Ore Geology Reviews 23 (2003) 277 – 297 www.elsevier.

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Environmental geochemistry of the Guanajuato Mining District, Mexico
´ ´ A. Carrillo-Chavez a,*, O. Morton-Bermea b, E. Gonzalez-Partida a, H. Rivas-Solorzano c, d e b ´ ´ G. Oesler , V. Garcıa-Meza , E. Hernandez , P. Morales f, E. Cienfuegos f
a

´ ´ ´ Centro de Geociencias, Univ. Nacional Autonoma de Mexico, Campus Juriquilla, Postal 1-742, Queretaro, QRO 76230, Mexico b ´ ´ ´ Inst. de Geofısica. Univ. Nacional Autonoma de Mexico, Mexico c ´ ´ Pos-grado en Ciencias de la Tierra. Univ. Nacional Autonoma de Mexico, Mexico d Department of Geology, University of Wyoming, USA e ´ ´ ´ Facultad de Quımica, Univ. Nacional Autonoma de Mexico, Mexico f ´ ´ ´ Inst. de Geologıa, Univ. Nacional Autonoma de Mexico, 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-Chavez). 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

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´ A. Carrillo-Chavez 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 technologic 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 activities 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 groundwater) (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 teamwork integrating all the expertise from the natural sciences and the engineering and economic sciences. It is also clear that the activities needed for equilibrated development of ore deposits and the environment 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 chemistry) 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 substances 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 sulfides), 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 liberation of heavy metals to the environment (Gray, 1997; Larocque and Rasmussen, 1998; Smith et al., 1994). However, during the last two decades, real problems of high concentration of heavy metals in groundwater 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; Bowell, 1994; King, 1995; Haneberg et al., 1993; Fyfe, 1998; 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;

Smedley and Kinniburgh. some 350 km west – northwest of Mexico City. 2000. 2000). Koretsky. 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. laboratory experiments and review on sources. and where are. 2001. natural water. we present analytical and experimental geochemical data from several materials of the Guanajuato mining district (sediments. The objectives of environmental geochemistry studies of ore deposits are to provide answers to the following questions:  50. The purpose of this research is: (a) to determine. mine tailings. and how much material is exposed?  How much metal is being introduced to the environment and what is its residence time.000 abandoned or inactive mine sites. This regional mineralized belt is related to . Carrillo-Chavez et al. All this geochemical information can be combined with hydrogeological data in order to predict and to model the behavior of heavy metals in groundwater (geometry of plumes. 1988. (c) to compare experimental and field observations with analytical data from the groundwater. 1986). Duddley et al. The use of stable and radiogenic isotopes also has found a solid place in the environmental geosciences (Ghomshei and Allen. 2000. is located in the core of the Guanajuato Mountain Range (Fig. One of the goals of this research is to present pioneering geochemical 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. 1991. between 100. 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..000 and 500. 1996). What are. biogeochemistry. in the United States there are more than 50 US Environmental Agency (US-EPA) Superfund restoration sites related to non-fuel mining activity (King. 2000. 1999. Tempel et al. 1).000 mine sites are abandoned or inactive (King.. residence time. Currently in Mexico. Wuolo. 1995). 1994. 2000. Toner et al. both experimentally and in the field. 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. and no federal program for restoration of sites exists.. Site description The Guanajuato Mining District. This mining district represents the central zone of a regional polymetallic mineralized belt that runs from Taxco (south central Mexico) to Guanajuato (central Mexico). 1995.. / Ore Geology Reviews 23 (2003) 277–297 279 Chavez and Walder. 1994). 2003). (d) to determine processes of the hydrogeochemical evolution. Other researches have determined the geochemical baselines to distinguish between natural and anthropogenic sources of metals in the environment (Matschullat et al. Smith et al. 2002. and (e) to quantify the natural background values and anthropogenic pollution in the region. 2000. Brown et al. In Mexico. Bener et al.. velocity. the number of mining sites is unknown. Stumm and Morgan. behavior and distribution of individual elements in the near-surface environment (Banwart and Malmstrom. and leachates from column and humidity cell experiments). Eary..) (Drever.. 1997. Additional environmental geochemical research concerning ore deposits involves geochemical and mathematical modeling. as a base for future restoration programs. 1998. Barbara. Plant et al.. Plumlee and Severson. Chihuahua (north-central Mexico). 2001). the potential sources of potential contaminant metal located. 1999. molecular environmental geochemistry. O’Day. there are relatively few environmental studies on mining sites. 1998. ¨ 2001. Fein et al. Mazor. Blowes et al.000 to 2. but there are estimates of 10. 1995).. etc.´ A. In this paper. Currently. (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).. and to Sta.

