Rhenium
<p>Rhenium is one of the rarest elements in Earth’s continental crust; its estimated average crustal abundance is less than 1 part per billion. Rhenium is a…
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Rhenium Chapter P of Critical Mineral Resources of the United States—Economic and Environmental Geology and Prospects for Future Supply Professional Paper 1802-P U.S. Department of the Interior U.S. Geological Survey
Periodic Table of Elements Ta bl e El em en ts Modified from Los Alamos National Laboratory Chemistry Division; available at ://periodic.lanl.gov/images/periodictable.pdf. Cover. Photographs of rhenium and rhenium compounds. Upper left, a single crystal of high-purity (99.999%) rhenium, a remelted rhenium bar, and a 1-cubic-centimeter rhenium cube. Photograph courtesy of Alchemist-hp/CC-BY-NC-ND-3.0 (://commons. wikimedia.org/wiki/File:Rhenium_single_crystal_bar_and_1cm3_cube.jpg). Upper right, rhenium powder. Photograph courtesy of H.C. Starck. Lower left, ammonium perrhenate (NH4ReO4) powder, which is the most widely marketed form of rhenium. Photograph courtesy of Stanford Advanced Materials (://www.samaterials.com/847/ammonium-perrhenate.jpg). Lower right, rheniite (ReS2 ) crystals from high-temperature fumaroles on the Kudryavyy volcano, which is located on Iturup Island in Sakhalinskaya Oblast', Russia. Photograph courtesy of The Arkenstone, iRocks.com (://www.irocks.com/minerals/specimen/42387).
Rhenium By David A. John, Robert R. Seal II, and Désirée E. Polyak Chapter P of Critical Mineral Resources of the United States—Economic and Environmental Geology and Prospects for Future Supply Edited by Klaus J. Schulz, John H. DeYoung, Jr., Robert R. Seal II, and Dwight C. Bradley Professional Paper 1802-P U.S. Department of the Interior U.S. Geological Survey
U.S. Department of the Interior RYAN K. ZINKE, Secretary U.S. Geological Survey William H. Werkheiser, Acting Director U.S. Geological Survey, Reston, Virginia: 2017 For more information on the USGS—the Federal source for science about the Earth, its natural and living resources, natural hazards, and the environment—visit ://www.usgs.gov or call 1-888-ASK-USGS. For an overview of USGS information products, including maps, imagery, and publications, visit ://store.usgs.gov/. Any use of trade, firm, or product names is for descriptive purposes only and does not imply endorsement by the U.S. Government. Although this information product, for the most part, is in the public domain, it also may contain copyrighted materials as noted in the text. Permission to reproduce copyrighted items must be secured from the copyright owner. Suggested citation: John, D.A., Seal, R.R., II, and Polyak, D.E., 2017, Rhenium, chap. P of Schulz, K.J., DeYoung, J.H., Jr., Seal, R.R., II, and Bradley, D.C., eds., Critical mineral resources of the United States—Economic and environmental geology and pros pects for future supply: U.S. Geological Survey Professional Paper 1802, p. P1- P49, ://doi.org/10.3133/pp1802P. ISSN 2330-7102 (online)
Contents Abstract P1 Introduction P1 Uses, Demand, and Availability of Supply P1 Substitutes for Rhenium P3 Geology P3 Geochemistry P3 Mineralogy P4 Deposit Types P4 Rhenium in Porphyry Copper Deposits P10 Rhenium in Sediment-Hosted Strata-Bound Copper Deposits P12 Occurrences in Sandstone-Type Strata-Bound Copper Deposits P14 Occurrences in Reduced-Facies-Type (Kupferschiefer) Strata-Bound Copper Deposits P14 Rhenium in Sandstone-Type Uranium Deposits P15 Rhenium in the Merlin Deposit P17 Resources and Production P18 Identified Resources P18 Production P18 Undiscovered Resources P18 Exploration for New Deposits P19 Environmental Considerations P19 Sources and Fate in the Environment P20 Mine Waste Characteristics P21 Human Health Concerns P23 Ecological Health Concerns P24 Carbon Footprint P25 Mine Closure P25 Problems and Future Research P25 Acknowledgments P25 References Cited P26 Appendix P1. Rhenium Data Sources and Limitations of Data Used in Rhenium Resource Estimates P48
Figures
P1. Photographs of rhenium and rhenium compounds P2
P2. Pie chart showing major end uses of primary rhenium as a percentage of world consumption in 2012 P3
P3. World map showing locations of major rhenium-bearing deposits listed in table P1 P5
P4. Plot of rhenium grade versus deposit tonnage for major rhenium-bearing deposits in the world, including those shown in figure P3 P10
P5. Cross sections illustrating rhenium occurrences in major deposit types from which rhenium is recovered or potentially recoverable P11
P6. Pie chart showing world rhenium mine production in 2012, by country and percent of world total P18 Tables
P1. Summary of rhenium, copper, and molybdenum grades, deposit tonnage, and amount of contained rhenium in the rhenium-bearing deposits shown in figure P3 P6
P2. Rhenium data for selected porphyry copper and porphyry molybdenum deposits of the world P38
P3. Rhenium concentrations in rocks, soils, biota, waters, and sediments P20
Conversion Factors International System of Units to Inch/Pound Multiply By To obtain Length angstrom (Å) (0.1 nanometer) microinch angstrom (Å) (0.1 nanometer) 0.000003937 mil micrometer (µm) [or micron] mil millimeter (mm) inch (in.) centimeter (cm) inch (in.) meter (m) foot (ft) meter (m) yard (yd) kilometer (km) mile (mi) Area hectare (ha) acre square kilometer (km2) acre square meter (m2) square foot (ft2) square centimeter (cm2) square inch (ft2) square kilometer (km2) square mile (mi2) Volume milliliter (mL) ounce, fluid (fl. oz) liter (L) ounce, fluid (fl. oz) liter (L) quart (qt) liter (L) gallon (gal) cubic meter (m3) gallon (gal) cubic centimeter (cm3) cubic inch (in3) cubic meter (m3) cubic yard (yd3) cubic kilometer (km3) cubic mile (mi3) Mass microgram (μg) 0.00000003527 ounce, avoirdupois (oz) milligram (mg) 0.00003527 ounce, avoirdupois (oz) gram (g) ounce, avoirdupois (oz) gram (g) 0.03215075 ounce, troy kilogram (kg) ounce, troy kilogram (kg) pound avoirdupois (lb) ton, metric (t) ton, short [2,000 lb] ton, metric (t) ton, long [2,240 lb] Deposit grade gram per metric ton (g/t) 0.0291667 ounce per short ton (2,000 lb) (oz/T) Pressure megapascal (MPa) bar gigapascal (GPa) 10,000 bar Density gram per cubic centimeter (g/cm3) pound per cubic foot (lb/ft3) milligram per cubic meter (mg/m3) 0.00000006243 pound per cubic foot (lb/ft3) Energy joule (J) 0.0000002 kilowatthour (kWh) joule (J) 6.241 × 1018 electronvolt (eV) joule (J) calorie (cal) kilojoule (kJ) 0.0002388 kilocalorie (kcal)
International System of Units to Inch/Pound Multiply By To obtain Radioactivity becquerel (Bq) 0.00002703 microcurie (μCi) kilobecquerel (kBq) microcurie (μCi) Electrical resistivity ohm meter (Ω-m) ohm inch (Ω-in.) ohm-centimeter (Ω-cm) ohm inch (Ω-in.) Thermal conductivity watt per centimeter per degree Celsius (watt/cm °C) International British thermal unit inch per hour per square foot per degree Fahrenheit (Btu in/h ft2 °F) watt per meter kelvin (W/m-K) International British thermal unit inch per hour per square foot per degree Fahrenheit (Btu in/h ft2 °F) Inch/Pound to International System of Units Length mil micrometer (µm) [or micron] inch (in.) centimeter (cm) inch (in.) millimeter (mm) foot (ft) meter (m) mile (mi) kilometer (km) Volume ounce, fluid (fl. oz) milliliter (mL) ounce, fluid (fl. oz) liter (L) Mass ounce, avoirdupois (oz) 28,350,000 microgram ounce, avoirdupois (oz) 28,350 milligram ounce, avoirdupois (oz) gram (g) ounce, troy 31.10 348 gram (g) ounce, troy 0.03110348 kilogram (kg) pound, avoirdupois (lb) kilogram (kg) ton, short (2,000 lb) ton, metric (t) ton, long (2,240 lb) ton, metric (t) Deposit grade ounce per short ton (2,000 lb) (oz/T) 34.285714 gram per metric ton (g/t) Energy kilowatthour (kWh) 3,600,000 joule (J) electronvolt (eV) 1.602 × 10-19 joule (J) Radioactivity microcurie (μCi) 37,000 becquerel (Bq) microcurie (μCi) kilobecquerel (kBq) Temperature in degrees Celsius (°C) may be converted to degrees Fahrenheit (°F) as follows:
°F (1.8 × °C) + 32 Temperature in degrees Celsius (°C) may be converted to kelvin (K) as follows:
K °C + 273.15 Temperature in degrees Fahrenheit (°F) may be converted to degrees Celsius (°C) as follows:
°C (°F - 32) / 1.8
Datum Unless otherwise stated, vertical and horizontal coordinate information is referenced to the World Geodetic System of 1984 (WGS 84). Altitude, as used in this report, refers to distance above the vertical datum. Supplemental Information Specific conductance is given in microsiemens per centimeter at 25 degrees Celsius (µS/cm at 25 °C). Concentrations of chemical constituents in soils and (or) sediment are given in milligrams per kilogram (mg/kg), parts per million (ppm), or parts per billion (ppb). Concentrations of chemical constituents in water are given in milligrams per liter (mg/L), micrograms per liter (µg/L), nanogams per liter (ng/L), nanomoles per kilogram (nmol/kg), parts per million (ppm), parts per billion (ppb), or parts per trillion (ppt). Concentrations of suspended particulates in water are given in micrograms per gram (µg/g), milligrams per kilogram (mg/kg), or femtograms per gram (fg/g). Concentrations of chemicals in air are given in units of the mass of the chemical (milligrams, micrograms, nanograms, or picograms) per volume of air (cubic meter). Activities for radioactive constituents in air are given in microcuries per milliliter (μCi/mL). Deposit grades are commonly given in percent, grams per metric ton (g/t)—which is equivalent to parts per million (ppm)—or troy ounces per short ton (oz/T). Geologic ages are expressed in mega-annum (Ma, million years before present, or 10 6 years ago) or giga-annum (Ga, billion years before present, or 10 9 years ago). For ranges of years, "to" and (or) the en dash ("-") mean "up to and including." Concentration unit Equals milligram per kilogram (mg/kg) part per million microgram per gram (µg/g) part per million microgram per kilogram (μg/kg) part per billion (109) Equivalencies part per million (ppm): 1 ppm 1,000 ppb 1,000,000 ppt 0.0001 percent part per billion (ppb): 0.001 ppm 1 ppb 1,000 ppt 0.0000001 percent part per trillion (ppt): 0.000001 ppm 0.001 ppb 1 ppt 0.0000000001 percent Metric system prefixes tera- (T-) 1 trillion giga- (G-) 1 billion mega- (M-) 1 million kilo- (k-) 1 thousand hecto- (h-) 1 hundred deka- (da-) 1 ten deci- (d-) 10-1 1 tenth centi- (c-) 10-2 1 hundredth milli- (m-) 10-3 1 thousandth micro- (µ-) 10-6 1 millionth nano- (n-) 10-9 1 billionth pico- (p-) 10-12 1 trillionth femto- (f-) 10-15 1 quadrillionth atto- (a-) 10-18 1 quintillionth
