GEXPLO-05355; No of Pages 9

Journal of Geochemical Exploration xxx (2014) xxxxxx

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Journal of Geochemical Exploration

journal homepage: www.elsevier.com/locate/jgeoexp

Geochemistry and mineralogy of mine-waste material from a skarn-type deposit in

central Mexico: Modeling geochemical controls of metals in the surface environment
Alejandro Carrillo-Chvez a,, Erick Salas-Megchn b, Gilles Levresse a, Carolina Muoz-Torres a,
Ofelia Prez-Arvizu a, Tammie Gerke c
a
Centro de GeocienciasUNAM, Campus Juriquilla, Queretaro 76230, Mexico
b
Posgrado en Ciencias de la Tierra, Centro de GeocienciasUNAM, Campus Juriquilla, Queretaro 76230, Mexico
c
Department of Geology, University of Cincinnati, OH 45221, USA

a r t i c l e i n f o a b s t r a c t

Article history: Several metal sulde ore deposits (epithermal veins and skarn-type deposits) occur in the central east portion of
Received 14 October 2013 Mexico (Sierra Madre Oriental). Historically, some of these deposits have been exploited since the 1500s and
Revised 6 March 2014 1600s. Currently, there are millions of tons of mine waste materials with high content of potentially toxic
Accepted 14 March 2014
heavy metals. This work focuses on geochemistry and mineralogy and modeling of redox and acidbase reactions
Available online xxxx
of mine waste material from the Xich mining area (Aurora Mine), Guanajuato state. The processed ore material
Keywords:
at Xich (circa 1 million tons) consisted of pyrite, arsenopyrite, galena, sphalerite, chalcopyrite, and minerals
Heavy metals with Ag and some Au. The mine waste material contains considerable amounts of As, Fe, Pb, Zn, and Cu, in
Mine tailings different mineral phases mostly, Fe-oxides and oxyhydroxides, sulfo-salts and traces of primary suldes.
Abandoned mines Potential metal liberation and mobility pose a threat to the local population. Redox reactions locally produce pH
Environmental geochemical controls around 2 in leachates with high metal content. Secondary mineralogy includes goethite, hematite, ferrihydrite,
Geochemical modeling jarosite group minerals, gypsum and minor carbonates, among others. The geochemical dynamics is controlled by
Geochemist's workbench the seasonal rains (from June to September), along with high evaporation rates. These factors produce minor acid
mine drainage and metal leaching. Redox and dissolutionprecipitation reactions control the mobility of heavy
metals into the surrounding environment. Arsenic and heavy metal content in tailings is up to 37% Fe, 62 gr/Kg of
As, 2.4 gr/Kg of Cu, 13 gr/Kg of Zn and 17 gr/Kg of Pb. Sequential extraction experiments indicated that most of
the As is bounded to Fe oxyhydroxides; Zn and Cu are mostly bounded to soluble phases and Pb is mostly bounded
to sulde. Mineralogical changes are controlled seasonally mainly by dissolution and precipitation of secondary
phases: jarosite, gypsum, goethite and hematite and minor metal carbonates. Locally, some highly evaporated
ponds have low pH (between 2 and 3) and very high concentrations of As and metals. The Geochemist's Workbench
(Act2 module) software was used to model the redox conditions for the dissolutionprecipitation reaction
controlling liberation and mobility of As and metals into the environment. It seems that most of the As and metals
are involved in a dissolutionprecipitation cycle in the tailings piles and very few are released into the environment.
2014 Elsevier B.V. All rights reserved.

Introduction
Metals exploitation plays a very important role in the economical,
technological and industrial development of the human society. We,
as modern human society, are hungry for great amounts of metals to
satisfy our needs for modern industry and technology. However, along
with the priority for metals exploration comes the basic need for the
preservation of a clean environment (sustainable mining development)
(Fyfe, 1998; Hill, 1997; Hudson-Edwards et al., 2011; Kesler, 1994; Plant
et al., 2001). Regretfully, in most of the historical cases, the exploitation
Corresponding author.
E-mail address: ambiente@geociencias.unam.mx (A. Carrillo-Chvez).
of ore deposits has been accompanied with a negative impact to the
environment (Carrillo et al., 2003; Guogh, 1993; King, 1995; Navarro
et al., 2008). It is a fundamental task for all of us to nd a balance
between exploration and exploitation of metallic ore deposits with the
preservation of a clean environment for ourselves and for future gener-
ations (Hill, 1997; Hudson-Edwards et al., 2011; Jambor, 1994; Nriagu,
1990; Plant et al., 2001). To face and solve these problems, we need to
use all available tools. There is a need for scientic teamwork integrat-
ing all the expertise from the natural sciences, the engineering and
economic sciences. It is also clear that the activities needed for equilibrat-
ed development of ore deposits and the environment are of multidisci-
plinary character. However, punctual actions, such as environmental
geochemistry, mineralogy and geochemical modeling assessments, are
basic for future decision-making activities.

http://dx.doi.org/10.1016/j.gexplo.2014.03.017
0375-6742/ 2014 Elsevier B.V. All rights reserved.