1. Valenciana. San Nicolas and Noria Alta). The mineral zoning allowed Buchanan (1980) to define a mineralization model and the distribution of an upper zone (precious metals: Au and Ag). 1992). with which the mineralized vein sys- tems are associated (Randall. / Ore Geology Reviews 23 (2003) 277–297 Fig. Gold and . 1994. and a deeper zone (base metal: Cu. 1990. The older rocks have been partially covered by volcanic rocks related to a caldera center. Regional location of the Guanajuato District in central Mexico and location of four historical tailings sites around the city of Guanajuato (La Luz. 1994). subduction processes during the Middle Tertiary and extensional tectonic stress defined by the NW – SE orientation of the mineralized veins (Randall et al. an intermediate zone (transition). calcite and adularia. Pb). Martinez-Reyes. Zn.. Buchanan (1980) described three mineralizing stages in epithermal veins with abundant quartz.280 ´ A. The geology of the region consists of a Cretaceous volcano-sedimentary sequence covered by mafic igneous rocks and intruded by Tertiary granodiorite batholithic rocks.. Randall et al. Carrillo-Chavez et al.

pearceite. Based on this total production. This mine-waste material is derived from the La Luz and other mines in the La Luz vein system (westernmost mineralization in Guanajuato). The tailings pile consists of three different layers deposited on the southeast side of one steep hill. / Ore Geology Reviews 23 (2003) 277–297 281 silver occur in veins and stockworks (Veta Madre— ‘‘Mother lode’’. historically. The oldest and thickest layer is at the bottom. based on some anthropogenic material found in the deposit). 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. Some tailings areas have been covered and used as a flat foundation for urban developments. Ag. These historic tailings are dispersed around Guanajuato city. chalcopyrite. The estimated volume of tailings is 1 million tonnes. and it is topped by two thinner and younger layers (Oelsner. Other piles are partially covered by vegetation. located west of the mining district. The first discovery of silver ore was in 1548 (Wandke and Martinez. acanthite. calcite and adularia. Whatever the ultimate source for metals and sulfur at the mineralized district. 1991). 2. We will focus our analysis and discussion on the historic tailings. In Guanajuato. These tailings are located on the side of one hill covering an area of some 0. 1906).´ A. 1992). Most of the eroded tailings material was deposited on the alluvial plain of Presa de Mata. three mining companies are active and are extracting a total of about 300 kg of gold and 50 t of silver monthly. but has environmental importance because this material is among the oldest in the region. 2001). marcasite. The combined volume of tailings is about 5 million tonnes. 1972. This locality is not within the Guanajuato city catchment area. argentite. but both parties conclude that the origin of the sulfur for the metal sulfides is unclear.000 t of silver and 170 t of gold (Cardenas. which has transported approximately 40% of the material downstream into a creek ´ draining towards the Silao-Leon aquifer. this mother lode is still producing. 2. Pb and Cu. polybasite. Mango et al. The modern tailings impoundments of the mining companies are environmentally controlled and fulfill the current environmental law. minerals of tellurium and selenium associated with gold are not rare. the tailings piles were seriously eroded and a canyon was cut to a depth of 25 m in the tailings pile. The material is quite uniform in texture (sandy) and highly unconsolidated. arsenopyrite. and was of the first to be treated with cyanide heap leaching (Martin. Veta Madre ( + 20 km in length and F 8 m wide) was discovered in 1550. sphalerite. several other epithermal vein systems have been intensely exploited for Au.1. The debate continues. This ore deposit is characteristic of hydrothermal low sulfidation deposits. with approximately 25% of the original material removed during a heavy rainy season. and for silver is 260 to 450 g/t. These alteration assemblages are overprinted by silicification. 1991). The average grade for gold is 4. Carrillo-Chavez et al. tetrahedrite. and after 451 years of production. 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. we estimate that there are more than 150 million tonnes of waste material scattered in the mining district.. Currently. pyrrhotite and aguilarite (Querol et al. The mineralized district has been used as a model of epithermal mineralization due to its primary mineral alteration assemblages (Buchanan. The gangue minerals are quartz. and yet others have been partially eroded and remobi- lized.2. Total metal production of the Guanajuato mining district is more than 33.03 km2 with an average thickness of 15 m. one thing is certain. galena. These tailings are heavily eroded. The tailings pile is highly eroded. Mineral La Luz tailings pile These tailings are located approximately 8 km northwest of the city of Guanajuato. The most abundant sulfide minerals are: pyrite. a water reservoir 3 km downstream from the San Nicolas . It is believed that during a major storm event (some 40 years ago. pyrargyrite.5 g/t. 1928). This mine operated since the late 1700s and until the 1920s. 1975. Gross. Guanajuato district has been one of the major silver producers of the world.. The hydrothermal wall-rock alteration consists dominantly of propylitic assemblages and minor argillic + phyllic assemblages. 1980). Veta La Luz and Veta La Sierra systems). Since 1550.