Abbreviations and Symbols °C degree Celsius µm micrometer AFRG alkali-feldspar rhyolite-granite g/t gram per metric ton kg kilogram kg CaCO3/t kilogram of calcium carbonate per ton km kilometer km2 square kilometer m meter Ma mega-annum mg/L milligram per liter OPEC Organization of the Petroleum Exporting Countries PGE platinum-group element ppb part per billion ppm part per million ppt part per trillion SX-EW solvent extraction-electrowinning USGS U.S. Geological Survey WHO World Health Organization wt. % weight percent
Rhenium By David A. John, Robert R. Seal II, and Désirée E. Polyak Abstract Rhenium is one of the rarest elements in Earth's continental crust; its estimated average crustal abundance is less than 1 part per billion. Rhenium is a metal that has an extremely high melting point and a heat-stable crystalline structure. More than 80 percent of the rhenium consumed in the world is used in high-temperature superalloys, especially those used to make turbine blades for jet aircraft engines. Rhenium's other major application is in platinum-rhenium catalysts used in petroleum refining. Rhenium rarely occurs as a native element or as its own sulfide mineral; most rhenium is present as a substitute for molybdenum in molybdenite. Annual world mine production of rhenium is about 50 metric tons. Nearly all primary rhenium production (that is, rhenium produced by mining rather than through recycling) is as a byproduct of copper mining, and about 80 percent of the rhenium obtained through mining is recovered from the flue dust produced during the roasting of molybdenite concentrates from porphyry copper deposits. Molybdenite in porphyry copper deposits can contain hundreds to several thousand grams per metric ton of rhenium, although the estimated rhenium grades of these deposits range from less than 0.1 gram per metric ton to about 0.6 gram per metric ton. Continental-arc porphyry copper-molybdenum-gold deposits supply most of the world's rhenium production and have large inferred rhenium resources. Porphyry copper mines in Chile account for about 55 percent of the world's mine production of rhenium; rhenium is also recovered from porphyry copper deposits in the United States, Armenia, Kazakhstan, Mexico, Peru, Russia, and Uzbekistan. Sediment-hosted strata-bound copper deposits in Kazakhstan (of the sandstone type) and in Poland (of the reduced-facies, or Kupferschiefer, type) account for most other rhenium produced by mining. These types of deposits also have large amounts of identified rhenium resources. The future supply of rhenium is likely to depend largely on the capacity of the specialized processing facilities needed to recover rhenium from molybdenite concentrates. The environmental consequences of rhenium recovery are closely linked to the consequences of mining large porphyry copper and strata-bound copper deposits; no additional environmental impact from recovery of rhenium from these deposits has been identified. No information is available regarding the potential toxic effects of rhenium on humans, partly because of the low natural abundance of rhenium. Introduction Rhenium (Re) is one of the rarest elements in Earth's continental crust; its average crustal abundance is about 0.4 part per billion (ppb), although estimates range from 0.2 to 2 ppb (Taylor and McLennan, 1995; Rudnick and Gao, 2003; Sun and others, 2003). This silvery-white metallic element's extremely high melting point (3,180 degrees Celsius [°C]) and heat-stable crystalline structure make it an excellent refractory metal (fig. P1). Rhenium was the last stable, naturally occurring element discovered, although its existence was long predicted from the periodic table. The element was discovered in 1925 by German chemists Walter Noddack, Ida Tacke, and Otto Berg, who concentrated rhenium from gadolinite ore that contained about 10 parts per million (ppm) rhenium (Emsley, 2001). The German chemists subsequently separated 1 gram of rhenium from 660 kilograms (kg) of molybdenum ore. Uses, Demand, and Availability of Supply Since the late 1980s, the two most important uses of rhenium have been in high-temperature superalloys and in platinum-rhenium catalysts (fig. P2). The high-temperature alloys in which rhenium is used include several nickel-base superalloys that are used mainly in the manufacture of turbine blades for jet aircraft engines and in power-generation applications. The high-temperature properties of rhenium allow turbine engines to be designed with closer tolerances, thus enabling increased thrust and higher operating efficiency. Because the life cycle of turbine blades in jet engines is only about 10 years, significant quantities of used blades (which
P2 Critical Mineral Resources of the United States— Rhenium P
Figure P1. Photographs of rhenium and rhenium compounds. A, A single crystal of high-purity (99.999%) rhenium (left), a remelted rhenium bar (center), and a 1-cubic-centimeter rhenium cube (right). Photograph courtesy of Alchemist-hp/CC-BY-NC-ND-3.0 (://commons.wikimedia.org/wiki/File:Rhenium_single_crystal_bar_and_1cm3_cube.jpg). B , Rhenium powder. Photograph courtesy of H.C. Starck. C , Ammonium perrhenate (NH4ReO4) powder, which is the most widely marketed form of rhenium. Photograph courtesy of Stanford Advanced Materials (://www.samaterials.com/847/ammonium-perrhenate.jpg). D , Rheniite (ReS2 ) crystals from hightemperature fumaroles on the Kudryavyy volcano, which is located on Iturup Island in Sakhalinskaya Oblast', Russia. Photograph courtesy of The Arkenstone, iRocks.com (://www.irocks.com/minerals/specimen/42387). typically contain 3 percent rhenium, although some alloys contain 6 percent rhenium) are accumulating. Technology is continuing to be developed to allow recycling of these blades to recover the rhenium, which can then be used in the manufacture of new, second-generation blades. Recycling of rhenium from used turbine blades could potentially reduce the requirement for primary rhenium (that is, rhenium produced by mining rather than through recycling) by about 50 percent. Most rhenium recycling is currently performed in the United States and Germany. World consumption of rhenium from primary sources was estimated to be between 50 and 54 metric tons in 2012 (Polyak, 2014). Approximately 83 percent (45 metric tons) of rhenium from primary sources was used in making superalloys, mainly for the aerospace industry (fig. P2). New types of catalysts in the petrochemical industry accounted for about an additional 10 percent (5 metric tons). The remaining 7 percent (4 metric tons) of world consumption in 2012—primarily in the form of tungsten-rhenium and molybdenum-rhenium alloys—was used in a variety of other applications, including in the manufacture of electrical contact points, flashbulbs, heating elements, vacuum tubes, and X-ray tubes and targets. An additional 15 metric tons of rhenium is recycled each year from spent cata lysts and is not included in the world consumption total shown in figure P2 (Lipmann Walton & Co. Ltd., 2010; Minor Metals Trade Association, 2012). Platinum-rhenium catalysts are used to produce highoctane lead-free gasoline. In the early 1970s, Chevron Corp. of the United States developed a series of platinum-rhenium catalysts that do not react with sulfur. As a response to the Organization of the Petroleum Exporting Countries (OPEC) oil embargo in the 1970s and the oil crisis of the early 1980s, a second generation of more-efficient catalysts was developed with double the platinum-rhenium content, which boosted