Please cite this article as: Carrillo-Chvez, A., et al., Geochemistry and mineralogy of mine-waste material from a skarn-type deposit in central
Mexico: Modeling geochemical controls of..., J. Geochem. Explor. (2014), http://dx.doi.org/10.1016/j.gexplo.2014.03.017
2 A. Carrillo-Chvez et al. / Journal of Geochemical Exploration xxx (2014) xxxxxx
Environmental geochemistry is a relatively new branch of natural
sciences (some 30 years) and deals with the analysis of the geologic,
mineralogical and chemical processes that introduce and control the
concentrations, reactions and mobility of elements or substances poten-
tially contaminant to the environment (Hudson-Edwards et al., 2011;
Plant et al., 2001). The distribution of most of these elements or
substances could be natural in the environment, but when their concen-
trations are above certain levels, they become toxic to the ecosystem.
The main environmental problems related to ore deposits are acid
mine drainage resulting from the oxidation of suldes (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.). Since the second half of the 1980s and during the 1990s the
environmental research on the impact of mining activities has increased
considerably. Some of these research have been focused on the effects of
acid mine drainage and high concentrations of heavy metals on surface
and groundwater and soil (Alpers and Blowes, 1994; Bowell, 1994; Fyfe,
1998; Haneberg et al., 1993; King, 1995; Larocque and Rasmussen,
1998; Rosner, 1998). Other works have focused on the mineralogical
and chemical characterization of metallic ore deposits and their
respective wastes (Carrillo and Drever, 1997; Chavez and Walder,
1995; Plumlee and Severson, 1994; Smith et al., 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; Putins
and Ruiz-Agudo, 2013; Wuolo, 1986). Still other researches have deter-
mined 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 and
recently the use of metal stable isotopes also have found a solid place in
environmental geosciences (Bullen and Eisenhauer, 2009; Ghomshei
and Allen, 2000; Toner et al., 2003). In addition, environmental geo-
chemical research concerning ore deposits involves geochemical and
mathematical modeling, biogeochemistry, molecular environmental
geochemistry, laboratory experiments and review on sources, behavior
and distribution of individual elements in the near-surface environment
(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; Zhu and Anderson, 2002). All these geochemical informa-
tion can be combined with hydrogeological data in order to predict
and to model the behavior of heavy metals in groundwater (geometry
of plumes, velocity, residence time, etc.). Mine waste materials (mine
tailings) account for the world's largest waste material (volumetrically).
The geochemical research in all the expertise elds (eld and experimen-
tal work, analytical, stable isotopes, biogeochemistry and modeling) must
increase in order to understand and sustainably manage the historic,
contemporary and future mine tailings.
Computational modeling has provided a powerful tool for simulating
detailed physical and chemical processes involved in both ore-forming
and geo-environmental systems (Gow et al., 2002; Hobbs et al., 2000,
2004, 2007, 2008; Ord et al., 2002; Schaubs and Zhao, 2002; Sorjonen-
Ward and Zhang, 2002; Zhang et al., 2003, 2008; Zhao et al., 2008a,b
and the references therein included). This enables us to predict the
spatial distribution of either ore deposits in an ore-forming system
or contaminants in a geo-environmental system with time. For this
reason, computational modeling has been widely used to solve var-
ious types of geological and geo-environmental problems (Awadh
et al., 2013; Charifo et al., 2013; Ju et al., 2011; Khalil et al., 2013;
Lin et al., 2003, 2006, 2008, 2009; Liu and Zhao, 2010; Liu et al.,
2005, 2008, 2011; Mugler et al., 2012; Xing and Makinouchi, 2008;
Yan et al., 2003; Zhao, 2009). In particular, reactive transport modeling,
which includes uid ow, solute diffusion/dispersion and geochemical
reaction path, has become an important part of the computational model-
ing in the eld of the emerging computational geoscience (Alt-Epping and