5 km2. The water from this reservoir is mostly used for industrial processes (mineral extraction). The wells are located in the same regional basin (Leon-Silao aquifer). San Vicente). whereas non-acidified samples were collected for anion and stable isotope analysis. samples were taken for humidity cell test (HCT) and column experiments. some oxidation horizons can be observed in this material. All water samples were filtered in the field (0. These deposits are highly dispersed in an area of more than 0. Sampling and laboratory methods 3. Kinetic and static tests Humidity cell testing is one form of kinetic test. Samples for cation analysis were acidified (concentrated HNO3 to pH = 2).3. a shallow pool forms in the surface of the upper tailings impoundment. UNAM. Locally. The material is fairly uniform with a sandy texture and is highly unconsolidated. 2.5 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). with a total volume between 5 and 7 million tonnes. The mine waste accumulated in these piles came from several mines (Valenciana.282 ´ A. 1999) for saturation index and advanced modeling. The Guanajuato mining area is within a mountainous region with local relief of 400 to 500 m with respect to the regional alluvial valley. indicating the relatively low vertical permeability of the clay horizons. A high concentration of Zn (0. Sampling and analytical methods Samples of tailings material. This testing provides data on the rates of metal leach- . Bulk tailings samples were taken from historical tailings piles for total digestion and trace metal analyses. But for some years. Within the mountains there are some water reservoirs for use as municipal water along with some groundwater wells. the urban developments have some constructions over the tailings. Noria Alta tailings These tailings are located on the west side of the city of Guanajuato. Natural water samples were taken from the wells (140-m depth average) that supply the city of Guanajuato. During the rainy season. The mine tailings were accumulated on a steep hill along a creek just north of the city of Guanajuato. and the material is an inter-layering of sandy and clay horizons. In the alluvial plain.2. The pool could remain during several months. In the field.3 km2. at the peak of the dry season (April –May). The bulk solid samples for chemical analyses and HCT were taken in double-sealed plastic bags. and from runoff water from tailings piles after heavy rains (natural leaching in the San Nicolas area). from three different reservoirs (Soledad. Their combined volume is around 20 million tonnes of material covering an area of some 0. water in the reservoir is used for Guanajuato municipal use. 2. Valenciana Mine tailings The Valenciana Mine is perhaps the most famous of all the Guanajuato mines. surface water. 1999). There are two tailings impoundments located sequentially on the hillside.45 Am). Also. and the Geochemical Laboratory of the University of Wyoming. 3. 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. a more or less continuous layer of tailings-rich material of 10-cm thickness can be observed during the dry season (low water capacity periods of the reservoir). 3. sediments. / Ore Geology Reviews 23 (2003) 277–297 area. The samples for column experiments were taken in-situ with 25-cm diameter and 1-m long high-density PVC pipes. Rayas. with several ‘‘bonanzas’’ in the ´ 1700s and 1800s (Garcıa. This mine-waste material comes mostly from the mining of the Mother Lode.1.4. The mine started exploitation in the earliest 1600s. The general public view is that the mining activities (mostly the mine tailings) have contributed to the pollution of the regional aquifer with heavy metals. pH. During the last 15 to 20 years. Esperanza and Purisima) in the region (surface water). but mostly from the main Mother Lode (Veta Madre). groundwater and water from the interior of some mines were taken during a 3-year period from 1998 to 2001. These tailings piles have a thickness of 10 to 15 m. electric conductivity and total alkalinity were measured. Hydrochemical modeling was done with PHREEQC (Parkhurst and Appelo. Carrillo-Chavez et al.

After the equilibration. Seven individual cells were connected to a regulated source of compressed air ( f 5 l/min) using 1.01 M NaNO3 were used for different experiments. filtered through 0. 3. An air inlet feeds into the center of the top and a drain fitting is located in the bottom of each cell. Total metal (Pb. especially heavy metal leaching to the environment (groundwater and/or soil) and acidproducing and acid-consuming processes that occur in the natural environment (Sobbek et al.3-cm diameter Tygon tubing. At the end of the humidified-air cycle.12 M HCl. Cu. One was used for alkalinity titration and anion analysis by anion chromatography (AC). / Ore Geology Reviews 23 (2003) 277–297 283 ing. 3. Carrillo-Chavez et al.. transferred to a vial and stored in the dark at 4 jC overnight for total Pb. 0.4. The humidity cell experiments (HC) used in this work are plastic containers with tight-fitting lids. The humidity cell test is a kinetic method that tries to simulate the weathering conditions of the tailings piles in the field. these rates provide important information needed to predict drainage chemistry (Morin and Hutt. and the second was acidified to pH 2 for cation analysis using ICP. 1978). ABA measures the balance between the acid-producing potential (AP) and acid-neutralizing potential (NP) of each mine (White et al. The leachates were collected using glass beakers. Cu. At the Guanajuato quartz and calcite-rich epithermal veins and corresponding tailings material. 3. Humidified air was generated using a 20-l glass carboy that was half-filled with deionized water. It is now used to evaluate both coal. Cd and As analysis by atomic absorption spectrometry (AA). Zn.45-Am membrane. HCl or NaOH was added to solutions to adjust the pH. Adsorption experiments These experiments were carried out using plastic containers as batch reactors with 20 ml of doubledeionized MILLI-Q water. the final pH was measured and the suspension was centrifuged for 10 min at 10. For the present research work. The ABA test was originally designed to evaluate acid-producing capability of coal-mine waters. The material collected. The pipes were hammered all the way down into the tailings material. is considered to be representative of the alluvial material of the shallow aquifer of the region. far more important than the acidity generation and consuming processes is the amount of heavy metals that are being released to the environment. Each cell is about 7-cm high and has about 50-cm2 cross-sectional area. 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. All the glassware and plasticware were cleaned with detergent.. and rinsed with deionized water. The most commonly used static test is known as acid – base accounting (ABA). As) concentrations used ranged between 3 Â 10À 5 and 7 Â 10À 5 M.01 and 0. Zn. acid generation and acid neutralization for a selected sample.000 rpm. Different amounts of natural material from the Mata basin alluvial plain were used to get total solid-phase iron concentrations between 0. Cd.45-Am Micro-pore membranes and divided into two subsamples.001 M. and then a hole around the pipe was dug to extract the pipe and avoid loss of material. 1999). 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. In turn. three samples from the tailings piles were used for the ABA test. and used for these experiments.5.1 and 0. Metal solutions were prepared from stock standard solution. The experimental solutions were equilibrated for 24 h in the batch reactor with continuous shaking to maintain a constant solid/liquid ratio. 1997).3. Background solutions with ionic strengths of 0. The leachates were stored overnight at 4 jC before analysis.´ A. 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). Surface titration Four surface titration experiments were performed on the natural aquifer material of the San Nicolas area . 10 ml of the supernatant was filtered through a 0.and metal-mine wastes. which receives the surface groundwater and holds the main interaction between solid-solution (surface complexation reactions). 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).