Geology P3 P2 - Pie Ch art Showing Maj or En d Figure P2. Pie chart showing major end uses of primary rhenium as a percentage of world consumption in 2012. Total world production for the year was between 50 and 54 metric tons. Approximately 83 percent of the rhenium from primary sources was used to make superalloys, mainly for the aerospace industry. the refinery efficiency and the gasoline's octane levels. Ammonium perrhenate (NH4ReO4 ) is the most common form of rhenium used by catalyst manufacturers (fig. P1C ). Petroleum-reforming platinum-rhenium catalysts are used mainly in North America and Europe, where demand for gasoline and diesel fuel is highest. These are also the locations of the major rhenium-platinum catalyst manufacturers. The recovery of rhenium from platinum-rhenium catalysts is a mature business. A closed-loop recycling system operated by catalyst manufacturers, refiners, and secondary rhenium producers ensures that consumption of newly mined rhenium is kept to a minimum. The catalysts are recycled mainly to recover the platinum content, so much of the rhenium is recycled only because of the platinum content of the catalysts. Rhenium in molybdenite concentrates derived from porphyry copper ores is recovered at some mines as a byproduct during the molybdenite roasting process. In the United States in 2012, three molybdenum mines had roasters associated with mines, but only one of the roasters was equipped to recover rhenium. This roaster, which is located at the Sierrita facility in Arizona, is operated by FreeportMcMoran Copper & Gold Inc. of the United States. This facility processes all the byproduct molybdenite concentrates from Freeport-McMoran mines and processes molybdenite concentrates on a toll basis for third parties. In contrast, Kennecott Utah Copper Corp. (which is owned by Rio Tinto plc of the United Kingdom) sends byproduct molybdenite concentrates from the Bingham Canyon Mine in Utah to Molymex S.A. de C.V.'s plant in Mexico for roasting; the recovered rhenium concentrate is then sent to Molibdenos y Metales S.A. (Molymet) in Chile for purification. Substitutes for Rhenium Substitutes for rhenium in platinum-rhenium catalysts are being evaluated on an ongoing basis. Iridium and tin have achieved commercial success in one application. Other metals being evaluated as possible substitutes for rhenium in catalysts include gallium, germanium, indium, selenium, silicon, tungsten, and vanadium. The use of these and other metals in catalysts might someday decrease rhenium's share of the existing catalyst market; however, rhenium-bearing catalysts that are being considered for use in several proposed gas-toliquid projects likely would offset this decrease. Materials that can substitute for rhenium in various end uses are cobalt and tungsten for coatings on copper X-ray targets, rhodium and rhodium-iridium for high-temperature thermocouples, tungsten and platinum-ruthenium for coatings on electrical contacts, and tungsten and tantalum for electron emitters (Polyak, 2013). Aerospace superalloy producers continue to research new alloys with smaller quantities of rhenium; however, it has proven difficult to develop alloys with lower rhenium content for use in jet engines without a loss in performance. Geology Geochemistry Rhenium has an atomic number of 75 and an atomic mass of 186.2 grams per mole. In the periodic table of elements, rhenium is a third row, heavy transition metal located in column 7B below manganese and technetium, adjacent to tungsten and the platinum-group elements (PGEs), and diagonally below molybdenum. Rhenium has a density of 21.02 grams per cubic centi meter, making it the fourth densest element (iridium, osmium, and platinum have higher densities). It has a hexagonal close-packed crystal structure. The 3,180 °C melting point of rhenium is the third highest melting point of all the elements; only carbon (3,500 °C) and tungsten (3,422 °C) have higher melting points. Rhenium has the widest range of valences of any element—nine in total, ranging from -1 to +7— although +7, +6, +4, and +2 are the most common ions. Rhenium forms three stable oxides—rhenium heptoxide (Re2O7 ), rhenium trioxide (ReO3 ), and rhenium dioxide (ReO2 ) —of which rhenium heptoxide is the most common. Rhenium heptoxide is a bright yellow volatile solid that dissolves in water to form rhenic acid (HReO4). Rhenium has a marked affinity for sulfur and occurs mostly in nature as a substitute (solid solution) for molybdenum in molybdenite (MoS2). Unusual features of rhenium compounds include the unusually high volatility of rhenium heptoxide and the high solubility of rhenium heptoxide in water. These properties facilitate rhenium's recovery from flue dusts produced by roasting of molybdenite concentrates.
P4 Critical Mineral Resources of the United States— Rhenium The two dominant naturally occurring rhenium isotopes are 185Re, which is stable and accounts for 37.4 percent of naturally occurring rhenium, and 187Re, which is radiogenic and accounts for 62.6 percent of naturally occurring rhenium. Twenty-six other radioactive isotopes of rhenium have been recognized. 187Re decays to 187Os by beta decay and has a halflife of about 4.1×1010 years. The rhenium-osmium isotopic system is used to date sulfide minerals (most commonly molybdenite) in mineral deposits (McCandless and Ruiz, 1993; Stein and others, 2001). Mineralogy Rhenium rarely occurs as a native element or as its own sulfide mineral. Trace amounts of native rhenium (Re0 ) were recently discovered in ultramafic rocks in Ukraine (Bobrov and others, 2008). Microscopic crystals of rheniite (ReS2 ) were first reported in 1986 in volcanic fumaroles on Mount Usu, Japan (Bernard and Dumortier, 1986), and megascopic crystals of rheniite were discovered in 1992 in high-temperature fumaroles on the Kudryavyy (also spelled Kudriavy) volcano on Iturup Island in Sakhalinskaya Oblast', Russia (fig. P1D; Korzhinsky and others, 1994). Rheniite also has been reported in the Pagoni Rachi porphyry copper-molybdenum prospect in northern Greece (Voudouris and others, 2009). Microscopic (≤ 75 micrometers [µm]) crystals of rhenium-rich tarkianite ) have been discovered in sulfide concentrates from the Hitura nickel-copper-PGE mine at Nivala, Finland (Kojonen and others, 2004). None of these rhenium-rich minerals are economic sources of rhenium, however. Dzhezkazganite forms microscopic collomorphic aggregates and veinlets in bornite, chalcocite, and galena and replaces bornite in sandstone-hosted strata-bound copper deposits at the Dzhezkazgan Mine in Qaraghandy, Kazakhstan (Poplavko and others, 1962; Abisheva and others, 2001). Dzhezkazganite was first inferred as a copper-rhenium sulfide (CuReS4 ) mineral (Poplavko and others, 1962), but subsequent electron microprobe analyses suggest that it has a chemical formula of ReMoCu2PbS6 (Genkin and others, 1994). It is not a recognized mineral species by the International Mineralogical Association, however, because of the lack of structural data and uncertainty in its chemical formula (Fleischer, 1963). Molybdenite is the principal source of rhenium. The rhenium content of molybdenite varies widely from less than 1 ppm to several weight percent, but molybdenite in porphyry copper deposits typically contains about 100 to 3,000 ppm rhenium (tables P1 and P2 at back of chapter; Fleischer, 1959; Giles and Schilling, 1972; Newberry, 1979; Berzina and others, 2005; Sinclair and others, 2009; John and Taylor, 2016). In contrast, the rhenium content of molybdenite in porphyry molybdenum deposits generally is much lower, in many cases less than 20 ppm (table P2). Rhenium contents of molybdenite in other types of porphyry deposits and in quartz veins typically also are low (<10 to about 200 ppm) (for example, Terada and others, 1971; Giles and Schilling, 1972; Ishihara, 1988; Sinclair and others, 2009; Millensifer and others, 2014). Molybdenite in Australia's Merlin molybdenum-rhenium deposit (discussed below), however, averages about 1,000 ppm rhenium (Brown and others, 2010). The rhenium content of molybdenite also varies widely within some porphyry copper deposits (for example, it ranges from 130 to 2,000 ppm at Bingham, Utah) (Giles and Schilling, 1972). The variable rhenium content, both within deposits and between different types of porphyry deposits, is not completely understood. Variations in the rhenium content of molybdenite within deposits may represent multiple generations of molyb denite that have different rhenium contents (for example, the Sar Cheshmeh Mine in Kermān Province, Iran; Aminzadeh and others, 2011). Rhenium concentration differences reflect a combination of factors, including changes in temperature and pressure, fluid composition (especially pH and sulfur content), oxidation state, and (or) transport mechanism (that is, brine, moderate-density liquid, or low-density vapor) during the complex magmatic-hydrothermal history of these deposits (John and Taylor, 2016). Deposit Types Nearly all primary rhenium production (rhenium produced by mining rather than through recycling) is as a byproduct of copper mining. Rhenium resources are dominantly contained in porphyry copper-molybdenum-gold deposits, which supply about 80 percent of the rhenium produced by mining (Polyak, 2013). Rhenium in porphyry copper deposits is contained primarily as ReS2 in solid solution in molybdenite (Fleischer, 1959). Most of the remaining rhenium production is as a byproduct of mining sediment-hosted strata-bound copper deposits, both the sandstone (red bed) types in Kazakhstan and the reduced-facies (Kupferschiefer) types in Poland (Hitzman and others, 2005; Zientek and others, 2013). Smaller amounts of rhenium are recovered from the processing of roll-front-type sandstone uranium ore in Kazakhstan (Dahlkamp, 2009a). The Merlin molybdenum-rhenium zone of the Mount Dore copper deposit in Queensland, Australia, is a potential source of highgrade rhenium ore and is the only deposit known in which rhenium could be a primary commodity (Brown and others, 2010). The world's major rhenium-bearing deposits that are described in the text and (or) listed in table P1 are shown on the map in figure P3.
