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A study of the mineralogical, hydrological and biogeochemical controls on drainage from waste rock at… Beckie, Roger D.; Aranda, Celedonio; Blackmore, Sharon R.; Peterson, Holly E.; Hirsche, D. Trevor; Javadi, Mehrnoush; Blaskovich, Randy; Haupt, Charlene; Dockrey, John; Conlan, Michael; Bay, Danny; Harrison, Bevin; Brienne, Stephane; Smith, Leslie; Klein, Bernhard; Mayer, K. Ulrich 2011-11

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Proceedings Tailings and Mine Waste 2011 Vancouver, BC, November 6 to 9, 2011 A Study of the Mineralogical, Hydrological and Biogeochemical Controls on Drainage from Waste Rock at the Antamina Mine, Peru: An Overview Roger D. Beckie1, Celedonio Aranda2, Sharon R. Blackmore1, Holly E. Peterson1, D. Trevor Hirsche1, Mehrnoush Javadi1, Randy Blaskovich3, Charlene Haupt4, John Dockrey1, Michael Conlan1, Danny Bay1,5, Bevin Harrison2, Stephane Brienne3,  Leslie Smith1, Bernhard Klein4, K. Ulrich Mayer1 1Department of Earth and Ocean Sciences, University of British Columbia, Vancouver, Canada 2Compañía Minera Antamina S.A., Lima, Perú 3Teck Metals Ltd., Applied Research and Technology, Trail, British Columbia. 4Mining Engineering, University of British Columbia, Vancouver, Canada 5 MWH S.A., Lima, Perú Abstract A multi-scale study of solute release, transport, and attenuation mechanisms in waste rock under neutral drainage conditions is underway at the open-pit Cu-Zn-Mo Antamina mine in the Peruvian Andes. The objectives of the project are to better understand the mechanisms that control the fate of elements of concern, principally Zn, Mo, Cu, and As, and to develop field- and laboratory-derived scale-up relationships that provide a framework for prediction of waste-rock drainage quality at field scales and over long times. Five 36 m x 36 m x 11 m high instrumented experimental waste-rock piles have been constructed on site to provide insight into the hydrological and geochemical behavior of distinct combinations of waste rock under field conditions. Field cells constructed from 60 L barrels provide data on leaching behavior of the distinct rock types. Our results allow us to constrain the water balance, demonstrate that mixing of distinct waste-rock types may enhance attenuation of Zn and Mo in drainageand suggest that sulfide mineral oxidation may become O2-limited in fine-grained reactive material. Introduction The ~260,000 tons of waste rock mined each day at the Antamina Mine is end dumped in piles that can reach over 300 m tall. Ongoing efforts at Antamina since the initial environmental assessment in 1998 have been directed towards understanding geochemical and hydrological processes that control the quality and quantity of the drainage from waste rock. In 2005, Antamina Mine embarked on an integrated research project with Teck Metals Applied Research and Technology group and the University of British Columbia with the goal to improve the understanding of the hydrologic and geochemical processes that control drainage from waste rock and to use this understanding to inform operations and closure planning. In this paper we provide an overview of the Antamina-Teck-UBC research project. Site The Antamina Mine produces zinc, copper and molybdenum from a carbonate-hosted polymetalic skarn deposit. The mine is located in Ancash, Perú, 270 km directly north of Lima and 50 km east of Huaraz (Figure 1) and lies at an elevation of between 4100 and 4700 masl. At the site the mean annual precipitation, almost entirely rain,  is 1200 mm, with a mean annual temperature of 5.5 – 6 °C and a temperature range between -4 and 23 °C. A distinct wet season begins in October and lasts until April. Proceedings Tailings and Mine Waste 2011 Vancouver, BC, November 6 to 9, 2011   Figure 1  Antamina mine location. Waste rock There are 5 principal rock types at Antamina: limestone, marble, hornfels, intrusive and skarn (subdivided into endoskarn and exoskarn). The geochemical and physical properties of the rocks are highly variable: marbles and hornfels tend to have lower sulfide content and coarse rock-like texture whereas the intrusive and skarns tend to have higher sulfide contents and a finer grained texture. The majority of the rock has carbonate content sufficient to maintain neutral pH drainage from most seeps. Presently, waste rock at the site is classified into one of three categories on the basis of sulfur and metal contents and lithology (Aranda, 2010): Class A – high potential for producing undesirable leachate, Class B – intermediate potential for producing undesirable leachate and Class C – low potential for producing undesirable leachate. Under the prevailing neutral – pH conditions, oxyanion metalloids such as arsenic and molybdenum as well as weakly hydrolyzing metals such as zinc are mobile in solution and present a concern in the drainage. Waste rock with high and intermediate potential for producing