David L. Fey

Environmental geochemistry of abandoned mercury mines in West-Central Nevada, USA

Abstract The Humboldt River is a closed basin and is the longest river in Nevada. Numerous abandoned Hg mines are located within the basin, and because Hg is a toxic heavy metal, the potential transport of Hg from these mines into surrounding ecosystems, including the Humboldt River, is of environmental concern. Samples of ore, sediment, water, calcines (roasted ore), and leachates of the calcines were analyzed for Hg and other heavy metals to evaluate geochemical dispersion from the mines. Cinnabar-bearing ore samples collected from the mines contain highly elevated Hg concentrations, up to 6.9 %, whereas calcines collected from the mines contain up to 2000 mg Hg/kg. Stream-sediment samples collected within 1 km of the mines contain as much as 170 mg Hg/kg, but those collected distal from the mines (>5 km) contain 8 km from the Humboldt River, and Hg is transported and diluted through a large volume of pediment before it reaches the Humboldt River.

Development of a new toxic‐unit model for the bioassessment of metals in streams

Two toxic-unit models that estimate the toxicity of trace-metal mixtures to benthic communities were compared. The chronic criterion accumulation ratio (CCAR), a modification of biotic ligand model (BLM) outputs for use as a toxic-unit model, accounts for the modifying and competitive influences of major cations (Ca²(+), Mg²(+), Na(+), K(+), H(+)), anions (HCO₃⁻, CO²⁻₃ ,SO²⁻₄, Cl⁻, S²⁻) and dissolved organic carbon (DOC) in determining the free metal ion available for accumulation on the biotic ligand. The cumulative criterion unit (CCU) model, an empirical statistical model of trace-metal toxicity, considers only the ameliorative properties of Ca²(+) and Mg²(+) (hardness) in determining the toxicity of total dissolved trace metals. Differences in the contribution of a metal (e.g., Cu, Cd, Zn) to toxic units as determined by CCAR or CCU were observed and attributed to how each model incorporates the influences of DOC, pH, and alkalinity. Akaike information criteria demonstrate that CCAR is an improved predictor of benthic macroinvertebrate community metrics as compared with CCU. Piecewise models depict great declines (thresholds) in benthic macroinvertebrate communities at CCAR of 1 or more, while negative changes in benthic communities were detected at a CCAR of less than 1. We observed a 7% reduction in total taxa richness and a 43% decrease in Heptageniid abundance between background (CCAR = 0.1) and the threshold of chronic toxicity on the basis of continuous chronic criteria (CCAR = 1). In this first application of the BLM as a toxic-unit model, we found it superior to CCU.

Porphyry Cu indicator minerals in till as an exploration tool: example from the giant Pebble porphyry Cu-Au-Mo deposit, Alaska, USA

ABSTRACT Porphyry Cu indicator minerals are mineral species in clastic sediments that indicate the presence of mineralization and hydrothermal alteration associated with porphyry Cu and associated skarn deposits. Porphyry Cu indicator minerals recovered from shallow till samples near the giant Pebble Cu-Au-Mo porphyry deposit in SW Alaska, USA, include apatite, andradite garnet, Mn-epidote, visible gold, jarosite, pyrite, and cinnabar. Sulphide minerals other than pyrite are absent from till, most likely due to the oxidation of the till. The distribution of till samples with abundant apatite and cinnabar suggest sources other than the Pebble deposit. With three exceptions, all till samples up-ice of the Pebble deposit contain <10 grains/10kg of garnet (0.25–0.5 mm). Samples in the immediate vicinity of the Pebble deposit contain 10–20 grains, whereas samples with the most grains (>40grains/10kg) are in close proximity to smaller porphyry and skarn occurrences in the region. The distribution of Mn-epidote closely mimics the distribution of garnet in the till samples and further supports the interpretation that these minerals most likely reflect skarns associated with the porphyry deposits. All but two till samples, including those up-ice from the deposit, contain some gold grains. However, tills immediately west and down-ice of Pebble contain more abundant gold grains, and the overall number of grains decreases in the down-ice direction. Furthermore, all samples in the immediate vicinity of Pebble contain more than 65 % pristine and modified grains compared to mostly re-shaped grains in distal samples. The pristine gold in till reflects short transport distances and/or liberation of gold during in-situ weathering of transported chalcopyrite grains. Jarosite is also abundant (1–2 500 grains/10kg) in samples adjacent to and up to 7 km down-ice from the deposit. Most jarosite grains are rounded and preliminary Ar/Ar dates suggest the jarosite formed prior to glaciation and it implies that a supergene cap existed over Pebble West. Assuming this interpretation is accurate, it suggests a shallow level of erosion of the Pebble deposit by glacial processes. Overall the results of this study indicate that porphyry Cu indicator minerals in till samples may be useful in the exploration for porphyry deposits in SW Alaska.