X-ray diffraction data indicate that the tailings from the different piles consist mostly of quartz. The setup for the surface titration was the following: a 200-ml plastic bottle with 20-ml double-deionized water and a magnetic stirrer was used as a batch reactor. (+) Indicates the most abundant minerals in each group. Petruk and Owens. except from San Nicolas area where a profile sampling was taken. 1994. Zn and Pb increase in concentration with depth. 1928). pH readings were made after the 5-min equilibration time. The upper part of the profiles is highly oxidized (0. Quartz (+) Calcite (+) Dolomite Siderite Rhodocrosite Chalcopyrite Adularia Marcasite Sphalerite Galena Pearceite Tetrahedrite Arsenopyrite Pyrrhotite Amethyst Chlorite 4. calcite and adularia (Gross.7.01 M) solutions were added to raise or lower the pH at constant intervals of time (5 min).to 1-m depth). Results and discussion 4.1. the trace element content is essen- .00125 M) and HCl (0. 1962).. As = 20 mg/kg and Se < 5 mg/kg. Acid – base accounting static analysis (ABA) was performed on several tailings samples. chlorite. feldspar follows in concentration. but in general Cu. precipitation of secondary – tertiary phases. Alpers and Blowes. which corresponds to a Fe solid phase concentration of f 2 Â 10À 2 M. it has been recognized that pyrite occurs in less than 1% of the ore. This calcite/pyrite ratio in the tailings material (and also in the mineralized veins) indicates that any acidity generated by the oxidation of metal sulfides (mostly pyrite) would be neutralized by the Montmorillonite Ankerite Nontronite Chalcedony Apophyllite Datolite Laumonite Stilbite Saponite (Petruk and Owens. Ore minerals (silver and gold) are distributed in bands alternating with gangue minerals (Table 1). 1974). 2001).3 and 5. A background electrolyte of NaNO3 at different ionic strengths was used. calcite. in the field. It can be observed that despite the different location.04 g of sediment material was used. / Ore Geology Reviews 23 (2003) 277–297 Table 1 List of minerals reported in the low sulfidation epithermal vein mineralization of the Guanajuato District GoldSilverbearing bearing minerals minerals Native Native gold silver Electrum Acanthie (+) Aguilarite (+) Polybasite (+) Pyrargyrite Naumanite Sulfide minerals Pyrite (+) Silicates Carbonates in order to compare the resulting Point of Zero Charge (PZC) with that of the iron oxy-hydroxides (Parks and deBruyn. Nitrogen gas was bubbled through Tygon tubing to the solution to exclude CO2 from the system. NaOH (0. However. Oelsner. Both Gross (1975) and Buchanan (1980) recognize three mineral assemblages in the mineralization of Guanajuato: (a) ‘‘upper’’ (precious metals). The mineralogy of the epithermal veins is dominated by quartz. The samples were taken from the surface of the tailings piles and up to a depth of 1 m. Fig. calcite and feldspar. These low sulfidation deposits are considered to have a relatively low acid mine drainage potential due to their high ratio of carbonates/sulfides. Mineralogy and geochemistry of tailings Mineralization at the Guanajuato District occurs mostly in vein structures and minor stockworks. Calcite is in 10% and pyrite in less than 1%. redox. 2 shows the content of some trace elements in the different tailings materials. The results of the ratio (NP/AP) of neutralization potential (NP) and acidity potential (AP) from the ABA tests range between 1. 1975.284 ´ A. Other trace elements are in relatively very low concentrations. 1999).25. 1994). Since early studies (Wandke and Martinez. which indicate the high neutralization capacity of the material (White et al. it is possible to observe dramatic variation in coloration (profile in some trenches) of some tailings. etc. ‘‘middle’’ (transition zone) and (c) ‘‘lower’’ (base metals zone). 1974.. adsorption. 1991). Zinc content averages 400 mg/kg (ppm). kaolin and pyrite (Ramos. feldspar. Base metals are relatively low. It has been documented that in the upper part of such tailings (unsaturated zone) highly complex geochemical processes take place (dissolution. Jambor. Quartz represents 60% of the total. Carrillo-Chavez et al. Pb = 100 mg/kg. About 0.