undesirable leachate, (Classes A and B) is placed in the East Dump, whose leachate flows into the tailings pond, whereas waste rock with a low potential for producing undesirable leachate (Class C), is placed in the Tucush Dump, whose leachate flows into an engineered wet land. Improved understanding of waste-rock leaching potential will allow Antamina to engineer disposal locations, and to place waste with high leaching potential in locations where drainage can be controlled and treated. Research Program There are four principal components of this research: Proceedings Tailings and Mine Waste 2011 Vancouver, BC, November 6 to 9, 2011 1. Laboratory experiments: whole-rock analysis, kinetic testing including column experiments and humidity cells, and various types of characterization including microbiological, mineralogical, and physical analyses such as grain size and soil-water characteristic measurement. 2. Field experiments: a suite of barrel-sized field cells (Aranda et al., 2009) where distinct rock types are examined in isolation as well as 5 instrumented experimental waste-rock piles  36 m x 36 m x 11 m high where the combined effects of physical and geochemical processes can be studied (Bay et al., 2009; Corazao et al., 2007). 3. Interpretation of results using mechanistic models and scaling to field-scale: integration of results from laboratory and field experiments using mechanistic models to understand principal controls of field-scale drainage of full scale piles and predict future drainage quality. 4. Cover study: test a variety of locally available cover materials and their effectiveness at reducing infiltration of water and ingress of oxygen. This component of the research will be described by in these proceedings by Urrutia and Wilson, 2011. A theme that runs through the research is scale. For operations and closure planning, owners require predictions of drainage quality from field-scale piles over long time scales, yet at the permitting and early operations phase of the mine they must make these predictions based upon smaller-scale tests run over relatively short time scales. A strategy of this project is to investigate processes at a range of scales and then use mechanistic process models to integrate the understanding together and support predictions at field scales and over long time frames. Laboratory studies It is important to understand which minerals and processes control the release and attenuation of elements of concern.  Conlan et al (2011) examined the secondary mineral controls on dissolved molybdenum.  A series of batch reactors were constructed where molybdenum – bearing solutions were added in the presence of sulphate and lead. Flow-through column studies examined mixing of these solutions in a bed of calcite. The solutions and mineral precipitates were examined to determine molybdenum attenuation processes. While microbes are known to be important catalysts of mineral oxidation under acidic conditions, it is not clear what role they play under neutral pH conditions. Dockrey (2010) examined bacterial communities on a variety of waste rock types and found that neutrophilic sulfur oxidizing bacteria dominate the microbial populations, although acidicophilic iron oxidizing bacteria were also found suggesting ferric iron mediated sulfide weathering is also occurring. Detail microscopy and focused ion beam analysis indicates that these acidophilic bacteria live within the context of a bulk neutral pH system in acidic microenvironments in porous schwertmannite (Fe8O8(OH)6-4.5(SO4)1-1.75) found adjacent to primary sulfide mineral phases. Ongoing studies include the use of mineral liberation analysis to correlate sulfide and buffer mineral liberation (exposure on the surface of waste-rock particles), and to identify primary – secondary mineral associations. Humidity cells are being used to investigate weathering rates of matrix material and to confirm effects of mixing of waste rock types on mineral attenuation. Selective and sequential leaching procedures are being used to evaluate which rock types are most likely to release elements of concern. A selective leach operates by exposing waste rock to a solution that in principle selectively dissolves specific mineral phases of interest, for example arsenic sulfides. By analyzing that which dissolved into solution, one can characterize both the abundance of the target phase as well as the tendency of that phase to dissolve under the conditions in the solution. A sequential leach procedure utilizes a sequence of such solutions (see e.g. Keon et al (2001)). Physical analyses include grain-size, Proceedings Tailings and Mine Waste 2011 Vancouver, BC, November 6 to 9, 2011 the use of the measured particle-size distributions to predict soil-water characteristic curves of matrix material and the direct measurement of soil-water characteristic curves using Tempe Cells. Field studies The quality and quantity of drainage