Zhao, 2010; Schmidt Mumm et al., 2010; Zhao et al., 2009, 2010). From
the scientic point of view, reactive transport modeling should be used
Please cite this article as: Carrillo-Chvez, A., et al., Geochemistry and mineralogy of mine-waste material from a skarn-type deposit in central
Mexico: Modeling geochemical controls of..., J. Geochem. Explor. (2014), http://dx.doi.org/10.1016/j.gexplo.2014.03.017
to simulate the spatial distributions of contaminants (such as toxic
heavy metals) in geo-environmental systems with time.
In this paper, we present analytical, experimental geochemical data
from mine waste materials and some geochemical modeling runs using
Geochemist's WorkBench (Bethke, 1996) to asses the reaction paths
and mobility of heavy metals in one abandoned mine at the mountainous
region of Xich, Guanajuato State, central-east Mexico. The purposes of
this research are:
(1) to determine the chemical concentrations of heavy metals in the
mine waste material;
(2) to determine the mineralogical phases in which the heavy metals
are bound using sequential extractions;
(3) to use geochemical modeling (Geochemist's WorkBench) to
asses the reaction paths and mobility of heavy metals from the
mine's waste material to the environment;
(4) to provide essential information that can be used to construct
reactive transport models in the eld of the emerging computa-
tional geoscience (Zhao et al., 2009).
Site description
The Xich mining district, some 128 Km northeast of Guanajuato
City, is located in the core of the natural national preserve of Sierra
Gorda mountain range (Fig. 1). This mining district is located at the
central zone of the folded belt of Jurassic and Cretacic carbonate rocks
(Sierra Madre Oriental) of Mexico (Campa and Coney, 1983). Historical-
ly, the Aurora mine, located 3 km from the Town of Xich was exploited
since the 1600's, with different periods of exploitation, the last one shut-
ting down operations in 1957. Currently, there are approximately one
million ton of mine waste materials with high content of potentially
toxic metals. The ore material contains chalcopyrite, galena, sphalerite,
and minerals with Ag, Au and As. The mine waste material contains
considerable amounts of As, Fe, Cu, Pb, Zn, Cu and Cd posing a threat to
the local population. The regional mineralized belt, that includes the
Xich mining district, is related to calc-alkaline igneous intrusions and
extensional tectonic stress dened by the NWSE faulting and fracturing
(Randall et al., 1994). At the Aurora Mine, the mineralization is skarn-type
with metallic sulde bodies (Zn, Cu, Pb and Ag). The Ag grade reported
was between 350 and 900 gr/tn (COREMI, 1978). The grades reported
for other metals were: Zn, 12.12%; Cu, 0.05%; and Pb, 0.45%. The reported
ore mineralogy was: pyrite, hematite, galena, sphalerite, and chalcopyrite.
The Xich mines are located at the bottom of the river valley with a
marked topographic difference of more than 800 m from the top of
the range to the bottom of the valley. More than 1 million ton of
metal suldes-rich mine waste material is located in 4 piles along the
Xich river.
Methodology
Field procedures
The mine waste material is concentrated in four tailing piles along
the Xich River. The tailing piles were labeled tailings 1, tailings 2,
tailings 3, and tailings 4 (Fig. 2), from the oldest to the youngest mine
waste material. A total of 47 samples were collected from the four
tailing piles. The tailing piles have a general stratied structure, with
reddish and grayish horizontal layers, and a general hard layer (some
3 cm thick) on the surface composed by Fe oxides and oxyhydroxides
protecting sulde rich material. The samples were collected from a
depth of 10 cm (removing the oxidized surface layer) using sterile and
previously cleaned plastic ware (hand shovel and bags). Some samples
were taken from the same locality and on different layers of the tailing
pile (vertical section). Fig. 2 shows the general location of the tailing
piles along the Xich river and the inuence zone, the non-inuence
zone and the mixing zone along the river. In this work, we focus on
 A. Carrillo-Chvez et al. / Journal of Geochemical Exploration xxx (2014) xxxxxx 3