Geology P5 P3 - Wor ld Map S how ing Loc atio ns of Maj or Rhe niu m Figure P3. World map showing locations of major rhenium-bearing deposits listed in table P1, including porphyry copper-molybdenum-gold deposits; sediment-hosted strata-bound copper deposits in Poland (of the reduced-facies, or Kupferschiefer, type) and Kazakhstan (of the sandstone type); roll-front-type sandstone uranium deposits in Kazakhstan and Uzbekistan; and the Merlin (Mount Dore) molybdenum-rhenium deposit in Queensland, Australia. Additional information about the rhenium resources in these deposits is in table P1. Au, gold; Cu, copper; Mo, molybdenum; Re, rhenium; U, uranium
P6 Critical Mineral Resources of the United States— Rhenium Table P1. Summary of rhenium, copper, and molybdenum grades, deposit tonnage, and amount of contained rhenium in the rheniumbearing deposits shown in figure P3.—Continued [The names, locations, and types of most of the deposits are taken from the U.S. Geological Survey Mineral Resources Data System (MRDS) (U.S. Geological Survey, 2014). The minimum and maximum values are concentrations of rhenium in molybdenite separates; the estimated average is based on mill concentrates. Elements and compounds: Au, gold; Cu, copper; Mo, molybdenum; MoS2, molybdenite; Os, osmium; Re, rhenium; U, uranium. Units of measure: g/t, gram per metric ton; Mt, million metric tons; ppm, part per million; t, metric ton; wt. %, weight percent. —, no data; n.a., not applicable to the deposit] Deposit name Country (State/Province) Deposit type Tectonic setting1 Deposit tonnage (Mt) Grade (wt. % Cu) Grade (wt. % Mo) Minimum Re in MoS2 (ppm) Maximum Re in MoS2 (ppm) Estimated aver age Re in MoS2 (ppm) Bagdad United States (Arizona) Porphyry Cu- (Mo-Au) CA 1,600 Bingham United States (Utah) Porphyry Cu- (Mo-Au) PC 3,230 2,000 Butte United States (Montana) Porphyry Cu- (Mo-Au) CA 5,220 — — Morenci United States (Arizona) Porphyry Cu- (Mo-Au) CA 6,470 Pebble United States (Alaska) Porphyry Cu- (Mo-Au) PC 5,940 2,070 1,100 Santa Rita United States (New Mexico) Porphyry Cu- (Mo-Au) CA 3,030 1,200 SierritaEsperanza United States (Arizona) Porphyry Cu- (Mo-Au) CA 2,262 1,800 ChuquicamataRadomiro Tomic Chile Porphyry Cu- (Mo-Au) CA 21,277 El Salvador Chile Porphyry Cu- (Mo-Au) CA 3,836 — — El Teniente Chile Porphyry Cu- (Mo-Au) CA 20,731 1,154 La Escondida Chile Porphyry Cu- (Mo-Au) CA 11,158 1,805 Los Bronces- Rio Blanco Chile Porphyry Cu- (Mo-Au) CA 16,816 Los Pelambres Chile Porphyry Cu- (Mo-Au) CA 7,458 La Caridad Mexico (Sonora) Porphyry Cu- (Mo-Au) CA 1,800 Cerro Verde Peru Porphyry Cu- (Mo-Au) CA 2,258 3,060 3,497 3,280 Toquepala Peru Porphyry Cu- (Mo-Au) CA 2,320 1,496 Kadjaran (Kadzharan) Armenia Porphyry Cu- (Mo-Au) CA 1,700 2,620
Geology P7 Table P1. Summary of rhenium, copper, and molybdenum grades, deposit tonnage, and amount of contained rhenium in the rheniumbearing deposits shown in figure 3.—Continued [The names, locations, and types of most of the deposits are taken from the U.S. Geological Survey Mineral Resources Data System (MRDS) (U.S. Geological Survey, 2014). The minimum and maximum values are concentrations of rhenium in molybdenite separates; the estimated average is based on mill concentrates. Elements and compounds: Au, gold; Cu, copper; Mo, molybdenum; MoS , molybdenite; Os, osmium; Re, rhenium; U, uranium. Units of measure: g/t, gram per metric ton; Mt, million metric tons; ppm, part per million; t, metric ton; wt. %, weight percent. —, no data; n.a., not applicable to the deposit] Number of Re analyses Selected sample type2 Grade (g/t Re) Contained Re (t) Mo:Re ratio Notes Data sources Deposit name 2,650 3,800 2,760 1,030 1,500 1,120 1,200 2,400 2,500 1,320 2,520 2,300 1,020 1,430 2,300 1,000 1,050 1,000 2,140 None None None None Re grade from bulk molybdenite concentrate samples with 52% Mo; measured and indicated resources None None None None None None None None None None None None Sutulov, 1974; Nadler, 1997; Barra and others, 2003; Singer and others, 2008 Giles and Schilling, 1972; McCandless and Ruiz, 1993; Chesley and Ruiz, 1998; Singer and others, 2008; Austen and Ballantyne, 2010; J. Chesley, written commun., 2013 Giles and Schilling, 1972; Singer and others, 2008 Giles and Schilling, 1972; McCandless and Ruiz, 1993; Singer and others, 2008 Ghaffari and others, 2011; Lang and others, 2013 Giles and Schilling, 1972; Sutulov, 1974; Singer and others, 2008 Giles and Schilling, 1972; Sutulov, 1974; Nadler, 1997; Singer and others, 2008 Giles and Schilling, 1972; Sutulov, 1974; Nadler, 1997; Singer and others, 2008; Barra and others, 2013 Giles and Schilling, 1972; Sutulov, 1974; Nadler, 1997; Singer and others, 2008 Giles and Schilling, 1972; Sutulov, 1974; Nadler, 1997; Maksaev and others, 2004; Singer and others, 2008 Mathur and others, 2001; Singer and others, 2008; Romero and others, 2010 Mathur and others 2001; Singer and others, 2008; Deckart and others, 2013 Mathur and others 2001; Singer and others, 2008 Nadler, 1997; Valencia and others, 2005; Singer and others, 2008 Mathur and others, 2001; Singer and others, 2008 Giles and Schilling, 1972; Sutulov, 1974; Nadler, 1997; Mathur and others, 2001; Singer and others, 2008 Nadler, 1997; Berzina and others, 2005; Singer and others, 2008 Bagdad Bingham Butte Morenci Pebble Santa Rita Sierrita- Esperanza ChuquicamataRadomiro Tomic El Salvador El Teniente La Escondida Los BroncesRio Blanco Los Pelambres La Caridad Cerro Verde Toquepala Kadjaran (Kadzharan)
P8 Critical Mineral Resources of the United States— Rhenium Table P1. Summary of rhenium, copper, and molybdenum grades, deposit tonnage, and amount of contained rhenium in the rheniumbearing deposits shown in figure P3.—Continued [The names, locations, and types of most of the deposits are taken from the U.S. Geological Survey Mineral Resources Data System (MRDS) (U.S. Geological Survey, 2014). The minimum and maximum values are concentrations of rhenium in molybdenite separates; the estimated average is based on mill concentrates. Elements and compounds: Au, gold; Cu, copper; Mo, molybdenum; MoS , molybdenite; Os, osmium; Re, rhenium; U, uranium. Units of measure: g/t, gram per metric ton; Mt, million metric tons; ppm, part per million; t, metric ton; wt. %, weight percent. —, no data; n.a., not applicable to the deposit] Deposit name Country (State/Province) Deposit type Tectonic setting1 Deposit tonnage (Mt) Grade (wt. % Cu) Grade (wt. % Mo) Minimum Re in MoS (ppm) Maximum Re in MoS (ppm) Estimated average Re in MoS (ppm) Kalmakyr (Almalyk) Zuun Mod Molybdenum Lubin- Sieroszowice MansfeldSangerhausen MansfeldSangerhausen Dzhezkazgan Zhaman-Aibat (or ZhamanAybat) (Zhomart) Merlin Sugraly Suluchekinskoye Uzbekistan Mongolia Poland Germany Germany Kazakhstan Kazakhstan Australia (Queensland) Uzbekistan Kazakhstan Porphyry Cu- (Mo-Au) Porphyry Cu- (Mo-Au) Reduced-facies (Kupferschiefer) stratabound Cu Reduced-facies (Kupferschiefer) stratabound Cu Reduced-facies (Kupferschiefer) stratabound Cu Sandstone stratabound Cu Sandstone stratabound Cu Undefined Mo-Re Roll-front sandstone U Roll-front sandstone U CA CA n.a. n.a. n.a. n.a. n.a. n.a. n.a. n.a. 2,000 1,181 2,000 — — — — — — — — — — — — — — — — 2,000 — — — — — — — — 1,500 — — — — — — — — 1Tectonic setting of porphyry copper deposits: CA, continental arc; PC, post-collisional. 2Sample type used in calculating Re grade: 1, molybdenite separate; 2, molybdenite separate used in Re-Os dating; 3, molybdenite mill concentrate.