from waste rock depends on hydrological and geochemical processes that occur within waste rock piles (Smith and Beckie, 2003). To study these processes at practical field scales, 5 experimental waste rock piles were constructed at Antamina between 2007 and 2010. Each pile is 36 m x 36 m x 10 m high, and contains approximately 20 – 25,000 tons of waste rock (Figure 2). Pile 1 contains intermediate potential for leaching (Class B) marble and hornfels, Piles 2 and 3 contain high potential for leaching (Class A) intrusive and high potential for leaching exoskarn respectively. Pile 4 contains a mixture of intermediate potential marble and hornfels and high potential marble and hornfels, and Pile 5 contains high potential intrusive and low potential marble and hornfels.  Figure 2:  Five experimental waste rock piles viewed from above. All drainage from the pile is collected by a whole-pile basal lysimeter (Lysimeter D) and 4 sub- lysimeters (A,B,C), which are placed within the footprint of Lysimeter D (Figure 3). Drainage from the pile is conveyed to an instrument hut where the flow rate is measured with tipping-bucket meters, electrical conductivity is continuously logged using electrodes in a flow-through cell, and samples for geochemical analysis can be collected. Instruments are also installed within each pile at several depths along four vertical instrumentation lines (Figure 3, right) and along two horizontally lying lines to provide a three-dimensional grid of monitoring points. During pauses in dumping in pile construction, instruments on vertical lines were installed on tipping faces in finer grained material (Corazao et al., 2007), and then covered by subsequent discharges of waste rock onto the pile. Moisture content is measured using time domain reflectometry (TDR) probes in Pile 1 and by TDR and commercial reflectance probes in Piles 2 – 5. Temperature is measured with a network of thermistors. Solutions can be sampled from the unsaturated zone using suction lysimeters. Gas samples can be collected by pumping on 1/8 inch tubes with a fine mesh filter that are placed in each the pile, and measuring concentrations using a portable gas chromatograph. Seasonal and daily fluctuations are captured by an automated gas measurement system that has been installed in Pile 2 where O2 and CO2 are measured every 15 minutes from 60 ports. Similar automated systems will be installed in Piles 3 and 5 in the fall of 2011. Proceedings Tailings and Mine Waste 2011 Vancouver, BC, November 6 to 9, 2011  Figure 3:  Left: Base of Pile 2 during construction showing three sub-lysimeters (A, B, C) within the  footprint of whole-pile basal lysimeter (D); Right: schematic cross section showing location of instrument lines, and basal lysimeters. Complementing the test piles are field cells (Figure 4, left) which are used to evaluate the leaching behaviour of relatively small single rock types under field conditions. At Antamina, the field cells are constructed from 60 L plastic barrels and contain approximately 300 kg of rock. A field cell has been established from samples collected from each tipping event for each pile, approximately 70 in total.  Figure 4:  Left: Field cell;  Right: stacked  field cells. Field cells are placed outdoors and subject to mine-site climate, and drainage is collected for chemical analysis weekly or biweekly during the wet season. In stacked field cell experiments (Figure 4, right) one rock type, typically a zinc or molybdenum releasing material, is stacked above another rock type that is hypothesized to attenuate these elements. This allows one to study the effects of mixing of leachate from different rock types. Field cells cannot be expected to yield drainage of the same quantity or quality as the test piles or full- scale piles. Their size means that large particles and boulders are excluded and they likely experience less preferential flow. They are subject to greater temperature and moisture fluctuations than the full piles, which affects geochemical conditions and effluent concentrations. Finally, water has a relatively Proceedings Tailings and Mine Waste 2011 Vancouver, BC, November 6 to 9, 2011 short residence time in the field cells compared to the much larger test piles.  