Fig. 1. General location of the Xich mining district and Mina Aurora at Guanajuato State, central Mexico.

the mine geochemistry and mineralogy of the four tailing piles. Other Results of Chemical, sequential extraction and mineralogical analyses
work will discuss the distribution of heavy metals on sediments and
soils along the Xich river and the concentration of metals on the Table 1 shows the highest and lowest concentrations of As, Cd, Cu, Fe,
three different zones (inuenced, non inuence and mixing). The tailing Pb and Zn in the four different tailing piles at Xich (Tailings 1, Tailings 2,
samples were dried (50C), grounded and analyzed for heavy metals. Tailings 3 and Tailings 4, see Fig. 1 for location). The most abundant
element is iron (Fe) with a minimum concentration of 3.5%
(35,399.28 mg/kg) and a maximum of 37% (370,733.93 mg/kg).
Laboratory procedures
For As we have a minimum of 0.17% (1753.43 mg/kg), and a maxi-
mum of 6.23% (62,302.14 mg/kg). Lead (Pb) concentrations vary
The 4H1a1 method for microwave oven acid digestion was used to
from N 0.07% to 1.7% mg/kg. Zinc (Zn) concentrations vary from
bring the tailings sample into solution (variation of the EPA 3051 meth-
0.53% to 1.33% mg/kg. Cooper (Cu) concentrations vary from 0.02%
od). This 4H1a1 digestion method uses HNO3 + HCl and ICP-OES. The
to 0.24% mg/Kg. And Cd concentrations vary from 0.00% to
approach of this digestion methodology is to maximize the extractable
0.02% mg/kg. So, the general order of abundance of heavy metals
concentration of elements in digested material (mine tailings) while
in the tailings is Fe N As N Pb N Zn N Cu N Cd. This order gives an
minimizing the matrix interferences such as found in digestion proce-
idea of the primary mineralogy before processing the ore: Pyrite N Arse-
dures that use HF acid. This method (4H1a1) follows EPA Method
nopyrite N Galena N Sphalerite N Chalcopyrite, with some Cd in the
3051A. A 500-mg b 2-mm sample separation which has been air-dried
sphalerite.
and ground to b200 mesh (75 m) is weighed into a 100-ml Teon
A sequential extraction process was used in order to determine the
(PFA) sample digestion vessel. To the vessel, 9.0 mL HNO3 and 3.0 mL
mineral phases where the heavy metals are bound in the tailing materi-
HCl are added. The vessel is inserted into a protection shield and covered,
al. The method used in this work is described in detail by Dold (2003).
and placed into a rotor with temperature control. Following microwave
Table 2 shows a summary of the ve step sequential extraction. Step
digestion, the rotor and samples are cooled, and digestate quantitatively
1: metals bound to water-soluble phases, these include gypsum and
transferred into a 50-ml glass of volumetric high purity reverse osmosis
Jarosite. Step 2: metals bound to adsorbed and exchangeable ions,
deionized water. The volumetrics are allowed to stand overnight, lled
these include clays, minerals and carbonates. Step 3: metals bound to
to volume, and samples transferred into appropriate acid-washed poly-
amorphous Fe (III), these includes Fe (III) precipitates (goethite, ferrihy-
propylene containers for analysis (Burt, 2004). All the samples were ana-
drite, jarosite, schwermannite). Step 4: metals bound to Fe (III) oxides,
lyzed by duplicate and a reference material (Montana Soil 2710a NIST)
these includes hematite, goethite. Step 5: metals bound to suldes,
was use for quality control of the data. A ve step sequential extraction
these include residual sulde in the tailing piles (pyrite, chalcopyrite,
method was used on selected samples in order to determine the mineral
sphalerite, galena).
phases where the heavy metals are bound. Table 2 shows the ves steps
for extraction, the procedure and the most likely dissolved minerals in For the sequential extraction, only two samples from each of Tailings
each step. 1, Tailings 2 and Tailings 3, and three samples from Tailings 4 were

Please cite this article as: Carrillo-Chvez, A., et al., Geochemistry and mineralogy of mine-waste material from a skarn-type deposit in central
Mexico: Modeling geochemical controls of..., J. Geochem. Explor. (2014), http://dx.doi.org/10.1016/j.gexplo.2014.03.017
4 A. Carrillo-Chvez et al. / Journal of Geochemical Exploration xxx (2014) xxxxxx

Fig. 2. Location of the four mine waste material (tailings) piles along the Xich River. The gure also shows the affected zone along the Xich River, the non-affected zone to the northwest,
and the mixing zone. The study focuses on the affected zone.

selected (9 samples in total). The two samples selected from each tailing
piles (three from Tailings 4) were the samples with the highest concen-
tration of arsenic and the samples with the lowest As concentration
(and the sample with medium concentration in Tailings 4). However,
the results for all the 9 samples (4 samples with the highest As concen-
tration, 4 samples with the lowest As concentration, and one with the
medium concentration of As) were, respectively, very similar. So, in
order to avoid needless repetition of similar concentrations, in this
work only results from sequential extraction on samples for Tailings 1
are reported and considered as representative samples from all the
mine tailing piles in the area. The samples are: Tailings 12 are the sam-
ples with highest As concentration in Tailings 1; and Tailings 16 are the
samples with the lowest As concentration in Tailings 1. Results from the
sequential extractions are shown in Table 3 and Fig. 3. Fig. 3 shows the
relative extraction for each step and the mineral phase most likely to
bind the metals (Soluble phases), carbonates, Fe (oxy) hydroxides, Fe
oxides and Suldes on the samples of Tailings 12 (highest As content)
and Tailings 16 (lowest As content). Table 3 shows same data for the
samples of Tailings 12 and Tailings 16. The selection of the samples
with highest and lowest As concentration was done because As is the
overall toxic element with the highest concentration in all the tailings
(just below Fe, Table 1).
From Table 3 it can be observed that Fe is mostly bound to prima-
ry suldes (pyrite), oxides (hematite, goethite) and oxyhydroxides
(ferrihydrite). Arsenic is also mostly bound to primary suldes (arseno-
pyrite), and adsorbed (or coprecipitated) on oxides (hematite, goethite)
and oxyhydroxides (ferrihydrite). Zinc is bound mostly to soluble inter-
changeable phases. Lead is bound mostly on primary suldes (galena).

