vol. 3 (53), pp. 403 – 414.
Ramos, E.R., 1991. Reconstrucción mineralógica de los jales de
Guanajuato y estudio sobre el seguimiento de las especies qui-
297
micas contenidas en sus componentes no metálicos. Tesis de
Mestrı́a. Facultad de Ciencias Quı́micas, Universidad de Gua-
najuato. 135 pp.
Randall, R.J.A., 1990. Geology of El Cubo mine and Area, Gua-
najuato, Mexico. In: Clark, K.F. (Ed.), Mexican Silver Deposits
Guidebook prepared for the Society of Economic Geologists
Field Conference 2 – 11 March, 1990. SEG Guidebook Series,
vol. 6, pp. 213 – 227.
Randall, R.J.A., Saldaña, E., Clark, K.F., 1994. Exploration in a
Volcano-Plutonic center at Guanajuato, Mexico. Econ. Geol. 89,
1722 – 1751.
Rivas-Solorzanao, H.N., 2001. Adosrción de As, Cu, Cd, Pb y Zn
derivados de material de desecho de la minerı́a en sedimentos
naturales de la cuenca de la Presa de Mata, Guanajuato: control
natural. MS Thesis, unpublished. Posgrado en Ciencias de la
Tierra, UNAM. Mexico. 94 pp.
Rösner, U., 1998. Effects of historical mining activities on surface
water and ground-water- an example from northwest Arizona.
Environ. Geol. 33 (4), 224 – 230.
Smedley, P.L., Kinniburgh, D.G., 2002. A review of the source,
behavior and distribution of arsenic in natural waters. Appl.
Geochem. 17, 517 – 568.
Smith, K., Plumlee, G., Ficklin, W., 1994. Predicting water con-
tamination from metal mines and mining wastes. USGS, Work-
shop 2.
Sobbek, A.A., Schuller, W.A., Freeman, J.R., Simt, R.M., 1978.
Field and laboratory methods applicable to overburden and
minesoils. EPA 600/2-78-054. 203 pp.
Stumm, W., Morgan, J.J., 1996. Aquatic chemistry: chemical equi-
libria and rates in natural waters, 3rd ed. Wiley, New York.
1022 pp.
Taylor, P.S., 1972. Mineral variations in the silver veins of Guana-
juato. PhD dissertation thesis. Dartmouth College. Unpublished.
139 pp.
Tempel, R.N., Shevenell, L.A., Lechler, P., Price, J., 2000. Geo-
chemical modeling approach to predict arsenic concentrations in
a mine pit lake. Appl. Geochem. 15, 475 – 492.
Toner, R.N., Frost, C.D., Chamberlain, K.R., 2003. Isotopic iden-
tification of natural vs. anthropogenic sources of Pb in Lara-
mie basin groundwater, Wyoming, USA. Environ. Geol. 43,
580 – 591.
Wandke, A., Martinez, J., 1928. The Guanajuato mining district,
Guanajuato, Mexico. Econ. Geol. 23, 1 – 44.
White III, W.W., Lapakko, K.A., Cox, R.L., 1999. Static-test meth-
ods most commonly used to predict acid-mine drainage: prac-
tical guidelines for use and interpretation. In: Plumlee, Logsdon
(Eds.), The environmental Geochemistry of Mineral Deposits.
Rev. Econ. Geol., SEG 6, pp. 325 – 338.
Wuolo, R.W., 1986. Laboratory studies of arsenic adsorption in
alluvium contaminated with gold-mine tailings along White-
wood Creek, Blackhills, South Dakota. MSc Thesis. South Da-
kota School of Mines. 162 pp.