Despite these considerations, field cells are a practical, convenient and relatively low-cost way to assess leaching potential without the confounding effects of mixtures of rock types found in field-scale piles. In this project, they are used to examine end-member behaviours. Selected results Waste rock characterization All marble, limestone and hornfels samples and a few skarn and intrusive samples were shown through acid-base accounting to contain high amounts of carbonate and likely to always yield neutral pH drainage. Although they contain sufficient neutralization capacity, they still have the potential to leach metals such as zinc and molybdenum at neutral pH. The acid base accounting also showed that some of the skarn and intrusive samples are potentially acid generating. Hydrology of piles Outflow from each pile has been monitored since each was constructed. Precipitation has been monitored at local rain gauges. Comparing precipitation allows estimates of infiltration and evapotranspiration. The infiltration estimates for the five piles are given in Table 1. . Pile Material type Infiltration as % of precipitation Water year used for analysis 1 Marble and hornfels 41 2007-2008 2 Intrusive 52* 2008-2009 3 Exoskarn 36* 2008-2009 4 Marble (17%) + hornfels  (83%) 49 2009-2010 5 Intrusive (34%) + marble (66%) 45 2009-2010 * Preliminary estimates. Table 1:  Infiltration estimates for test piles. The infiltration at Antamina is approximately 50% of precipitation, ranging from a low of 36% for Pile 3 endoskarn to 52% for the fine-grained intrusive Pile 2. The piles typically required 3 – 4 months to wet up before the first outflow was measured at the base. The water balance for Pile 1 in Figure 5 shows the distinct wet seasons (shaded) during which discharge can peak in response to rain events. In the dry season (April – October), discharge from pile follows a relatively smooth reduction as the pile slowly drains by matrix flow (in the fine grain component). Flow is estimated to move at between 1 and 5 cm per day through the matrix. It is expected that a proportion of water will move relatively quickly through the pile as preferential flow, which is favoured under relatively wet conditions, and the remainder will move relatively slowly through the matrix as matrix flow. Tracer tests (not presented here) are being used to estimate water residence time distributions and the relative proportion of preferential and matrix flow. Proceedings Tailings and Mine Waste 2011 Vancouver, BC, November 6 to 9, 2011  Figure 5:  Pile 1 water balance January 2007 - October 2008. Loadings Loadings here are defined as the mass of solute discharged from the base of the pile as determined from flow and concentration measurements. They are typically reported as mg of solute released per kg of waste rock per week. The loadings are controlled by both release and attenuation mechanisms in the waste rock. Sulphate loadings range from 0.84 mg/kg/wk from Pile 1 to 3.5 mg/kg/wk from Pile 3. The corresponding field cells each over predict pile loading rates by factors between 5 times for Pile 2 and 13 times for Pile 1. This pattern is consistent for zinc (Table 2) and molybdenum (not shown). While sulphate loadings are fairly similar for each pile, perhaps indicative of similar primary sulphide oxidation rates, zinc (Table 2) and molybdenum loadings differ dramatically. Metals concentrations are observed to be seasonal, and tend to decrease as the wet season progresses. Zinc (mg/kg/wk)  Wet  Dry Field Cell: Pile Ratio Pile 1  9.2x10-4  1.2x10-4     - Field Cells  8.2x10-2   89 Pile 2  2.9x10-2  8.6x10-4    - Field Cells  2.0x10-1   7 Pile 3  5.3x10-2  4.5x10-3   - Field Cells  2.8x10-1   5 Proceedings Tailings and Mine Waste 2011 Vancouver, BC, November 6 to 9, 2011 Pile 4  8.9x10-4  6.2x10-5   - Field Cells: B  4.9x10-3   6   - Field Cells: C  3.6x10-3   4 Pile 5  4.5x10-4  2.9x10-5   - Field Cells: A  5.3x10-3   12   - Field Cells: C  3.0x10-3   7 Table 2:  Zinc loadings for piles and corresponding field cells. Wet season loadings are averaged from weekly February loadings. Dry season loadings are averaged from weekly August loadings. Dry season loadings not observed for field cells due to insufficient flow. The discrepancy between field cells and pile loadings highlights the need to understand the relationship between smaller- and larger-scale experiments. Mechanistic Modelling Attenuation mechanisms (Conlan et al., 2011) found that under the conditions that prevail in Antamina waste rock, powellite (CaMoO4) can form to control molybdenum concentrations, however the precipitation rate is kinetically controlled. If there is lead in solution, wulfenite (PbMoO4) forms rapidly, reducing molybdenum concentrations.  X-ray diffraction analyses of samples collected from field cells confirmed that powellite is forming in site waste rock. These observations led to the hypothesis that mixing of waste rock could enhance attenuation by placing metal-releasing material above metal- attenuating material.  Figure 6:  Stacked field cell results showing high Mo release from upper cell and strong attenuation in lower cell. Proceedings Tailings and Mine Waste 2011 Vancouver, BC, November 6 to 9, 2011 The stacked field cells and Piles 4 and 5 have provided evidence that judicious mixing of waste rock can reduce zinc or molybdenum concentrations. Figure 6 shows the results of one stacked field cell. In the figure the lysimeter leachate characterizes the Mo concentration of drainage from the intrusive above, the Mo-rich leachate is from a single field cell with the same intrusive material which provided more drainage for analysis and the basal leachate is the concentration after flowing through the lower cell which contains lead-rich marble. Laboratory- based humidity-cell experiments confirm this behavior. It is hypothesized that wulfenite (PbMoO4) is forming and attenuating molybdenate. Pore gas The rate of oxygen consumption and CO2 production can be used to estimate pile-average oxidation rates.  