Table 1
Results of the highest and lowest concentrations of As, Cd, Cu, Fe, Pb and Zn listed in the 4 tailings piles (Tailings 1 through 4). The concentrations are in mg/Kg.

mg/Kg As Cd Cu Fe Pb Zn

Highest Tailings 1 62,302.14 233.19 2427.96 318,342.61 10,795.98 13,289.63

Tailings 2 10,536.34 61.51 553.65 273,513.55 10,816.19 5290.77
Tailings 3 38,631.14 83.04 1636.61 370,733.93 14,945.85 11,180.29
Tailings 4 16,054.99 125.58 916.77 327,518.50 17,426.35 8758.50
Lowest Tailings 1 7793.67 0.00 337.99 182,236.41 2042.55 2251.66
Tailings 2 4963.52 11.44 309.37 211,611.65 3878.97 1255.77
Tailings 3 2329.62 0.00 473.89 56,611.91 669.07 1186.06
Tailings 4 1753.43 3.70 188.37 35,399.28 1512.41 1679.98

Please cite this article as: Carrillo-Chvez, A., et al., Geochemistry and mineralogy of mine-waste material from a skarn-type deposit in central
Mexico: Modeling geochemical controls of..., J. Geochem. Explor. (2014), http://dx.doi.org/10.1016/j.gexplo.2014.03.017
 A. Carrillo-Chvez et al. / Journal of Geochemical Exploration xxx (2014) xxxxxx 5

Table 2
Steps, solutions used and mineral phases preferentially dissolved during the sequential extraction experiments conducted on the samples with highest concentration of As (see Fig. 3 and
Table 3 for results). The method was adapted from Hall et al. (1996) and Dold (2003).

Sequence Procedure Preferentially dissolved minerals References

Step 1 Water-soluble
Step 2 AEC
Step 3 Fe(oxy)hydroxides
Step 4 Fe oxides
Step 5 Suldes
1.000 g of sample into 50 mL deionized H2O. Shake for 1 h at RT Water-soluble fraction, secondary sulfates, Dold (2003)
e.g., gypsum
Residue 1 + 20 mL of 1.0 M CH3COONa Adsorbed and exchangeable ions, carbonates Hall et al. (1996)
Shake for 6 h at RT
Residue 2 + 0.2 M (NH4)2C2O4 Amorphous Fe(III) precipitates, Dold (2003)
Shake for 1 h in the dark, at RT e.g., schw, fer, jt, go, MnO2
Residue 3 + 0.2 M (NH4)2C2O4 in water bath at 80 C for 2 h Residual Fe(III) precipitates (e.g., go, jt) and Dold (2003)
primary Fe(II) oxides (mgt, hem)
Residue 4 + 750 mg of KClO3 and 5 + 10 mL of 12 M HCl + 10 mL of 4 M Primary and supergene suldes and organics Hall et al. (1996),
HNO3, water bath at 90 C for 20 min Dold (2003)

RT: room temperature, AEC: adsorbed-exchangeable-carbonate, schw: schwermannite, fer: ferrihydrite, jt: jarosite, go: goethite, mgt: magnetite, and hem: hematite.

Cooper is mostly bound to soluble and interchangeable phases. Cadmium
is very likely bound to soluble and interchangeable phases along with Zn.
Fig. 3 shows graphically the fraction linked to the 6 elements analyzed: As,
Cd, Cu, Fe, Pb and Zn, and the concentrations extracted on the two
samples (16, lowest As concentration; 12 highest As concentration).
Table 4 shows that the mineralogy detected used X-Ray Diffractom-
eter. The XRD analyzes were done on the same sample before and after
the sequential extraction procedure. The column on the left shows the
samples of tailings 12 (highest concentration of As) and tailings 16
(lowest concentration on arsenic) and the minerals detected. These min-
erals include some primary sulde phases (sphalerite, pyrite, arsenopy-
rite), some secondary minerals (jarosite, goethite, cuprite), and tertiary
minerals (gypsum). The column on the right shows the after-sequential
extraction procedure mineralogy. This includes some primary suldes
(sphalerite, galena very likely not detected in the before extraction-
XRD run for its small percentage in the sample, pyrite; galena), and
some secondary minerals (cuprite, hematite, goethite, and jarosite). The
mineralogy in Table 4 indicates a logical sequence of minerals detected
before and after the sequential extraction procedure. This table excludes
any silicate minerals and focus only in metal minerals (suldes, oxides,
oxyhydroxides, and sulfo-salts). This dissolution and precipitation process
in these minerals are controlling the mobility of As and heavy metals into
the environment.
program that calculates and plots activityactivity diagrams. The Act2
software uses the general approach of equilibrium dissolution, speciation
and/or precipitation reactions. These reactions should include electron
transfer (e) and/or proton transfer (H+), so the pH (acidbase condi-
tions) and Eh (oxidationreduction conditions) limits of the reactions
can be plotted with a general equation of the straight line in the slope
and intercept form (y = mx + b), where y = pH and x = Eh. This class
of diagrams shows the stability of minerals and predominance of aqueous
species. (Bethke, 1996). Fig. 4 shows the pH vs Eh diagrams for the
systems H2OAsFeSO4K (top diagram); and H2OAsFeSO4KCa
(bottom diagram). The dissolution reactions for pyrite and arsenopyrite
can be represented by several reactions, some of them catalyzed by
micro-organisms (bacteria). The different possible reactions of pyrite
and arsenopyrite can be found in text books and a great deal of research
papers. In the present work we simplied the possible reactions.
Dissolution reactions of primary minerals
Pyrite + H2O + 3.5 O2(aq) = 2 H+ + Fe++ + 2 SO4
Arsenopyrite + 2.5 H2O + 2.75 O2(aq) = H + + Fe++ + SO4
+ As(OH)4