Electrogeochemical sampling with NEOCHIM — results of tests over buried gold deposits

Abstract Electrogeochemical extraction methods are based on the migration of ions in an electric field. Ions present in soil moisture are transported by an applied current into fluids contained in special electrodes placed on the soil. The fluids are then collected and analyzed. Extractions are governed by Faradays and Ohms laws and are modeled by the operation of a simple Hittorf transference apparatus. Calculations show that the volume of soil sampled in an ideal electrogeochemical extraction can be orders of magnitude greater than the volumes used in more popular geochemical extraction methods, although this has not been verified experimentally. chim is a method of in-situ electrogeochemical extraction that was developed in the former Soviet Union and has been tested and applied internationally to exploration for buried mineral deposits. Tests carried out at the United States Geological Survey ( usgs ) indicated that there were problems inherent in the use of chim technology. The cause of the problems was determined to be the diffusion of acid from the conventional electrode into the soil. The neochim electrode incorporates two compartments and a salt bridge in a design that inhibits diffusion of acid and enables the collection of anions or cations. Tests over a gold-enriched vein in Colorado and over buried, Carlin-type, disseminated gold deposits in northern Nevada show that there are similarities and differences between neochim results and those by partial extractions of soils which include simple extractions with water, dilute acids and solutions of salts used as collector fluids in the electrodes. Results of both differ from the results obtained by total chemical digestion. The results indicate that neochim responds to mineralized faults associated with disseminated gold deposits whereas partial and total chemical extraction methods do not. This suggests that faults are favored channels for the upward migration of metals and that neochim may be more effective in exploration for the deposits. It defines anomalies that are often narrow and intense, an observation previously made by chim researchers. The field tests show that neochim is less affected by surface contamination. A test over the Mike disseminated gold deposit indicates that the method may not be effective for locating deposits with impermeable cover. Faradaic extraction efficiencies of 20–30%, or more, are frequently achieved with neochim and the method generally shows good reproducibility, especially in extraction of major cations. However, ions of other metals that are useful in exploration, including Au and As, may be collected in low and temporally variable concentrations. The reason for this variability is unclear and requires further investigation.

An exploration hydrogeochemical study at the giant Pebble porphyry Cu-Au-Mo deposit, Alaska, USA, using high-resolution ICP-MS

A hydrogeochemical study using high resolution ICP-MS was undertaken at the giant Pebble porphyry Cu-Au-Mo deposit and surrounding mineral occurrences. Surface water and groundwater samples from regional background and the deposit area were collected at 168 sites. Rigorous quality control reveals impressive results at low nanogram per litre (ng/l) levels. Sites with pH values below 5.1 are from ponds in the Pebble West area, where sulphide-bearing rubble crop is thinly covered. Relative to other study area waters, anomalous concentrations of Cu, Cd, K, Ni, Re, the REE, Tl, SO42− and F− are present in water samples from Pebble West. Samples from circum-neutral waters at Pebble East and parts of Pebble West, where cover is much thicker, have anomalous concentrations of Ag, As, In, Mn, Mo, Sb, Th, U, V, and W. Low-level anomalous concentrations for most of these elements were also found in waters surrounding nearby porphyry and skarn mineral occurrences. Many of these elements are present in low ng/l concentration ranges and would not have been detected using traditional quadrupole ICP-MS. Hydrogeochemical exploration paired with high resolution ICP-MS is a powerful new tool in the search for concealed deposits.

