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Geochemical modeling of water-rock interactions in mining environments

Geochemical modeling is a powerful tool for evaluating geochemical processes in mining environments. Properly constrained and judiciously applied, modeling can provide valuable insights into processes controlling the release, transport, and fate of contaminants in mine drainage. This chapter contains 1) an overview of geochemical modeling, 2) discussion of the types of models and computer programs used, 3) description of a procedure for screening water analyses for modeling input, and 4) examples of the application of modeling for interpreting geochemical processes in mining environments. Three general strategies in current use to interpret water-rock interactions are statistical analysis, “inverse” modeling, and “forward” modeling. Multivariate correlation analysis, factor analysis, cluster analysis, and other statistical techniques can group water-chemistry data into sets that may relate to hydrogeochemical processes (Drever, 1988; Puckett and Bricker, 1992). In the field of geochemical exploration, statistical analysis is used widely to treat large data sets of rock and sediment chemistry (e.g., Garrett, 1989). No physical or chemical principles are involved directly in these statistical treatments, hence they are not considered further in this chapter. Nevertheless, statistical analysis can be a useful tool in organizing complex geochemical data for interpretation.

Book chapter

Microbial sulfate reduction and metal attenuation in pH 4 acid mine water

Sediments recovered from the flooded mine workings of the Penn Mine, a Cu-Zn mine abandoned since the early 1960s, were cultured for anaerobic bacteria over a range of pH (4.0 to 7.5). The molecular biology of sediments and cultures was studied to determine whether sulfate-reducing bacteria (SRB) were active in moderately acidic conditions present in the underground mine workings. Here we document multiple, independent analyses and show evidence that sulfate reduction and associated metal attenuation are occurring in the pH-4 mine environment. Water-chemistry analyses of the mine water reveal: (1) preferential complexation and precipitation by H2S of Cu and Cd, relative to Zn; (2) stable isotope ratios of 34S/32S and 18O/16O in dissolved SO4 that are 2-3 ??? heavier in the mine water, relative to those in surface waters; (3) reduction/oxidation conditions and dissolved gas concentrations consistent with conditions to support anaerobic processes such as sulfate reduction. Scanning electron microscope (SEM) analyses of sediment show 1.5-micrometer, spherical ZnS precipitates. Phospholipid fatty acid (PLFA) and denaturing gradient gel electrophoresis (DGGE) analyses of Penn Mine sediment show a high biomass level with a moderately diverse community structure composed primarily of iron- and sulfate-reducing bacteria. Cultures of sediment from the mine produced dissolved sulfide at pH values near 7 and near 4, forming precipitates of either iron sulfide or elemental sulfur. DGGE coupled with sequence and phylogenetic analysis of 16S rDNA gene segments showed populations of Desulfosporosinus and Desulfitobacterium in Penn Mine sediment and laboratory cultures. ?? 2007 Church et al; licensee BioMed Central Ltd.

Geochemical Transactions

Using an unmanned aerial vehicle water sampler to gather data in a pit-lake mining environment to assess closure and monitoring

Residual pit lakes from mining are often dangerous to sample for water quality. Thus, pit lakes may be rarely (or never) sampled. This study developed new technology in which water-sampling devices, mounted on an unmanned aerial vehicle (UAV), were used to sample three pit lakes in Nevada, USA, during 1 week in 2017. Water-quality datasets from two of the three pit lakes on public lands, Dexter and Clipper, are presented here. The current conditions of the Dexter pit lake were assessed by examining cation and anion concentration changes that have occurred over a 17-year period since the pit lake was last sampled in 2000. Data gathered during this sampling campaign assessed 2017 conditions of the Dexter and Clipper pit lakes by comparing constituent concentrations to the Nevada Division of Environmental Protection (NDEP) pit lake water-quality requirements, indicating that selenium concentrations exceeded regulatory standards. We compared our sampling data for Dexter lake to prior water-quality data from the Dexter pit lake collected in 1999 and 2000. This comparison for the Dexter pit lake indicates that evapoconcentration may have caused increasing cation and anion concentrations. This UAV sampling approach can potentially incorporate the use of additional multiparameter probes: pH, oxygen concentration, turbidity, or chlorophyll. Some limitations of this UAV water-sampling methodology are battery duration, weather conditions, and payload capacity.