Geochemical modeling
Sphalerite + 2 O2(aq) = SO4 + Zn++
Geochemical modeling is a very useful tool to test the physical
chemical conditions of the mine waste material piles, the control for
mobility of the heavy metal. A geochemical model is a highly simplied Chalcopyrite + 3.75 O2(aq) + .5 H2O = H + + Fe++ + 2 SO4
version of the chemical reactions taking place in the natural environ- + Cu+
ment (Bethke, 1996). The information obtained from the geochemical
models adds understanding to evaluate the behavior of metals in the
environment. The geochemical modeling was done using the software Calcite + H + = Ca++ + HCO3
Gechemist's WorkBench (Bethke, 1996). The database used was the
default GWB database. The module Act2 was used to construct pH vs Eh
diagrams (redox- acid base conditions) for different systems. Act2 is a K-feldspar + 4 H+ = 2 H2O + K+ + Al+++ + 3 SiO2(aq)

Table 3
Results from the sequential extraction experiments: Sample Tailings 16 are the samples with lowest As concentration in tailings pile 1. Sample Tailings 16 is the sample with the highest
As concentration in tailing pile 1. These tow samples were selected as representative of all the samples used in the sequential extraction procedure. Nine samples were used in total with
similar results. See text for further details on mineral phases bounding As and metals.

mg/Kg As Cd Cu Fe Pb Zn

Tailings Tailings Tailings Tailings Tailings Tailings Tailings Tailings Tailings Tailings Tailings Tailings Total
16 12 16 12 16 12 16 12 16 12 16 12

Soluble 0.0 98.0 14.1 32.8 109.1 647.5 0.0 2683.5 0.4 2.2 1000.0 1656.5 6244
Carbonates 0.0 0.0 3.1 9.0 1.6 66.4 0.0 143.5 0.0 0.0 75.5 427.6 727
Fe(oxy)hydroxides 276.9 353.4 0.0 0.0 38.6 131.1 1453.5 2223.5 0.0 0.0 177.6 216.3 4,871
Fe oxides 728.5 16,720.0 1.6 0.0 29.0 276.5 9265.0 15,950.0 0.0 0.0 76.7 246.4 43,294
Suldes 2699.5 17,025.0 10.1 16.2 80.7 205.8 35,435.0 21,940.0 45.1 100.4 372.5 252.0 78,182

Please cite this article as: Carrillo-Chvez, A., et al., Geochemistry and mineralogy of mine-waste material from a skarn-type deposit in central
Mexico: Modeling geochemical controls of..., J. Geochem. Explor. (2014), http://dx.doi.org/10.1016/j.gexplo.2014.03.017
6 A. Carrillo-Chvez et al. / Journal of Geochemical Exploration xxx (2014) xxxxxx

Fig. 3. Results from sequential extraction experiments on samples 12 (highest As concentration) and samples 16 (lowest arsenic concentration). The results show the amount of metal
extracted in each step (As, Cd, Cu, Fe, Pb and Zn). See text for details on the sequential extraction procedure.

Precipitationdissolution reactions for secondary minerals Cuprite + 2 H+ = H2O + 2 Cu+

Jarosite-K + 3 H + = 2 SO4 + 4.5 H2O + K + + 3 Fe++ + .75

O2(aq) Hematite + 4 H+ = 2 H2O + 2 Fe++ + .5 O2(aq)

Gypsum = SO4 + 2 H2O + Ca++ Fe(OH)3(ppd) + 2 H+ = 2.5 H2O + Fe++ + .25 O2(aq)

Goethite + 2 H+ = 1.5 H2O + Fe++ + .25 O2(aq) Fe(OH)3 + 2 H+ = 2.5 H2O + Fe++ + .25 O2(aq)

Table 4
List of minerals detected in XRD on samples Tailings 12 and tailings 16 (highest and lowest As content). The XRD analyzes were done before and after the sequential extraction proce-
dure.