Geology P9 Table P1. Summary of rhenium, copper, and molybdenum grades, deposit tonnage, and amount of contained rhenium in the rheniumbearing deposits shown in figure 3.—Continued [The names, locations, and types of most of the deposits are taken from the U.S. Geological Survey Mineral Resources Data System (MRDS) (U.S. Geological Survey, 2014). The minimum and maximum values are concentrations of rhenium in molybdenite separates; the estimated average is based on mill concentrates. Elements and compounds: Au, gold; Cu, copper; Mo, molybdenum; MoS , molybdenite; Os, osmium; Re, rhenium; U, uranium. Units of measure: g/t, gram per metric ton; Mt, million metric tons; ppm, part per million; t, metric ton; wt. %, weight percent. —, no data; n.a., not applicable to the deposit] Number of Re analyses Selected sample type2 Grade (g/t Re) Contained Re (t) Mo:Re ratio Notes Data sources Deposit name — — — — — — — — — — — — — — — — 3,300 3,000 2,190 — 0.5 to 1.2 — — — None Average of range of Re contents in MoS2 2011 end-of-year proven and probable reserves; average Re grade of ore mined in 2009 Estimated remaining resources after mining ceased in Estimated total resources before mining, which began in 1200 and ended in 1990 Ore averages 1 to 2 ppm Re None Average Re grade and tonnage of indicated and inferred resources Ore averages 10 to 15 ppm Re Ore averages 1 to 2 ppm Re and 0.07 to 0.13% U Sutulov, 1974; Singer and others, 2008; Pašava and others, 2010 Clark and Baudry, 2011 Smakowski and others, 2010; Bartlett and others, 2013 Jankowski, 1995 Jankowski, 1995 Seyfullin and others, 1974; Box and others, 2013 Box and others, 2013 Lycopodium Minerals QLD Pty Ltd., Dahlkamp, 2009b Dahlkamp, 2009a Kalmakyr (Almalyk) Zuun Mod Molybdenum Lubin- Sieroszowice MansfeldSangerhausen MansfeldSangerhausen Dzhezkazgan Zhaman-Aibat (or Zhaman-Aybat) (Zhomart) Merlin Sugraly Suluchekinskoye
P10 Critical Mineral Resources of the United States— Rhenium Rhenium in Porphyry Copper Deposits Large continental-margin arc porphyry coppermolybdenum-gold deposits dominate world rhenium resources (tables P1 and P2; figs. P3 and P4; John and Taylor, 2016). Porphyry copper deposits are large (in most cases, greater than 100 million metric tons), low-to-moderate grade (in most cases, 0.3 to 2.0 percent copper), disseminated, breccia and vein-hosted copper deposits (John and others, 2010). Porphyry copper deposits are parts of larger porphyry copper systems in which large volumes (10 to >100 cubic kilometers) of hydrothermally altered rock are centered on porphyry stocks and other intrusions. The deposits may include associated skarn, carbonate-replacement, sedimenthosted, and high- and intermediate-sulfidation epithermal base and precious-metal deposits (Sillitoe, 2010). Porphyry copper systems most commonly form above active subduc tion zones at convergent plate margins and are associated with calc-alkaline batholiths and volcanic arcs in both continental-margin and island-arc settings (Sillitoe, 1972; Richards, 2003). Some other porphyry copper systems form in post-collisional and other tectonic settings after subduction ends (Richards, 2009; Hou and others, 2011). Copper is the dominant metal produced from porphyry copper deposits; molybdenum, gold, and lesser amounts of silver, rhenium, and PGEs (mostly palladium) are important byproducts in some deposits. Hydrothermal alteration of porphyry-copper-related intrusive rocks and their wallrocks is widely developed and includes alkali-dominated assemblages (potassic, sodic, and sodic-calcic), acid (low pH) assemblages (advanced argillic and sericitic), and propylitic assemblages. Alteration zoning can be highly variable, but acidic alteration is typically distal and shallow and, where it is found in the center of a deposit, it is late relative to alkali alteration assemblages. The deeper parts of porphyry copper systems (typically paleodepths of approximately 2 to 10 kilometers [km]) contain central porphyry copper ± molybdenum ± gold mineralization (fig. P5A) and may contain flanking copper, gold, and (or) zinc skarn, silver-lead-zinc carbonate replacement, and gold-silver sediment-hosted deposits. The shallow, overlying parts of these systems may host high- and intermediate-sulfidation epithermal gold-silver ± copper deposits. Copper, gold, and molybdenum mineralization is generally associated with potassic and sericitic alteration. Rhenium is invariably associated with molybdenum mineralization. Rhenium is produced from several Tertiary porphyry copper deposits in the Andes Mountains in South America, including the giant Chuquicamata-Radomiro Tomic and El Teniente deposits in Chile, and Toquepala in Peru; from Late Cretaceous to mid-Tertiary deposits in the Western United States; and from deposits in Armenia, Kazakhstan, Russia, and Uzbekistan (fig. P3). Rhenium in porphyry copper P4 - Plot o f Rhenium Grade Ve rsus De posit Tonnag e Figure P4. Plot of rhenium grade versus deposit tonnage for major rhenium-bearing deposits in the world, including those shown in figure P3. The diagonal lines are isolines of contained rhenium, in metric tons. Additional resource data for these deposits, and sources, are given in table P1. AFRG, alkali-feldspar rhyolitegranite; t, metric ton. Elements: Au, gold; Cu, copper; Mo, molybdenum; Re, rhenium, U, uranium
Geology P11 P5 - Cross Sec tions Illu strating Rhenium O ccurrence s i n
Maj or De posit Type s Figure P5. Cross sections illustrating rhenium occurrences in major deposit types from which rhenium is recovered or potentially recoverable. A, Bingham Canyon porphyry copper-molybdenumgold (Cu-Mo-Au) deposit in Utah showing metal zoning around porphyry intrusions. Molybdenum (in molybdenite) is displaced to deeper levels than copper and gold, which are mostly deposited earlier than molybdenum. Rhenium (Re) grades apparently are highest in the copper-molybdenum-gold ores in the center of the deposit ("High Re") and lower in the deep molybdenum-only ore ("Lower Re") (Austen and Ballantyne, 2010). Figure modified from Landtwing and others (2010) and Seo and others (2012). ppm, part per million; wt.%, weight percent A
P12 Critical Mineral Resources of the United States— Rhenium deposits is contained primarily as ReS2 in solid solution in molybdenite (Fleischer, 1959) at concentrations ranging from less than 10 ppm to about 1 weight percent (table P1). Rhenium grades of porphyry copper deposits are low, gener ally less than 0.5 gram per metric ton (g/t) (table P1; fig. P4; Sinclair and others, 2009; John and Taylor, 2016), but the large tonnage of ore processed, the presence of sufficient molybdenite to make molybdenum recovery economic, and the presence of specialty circuits that allow recovery of the rhenium contained in molybdenite means that a relatively large proportion of rhenium production is from these deposits. Rhenium contents of molybdenite in porphyry molyb denum deposits are generally much lower than in molybdenite in porphyry copper deposits (table P2; Giles and Schilling, 1972; Sinclair and others, 2009; John and Taylor, 2015). Thus, despite their higher molybdenum grades, rhenium grades of porphyry molybdenum deposits are generally less than those of porphyry copper deposits (table P2; fig. P4). The relatively low grades and small sizes of most porphyry molybdenum deposits result in small rhenium resources (table P2; fig. P4), and rhenium is not recovered from these deposits. Rhenium is recovered from molybdenite concentrates that are separated from copper-iron sulfides by flotation methods. During roasting of the molybdenite concentrates to produce molybdenum oxide, rhenium is oxidized to Re2O7 and passes up the flue stack with the sulfur gases. When the flue dusts and gases are scrubbed, rhenium is dissolved in the resulting sulfuric acid and is eventually precipitated out as ammonium perrhenate (NH4ReO4 ) (Sutulov, 1974; Nadler, 1997). Ammonium perrhenate is a white crystalline powder that contains about 69 weight percent rhenium and is the principal form in which rhenium is marketed (fig. P1C ). Rhenium in Sediment-Hosted Strata-Bound Copper Deposits Sediment-hosted strata-bound copper deposits are the other major primary source of rhenium. Rhenium is recovered during processing of copper ores from sandstone-type (red bed) copper deposits in Kazakhstan and from reduced-facies (Kupferschiefer)-type copper-silver deposits in Poland. Sediment-hosted strata-bound copper mineralization consists of fine-grained copper and copper-iron sulfide minerals in strata-bound-to-stratiform disseminations in siliciclastic or dolomitic sedimentary rocks (Hitzman and others, 2005; Zientek and others, 2013). Ore minerals are characteristically zoned laterally and vertically across bedding from hematite to chalcocite to bornite to chalcopyrite to pyrite in the inferred direction of fluid flow (figs. P5B and P5C ). Deposits are hosted in reduced sedimentary strata within or above a thick section of oxidized red beds. These deposits are inferred to form by the flow of oxidized, metal-rich brines through permeable red-bed sedimentary rocks (mostly sandstones). Interaction of the oxidized ore fluids with a reducing agent, such as hydrocarbons (oil or natural gas), reduced organic carbon, and (or) sulfide minerals, results in deposition of the zoned sequence of iron, B P5 (Conti nued) - B - Sandsto ne-Type Stra ta-Bound C opper D eposit Figure P5 —Continued B , Sandstone-type strata-bound copper deposit at Dzhezkazgan, Qaraghandy, Kazakhstan, showing mineral zoning and rock type. Rhenium (Re) is enriched in all the ore zones, but the highest concentrations are thought to be in the copper zones, especially in chalcocite-bornite ore (Seyfullin and others, 1974). Figure modified from Box and others (2013) based on Daukeev and others (2004).