Nevada

Questa Baseline and Pre-Mining Ground-Water Quality Investigation. 24. Seismic Refraction Tomography for Volume Analysis of Saturated Alluvium in the Straight Creek Drainage and Its Confluence With Red River, Taos County, New Mexico

As part of a research effort directed by the New Mexico Environment Department to determine pre-mining water quality of the Red River at a molybdenum mining site in northern New Mexico, we used seismic refraction tomography to create subsurface compressional-wave velocity images along six lines that crossed the Straight Creek drainage and three that crossed the valley of Red River. Field work was performed in June 2002 (lines 1-4) and September 2003 (lines 5-9). We interpreted the images to determine depths to the water table and to the top of bedrock. Depths to water and bedrock in boreholes near the lines correlate well with our interpretations based on seismic data. In general, the images suggest that the alluvium in this area has a trapezoidal cross section. Using a U.S. Geological Survey digital elevation model grid of surface elevations of this region and the interpreted elevations to water table and bedrock obtained from the seismic data, we generated new models of the shape of the buried bedrock surface and the water table through surface interpolation and extrapolation. Then, using elevation differences between the two grids, we calculated volumes of dry and wet alluvium in the two drainages. The Red River alluvium is about 51 percent saturated, whereas the much smaller volume of alluvium in the tributary Straight Creek is only about 18 percent saturated. When combined with average ground-water velocity values, the information we present can be used to determine discharge of Straight Creek into Red River relative to the total discharge of Red River moving past Straight Creek. This information will contribute to more accurate models of ground-water flow, which are needed to determine the pre-mining water quality in the Red River.

Scientific Investigations Report

Sequestration of phosphorus by acid mine drainage floc

Solubilization and transport of phosphorus (P) to the water environment is a critical environmental issue. Flocs resulting from neutralizing acid mine drainage (AMD) were tested as a possible low-cost amendment to reduce the loss of soluble P from agricultural fields and animal wastewater. Flocs were prepared by neutralizing natural and synthetic solutions of AMD with limestone, lime, ammonium hydroxide, and sodium hydroxide. Phosphorus sequestration was tested in three distinct environments: water, soil, and manure storage basins. In water, flocs prepared from AMD adsorbed 10 to 20 g P kg −1 dry floc in equilibrium with 1 mg L −1 soluble P. Similar results were observed for both Fe-based and Al-based synthetic flocs. A local soil sample adsorbed about 0.1 g P kg −1 , about two orders of magnitude less. The AMD-derived flocs were mixed with a high-P soil at 5 to 80 g floc kg −1 soil, followed by water and acid (Mehlich-1) extractions. All flocs performed similarly. About 70% of the water-extractable P was sequestered by the floc when applied at a rate of 20 g floc kg −1 soil, whereas plant-available P only decreased by about 30%. Under anaerobic conditions simulating manure storage basins, all AMD flocs reduced soluble P by greater than 95% at a rate of 0.2 g floc g −1 rainbow trout ( Oncorhynchus mykiss ) manure. These findings indicate that AMD flocs could be an effective agent for preventing soluble P losses from soil and manure to the water environment, while at the same time decreasing the costs associated with AMD treatment.

Journal of Environmental Quality

Questa baseline and pre-mining ground-water quality investigation. 5. Well installation, water-level data, and surface- and ground-water geochemistry in the Straight Creek drainage basin, Red River Valley, New Mexico, 2001-03

The U.S. Geological Survey, in cooperation with the New Mexico Environment Department, is investigating the pre-mining ground-water chemistry at the Molycorp molybdenum mine in the Red River Valley, northern New Mexico. The primary approach is to determine the processes controlling ground-water chemistry at an unmined, off-site, proximal analog. The Straight Creek drainage basin, chosen for this purpose, consists of the same quartz-sericite-pyrite altered andesitic and rhyolitic volcanic rock of Tertiary age as the mine site. The weathered and rugged volcanic bedrock surface is overlain by heterogeneous debris-flow deposits that interfinger with alluvial deposits near the confluence of Straight Creek and the Red River. Pyritized rock in the upper part of the drainage basin is the source of acid rock drainage (pH 2.8-3.3) that infiltrates debris-flow deposits containing acidic ground water (pH 3.0-4.0) and bedrock containing water of circumneutral pH values (5.6-7.7). Eleven observation wells were installed in the Straight Creek drainage basin. The wells were completed in debris-flow deposits, bedrock, and interfingering debris-flow and Red River alluvial deposits. Chemical analyses of ground water from these wells, combined with chemical analyses of surface water, water-level data, and lithologic and geophysical logs, provided information used to develop an understanding of the processes contributing to the chemistry of ground water in the Straight Creek drainage basin. Surface- and ground-water samples were routinely collected for determination of total major cations and selected trace metals; dissolved major cations, selected trace metals, and rare-earth elements; anions and alkalinity; and dissolved-iron species. Rare-earth elements were determined on selected samples only. Samples were collected for determination of dissolved organic carbon, mercury, sulfur isotopic composition (34S and 18O of sulfate), and water isotopic composition (2H and 18O) during selected samplings. One set of ground-water samples was collected for helium-3/tritium and chlorofluorocarbon (CFC) age dating. Several lines of evidence indicate that surface water is the primary input to the Straight Creek ground-water system. Straight Creek streamflow and water levels in wells closest to the apex of the Straight Creek debris fan and closest to Straight Creek itself appear to respond to the same seasonal inputs. Oxygen and hydrogen isotopic compositions in Straight Creek surface water and ground water are similar, and concentrations of most dissolved constituents in most Straight Creek surface-water and shallow (debris-flow and alluvial) aquifer ground-water samples correlate strongly with sulfate (concentrations decrease linearly with sulfate in a downgradient direction). After infiltration of surface water, dilution along the flow path is the dominant mechanism controlling ground-water chemistry. However, concentrations of some constituents can be higher in ground water than can be accounted for by concentrations in Straight Creek surface water, and additional sources of these constituents must therefore be inferred. Constituents for which concentrations in ground water can be high relative to surface water include calcium, magnesium, strontium, silica, sodium, and potassium in ground water from debris-flow and alluvial aquifers and manganese, calcium, magnesium, strontium, sodium, and potassium in ground water from the bedrock aquifer. All ground water is a calcium sulfate type, often at or near gypsum saturation because of abundant gypsum in the aquifer material developed from co-existing calcite and pyrite mineralization. Calcite dissolution, the major buffering mechanism for bedrock aquifer ground water, also contributes to relatively higher calcium concentrations in some ground water. The main source of the second most abundant cation, magnesium, is probably dissolution of magnesium-rich carbonates or silicates.