All the other samples are very low in arsenic and selenium ( < 0. (b) a water spring from La Luz zone. which very likely indicate dynamic near-surface processes such as dissolution of calcite. Content of trace elements in different tailings material from the Guanajuato area. some other water samples were taken from water reservoirs (dams). Sulfate precipitation can be observed on the surface of some of the tailings impoundments (e. being saturated in these waters. and (d) groundwater from municipal water wells. dissolution of metallic sulfides. The surface water from the reservoirs (Soledad. The major ions geochemistry is shown in Fig. and plots mostly in the central part and lower section of the Piper diagram. Mata and Esperanza) presents the lowest total dissolved ions (TDS: ranging from 140 to 210 ppm). During spring 2001. thus creating a potential adsorbing substrate. it is not possible to distinguish between sulfate derived from dissolution of sulfides or sulfates. but Fe concentration decreases towards the groundwater (less than 0. the general concentrations of trace metals are very similar.01 ppm). 4. 2. Carrillo-Chavez et al. It is true that from the chemical data available. Major ion chemistry is dominated by bicarbonate.05 ppm). Geochemistry of natural water Fig. 4. 3 shows the trace elements concentration in water samples from: (a) Valenciana tailings pile pond (surface water accumulated during the rainy seasonhighly evaporated). very similar to mine- . Water is iron-rich in the Valenciana pond (up to 2. The evaporation arrow in Fig. sulfates and minor sulfides would mostly control the major elements hydrochemistry.´ A.2 ppm). The groundwater (wells 3. sulfate and calcium. Valenciana) as a gypsum ‘‘coating’’ due to evaporation of rainwater and precipitation of gypsum. nor Ca from other sources (aluminosilicates reactions).5 ppm) than in other localities.01 ppm) than any other locality. (c) La Purisima water reservoir (dam). / Ore Geology Reviews 23 (2003) 277–297 285 Fig. 4 indicates very likely processes in the surface water. reflecting the uniform mineralogy of the processed ore. Water from a spring at La Luz area is relatively higher in arsenic (0. 12 and 14) has TDS ranging from 470 to 560 ppm. Even though the locations are far apart. 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.2. Saturation index calculation using the code PHREEQC indicates that ferrihydrite. water wells (groundwater) and mine-water (interior of Valenciana and Torres mines).g.03 to 0. but the groundwater (samples from municipal water wells) is higher in Zn (ranging from 0. is precipitated as mineral surface coatings. and dissolution-precipitation of sulfates. The concentration of the different trace elements is generally low. But the X-ray diffraction data help to confirm that the carbonates.

However. As. respectively). The fracture 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. The highest TDS is for mine-water from Valenciana mine (range between 800 to 4500 ppm). Zn concentrations increase in the groundwater (D). Carrillo-Chavez et al. Minor element chemistry indicates low amounts of Fe. Groundwater (from water wells) is relatively high in Zn and Cu (up to 1. Iron is the most abundant element.5 and 0.286 ´ A. Ni. / Ore Geology Reviews 23 (2003) 277–297 water from Las Torres mine. This fact could represent zinc derived from the water pipes in the well or natural Zn in groundwater. Se and Pb in most of the samples ( < 0. Fig.01 ppm).3 ppm. 3. . This water plots in the upper corner of the Piper diagram and indicates gypsum dissolution-dominated processes. 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). The Zn amount has been constantly high in most of the groundwater samples for a 3-year period. indicating the deep infiltration accompanied of dissolution processes. Trace element content of natural water from different location of the Guanajuato area.

According to Craig and Gordon (1965) and Kendall and Caldwell (2000). In the Torres mine-water. 5. where the remaining water becomes ‘‘heavier’’. 5 and 10 m below the surface. / Ore Geology Reviews 23 (2003) 277–297 287 Fig. well nos.5x whereas at the .5xto À 74. three municipal water wells (regional groundwater. On ‘‘dry’’ climates. 12 and 14). 3. with low vapor content in the environment.5x À 62. the isotope fractionation processes are . 4. water samples were taken from the surface and depths of 2. Esperanza and Mata dams).6x À 8.3. The other samples lie between these two extremes. 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. the values range from d18O = À 10. The isotopic data at the Esperanza reservoir do not seem to reflect any evolution or change with depth.00x to and dD = À 78.7x to and dD = À 56. the surface evaporation produces isotopic fractioning. From Esperanza and Mata reservoirs.7x À 11. The results are shown in Fig. Carrillo-Chavez et al. while the rain becomes ‘‘lighter’’. 3 (continued). and three water reservoirs (Soledad.´ A.9x to . Esperanza reservoir the values range from d18O = À 7.

The kinetic isotopic fractionation defines a slope for the local evaporation curve of dD = 5. Soledad. 4. The water general types fall between bicarbonate.04xdetermined by the water vapor content in the . environment.288 ´ A. the Esperanza reservoir is an ‘‘isotopic open system’’ (allowing high evaporation) with a much higher volume of water being evaporated. surface water reservoirs (dams: Esperanza.and sulfate-rich type. . 1981. It is considered that the Torres mine environment is close to 100% of vapor saturation (deep inside the mine). Gat. Mata). Carrillo-Chavez et al. controlled mostly by evaporation. On the other hand. On the other hand. 12 and 14). / Ore Geology Reviews 23 (2003) 277–297 Fig. Piper diagram for water samples from groundwater (wells 3. mine-water (Valenciana and Torres). 1996).93xd18O = 13. and could well be considered an ‘‘isotopic closed environment’’. in ‘‘wet’’ environments with high vapor saturation (close to 100%) the vapor tends to be less fractionated (Gat and Gonfiantini.