If oxidation rates exceed the rate at which oxygen can be replenished by transport from the atmosphere, then anaerobic conditions can be established and oxidation terminated. Failure to account for gas transport in a mechanistic model can lead to an over estimation of whole-pile oxidation rates. Oxygen transport is limited by high moisture contents (gas flows in the dry pores), and long flow paths, which are more important at larger scales. Furthermore, heat from exothermic sulfide oxidation can lead to thermally driven gas flow in piles. Accordingly, monitoring of gas composition and temperature provides insight into geochemical and physical transport processes occuring in waste rock piles. Sulphate loadings from all piles indicate that oxidation of sulfides is occurring, but only Pile 2 displays a large thermal and oxygen anomally (Figure 7). The left panel shows that near the top of the pile oxygen concentrations have been depleted at times to less than 50% of surface concentrations. This depletion, although significant, is not likely to limit oxidation rates within the pile. The right panel shows that temperatures within the pile are 5 – 6 °C above mean annual values, indicating substantial release of heat.  In full-scale piles of this material, the longer transport distances could produce even stronger depletion and lead to anaerobic zones where oxidation  is reduced.  Figure 7:  Pile 2 oxygen and temperature data along instrument line 4. The measurement depth is inversely related to instrument number (L4-G1 deepest, L4-G10 shallowest). Air indicates surface air temperature. Summary Small-scale laboratory studies allow investigation of  important geochemical processes and minerals that govern waste-rock leachate quality under controlled conditions. At field scales, pile experiments characterize the water balance, the effect of physical mixing of material types and pore gases. Field Proceedings Tailings and Mine Waste 2011 Vancouver, BC, November 6 to 9, 2011 cells are a convenient and cost-effective way to analyse the leaching of individual rock types, but their results are not directly transferable to field scales. Pore gas analyses show that substantial oxygen depletions are observed in test piles and could manifest in anaerobic zones and reduced net oxidation in full scale piles. The results of these studies are presently being integrated with mechanistic models. The component processes as characterized at smaller scales will be used to parameterize the models and investigate how the coupling of these processes manifests at larger scales. References Aranda, C.A., 2010. Assessment of waste rock weathering characteristics at the Antamina Mine based on field cells experiment, British Columbia, Vancouver, British Columbia, 244 pp. Aranda, C.A., Klein, B., Beckie, R. and Mayer, K.U., 2009. Assessment of waste rock weathering characteristics at the Antamina mine based on field cells experiment, Securing the future and the 8th International Conference on Acid Rock Drainage, Skellefteå, Sweden, pp. 12 pages. Bay, D.S., Peterson, H.E., Singurindy, O., Aranda, C.A., Dockrey, J.W., Sifuentes Vargas, F., Mayer, K.U., Smith, J.L., Klein, B. and Beckie, R., 2009. Assessment of neutral pH drainage from three experimental waste- rock piles at the Antamina mine, Peru, Securing the Future and 8th International Conference on Acid Rock Drainage, Skellefteå, Sweden, pp. 11 pages. Conlan, M.J.W., Mayer, K.U., Blaskovich, R. and Beckie, R.D., 2011. Solubility controls for molybdenum in neutral rock drainage. Geochemistry: Exploration, Environment, Analysis, In press. Corazao, J.C., Bay, D., Beckie, R., Klein, B., Mayer, K.U., Smith, J.L., Wilson, G.W., Brienne, S. and Letient, H., 2007. Design and construction of field-scale waste rock test piles at the Antamina Mine, Peru. Geotechnical News, 25(1): 49-53. Dockrey, J.W., 2010. Microbiology and geochemistry of neutral pH waste rock from the Antamina Mine, Peru, University of British Columbia, Vancouver, British Columbia, 211 pp. Keon, N.E., Swartz, C.H., Brabander, D.J., Harvey, C. and Hemond, H.F., 2001. Validation of an arsenic sequential extraction method for evaluating mobility in sediments. Environmental Science & Technology, 35(13): 2778-2784. Smith, L. and Beckie, R.D., 2003. Hydrologic and geochemical transport processes in mine waste rock. In: J.L. Jambor, D.W. Blowes and A.I.M. Ritchie (Editors), Environmental aspects of mine wastes. Short course series. Mineralogical Association of Canada, Ottawa, pp. 51-72.  


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