New Mexico

Questa baseline and pre-mining ground-water quality investigation. 14. Interpretation of ground-water geochemistry in catchments other than the Straight Creek catchment, Red River Valley, Taos County, New Mexico, 2002-2003

The U.S. Geological Survey, in cooperation with the New Mexico Environment Department, is investigating the pre-mining ground-water chemistry at the Molycorp molybdenum mine in the Red River Valley, New Mexico. The primary approach is to determine the processes controlling ground-water chemistry at an unmined, off-site but proximal analog. The Straight Creek catchment, chosen for this purpose, consists of the same Tertiary-age quartz-sericite-pyrite altered andesite and rhyolitic volcanics as the mine site. Straight Creek is about 5 kilometers east of the eastern boundary of the mine site. Both Straight Creek and the mine site are at approximately the same altitude, face south, and have the same climatic conditions. Thirteen wells in the proximal analog drainage catchment were sampled for ground-water chemistry. Eleven wells were installed for this study and two existing wells at the Advanced Waste-Water Treatment (AWWT) facility were included in this study. Eight wells were sampled outside the Straight Creek catchment: one each in the Hansen, Hottentot, and La Bobita debris fans, four in a well cluster in upper Capulin Canyon (three in alluvial deposits and one in bedrock), and an existing well at the U.S. Forest Service Questa Ranger Station in Red River alluvial deposits. Two surface waters from the Hansen Creek catchment and two from the Hottentot drainage catchment also were sampled for comparison to ground-water compositions. In this report, these samples are evaluated to determine if the geochemical interpretations from the Straight Creek ground-water geochemistry could be extended to other ground waters in the Red River Valley , including the mine site. Total-recoverable major cations and trace metals and dissolved major cations, selected trace metals, anions, alkalinity; and iron-redox species were determined for all surface- and ground-water samples. Rare-earth elements and low-level As, Bi, Mo, Rb, Re, Sb, Se, Te, Th, U, Tl, V, W, Y, and Zr were determined on selected samples. Dissolved organic carbon (DOC), mercury, sulfate stable isotope composition (δ 34 S and δ 18 O of sulfate), stable isotope composition of water (δ 2 H and δ 18 O of water) were measured for selected samples. Chlorofluorocarbons (CFC) and 3 He and 3 H were measured for age dating on selected samples. Linear regressions from the Straight Creek ground-water data were used to compare ground-water chemistry trends in non-Straight Creek ground waters with Straight Creek alluvial ground-water chemistry dilution trends. Most of the solute trends for the ground waters are similar to those for Straight Creek but there are some notable exceptions. In lithologies that contain substantial pyrite mineralization, acid waters form with similar chemistries to those in Straight Creek and all the waters tend to be calcium-sulfate type. Hottentot ground waters contain substantially lower calcium concentrations relative to those in Straight Creek. This anomaly results from the exposure of rhyolite porphyry in the Hottentot scar and weathering zone. The rhyolite contains less calcium than the altered andesites and tuffs in the Straight Creek catchment and probably does not have the abundant gypsum and calcite. The Hansen ground waters have reached gypsum saturation and have similar calcium, magnesium, and beryllium concentrations as Straight Creek ground waters but have lower concentrations of fluoride, manganese, zinc, cobalt, nickel, copper, and lithium. Lower concentrations of elements related to mineralization at Hansen likely reflect the more distal location of Hansen with respect to intrusive centers that provided the heat source for hydrothermal alteration. The other ground water with water chemistry trends that are outside the Straight Creek trends was from an alluvial well from Capulin Canyon (CC2A). Although it had pH values near 6.0 and most major ions similar to the other Capulin Canyon ground waters, it contained high concentrations of fluoride, manganese, aluminum, iron, beryllium, and zinc similar to a mineralized zone and had low alkalinity. Saturation indices indicate that solubility constraints continue to provide upper limits on some solute concentrations. Siderite, ferrihydrite, calcite, gypsum, rhodochrosite, and barite provide limits for concentrations of Fe(II), Fe(III), Ca, Mn, and Ba, respectively. Beryllium concentrations may be subject to an upper concentration limit by the solubility of Be(OH) 2 but these concentrations probably are not reached in the ground waters. Ground-water isotopic data were consistent with the meteoric water line estimated for precipitation in the Red River Valley, indicating that all the ground waters examined in this study were meteoric, recent in origin, and showed no substantial indication of evaporation. Tritium-helium-3 and chlorofluorocarbon (CFC) age dating were partially successful. Generally, dates were consistent with location and depth of wells. Two samples had good agreement between CFC dates and tritium-helium dates, whereas a third reflected either substantial mixing with younger or older waters or complications arising from excess helium-4. The well at La Bobita appeared to contain a large component of modern water, most likely as a result of mixing with water from Red River alluvial deposits.