Geochemistry of leachates from humidity cell and column experiments Fig. Esperanza and Soledad) is along highly anisotropic. Esperanza and Mata dams). when proper handled.´ A. 12 and 14).6 g/cm3). 3. 4. 1997). dD vs.1. 5 and 10 m below the surface. the general trend of all metals was to decrease). Samples were taken from a variety of environments: mine-water from Valenciana and Torres mines. 2 and discussed in Section 4. It is very true that humidity cell data are not easy to interpret. In general. 6D). 6 shows the trace element content in leachates from humidity cell test (HCT) experiments for 10 weeks (after 10 weeks. 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. Esperanza and Torres water are the end-members of the fractionation processes. / Ore Geology Reviews 23 (2003) 277–297 289 Fig. with sporadic spikes of Zn. The groundwater flow in the mountainous region (Valenciana. allowing isotopic fractionation and dissolution of gypsum (high SO4 and Ca content). As in most tailings environments. the general content of trace elements in the leachates is quite low ( < 0. whereas at Valenciana the infiltration is slow at the surface.1 ppm). Trace element content of these solid materials is shown in Fig. from Esperanza and Mata dams. respectively). The filling material for the HCT was taken from the tailings impoundment of Valenciana (new and old. three municipal water wells (regional groundwater. and grain density of 2. Several efforts have been made to estimates rates of weathering and to scale laboratory tests to predict field rates of weathering (Frostad et al. The details on the topic of evaluating weathering rates are beyond the scope of this work. the flow conditions at the different tailings piles in Guanajuato are unsaturated. Under these weathering conditions. well nos. The key objectives of the humidity cell tests are: (a) long-term stable reaction under kinetic conditions and (b) depletion times for acidgenerating. 2000a. 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). At the alluvial valley (groundwater wells) the water is a mix of quick and slow infiltrated water that plots along the evaporation line. . Fig. but also it is true that these data. tailings pile from La Luz (Fig. Torres..b). acid-neutralizing and meta-leaching minerals (Morin and Hutt. and three water reservoirs (Soledad. 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. fractured igneous and metamorphic rocks. Carrillo-Chavez et al. As and Se.4. d18O plot for some water in the Guanajuato district. 6A and B. all the mine-waste materials decrease their leachate concentrations after 3 or 4 weeks. 5. give good estimates of heavy metal leaching potential and acid mine drainage. 6C) and tailings pile at San Nicolas (Fig. water samples were taken from the surface and depths of 2.

the solution must be acidic. the near-neutral pH of the leachates indicates that the acid-consuming reactions surpass the acid-producing reactions. 7). Even though some ‘‘oxide’’ coatings can be observed in the tail- Fig.5. / Ore Geology Reviews 23 (2003) 277–297 The leachates from Valenciana ‘‘new’’ present the lowest concentrations of metals from all the material tested ( < 0. indicating some potential for arsenic release. very likely derived from some Zn within secondary or tertiary phases. Se and Pb. < 0.8 ppm).001 ppm Cd). Zinc concentrations present 2 weeks of relatively high concentration (0. 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. . Las Luz leachates present the highest concentration of As. but still this is low (< 0. Fig. Leachates from San Nicolas present the same general trends of decreasing concentration with time and some highs on Zn. the As values have a ‘‘high’’ during week 10. As. 6. Carrillo-Chavez et al. The concentrations of metal in the leachates from these experiments are relatively low.290 ´ A. but with some ‘‘peaks’’ of Zn. Trace elements in leachates of the humidity cell experiments (10 weeks). Interestingly. The main acidity is generated in the leachates by the oxidation of metallic sulfide (Smith et al. zinc and other heavy metals to the environment.1 ppm for Cu. The leachates from Valenciana2 (old material) have a general trend to decrease in concentrations of metals. which is compatible with the results of the ABA test (pH of oxidized tailings between 7 and 9. along with results of the humidity cell test results.1 ppm). indicate that there is a low potential for release of arsenic. The general trend is to decrease with time. 1994): FeS2 þ 3:5O2 þ H2 O ¼ Fe2þ þ 2SO2À þ 2Hþ 4 However.. The geochemical and mineralogical analyses.

The concentration of trace elements in the leachates is relatively low when compared with leachates from other type of sulfide-rich ore deposits. Carrillo-Chavez et al. Fiklin . Zinc could be present in different secondary and/or tertiary solid phases. X-ray diffraction data do not show any zinc mineral phases. ings. at pH values between 3 and 5. / Ore Geology Reviews 23 (2003) 277–297 291 Fig. besides the primary mineral sphalerite. But the chemical analyses indicate an average of 400 mg/kg Zn in the tailings material (see Section 4. On the other hand.1). But the low Zn content of the leachates indicates that: (a) a small amount of Zn phases is present in the tailings material. 2 mol H+ is consumed.´ A. Even though a minor phase in the system. Zn is important because groundwater increases its content with respect to the leaching experiments. and/or (b) a slow dissolution rate of the Zn phases present. calcite and ‘‘oxide’’ coatings present in the tailings indicates that the acid-consuming processes surpass the acidgenerating processes by a factor of 12. Zinc is a minor element in the system. An acidity-budget calculation shows that. 6 (continued). A simple estimation on the amount of sulfides. 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. the contribution to acidity of these reactions is considered to be negligible. for every mole of calcite dissolved. 2 mol H+ is released. for every mole of FeS2 dissolved. On the other hand. so there is insufficient time for dissolution. so its contribution to the consuming acidity process is neglected.