Geology P13 Figure P5.— Continued C, Kupferschiefer (reduced-facies-type) strata-bound copper deposits showing lithology (top cross section) and copper ore distribution (stippled pattern) and metal and mineral zoning (bottom cross section). Rhenium is concentrated in copper ore in the Kupferschiefer black shale. Transitions between predominant sulfide minerals are gradational. Figure is based on Jowett (1986) and Oszczepalski (1999). P5 (Contin ued) - C-K upfers chiefer StrataBound Copp er
P14 Critical Mineral Resources of the United States— Rhenium copper, lead, and zinc sulfide and oxide minerals. Unlike porphyry copper deposits, in which rhenium is clearly associ ated with molybdenite and is derived from magmatic sources, the site and source of rhenium in sediment-hosted strata-bound copper deposits are poorly understood. Occurrences in Sandstone-Type Strata-Bound Copper Deposits In central Kazakhstan, rhenium is recovered from Late Paleozoic sandstone-type strata-bound copper deposits in the Chu-Sarysu basin (Dzhezkazgan and Zhaman-Aybat [also spelled Zhaman-Aibat] deposits) (fig. P3; Box and others, 2013). The deposits consist of copper sulfide minerals (bornite, chalcocite, and chalcopyrite) that form intergranular cement and replace grains in sandstone and conglomerate within a 600- to 1,000-m-thick Pennsylvanian fluvial red-bed sequence. Copper grades of individual deposits range from about 0.8 to 1.7 percent and average 1.1 percent, and the deposits contain significant quantities of silver and rhenium. The copper minerals are inferred to have precipitated from an oxidized, metal-rich brine that was progressively reduced by interaction with hydrogen sulfide (H2S)-bearing petroleum fluids as it flowed through permeable sandstone beds. The copper minerals are zoned from chalcocite to bornite to chalcopyrite in the inferred direction of the fluid (brine) flow (fig. P5B). The main deposits in Kazakhstan from which rhenium is recovered are the Zhaman-Aybat deposit (which has an average rhenium grade of 1.45 g/t and includes local zones that exceed 9 g/t), and the Dzhezkazgan deposit (which has an average grade of 1 to 2 g/t rhenium). Both deposits are located in Qaraghandy Province. In the Zhaman-Aybat deposit, the highest rhenium grades (>9 g/t) are associated with the boundary between the chalcopyrite and the bornitechalcocite zones in more central parts of the deposit. The occurrence and mineralogy of rhenium in the Kazakhstan deposits is uncertain. Satpaeva and others (1959, summarized in Fleischer, 1960) and Seyfullin and others (1974) reported rhenium contents of different types of ores at Dzhezkazgan and other strata-bound copper deposits in Kazakhstan. Their data show that rhenium is present in appre ciable abundances in lead-rich and zinc-rich ores, as well as in copper-rich ores, and that rhenium apparently is not associated with molybdenite. In particular, Seyfullin and others (1974) showed that the ratio of molybdenum to rhenium (Mo:Re) in copper ore averaged 1.2 in the Dzhezkazgan deposit and varied from 0.4 to 75 in other deposits in Kazakhstan, which indicates significant enrichment of rhenium relative to molybdenum in these deposits. For comparison, Mo:Re ratios in porphyry copper deposits range from about 100 to >10,000 and average about 2,050 (table P2), which is close to estimates for the average Mo:Re ratios in continental crust, which range from 2,500 to 2,750 (Taylor and McLennan, 1995; Rudnick and Gao, 2003). Poplavko and others (1962) reported discovery of dzhezkazganite, a new rhenium mineral, at the Dzhezkazgan deposit and suggested that it had a chemical formula of CuReS4. Subsequent electron microprobe analyses suggested a more complex formula of ReMoCu2PbS6 for this microscopic (typically µm) phase (Genkin and others, 1994). Recent analyses of copper ore minerals in two samples from the Dzhezkazgan deposit show that the rhenium contents of chalcopyrite and bornite range from 3.3 to 10.1 ppm (Box and others, 2013), which are extremely high concentrations of rhenium in nonmolybdenite samples (Ruiz and Mathur, 1999; Selby and others, 2009). These data suggest that significant amounts of rhenium may be present in copper-iron sulfide minerals, although mass balance relations between copper and rhenium indicate that most of the rhenium is likely present in dzhezkazganite. Occurrences in Reduced-Facies-Type (Kupferschiefer) Strata-Bound Copper Deposits The thin black shale that forms the Upper Permian Kupferschiefer (copper slate) hosts the largest copper and silver deposits in Europe (Mansfeld-Sangerhausen and Lubin-Sieroszowice deposits) (fig. P3; Vaughan and others, 1989; Jankowski, 1995; Kucha, 2003; Hitzman and others, 2005). These reduced-facies-type strata-bound copper deposits also contain large rhenium resources. In the Kupferschiefer, rhenium is currently produced from the Lubin-Sieroszowice orebody in southwestern Poland (Bartlett and others, 2013), and high rhenium contents have been reported in the formerly mined Mansfeld-Sangerhausen deposits in southern Germany (Jankowski, 1995). Ore reserves in these deposits are large; 2011 end-of-year reserves for the Legnica-Glogów copper belt in Poland, which includes the Lubin-Sieroszowice orebody, were 1,181 million metric tons of ore at average grades of 1.58 percent copper and 48 g/t silver (Bartlett and others, 2013); large undeveloped deposits have also been identified elsewhere in the Kupferschiefer in Poland. The average rhenium content of the Polish copper ores mined in 2009 was 0.6 g/t, but the rhenium grade varied from about 1.1 g/t in shale ore to about 0.4 g/t in sandstone ore (Smakowski and others, 2010). In contrast, Jankowski (1995) reported a much larger average rhenium content of 21 ppm in Kupferschiefer ores in the Mansfeld-Sangerhausen deposits in Germany, suggesting that more than 2,500 metric tons of rhenium was contained in ores mined from 1200 through 1990. Only small amounts of rhenium were recovered from flue dusts near the end of mining of these deposits, however, and production data from 1962 suggests that rhenium recovery was only about 0.1 g/t (Kruger, 2006). The Kupferschiefer deposits occur along the southern margin of the Rotliegendes-Zechstein basin (part of an Early Permian intracontinental rift basin) where it overlies Paleozoic continental sedimentary and bimodal volcanic rocks (Vaughan and others, 1989; Kucha, 2003; Hitzman and others, 2005). The volcanic rocks in the Lower Rotliegendes are extensively albitized and may have supplied some of the copper in the Kupferschiefer deposits (Hitzman and others, 2005). The overlying Upper Rotliegendes is a thick red-bed sequence
Geology P15 composed of fluvial, eolian, and playa (sabkha) deposits that is locally overlain by white eolian sandstones (Weissliegendes). The Upper Permian Kupferschiefer is a thin (typically 30 to 70 centimeters thick) organic carbon-rich black shale that covers more than 800,000 square kilometers (km2) in central Europe. It forms the basal unit of the Zechstein layer and was deposited during the initial stages of a rapid marine transgression over the Rotliegendes-Weissliegendes sequence. The Kupferschiefer black shale is overlain by Zechstein carbonates (dolomite and limestone) and evaporites (anhydrite and halite), which may have supplied some of the sulfur in the ores. Copper, gold, PGEs, and silver are hosted by both the black shales and the underlying white sandstones (fig. P5C ). Thin base-metal sulfide zones in the Kupferschiefer are tens to hundreds of square kilometers in area, and immediately adjacent hematitic alteration (in the Rote Fäule) covers more than 40,000 km2. In the Kupferschiefer deposits, hydrothermal minerals and metals typically are zoned upward from hematite (Fe3+) to the sequence of covellite, chalcocite, bornite, chalcopyrite (copper zone), to galena (lead zone), to sphalerite (zinc zone), and finally to pyrite (Fe2+ ) (fig. P5C; Oszczepalski, 1999; Kucha, 2003; Hitzman and others, 2005). Gold and PGEs are concentrated in the transition zone between hematite and copper minerals, and silver is concentrated in the copper ores. The Kupferschiefer mineralization is complex, probably formed in multiple stages, and likely involved influx of oxidizing, metal-rich brines that moved through the oxidized red beds (Rote Fäule) from the Rotliegendes basin into the reduced Kupferschiefer (Zechstein) sediments (fig. P5C; see summary in Hitzman and others, 2005). The three main stages of ore formation involved (1) early diagenetic formation of iron monosulfides and possibly chalcocite near the sediment-water interface; (2) diagenetic replacement of iron monosulfides and (or) pyrite by copper-iron sulfides at least partly associated with Rote Fäule alteration, and (3) diagenetic remobilization of earlier copper sulfide mineralization during later Rote Fäule alteration and formation of gold-PGE mineralization (for example, Vaughan and others, 1989; Wodzicki and Piestrzynski, 1994; Kucha, 2003; Hitzman and others, 2005). Rhenium in the Kupferschiefer is associated with molybdenum in copper-rich shale ore (Hammer and others, 1990; Kucha, 2003). Kucha (2003) stated that copper, lead, and potassium-castaingite (cuprian molybdenite) have molybdenum-to-rhenium ratio of 70:1, although he did not report actual rhenium analyses. Jankowski (1995) reported molybdenum-to-rhenium ratio of 7:1 for ores in the MansfeldSangerhausen mines but did not report rhenium mineralogy. As in the Kazakhstan strata-bound copper deposits, these molybdenum-to-rhenium ratios suggest significant rhenium enrichment relative to molybdenum. Geochemical studies of the Sangerhausen basin in Germany show large variations in the rhenium content of rocks; the content ranges from 0.24 to 27 ppm, and the highest rhenium concentrations are in the copper facies of the Kupferschiefer (Hammer and others, 1990). Pašava and others (2010) reported rhenium concentrations ranging from 63.6 to 1,380 ppb in six samples of unmineralized Kupferschiefer black shale in Poland (the copper content was less than or equal to 106 ppm and the molybdenum content was between 20 and 340 ppm). In these samples, rhenium strongly correlates with molybdenum (r2 0.93) and is concentrated in the lower part of the black shale. Pašava and others (2007b) reported rhenium concentrations ranging from 249 to 22,000 ppb for six copper-rich black shale samples (the average copper grade was 4.9 percent and no molybdenum content was reported), whereas six samples from PGE- and gold-rich but copper-poor horizons had rhenium concen trations that ranged from 221 to 558 ppb (Pašava and others, 2007a). Comparison of the minor element composition of unmineralized Kupferschiefer sediments in the Lower Rhine basin in northwestern Germany to black shales in the Late Devonian Exshaw Formation in Canada and to modern black shales indicate similar high levels of enrichment in arsenic, cadmium, molybdenum, nickel, rhenium, antimony, uranium, and vanadium, which are typical of syngenetic mineralization (Lüschen and others, 2000a, b). These data suggest that rhenium in Kupferschiefer ores could have been derived from the black shales and was locally remobilized into the copperrich zones. Rhenium is produced from the Kupferschiefer deposits by roasting copper ore. During roasting, sulfur and rhenium are released as gases that precipitate in the flues. Wet scrub bing of the flue dusts produces sulfuric acid that contains dissolved rhenium. Resins are then used to adsorb the rhenium from the acid, and the rhenium is ultimately precipitated as ammonium perrhenate. All processing of Kupferschiefer ores and recovery of rhenium are done by KGHM Polska Miedź S.A. at their facilities in Lubin, Poland. Rhenium in Sandstone-Type Uranium Deposits Rhenium was formerly produced as a byproduct from roll-front-type sandstone uranium deposits in Uzbekistan, and rhenium is currently recovered from similar uranium deposits in Kazakhstan (figs. P3 and P5D; Dahlkamp, 2009a, b; Seltmann and others, 2012). Small amounts of rhenium were also recovered from sandstone uranium deposits in Texas from 1969 to 1974 (Millensifer, 1997). Sandstone uranium deposits are generally hosted in permeable medium- to coarse-grained sandstones that were deposited in fluvial or nearshore marine environments. The large sandstone deposits in Kazakhstan and Uzbekistan are hosted in large Cretaceous to early Tertiary continental basins. The deposits form by the dissolving of uranium from nearby strata in oxidized groundwaters that flow through the sandstones. Uranium is precipitated at a redox boundary (the "roll-front") when the oxidized ore fluids intersect and react with reducing agents in sandstone host rocks, such as carbonaceous (plant and algal) material, sulfide minerals, hydrocarbons, or interbedded volcanic rocks. Rollfront-type uranium deposits are crescent-shaped orebodies that crosscut the bedding in the sandstones (fig. P5D).