New Mexico

Questa baseline and pre-mining ground-water quality investigation 22 — Groundwater budget for the Straight Creek drainage basin, Red River Valley, New Mexico, with a section on Sulphur Gulch water budget

In April 2001, the U.S. Geological Survey (USGS) and the New Mexico Environment Department (NMED) began a cooperative study to infer the pre-mining ground-water chemistry at the Molycorp molybdenum mine site in the Red River Valley. The Molycorp mine has been in operation since the 1920s. Because ground-water conditions prior to mining are not available, sites analogous to the pre-mining conditions at the mine site must be studied to infer those pre-mining conditions. The Straight Creek drainage basin (watershed) was selected as the primary analog site for this study because of its similar terrain and geology to the mine site, accessibility, potential for well construction, and minimal anthropogenic activity. The purpose of this report is to present results of a water-budget analysis of the debris-flow aquifer in the Straight Creek watershed. The water budget is based on mean annual conditions and is assumed to be steady state. For this study, the Straight Creek watershed was divided into sub-watersheds on the basis of locations of seismic lines, which were used to calculate cross-section area through the Straight Creek debris-flow deposits and underlying fractured and weathered bedrock (regolith). Water-budget components were calculated for areas upstream from and between the seismic lines. Components of the water budget were precipitation, evapotranspiration, surface-water flow, and ground-water flow under a steady-state mean annual condition. Watershed yield, defined as precipitation minus evapotranspiration, was separated into surface-water flow, ground-water flow through the debris-flow deposits and regolith, and ground-water flow through fractured bedrock. The approach to this calculation was to use Darcy's Law to calculate the flow through the cross-section area of the saturated debris-flow deposits and underlying regolith as defined by the interpreted seismic data. The amount of watershed yield unaccounted for through this section then was attributed to either surface-water flow or the component of ground-water flow through fractured bedrock. The inflow to the watershed, calculated to be 701 gallons per minute, is from precipitation. The calculated outflow from the watershed at or upstream from seismic-line 5 (the downstream-most line in Straight Creek prior to entering the Red River Valley) is 540 gallons per minute of evapotranspiration in the watershed upstream from line 5 (77.0 percent of precipitation), 5 gallons per minute of surface-water flow (0.7 percent of precipitation), 122 gallons per minute of ground-water flow through the debris-flow deposits and underlying regolith defined by the seismic data (17.4 percent of precipitation), and 34 gallons per minute of ground-water flow through fractured bedrock below the defined seismic line (4.9 percent of precipitation). The ground-water flow through the alluvium and inter-tonguing debris-flow deposits of the Red River Valley was calculated to be 5,227 gallons per minute at seismic-line 7, the first seismic line in the Red River Valley downstream from Straight Creek. The water budget indicates the amount of ground-water flow that enters the Red River alluvium from the debris-flow deposits and regolith in Straight Creek is small (about 2.3 percent; 122 gallons per minute) compared to the volume of flow that moves through the Red River alluvium. The total amount of ground-water flow from Straight Creek (156 gallons per minute; 122 gallons per minute from debris-flow deposits and regolith plus 34 gallons per minute through fractured bedrock) is about 3.0 percent of the ground-water flow calculated at line 7 for the Red River alluvium.