6. whereas pH is neutral and remains between 7. The variation between the two sampling seasons is very small and only Fe and Mn show significant concentrations in both sampling. 9 shows the results of the different adsorption experiments. Modeling with PHREEQC shows that the stream water is never saturated with respect to gypsum or calcite. 7. 4. probably iron sulfide. and from a creek formed by the mixing of upstream. Natural leaching from the tailings Water samples at San Nicolas area were taken directly from the base of the tailings piles. 1999). Fig. from a creek flowing directly from the tailings pile. It was determined that water downstream of the tailings pile does not contain significant concentrations of heavy metals. Major ion chemistry indicates that dissolution of calcite and minor sulfides and gypsum (gypsum is present mostly as hardpans on the tailings impoundments and it is not rare to find gypsum in fractures in tunnels in the mines) controls the hydrochemistry of the region.292 ´ A. with Fe and Mn being the trace elements with the highest concentration (1 to 2 ppm). Pb. The low concentrations in trace metals can be attributed to several factors: low concentration of metal in solid tailings. unpolluted waters. Carrillo-Chavez et al. as it flowed to Mata reservoir. 9A shows the percent adsorbed by the natural material vs. and the creek from the tailings. diagrams (sum of Zn. not enough time for dissolution. The topology of the curves is appropriate for cation adsorption (higher adsorption at high pH and lower . which in turn becomes a good adsorbing surface for many metals. so it is assumed that Mn in sediments and leachates could be derived from both natural and anthropogenic sources. Diagram indicating the pH variations during the humidity cell experiments.1 and 8. pH on Cd. / Ore Geology Reviews 23 (2003) 277–297 Fig. Cd. Column experiments described in Section 3 indicate that the results are similar to the HCT leachates for all the material tested. which is high enough for most metals to be insoluble. Iron seems to be derived from a natural source. Manganese is ubiquitous in most of mineralized terrains. it is known that Mn balls were used to crush the ore. see text for details). The samples were taken at the beginning and the peak of the rainy season (April –August). metal fixed to insoluble phases. 8 shows the analytical data from this water samples. All the samples have a similar composition in major and minor elements. Iron is high enough to precipitate ferrihydrite (PHREEQC modeling). Adsorption of heavy metals by natural material Fig. Cu. pH) of the leachates show the low concentrations and near-neutral pH characteristic of quartz– calcite vein ore deposits (Plumlee. pH of the water near neutral. But also.5. Fig. The pH remains near neutral due to the high acid-consuming capacity of the material in the tailings (high ratio calcite/sulfides.3 in all the samplings. The sampling was done after several heavy rainstorms (natural leaching). Co and Ni vs. Total dissolved solids is higher in samples near the tailings pile. 4.

indicating quick infiltration with no time for dissolution of metal phases contained in the tailings material. Experimental results from the adsorption experiments of Cd.1 and I = 0.´ A.01). This is probably due to the presence of arsenite (H3AsO3) besides arsenate (H3AsO4) in the solution. This experiment was in NaNO3 0. The material is relatively rich in Fe2O3 content (f 10%). but a lower ionic strength was used (I = 0. 9). 8.01 M). Trace metals content in natural leachates. Cu. Fig. 9B shows the adsorption of Pb by the natural material. . The concentrations are lower than the experiments of the humidity cell. 9. The natural material is relatively rich in iron and has very high capacity for adsorbing dissolved metals. Fig. 9C and D shows the same experiment but for Cu and Zn.01). Arsenic adsorption experiments were also conducted (not shown in Fig. / Ore Geology Reviews 23 (2003) 277–297 293 Fig. See text for details. It has been shown that arsenite is less adsorbed onto iron oxy-hydroxide surfaces than arsenate under similar conditions (Dzombak and Morel. This experiment used the same amount of solid total Fe phase (0. Experiments were carried out with a NaNO3 background electrolyte (I = 0. The high adsorption (f 100%) even at pH 7 is probably due to the highest solid/solution ratio used (total Fe = 0. the highest percent of adsorption obtained was about also 100%. Fig. but in this case. but the lowest adsorption dropped to near 60%.01 M) as the first set of experiments for Cd. The four experiments look very similar even though they were conducted in solutions with different ionic strengths. but the natural environment in Guanajuato is highly oxidized. 1990).1 M background electrolyte. Pb and Zn onto natural material from the Guanajuato mining area. The samples were taken directly at the base of the tailings piles after heavy rain to assure natural leaching from the tailings. Carrillo-Chavez et al. adsorption at low pH). A slight decrease is observed.