Samples Minerals Samples Minerals

Before extraction Tailings 12 Jarosite After extraction Tailings 12 Cuprite

a
Gypsum (Sphalerite)
a
Sphalerite (Jarosite)
Goethite
Tailings 16 Jarosite Tailings 16 Galena
Gypsum
Arsenopyrite
Tailings 21 Jarosite Tailings 21 Pyrite
Gypsum Hematite
a
Magnetite (Cuprite)
Cuprite
Tailings 26 Jarosite Tailings 26 Magnetite
a
Gypsum (Jarosite)
Sphalerite
Goethite
Tailings 34 Jarosite Tailings 34 Goethite
a
gypsum (Jarosite)
a
Sphalerite (Sphalerite)
b
Tailings 37 Jarosite Tailings 37
Gypsum
Magnetite
c
Tailings 310 Gypsum Tailings 310
Pyrite
Arsenopyrite
Cobaltite
Tailings 41 Pyrite Tailings 41 Jarosite
Sphalerite Magnetite
a
Tailings 43 Gypsum Tailings 43 (Cuprite)
Cuprite
a
Minerals not totally dissolved.
b
There was no analysis.
c
Only primary gangue minerals.

Please cite this article as: Carrillo-Chvez, A., et al., Geochemistry and mineralogy of mine-waste material from a skarn-type deposit in central
Mexico: Modeling geochemical controls of..., J. Geochem. Explor. (2014), http://dx.doi.org/10.1016/j.gexplo.2014.03.017
 A. Carrillo-Chvez et al. / Journal of Geochemical Exploration xxx (2014) xxxxxx 7

In the top diagram of Fig. 4, the system considered is: H2OAsO42Fe can be used to judge whether or not a chemical dissolution system is
(III)SO24 K. The reactions modeled are: unstable, using both the Zhao number and the critical Zhao number of
the chemical dissolution system (Zhao et al., 2009, 2010). Based on
Pyrite + H2O + 3.5 O2(aq) = 2 H+ + Fe++ + 2 SO4 this theoretical criterion, they have studied the effects of several factors,
such as the mineral surface area, mineral dissolution rate, solute disper-
sion, medium anisotropy, medium and uid compressibility and so
Arsenopyrite + 2.5 H2O + 2.75 O2(aq) = H + + Fe++ + SO4 forth, on the chemical dissolution front instability in chemical dissolu-
+ As(OH)4 tion systems (Zhao et al., 2009, 2010 and the references therein includ-
ed). To better understand the spatial distribution of toxic heavy metals
with time, the reactive transport modeling should be conducted to
simulate the mine waste site in the future research.
Jarosite-K + 3 H + = 2 SO4 + 4.5 H2O + K + + 3 Fe++ + .75
O2(aq)

In the bottom diagram of Fig. 4, the system considered is: H2O

AsO42Fe (III)SO2
4 K Ca
2
. The reactions modeled are:

Arsenopyrite + 2.5 H2O + 2.75 O2(aq) = H + + Fe++ + SO4 1 +

+ As(OH)4 FeSO 4

Dis Pre
Jarosite-K + 3 H + = 2 SO4 + 4.5 H2O + K + + 3 Fe++ + .75 .5 HSO 4
-

O2(aq)

Eh (volts)
J arosite-K

HAsS 2 --
SO 4
Gypsum = SO4 + 2 H2O + Ca++
0
-
AsS 2
The circle on the bottom (Pri) indicates the conditions (instability)
for suldes (pyrite and arsenopyrite) in the tailings pile. In reality, the Arsenopyrite
tailing piles are constituted by and outer crust formed by the precipita-
tion of Fe oxides and hydro-oxides, jarosite, gypsum and minor carbon- .5 Pri Pyrite
ate and oxide phases, and the inner material formed by a great amount 25C
of primary suldes and metal oxides. So, when exposed to water and at- 0 2 4 6 8 10 12 14
mosphere conditions those primary suldes (pyrite, arsenopyrite and pH CGEO Tue Aug 20 2013
others), dissolved generating acidity (moving to the left in the pHEh
diagram) under oxidizing conditions (moving upwards) (circle Dis).
Once in solution, the metals and sulfate quickly reach saturation
(under heavy evaporation) to form mineral precipitates (Jarosite-K, 1 +
FeSO 4
Gypsum and other minor phases not shown as Cu carbonates and
oxides; circle Pre). The two sided arrows indicate the reversible reac-
tions between the solid secondary (tertiary) mineral phases and disso-
lution. This process is controlled by the seasonal rains (monsoon type
rains) alternated with periods days of heavy solar radiation and
Dis
.5 HSO 4
-