New Mexico

Evaluation of airborne thermal infrared imagery for locating mine drainage sites in the Lower Kettle Creek and Cooks Run Basins, Pennsylvania, USA

High-resolution airborne thermal infrared (TIR) imagery data were collected over 90.6 km 2 (35 mi 2 ) of remote and rugged terrain in the Kettle Creek and Cooks Run Basins, tributaries of the West Branch of the Susquehanna River in north-central Pennsylvania. The purpose of this investigation was to evaluate the effectiveness of TIR for identifying sources of acid mine drainage (AMD) associated with abandoned coal mines. Coal mining from the late 1800s resulted in many AMD sources from abandoned mines in the area. However, very little detailed mine information was available, particularly on the source locations of AMD sites. Potential AMD sources were extracted from airborne TIR data employing custom image processing algorithms and GIS data analysis. Based on field reconnaissance of 103 TIR anomalies, 53 sites (51%) were classified as AMD. The AMD sources had low pH (<4) and elevated concentrations of iron and aluminum. Of the 53 sites, approximately 26 sites could be correlated with sites previously documented as AMD. The other 27 mine discharges identified in the TIR data were previously undocumented. This paper presents a summary of the procedures used to process the TIR data and extract potential mine drainage sites, methods used for field reconnaissance and verification of TIR data, and a brief summary of water-quality data.

Pennsylvania

Evaluation of airborne thermal infrared imagery for locating mine drainage sites in the Lower Youghiogheny River Basin, Pennsylvania, USA

Nighttime high-resolution airborne thermal infrared imagery (TIR) data were collected in the predawn hours during Feb 5-8 and March 11-12, 1999, from a helicopter platform for 72.4 km of the Youghiogheny River, from Connellsville to McKeesport, in southwestern Pennsylvania. The TIR data were used to identify sources of mine drainage from abandoned mines that discharge directly into the Youghiogheny River. Image-processing and geographic information systems (GIS) techniques were used to identify 70 sites within the study area as possible mine drainage sources. The combination of GIS datasets and the airborne TIR data provided a fast and accurate method to target the possible sources. After field reconnaissance, it was determined that 24 of the 70 sites were mine drainage. This paper summarizes: the procedures used to process the TIR data and extract potential mine-drainage sites; methods used for verification of the TIR data; a discussion of factors affecting the TIR data; and a brief summary of water quality.

Pennsylvania

Passive aerobic treatment of net-alkaline, iron-laden drainage from a flooded underground anthracite mine, Pennsylvania, USA

This report evaluates the results of a continuous 4.5-day laboratory aeration experiment and the first year of passive, aerobic treatment of abandoned mine drainage (AMD) from a typical flooded underground anthracite mine in eastern Pennsylvania, USA. During 1991-2006, the AMD source, locally known as the Otto Discharge, had flows from 20 to 270 L/s (median 92 L/s) and water quality that was consistently suboxic (median 0.9 mg/L O2) and circumneutral (pH ??? 6.0; net alkalinity >10) with moderate concentrations of dissolved iron and manganese and low concentrations of dissolved aluminum (medians of 11, 2.2, and <0.2 mg/L, respectively). In 2001, the laboratory aeration experiment demonstrated rapid oxidation of ferrous iron (Fe 2+) without supplemental alkalinity; the initial Fe2+ concentration of 16.4 mg/L decreased to less than 0.5 mg/L within 24 h; pH values increased rapidly from 5.8 to 7.2, ultimately attaining a steady-state value of 7.5. The increased pH coincided with a rapid decrease in the partial pressure of carbon dioxide (PCO2) from an initial value of 10 -1.1atm to a steady-state value of 10-3.1atm. From these results, a staged aerobic treatment system was conceptualized consisting of a 2 m deep pond with innovative aeration and recirculation to promote rapid oxidation of Fe2+, two 0.3 m deep wetlands to facilitate iron solids removal, and a supplemental oxic limestone drain for dissolved manganese and trace-metal removal. The system was constructed, but without the aeration mechanism, and began operation in June 2005. During the first 12 months of operation, estimated detention times in the treatment system ranged from 9 to 38 h. However, in contrast with 80-100% removal of Fe2+ over similar elapsed times during the laboratory aeration experiment, the treatment system typically removed less than 35% of the influent Fe2+. Although concentrations of dissolved CO2 decreased progressively within the treatment system, the PCO2 values for treated effluent remained elevated (10-2.4 to 10-1.7atm). The elevated PCO 2 maintained the pH within the system at values less than 7 and hence slowed the rate of Fe2+ oxidation compared to the aeration experiment. Kinetic models of Fe2+ oxidation that consider effects of pH and dissolved O2 were incorporated in the geochemical computer program PHREEQC to evaluate the effects of detention time, pH, and other variables on Fe2+ oxidation and removal rates. These models and the laboratory aeration experiment indicate that performance of this and other aerobic wetlands for treatment of net-alkaline AMD could be improved by aggressive, continuous aeration in the initial stage to decrease PCO 2, increase pH, and accelerate Fe2+ oxidation. ?? 2007 Springer-Verlag.