5. Discussion and conclusions The chemistry and mineralogy of the different tailings piles at Guanajuato reflect the vein mineralogy of the mining district. The possibility of a long travel time (longer than 200 years. but represents less than 0. The humidity cell experiments. These adsorbing processes. 1986). the possibility that Zn concentrations in groundwater are due to natural processes still remains. 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). 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.01 K (m/s) 1e À 06 1e À 04 1e À 02 n (%) 15 25 40 Time (year) 19. / Ore Geology Reviews 23 (2003) 277–297 so it is assumed that most of the arsenic must be arsenate (higher adsorption).422 324 5 Total time (year) 46. indicating that acidity generated by sulfides oxidation would be buffered by dissolution of calcite. there is not data on the groundwater velocity in the system. Carrillo-Chavez et al. dh/ds = 0.1%. along with the low metal concentration of heavy metals in the natural leachates. The tailings material is composed mostly of quartz. 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. A final experiment was the surface titration of the natural aquifer material. explain the very low concentrations in the natural waters. Even though these experiments have relatively few points. But so far. if not high Zn comes from the tailings piles. Cu. In summary. which currently are not available. These velocities indicate that there has been enough time for Zn to reach the area for the groundwater wells. the work by Rivas-Solorzanao (2001) demonstrated that the natural sediments in the Mata basin alluvial plain have a high capacity for adsorbing the low metal concentrations of Zn. 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. Because the lowest and highest values of hydraulic conductivity (K) and porosity (n) used in the calculation (Table 2) are the extreme cases.481 865 19 K = hydraulic conductivity.02 K (m/s) 1e À 08 1e À 06 1e À 04 n (%) 2 4 10 Time (year) 27. Pyrite is the most common sulfide. But. . Cd and As in solution. experiments for adsorption of different metals onto natural sediments of the Mata basin alluvial plain indicate the high adsorbing capacity of the sediments at near-neutral pH. The ratio of carbonates to sulfides is 12:1. the relatively abundance of calcite and clays indicates that some of the adsorbing processes are controlled by the surface complexation reactions. and the chemistry of the natural waters is controlled by dissolution of calcite and gypsum. The combination of all the analytical and experimental results indicates that the mine-waste material has very low potential for generation of acidity (AMD) and leaching of heavy metals to the environment.059 541 14 Valley zone. The results for the surface titration indicate that iron oxy-hydroxides are the most likely adsorbing surface in the environment. Natural leaching is also very low for most trace metals. n (%) = percent porosity. dh/ds = hydraulic head gradient. This calculation could be improved with field data for different water-wells. indicate very low potential for leaching metals. A blank titration was used to correct suspension titrations for supernatant effects (Machesjy and Anderson. feldspar and calcite. which is the average time for the most important 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). Furthermore. 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. and the base metals are present in very low concentrations. So. 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.294 ´ A. Pb. However. However. This ‘‘high Zn’’ area is located on a continuous groundwater flow path from the mineralized area. dh/ds = 0.

. S. Carrillo-Chavez et al. which increases concentration in the deep groundwater flow. 74. 2001. Infiltration of meteoric water through the Zn-poor tailings dissolves some As and Se phases. ACS Symposium. References Alpers. Some As and Se is dissolved from secondary phases within the tailings material.). 73 – 97. Banwart. Environmental geochemistry of sulfide oxidation. M. p. Surface runoff is iron-rich and other-metal-poor.´ A. Acknowledgements This work was supported by grant no. Deep infiltration allows dissolution of primary phases of Zn. or quickly infiltrated (non-fractionated) as the case of the Torres mine-water. Logsdon and Richard Kyle. The authors wish to thank the detailed and helpful reviews by Drs. fractured media in igneous and metamorphic rocks before reaching the granular aquifer in the alluvial valley. Schematic representation of the general geochemical processes taking place in the surface and near-surface environment in the Guanajuato area. (Eds. Buchanan’s (1980) mineralization model predicts an increase in base metals at depth in the district.N. Surface complexation of Fe oxy-hydroxides. Mark J. Fig. However. Groundwater extracted at the wells has more Zn than the surface runoff because of slow groundwater flow and more time for dissolution processes. Malmstrom. J. So. slow and deep infiltration 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. This variation in time of infiltration could cause dissolution of Zn sulfides at depth. 10.. D. it is reasonable to assume that Zn sulfides increase below the current mining operations. . 10 shows an schematic representation of the main environmental geochemistry processes taking place in the Guanajuato mining district. The authors also thank the enthusiastic assistance of Jorge Servin and Carolina ˜ Munoz in the field and laboratory works. Rainwater infiltration into the tailings dissolves relatively few metals because: (a) rapid infiltration or (b) low rate of dissolution. The meteoric water that infiltrates can be evaporated (highly fractionated) as is the water from the Esperanza dam. Blowes. 550. / Ore Geology Reviews 23 (2003) 277–297 295 Fig. and Eloisa Dominguez-Mariani for her skillful hand in drawing. C. Hydrochemical modelling ¨ for preliminary assessment of minewater pollution..A.E. Guanajuato groundwater despite the low leaching of Zn from tailings. 1994. Explor. The Zn concentrations 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. Geochem. The surface runoff is relatively poor in trace elements (base metals). calcite and clays and base metal (including As) adsorption onto these adsorbing surfaces control the mobility of trace elements in the nearsurface environment. Iron precipitates as Fe-oxy-hydroxides to enhance adsorption processes. Isotopic data (dD and d18O) of water samples from different environments in the area indicate infiltration of meteoric water into a highly anisotropic. 27821-T from CONACyT-Mexico.

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