Predicting toxic effects of copper on aquatic biota in mineralized areas by using the Biotic Ligand Model

The chemical speciation of metals influences their biological effects. The Biotic Ligand Model (BLM) is a computational approach to predict chemical speciation and acute toxicological effects of metals on aquatic biota. Recently, the U.S. Environmental Protection Agency incorporated the BLM into their regulatory waterquality criteria for copper. Results from three different laboratory copper toxicity tests were compared with BLM predictions for simulated test-waters. This was done to evaluate the ability of the BLM to accurately predict the effects of hardness and concentrations of dissolved organic carbon (DOC) and iron on aquatic toxicity. In addition, we evaluated whether the BLM and the three toxicity tests provide consistent results. Comparison of BLM predictions with two types of Ceriodaphnia dubia toxicity tests shows that there is fairly good agreement between predicted LC50 values computed by the BLM and LC50 values determined from the two toxicity tests. Specifically, the effect of increasing calcium concentration (and hardness) on copper toxicity appears to be minimal. Also, there is fairly good agreement between the BLM and the two toxicity tests for test solutions containing elevated DOC, for which the LC50 is 3-to-5 times greater (less toxic) than the LC50 for the lower-DOC test water. This illustrates the protective effects of DOC on copper toxicity and demonstrates the ability of the BLM to predict these protective effects. In contrast, for test solutions with added iron there is a decrease in LC50 values (increase in toxicity) in results from the two C. dubia toxicity tests, and the agreement between BLM LC50 predictions and results from these toxicity tests is poor. The inability of the BLM to account for competitive iron binding to DOC or DOC fractionation may be a significant shortcoming of the BLM for predicting site-specific water-quality criteria in streams affected by iron-rich acidic drainage in mined and mineralized areas. Additional

Metal contamination and post-remediation recovery in the Boulder River watershed, Jefferson County, Montana.

ABSTRACT The legacy of acid mine drainage and toxic trace metals left in streams by historical mining is being addressed by many important yet costly remediation efforts. Monitoring of environmental conditions frequently is not performed but is essential to evaluate remediation effectiveness, determine whether clean-up goals have been met, and assess which remediation strategies are most effective. Extensive pre- and post-remediation data for water and sediment quality for the Boulder River watershed in southwestern Montana provide an unusual opportunity to demonstrate the importance of monitoring. The most extensive restoration in the watershed occurred at the Comet mine on High Ore Creek and resulted in the most dramatic improvement in aquatic habitat. Removal of contaminated sediment and tailings, and stream-channel reconstruction reduced Cd and Zn concentrations in water such that fish are now present, and reduced metal concentrations in streambed sediment by a factor of c. 10, the largest improvement in the district. Waste removals at the Buckeye/Enterprise and Bullion mine sites produced limited or no improvement in water and sediment quality, and acidic drainage from mine adits continues to degrade stream aquatic habitat. Recontouring of hillslopes that had funnelled runoff into the workings of the Crystal mine substantially reduced metal concentrations in Uncle Sam Gulch, but did not eliminate all of the acidic adit drainage. Lead isotopic evidence suggests that the Crystal mine rather than the Comet mine is now the largest source of metals in streambed sediment of the Boulder River. The completed removal actions prevent additional contaminants from entering the stream, but it may take many years for erosional processes to diminish the effects of contaminated sediment already in streams. Although significant strides have been made, additional efforts to seal draining adits or treat the adit effluent at the Bullion and Crystal mines would need to be completed to achieve the desired restoration. SUPPLEMENTARY MATERIAL Analytical data for all post-remediation samples is available at: http://www.geolsoc.org.uk/SUP18344.