Pre
Eh (volts)

high evaporation. Similar pHEh diagrams were modeled for the system Jarosite-K
H2OFe (III)SO2 4 under the conditions of solubility and precipitation Gypsum
of Fe oxides and oxyhydroxides (not included in this work). HAsS 2
0
From the geochemical, mineralogical data and geochemical model- -
AsS 2
ing it seems that the metals in the mine waste piles are not being
released to the environment, or released at very slow rates. This is due Pyrite
to the isolation of the metals in different phases suldes, oxides, car-
bonates inside the piles by a hard crust of oxides in the surface. On
.5
Arsenopyrite
Pri
the surface of the piles there is a cycle of precipitation and dissolution 25C
of secondarytertiary phases (i.e. jarosite-K, hematite, goethite, ferrihy- 0 2 4 6 8 10 12 14
drite, gypsum, and minor carbonates). The real environment threat for pH
CGEO Wed Aug 21 2013
heavy metal dispersion is the physical breaking and dispersion of the
mine waste piles for a heavy rain. Fig. 4. pH vs Eh diagrams for the systems H2OAsO2 2
4 Fe (III)SO4 K (top diagram) and
It should be pointed out that in the geochemical path modeling, uid H2OAsO2 2
4 Fe (III)SO4 K Ca
2
(bottom diagram). The gures show the primary min-
ow, porosity/permeability evolution, solute diffusion and dispersion eralogy (pyrite and arsenopyrite) stability elds (Pri) and the oxidation dissolution path to
dissolution stability eld (Dis). The double arrow line indicates the reversible path between
processes in the mine waste site are not considered. These processes
precipitation of secondary (tertiary) mineral phases and dissolution. The conditions for the
can have signicant effects on the spatial distribution of toxic heavy top diagram are: H2OAsO2 2
4 Fe (III)SO4 K ; temperature: 25 C; pressure: 1.013 bars
metals in the mine waste site. In particular, Zhao and his coworkers (1 atm); the activity of H2O = 1; the activity of Fe (III) = 103 mol; the activity of
have carried out pioneering and systematic studies to investigate the AsO42 = 103 mol; the activity of SO2 4 = 103 mol; the activity of K = 106 mol;
effects of these processes on chemical dissolution front instability in the suppressed: Realgar, Orpiment, Troilite and Pyrrhotite. The conditions for the bottom

diagram are: H2OAsO2 2
4 Fe (III)SO4 K Ca
2
; temperature: 25 C; pressure: 1.013
ore-forming and geo-environmental systems (Zhao et al., 2008b, 2010
bars (1 atm); the activity of H2O = 1; the activity of Fe (III) = 103 mol; the activity of
and the references therein included). The signicant contribution of AsO24 = 103 mol; the activity of SO24 = 10
3
mol; the activity of K = 106 mol; the
Zhao et al.'s work is the establishment of a theoretical criterion, which activity of Ca2 = 102 mol; the suppressed: Realgar, Orpiment, Troilite and Pyrrhotite.

Please cite this article as: Carrillo-Chvez, A., et al., Geochemistry and mineralogy of mine-waste material from a skarn-type deposit in central
Mexico: Modeling geochemical controls of..., J. Geochem. Explor. (2014), http://dx.doi.org/10.1016/j.gexplo.2014.03.017
8 A. Carrillo-Chvez et al. / Journal of Geochemical Exploration xxx (2014) xxxxxx
Conclusions
The mine waste material (tailings) piles at Xich have been exposed
to weathering between 350 (oldest) and 70 years (youngest). However,
the As and heavy metal concentrations in the tailings are relatively very
high (up to 37% Fe, 62 gr/Kg of As, 2.4 gr/Kg of Cu, 13 gr/Kg of Zn and
17 gr/Kg of Pb). There are still some primary mineral phases in the
tailings (As and metal suldes). The reason of this is that the tailings
piles are covered by hard crust a few centimeters thick made of Fe
oxides and oxyhydroxides. These facts indicate that there is very slow
remotion and mobilization of As and heavy metals into the surrounding
environment. Most of the As and heavy metals are in a local cycle of pre-
cipitation into secondary and tertiary mineral phases and dissolution
during the rainy season. The main secondary and tertiary mineral
phases include Fe oxides and oxyhydroxides, jarosite-K, gypsum and
minor metal (Cu, Zn) oxides and carbonates. The real threat of these
high metal concentration tailings piles is breaking and dispersion due
to heavy rains. This conclusion needs to be further conrmed using
the reactive transport modeling in the eld of the emerging computa-
tional geoscience (Zhao et al., 2009).
Acknowledgements
This work was funded by a grant IN-112311 from PAPIIT-UNAM.
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