P16 Critical Mineral Resources of the United States— Rhenium Figure P5.—Continued D , Roll-front-type sandstone uranium deposit in the Moynkum-Tortkuduk sector of the Chu-Sarysu basin, Kazakhstan, showing lithological and reduction-oxidation (redox) control on uranium, rhenium, and selenium mineralization. Rhenium and uranium are enriched at the front of the roll in reduced rocks, whereas selenium is concentrated in oxidized rocks. The top cross section shows the oxidized zone; the bottom cross section shows the zone of selenium enrichment. Figure modified from Dahlkamp (2009a). ppm, part per million P5 (Continued) - D- Roll -Front-Type Sandstone Uranium Deposit D
Geology P17 At the Sugraly deposit in the Zarafshan mining district in Uzbekistan, rhenium was recovered along with selenium and molybdenum as byproducts of the mining of uranium deposits in Cretaceous to Eocene sandstone strata in the Kyzylkum basin (Dahlkamp, 2009b). Underground mining began in 1977 and was later switched to in situ leaching until mining ended in 1994. The Sugraly deposit was a typical roll-front-type deposit with complex uranium-selenium-molybdenumrhenium ores that formed orebodies that were from several hundred meters to 20 km long and from 100 to 500 meters (m) wide. Rhenium content varied from 10 to 15 ppm (Seltmann and others, 2012). Rhenium was reportedly present in the form of ReS2 and ReO2 (Dahlkamp, 2009b). Rhenium is reported in several roll-front-type sandstone uranium deposits in Kazakhstan (Dahlkamp, 2009a). These include deposits in the Moynkum (Moinkum), the Kanzhugan, and the Kenze-Budenovskaya mining districts in the Chu-Sarysu basin, and deposits in the Suluchekinskoye district. In the Moynkum and Kanzhugan districts, numerous uranium orebodies are associated with redox fronts in Paleogene sandstone aquifers. Rhenium grades generally range from 0.08 to 0.38 g/t with rhenium content of as much as 4.8 g/t in some deposits. In the Tortkuduk sector at the north end of the Moynkum deposit, uranium mineralization is contained in a 40-m-thick arenite unit sandwiched between clay-silt beds (fig. P5D). Uranium mineralization extends for about 10 km along a winding redox front. The forward sections of the rolls are about 20 m thick; tails may be up to several meters thick and more than 400 m long. A rhenium halo ( 0.1 ppm rhenium), which coincides with the uranium distribution, surrounds the front of the roll and extends for up to 60 m into the reduced rocks (fig. P5D). A selenium zone with greater than 50 ppm selenium is in the rear part of the roll (fig. P5D). At the Zhalpak and the Akdala deposits in the KenzeBudenovskaya mining district, Cretaceous sandstones host roll-front uranium mineralization. Several orebodies in these deposits have rhenium content of as much as 62 ppm (Dahlkamp, 2009a; Seltmann and others, 2012). Samples containing greater than 0.2 ppm rhenium have higher uranium contents. In the Suluchekinskoye district in the Ily basin, rollfront-type orebodies are hosted by Cretaceous to Paleogene sandstones. Orebodies are zoned laterally from rhenium in reduced rocks, followed by a uranium-rhenium zone at the redox boundary, and then a selenium zone that forms the rear of the roll in oxidized rocks. Rhenium contents range from 1 to 24 ppm and average 1 to 2 ppm. Uranium and rhenium in the Kazakhstan deposits are recovered using in situ leaching (also known as solution mining). In mining that uses in situ leaching, ore minerals are dissolved by circulating groundwater fortified with sulfuric or other acids through undisturbed underground deposits (World Nuclear Association, 2013). The resulting pregnant solutions are pumped to the surface, and uranium, rhenium, and other metals are recovered using methods similar to those used in processing milled uranium ore. Rhenium in the Merlin Deposit The Merlin molybdenum-rhenium deposit in the Mount Isa Inlier in northwestern Queensland, Australia, is a highgrade rhenium resource in which rhenium and molybdenum are the primary commodities and only minor amounts of copper are present (fig. P3; Brown and others, 2010; Lycopodium Minerals QLD Pty Ltd., 2012). Mineralized rock consists dominantly of molybdenite in veins, infilling breccias and stylolites, and disseminated grains in a zone that is about 1 km long and up to 20 m thick. Rhenium is contained in molyb denite grading an average of about 1,000 ppm rhenium. In 2012, indicated and inferred mineral resources were 6.9 million metric tons averaging 1.38 percent molybdenum and 22.7 ppm rhenium (Lycopodium Minerals QLD Pty Ltd., 2012). The Merlin deposit was discovered in 2008 during drilling of the northern extension of the Mount Dore copper deposit, which mostly lies above and south of the Merlin deposit (Brown and others, 2010). The Merlin and the Mount Dore deposits are hosted by Early Proterozoic carbonaceous metashale and metasiltstone that are structurally overlain by the 1,500-mega-annum (Ma) anorogenic Mount Dore Granite along a moderately dipping reverse fault. The Merlin molybdenum-rhenium mineralization is associated with silica-albite alteration and interstitial clays that formed along reactivated fractures and shear zones and replaced the matrix of structurally controlled breccias. At Mount Dore, early regional-scale sodic-calcic alteration is cut by potassic alteration and quartz veins and by breccias that host an early phase of copper mineralization. A second phase of brecciation was followed by deposition of dolomite and a second stage of copper mineralization. The molybdenum-rhenium minerali zation at the Merlin deposit cuts the copper mineralization in the Mount Dore deposit but is likely part of the same system. Zircon uranium-lead dating of the Mount Dore Granite and rhenium-osmium dating of molybdenite in the Mount Dore deposit show that both formed at about 1,500 Ma and suggest that copper-molybdenum mineralization at Mount Dore probably is related to a late-stage, evolved magmatic fluid that generated potassic alteration (Duncan and others, 2011). The average Mo:Re ratio of 600 is also consistent with an igneous origin.
P18 Critical Mineral Resources of the United States— Rhenium Resources and Production Identified Resources Estimates of grades and tonnages of major rheniumbearing deposits are shown in figure P4 and presented in tables P1 and P2. There are no published grade and tonnage models for rhenium in porphyry deposits, although Sinclair and others (2009) and Millensifer and others (2014) present plots of rhenium grade versus deposit tonnages for some porphyry and other types of deposits. Publicly available data on rhenium contents in porphyry deposits are limited and often inconsistent when more than one data source is available. Very few grade and tonnage data are available for other types of deposits that produce rhenium. Descriptions of data compila tion methods and limitations of these data are in appendix P1. Production Worldwide mine production of rhenium in 2012 was estimated to be 52,600 kg, of which about 27,000 kg, or 51 percent, was produced from porphyry copper mines in Chile (fig. P6; Polyak, 2014). Because specialized processing facilities are required to recover rhenium from molybdenite concentrates, however, a significant amount of rhenium (approximately 15 to 20 metric tons) is contained in molyb denite concentrates roasted at facilities other than where it is mined (for example, molybdenite concentrates from the Bingham Canyon Mine), thereby making estimates of the sources of rhenium difficult. In recent years, rhenium also was recovered from porphyry copper deposits in the United States, Armenia, Kazakhstan, Mexico, Peru, Russia, and Uzbekistan. Porphyry copper deposits formed in continental arcs are the main sources of both rhenium production and resources (tables P1 and P2; fig. P3). All primary rhenium production in the United States is from processing facilities at the Sierrita Mine in Arizona, where rhenium is recovered from molybdenite concentrates produced at several porphyry copper mines. Rhenium resources in the United States are located mainly in Arizona and Utah, although smaller resources are located in Montana, New Mexico, and Nevada. The Pebble deposit in Alaska also contains a large inferred rhenium resource. Sediment-hosted strata-bound copper deposits in Poland and Kazakhstan were the other major primary sources of rhenium in 2011, and both the Kupferschiefer deposits in Poland and the Dzhezkazgan deposit in Kazakhstan have large identified rhenium resources (fig. P4). Ore reserves in the underground deposits in Kupferschiefer deposits in the Legnica-Glogów copper belt, Poland, are sufficient to maintain the current production rate of about 30 million metric tons per year for 30 to 40 years (Bartlett and others, 2013). Sandstone uranium deposits in Kazakhstan produce some byproduct rhenium, and published grade and tonnage P6 - Pie Char t S howing World Rhenium Mine Production i n 2012 Figure P6. Pie chart showing world rhenium mine production in 2012, by country and percent of world total. Compiled using data from Polyak (2014). data suggest significant rhenium resources in some deposits (Dahlkamp, 2009a). The lack of grade and tonnage data for most deposits, however, precludes a thorough assessment of these resources (table P1; fig. P4). Similar deposits in the southern and middle Ural Mountains in Russia may produce rhenium, but no production or resource estimates are available (Khalezov, 2009). The Merlin molybdenum-rhenium deposit in Queensland, Australia, is unique because rhenium is a primary commodity. Despite its high rhenium grade (22.7 ppm), the contained rhenium resources are relatively small compared with the resources of other deposit types (fig. P4). Undiscovered Resources Rhenium resources likely are present in undiscovered porphyry copper deposits formed in continental arcs throughout the world. Recent U.S. Geological Survey (USGS) assessments of porphyry copper deposits in the Southwestern United States (Ludington and others, 1996), the Andes Mountains in South America (Cunningham and others, 2008), Mexico (Hammarstrom and others, 2010), the Province of British Columbia and the Yukon Territory in Canada (Mihalasky and others, 2013), and the Tethys region, including Armenia, Azerbaijan, Georgia, Iran, and Turkey