Mine Water and the Environment

Downflow limestone beds for treatment of net-acidic, oxic, iron-laden drainage from a flooded Anthracite Mine, Pennsylvania, USA: 1. Field evaluation

Passive-treatment systems that route acidic mine drainage (AMD) through crushed limestone and/or organic-rich substrates have been used to remove the acidity and metals from various AMD sources, with a wide range of effects. This study evaluates treatment of net-acidic, oxic, iron-laden AMD with limestone alone, and with organic-rich compost layered with the limestone. In the fall of 2003, a treatment system consisting of two parallel, 500-m2 downflow cells followed by a 400-m2 aerobic settling pond and wetland was installed to neutralize the AMD from the Bell Mine, a large source of AMD and baseflow to the Schuylkill River in the Southern Anthracite Coalfield, in east-central Pennsylvania. Each downflow cell consisted of a lower substrate layer of 1,090 metric tons (t) of dolomitic limestone (60 wt% CaCO3) and an upper layer of 300 t of calcitic limestone (95 wt% CaCO3); one of the downflow cells also included a 0.3 m thick layer of mushroom compost over the limestone. AMD with pH of 3.5-4.3, dissolved oxygen of 6.6-9.9 mg/L, iron of 1.9-5.4 mg/L, and aluminum of 0.8-1.9 mg/L flooded each cell to a depth 0.65 m above the treatment substrates, percolated through the substrates to underlying, perforated outflow pipes, and then flowed through the aerobic pond and wetland before discharging to the Schuylkill River. Data on the flow rates and chemistry of the effluent for the treatment system indicated substantial neutralization by the calcitic limestone but only marginal effects from the dolomitic limestone or compost. Because of its higher transmissivity, the treatment cell containing only limestone neutralized greater quantities of acidity than the cell containing compost and limestone. On average, the treatment system removed 62% of the influent acidity, 47% of the dissolved iron, 34% of the dissolved aluminum, and 8% of the dissolved manganese. Prior to treatment of the Bell Discharge, the Schuylkill River immediately below its confluence with the discharge had pH as low as 4.1 and supported few, if any, fish. However, within the first year of treatment, the pH was maintained at values of 5.0 or greater and native brook trout were documented immediately below the treatment system, though not above. ?? 2008 Springer-Verlag.

Mine Water and the Environment

Downflow limestone beds for treatment of net-acidic, oxic, iron-laden drainage from a flooded anthracite mine, Pennsylvania, USA: 2. Laboratory evaluation

Acidic mine drainage (AMD) containing elevated concentrations of dissolved iron and other metals can be neutralized to varying degrees by reactions with limestone in passive treatment systems. We evaluated the chemical and mineralogical characteristics and the effectiveness of calcitic and dolomitic limestone for the neutralization of net-acidic, oxic, iron-laden AMD from a flooded anthracite mine. The calcitic limestone, with CaCO3 and MgCO3 contents of 99.8 and <0.1 wt%, respectively, and the dolomitic limestone, with CaCO3 and MgCO3 contents of 60.3 and 40.2 wt%, were used to construct a downflow treatment system in 2003 at the Bell Mine, a large source of AMD and baseflow to the Schuylkill River in the Southern Anthracite Coalfield, in east-central Pennsylvania. In the winter of 2002-2003, laboratory neutralization-rate experiments evaluated the evolution of effluent quality during 2 weeks of continuous contact between AMD from the Bell Mine and the crushed calcitic or dolomitic limestone in closed, collapsible containers (cubitainers). The cubitainer tests showed that: (1) net-alkaline effluent could be achieved with detention times greater than 3 h, (2) effluent alkalinities and associated dissolution rates were equivalent for uncoated and Fe(OH)3-coated calcitic limestone, and (3) effluent alkalinities and associated dissolution rates for dolomitic limestone were about half those for calcitic limestone. The dissolution rate data for the cubitainer tests were used with data on the volume of effuent and surface area of limestone in the treatment system at the Bell Mine to evaluate the water-quality data for the first 1.5 years of operation of the treatment system. These rate models supported the interpretation of field results and indicated that treatment benefits were derived mainly from the dissolution of calcitic limestone, despite a greater quantity of dolomitic limestone within the treatment system. The dissolution-rate models were extrapolated on a decadal scale to indicate the expected decreases in the mass of limestone and associated alkalinities resulting from the long-term reaction of AMD with the treatment substrate. The models indicated the calcitic limestone would need to be replenished approaching the 5-year anniversary of treatment operations to maintain net-alkaline effluent quality. ?? 2008 Springer-Verlag.