TRACE-METAL SOURCES AND THEIR RELEASE FROM MINE WASTES: EXAMPLES FROM HUMIDITY CELL TESTS OF HARD-ROCK MINE WASTE AND FROM WARRIOR BASIN COAL

To assess the potential impact of metal and acid contamination from mine-waste piles, it is important to identify the mineralogic source of trace metals and their mode of occurrence. Microscopic analysis of mine-waste samples from both hard-rock and coalmine waste samples demonstrate a microstructural control, as well as mineralogic control, on the source and release of trace metals into local water systems. The samples discussed herein show multiple periods of sulfide mineralization with varying concentrations of trace metals. In the first case study, two proprietary hard-rock mine-waste samples exposed to a series of humidity cell tests (which simulate intense chemical weathering conditions) generated acid and released trace metals. Some trace elements of interest were: arsenic (45-120 ppm), copper (60-320 ppm), and zinc (30-2,500 ppm). Untested and humidity cell-exposed samples were studied by X-ray diffraction, scanning electron microscope with energy dispersive X-ray (SEM/EDX), and electron microprobe analysis. Studies of one sample set revealed arsenic-bearing pyrite in early iron- and magnesium-rich carbonate-filled microveins, and iron-, copper-, arsenic-, antimony-bearing sulfides in later crosscutting silica-filled microveins. Post humidity cell tests indicated that the carbonate minerals were removed by leaching in the humidity cells, exposing pyrite to oxidative conditions. However, sulfides in the silica-filled veins were more protected. Therefore, the trace metals contained in the sulfides within the silica-filled microveins may be released to the surface and (or) ground water system more slowly over a greater time period. In the second case study, trace metal-rich pyrite-bearing coals from the Warrior Basin, Alabama were analyzed. Arsenic-bearing pyrite was observed in a late-stage pyrite phase in microfaults and microveins that crosscut earlier arsenic-

Geochemical assessment of metals and dioxin in sediment from the San Carlos Reservoir and the Gila, San Carlos, and San Francisco Rivers, Arizona

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Determining the toxicity potential of mine-waste piles

When assessing the environmental impact from mining operations, an immediate question arises about potential impact and toxicity of mine-waste piles. This question is particularly difficult to assess for waste piles on abandoned mine lands in the western United States and coal-waste piles in the eastern United States. In many of these situations, there is no water in direct contact with the piles, except during meteorological events, yet it appears that the pile has caused significant ecological disturbance. For the past several years, scientists at the Colorado School of Mines and the U.S. Geological Survey have been studying the toxicity potential of waste-rock piles. Simple and practical methods have been developed for determining the potential of a waste- rock pile to cause significant contamination. For example, quick inexpensive field leaching tests have been developed that offer an evaluation of acid and trace-metal release from mine-waste material. Additionally, two-dimensional hydrologic and erosion models might be used to assess acid and metal sources and sinks. Such methods are presented for evaluating mine-waste piles from watershed scale, site scale, and microscopic scale, using geophysical, geochemical, and mineralogical methods. Current methods used to determine bioaccessibility and bioavailability of metals from wastes, such as extraction techniques, are described and assessed. Case studies with field and laboratory data illustrate these methods. These applications are used as the basis for a simple decision tree that has been developed to assess the potential impact of a waste-rock pile, and the scientific background that serves as the basis for decisions. Workshop Time: 8:30 am – 4:00 pm, June 1, 2003 Workshop Organizers: Dr. Thomas R. Wildeman Dr. Kathleen S. Smith Dept. of Chemistry & Geochemistry U.S. Geological Survey Colorado School of Mines M.S. 973, Denver Federal Cntr. Golden, CO 80401 Denver, CO 80225-0046 Phone: 303-273-3642 Phone: 303-236-5788 E mail: twildema@mines.edu E mail: ksmith@usgs.gov