Mine Water and the Environment

Spatially detailed quantification of metal loading for decision making: Metal mass loading to American fork and Mary Ellen Gulch, Utah

Effective remediation requires an understanding of the relative contributions of metals from all sources in a catchment, and that understanding must be based on a spatially detailed quantification of metal loading. A traditional approach to quantifying metal loading has been to measure discharge and chemistry at a catchment outlet. This approach can quantify annual loading and the temporal changes in load, but does not provide the needed spatial detail to evaluate specific sources, which is needed to support remediation decisions. A catchment or mass-loading approach provides spatial detail by combining tracer-injection and synoptic-sampling methods to quantify loading. Examples of studies in American Fork, Utah, and its tributary Mary Ellen Gulch illustrate this different approach. The mass-loading study in American Fork treated Mary Ellen Gulch as a single inflow. From that point of view, Mary Ellen Gulch was one of the greatest sources of Fe, Mn, Zn, and colloidal Pb loads to American Fork. But when Mary Ellen Gulch was evaluated in a separate catchment study, the detailed locations of metal loading were identified, and the extent of metal attenuation upstream from the mouth of Mary Ellen Gulch was quantified. The net, instantaneous load measured at the mouth of Mary Ellen Gulch for remediation planning would greatly underestimate the contributions of principal sources within the catchment. Extending the detailed sampling downstream from Mary Ellen Gulch indicated the possibility of diffuse groundwater inflow from Mary Ellen Gulch to American Fork. Comparing loads for Mary Ellen Gulch in the two studies indicates that metal loads could be substantially underestimated for planning purposes without the detailed catchment approach for the low-flow conditions in these studies. A mass-loading approach provides both the needed quantification of metal loading and the spatial detail to guide remediation decisions that would be the most effective in the catchments.

Mine Water and the Environment

Abandoned mine drainage in the Swatara Creek Basin, southern anthracite coalfield, Pennsylvania, USA: 1. stream quality trends coinciding with the return of fish

Acidic mine drainage (AMD) from legacy anthracite mines has contaminated Swatara Creek in eastern Pennsylvania. Intermittently collected base-flow data for 1959&ndash;1986 indicate that fish were absent immediately downstream from the mined area where pH ranged from 3.5 to 7.2 and concentrations of sulfate, dissolved iron, and dissolved aluminum were as high as 250, 2.0, and 4.7 mg/L, respectively. However, in the 1990s, fish returned to upper Swatara Creek, coinciding with the implementation of AMD treatment (limestone drains, limestone diversion wells, limestone sand, constructed wetlands) in the watershed. During 1996&ndash;2006, as many as 25 species of fish were identified in the reach downstream from the mined area, with base-flow pH from 5.8 to 7.6 and concentrations of sulfate, dissolved iron, and dissolved aluminum as high as 120, 1.2, and 0.43 mg/L, respectively. Several of the fish taxa are intolerant of pollution and low pH, such as river chub (Nocomis icropogon) and longnose dace (Rhinichthys cataractae). Cold-water species such as brook trout (Salvelinus fontinalis) and warm-water species such as rock bass (Ambloplites rupestris) varied in predominance depending on stream flow and stream temperature. Storm flow data for 1996&ndash;2007 indicated pH, alkalinity, and sulfate concentrations decreased as the stream flow and associated storm-runoff component increased, whereas iron and other metal concentrations were poorly correlated with stream flow because of hysteresis effects (greater metal concentrations during rising stage than falling stage). Prior to 1999, pH\5.0 was recorded during several storm events; however, since the implementation of AMD treatments, pH has been maintained near neutral. Flow-adjusted trends for1997&ndash;2006 indicated significant increases in calcium; decreases in hydrogen ion, dissolved aluminum, dissolved and total manganese, and total iron; and no change in sulfate or dissolved iron in Swatara Creek immediately downstream from the mined area. The increased pH and calcium from limestone in treatment systems can be important for mitigating toxic effects of dissolved metals. Thus, treatment of AMD during the 1990s improved pH buffering, reduced metals transport, and helped to decrease metals toxicity to fish.

Pennsylvania

Abandoned mine drainage in the Swatara Creek Basin, southern anthracite coalfield, Pennsylvania, USA: 2. performance of treatment systems

A variety of passive and semi-passive treatment systems were constructed by state and local agencies to neutralize acidic mine drainage (AMD) and reduce the transport of dissolved metals in the upper Swatara Creek Basin in the Southern Anthracite Coalfield in eastern Pennsylvania. To evaluate the effectiveness of selected treatment systems installed during 1995&ndash;2001, the US Geological Survey collected water-quality data at upstream and downstream locations relative to each system eight or more times annually for a minimum of 3 years at each site during 1996&ndash;2007. Performance was normalized among treatment types by dividing the acid load removed by the size of the treatment system. For the limestone sand, open limestone channel, oxic limestone drain, anoxic limestone drain (ALD), and limestone diversion well treatment systems, the size was indicated by the total mass of limestone; for the aerobic wetland systems, the size was indicated by the total surface area of ponds and wetlands. Additionally, the approximate cost per tonne of acid treated over an assumed service life of 20 years was computed. On the basis of these performance metrics, the limestone sand, ALD, oxic limestone drain, and limestone diversion wells had similar ranges of acid-removal efficiency and cost efficiency. However, the open limestone channel had lower removal efficiency and higher cost per ton of acid treated. The wetlands effectively attenuated metals transport but were relatively expensive considering metrics that evaluated acid removal and cost efficiency. Although the water-quality data indicated that all treatments reduced the acidity load from AMD, the ALD was most effective at producing near-neutral pH and attenuating acidity and dissolved metals. The diversion wells were effective at removing acidity and increasing pH of downstream water and exhibited unique potential to treat moderate to high flows associated with storm flow conditions.

Pennsylvania

AMDTreat 5.0+ with PHREEQC titration module to compute caustic chemical quantity, effluent quality, and sludge volume

Alkaline chemicals are commonly added to discharges from coal mines to increase pH and decrease concentrations of acidity and dissolved aluminum, iron, manganese, and associated metals. The annual cost of chemical treatment depends on the type and quantities of chemicals added and sludge produced. The AMDTreat computer program, initially developed in 2003, is widely used to compute such costs on the basis of the user-specified flow rate and water quality data for the untreated AMD. Although AMDTreat can use results of empirical titration of net-acidic or net-alkaline effluent with caustic chemicals to accurately estimate costs for treatment, such empirical data are rarely available. A titration simulation module using the geochemical program PHREEQC has been incorporated with AMDTreat 5.0+ to improve the capability of AMDTreat to estimate: (1) the quantity and cost of caustic chemicals to attain a target pH, (2) the chemical composition of the treated effluent, and (3) the volume of sludge produced by the treatment. The simulated titration results for selected caustic chemicals (NaOH, CaO, Ca(OH)2, Na2CO3, or NH3) without aeration or with pre-aeration can be compared with or used in place of empirical titration data to estimate chemical quantities, treated effluent composition, sludge volume (precipitated metals plus unreacted chemical), and associated treatment costs. This paper describes the development, evaluation, and potential utilization of the PHREEQC titration module with the new AMDTreat 5.0+ computer program available at http://www.amd.osmre.gov/.

Mine Water and the Environment

Exploration of diffuse and discrete sources of acid mine drainage to a headwater mountain stream in Colorado, USA

We investigated the impact of acid mine drainage (AMD) contamination from the Minnesota Mine, an inactive gold and silver mine, on Lion Creek, a headwater mountain stream near Empire, Colorado. The objective was to map the sources of AMD contamination, including discrete sources visible at the surface and diffuse inputs that were not readily apparent. This was achieved using geochemical sampling, in-stream and in-seep fluid electrical conductivity (EC) logging, and electrical resistivity imaging (ERI) of the subsurface. The low pH of the AMD-impacted water correlated to high fluid EC values that served as a target for the ERI. From ERI, we identified two likely sources of diffuse contamination entering the stream: (1) the subsurface extent of two seepage faces visible on the surface, and (2) rainfall runoff washing salts deposited on the streambank and in a tailings pile on the east bank of Lion Creek. Additionally, rainfall leaching through the tailings pile is a potential diffuse source of contamination if the subsurface beneath the tailings pile is hydraulically connected with the stream. In-stream fluid EC was lowest when stream discharge was highest in early summer and then increased throughout the summer as stream discharge decreased, indicating that the concentration of dissolved solids in the stream is largely controlled by mixing of groundwater and snowmelt. Total dissolved solids (TDS) load is greatest in early summer and displays a large diel signal. Identification of diffuse sources and variability in TDS load through time should allow for more targeted remediation options.

Colorado