Environmental Considerations P19 (Lukas Zürcher, U.S. Geological Survey, written commun., 2013) concluded that there is significant potential for undis covered porphyry copper deposits in these regions. Because known porphyry copper deposits in these areas contain some of the largest identified rhenium resources in the world, it is highly probable that significant rhenium resources remain to be discovered in these areas. In the United States, additional rhenium resources in porphyry copper deposits are most likely to occur in Arizona, where there are numerous identified deposits—several of which contain recoverable rhenium—and where there is a high probability of undiscovered deposits. Also, recent delineation of the giant Pebble porphyry copper-molybdenumgold deposit in Alaska, which has estimated rhenium resources that represent more than 40 years of production at the current level of worldwide mine production (Ghaffari and others, 2011; Lang and others, 2013), suggests that there is the potential for significant rhenium resources in undiscovered porphyry copper deposits in Alaska. Mongolia is another area where significant porphyry copper deposits have been discovered recently (for example, the giant Oyu Tolgoi porphyry copper-gold deposit in Omnogovi Aymag) (Khashgerel and others, 2006). The incompletely defined Zuun Mod molybdenum deposit has modest rhenium resources (table P1; Clark and Baudry, 2011). The presence of these deposits suggests the potential for significant undiscovered rhenium resources in Mongolia. According to the recent USGS assessment of sedimenthosted strata-bound copper deposits, a significant number of undiscovered reduced-facies-type strata-bound copper deposits that have large resources are likely present in the Kupferschiefer in Poland (M.L. Zientek, U.S. Geological Survey, written commun., 2013) and sandstone-type stratabound copper deposits in Kazakhstan (Box and others, 2012). Because known deposits in these areas are enriched in rhenium and contain significant rhenium resources (fig. P4), the undiscovered deposits also likely contain significant rhenium resources. Other large sediment-hosted strata-bound copper deposits, such as Udokan in the Transbaikalia Region in Russia and deposits in the Democratic Republic of the Congo, do not have reported anomalous rhenium contents (Hitzman and others, 2005; Zientek and others, 2013). The recent discovery of the Merlin deposit in Australia opens up the possibility that there are other high-grade molybdenum-rhenium deposits in which these metals are the primary commodities. Until the genesis of the Merlin deposit is better understood, however, it is premature to speculate on the probability of the occurrence of similar deposits. Exploration for New Deposits With the exception of the Merlin molybdenum-rhenium deposit, all identified rhenium resources are contained in deposits mined primarily for other mineral commodities. In porphyry copper deposits, rhenium is recovered mostly from molybdenum, which is another byproduct. Until a better understanding of the genesis of the Merlin deposit emerges and it is determined that this type of deposit is economic, exploration for other primary rhenium deposits is unlikely to take place. Therefore, the discovery of significant new rhenium resources is likely to depend on successful explora tion for porphyry copper deposits, especially in frontier areas, such as Alaska and Mongolia, where there have been recent discoveries of large porphyry copper deposits that may contain byproduct molybdenum and rhenium (for example, the Pebble and the Oyu Tolgoi deposits). Future exploration for porphyry copper deposits likely will involve increased remote sensing, geophysical (both potential field and electrical techniques), and lithogeochemical studies to discover covered deposits (for example, Graybeal and Vikre, 2010). Environmental Considerations Rhenium is present in Earth's crust at very low concen trations, and its production is nearly always as a byproduct commodity from copper mining. Therefore, the environmental characteristics of rhenium extraction are closely linked to those associated with the mining of the two types of copper deposits that represent its main sources. The primary source of rhenium is from the mineral molybdenite (the main ore mineral of molybdenum) derived from porphyry copper deposits. Rhenium is also produced from sediment-hosted copper deposits. The economic geology of the two mineral deposit types that are the predominant sources of byproduct rhenium are significantly different from one another, which means that the environmental geology of these deposit types are also different. The environ mental geology of porphyry copper deposits is dominated by their large size (which means that they are commonly mined by open pit methods), their low grade, and the variable potential of their solid mine wastes to generate minor amounts of acid drainage or neutralize it (John and others, 2010). The environ mental geology of sediment-hosted copper deposits is character ized by their moderate size, the tabular geometry of their ores, their low grade, and the low potential of their solid mine wastes to generate acid drainage (Hayes and others, 2015).
P20 Critical Mineral Resources of the United States— Rhenium Sources and Fate in the Environment Concentrations of rhenium in the natural environment, including in groundwater, surface water, sediment, soils, and biota, are low, which is a reflection of rhenium's low crustal abundance (table P3). The distribution of rhenium in environmental samples is further influenced by its relatively higher solubility in oxygenated waters and its lower solubility in oxygen-free (anoxic) waters. The overall concentration of rhenium in water is similarly lower than that of many other base and precious metals, as summarized by Colodner and others (1993) and Hodge and others (1996). In fact, the natural concentration of rhenium in surface water, groundwater, and seawater falls in the partsper-trillion range (table P3). Experimental studies suggest that the maximum solubility of ReO2 in water at room temperature (25 °C) is less than 160,000 parts per trillion (ppt) (0.16 ppm), but could be as low as 20 ppt (Kim and Boulègue, 2003; Xiong and others, 2006). Dissolved concentrations in the ocean average 8.3 ppt and do not vary with depth (Colodner and others, 1993). Variations in rivers span four orders of magnitude, from 0.004 to 76 ppt (Colodner and others, 1993; Rahaman and others, 2012). The geology of the watershed influences the rhenium concentration. Watersheds underlain by black shales typically have higher concentrations of rhenium than do those underlain by other rock types. Rhenium in seawater and surface water behaves conservatively, meaning that it stays dissolved and does not bind or adsorb to particu late matter, such as clays. Reducing sediments (sediments rich in organic matter and sulfide minerals) are known to be important for the removal of rhenium from the water column, however (Koide and others, 1986). The observation that black shales can serve as sources of elevated concentrations of rhenium in surface water is a reflection of this process operating in the geologic record (Rahaman and others, 2012). In solid environmental media (soil, sediment, and biological material), the rhenium concentrations are also low, although they are higher than those typically found in water (table P3). River sediments, oxygenated marine sediments, and soils all have concentrations that are comparable to the average crustal abundance (0.4 ppb). Organic-rich, anoxic sediments have concentrations that can be significantly higher (1.8 to 110 ppb) (Koide and others, 1986). Plants are known to accumulate rhenium at concentrations greater than local soil concentrations (Bozhkov and Borisova, 2003). Information on pre-mining environmental concentrations of rhenium is limited, in part because of its low concen trations. Leybourne and Cameron (2008) investigated the concentrations of arsenic, copper, molybdenum, rhenium, and selenium in groundwater associated with the undeveloped Spence porphyry copper deposit in the Atacama Desert in northern Chile. They found that groundwater concentrations within the deposit reached a maximum rhenium concentration of 30.7 ppb. Outside of the deposit, the minimum rhenium concentration was as low as 0.2 ppb. From an environmental perspective, baseline concentrations of other trace elements and related constituents associated with porphyry copper deposits or sediment-hosted copper deposits are of greater environmental interest than are those for rhenium because these elements can be present in significantly higher concentrations. Environmental baseline characterization studies of porphyry copper deposits are limited in the literature, particularly with regard to the diversity of climatic settings in which the deposits are found. Some information is available in mine permit applications for recently proposed mines, however. Studies from such diverse climates as the cold climate of southwestern Alaska (Fey and others, 2008); the tropical climate of Puerto Rico (Learned and Boissen, 1973; Plaza-Toledo, 2005); and the hot, arid climates of Table P3. Rhenium concentrations in rocks, soils, biota, waters, and sediments. [ppb, part per billion; ppt, part per trillion] Environment Rhenium concentration
Upper continental crust 0.4 ppb Taylor and McLennan (1995) Soils 0.208 to 1.72 ppb Uchida and others (2005) Leaves, dried, birch and fir, unimpacted 4 to 6 ppb Bozhkov and Borisova (2003) Leaves, dried, acacia, smelter and mine site vicinity 902 to 2,430 ppb Bozhkov and Borisova (2003) Seawater (Atlantic Ocean and Pacific Ocean) 8.3 ± 0.1 ppt Colodner and others (1993) Rivers 0.004 to 76.7 ppt Colodner and others (1993); Rahaman and others (2012) Groundwater 0.9 to 35.4 ppt Colodner and others (1993); Hodge and others (1996) Groundwater, porphyry copper deposits 0.09 to 30.7 ppb Leybourne and Cameron (2006) River sediment 0.233 to 0.285 ppb Uchida and others (2005) Pelagic sediments 0.1 ppb Koide and others (1986) Anoxic sediments 1.8 to 110 ppb Koide and others (1986)
Environmental Considerations P21 Arizona and Chile (Chaffee, 1976, 1977; Chaffee and others, 1981; Leybourne and Cameron, 2006, 2008) show similar geochemical features. Soils show elevated concentrations of, in decreasing order of maximum concentration, iron (2.3 to 7.4 weight percent), sulfur (0.02 to 0.87 weight percent), copper (3.2 to 1,830 ppm), zinc (36 to 142 ppm), arsenic (7 to 78 ppm), molybdenum (0.6 to 27.1 ppm), lead (7.1 to 17.4 ppm), and cadmium 0.1 to 0.6 ppm). Stream sediments show elevated concentrations of, in decreasing order of maximum concentration, iron (6.3 to 10.6 weight percent), copper (64 to 804 ppm), zinc (59 to 291 ppm), lead 4 to 17 ppm), molybdenum 2 to 10 ppm), arsenic 10 ppm), and cadmium 2 ppm). Only a limited amount of pre-mining baseline data are available in the literature for soil, stream sediment, groundwater, and surface water from a variety of deposits. Plaza-Toledo (2005) found that surface waters downstream from undeveloped porphyry copper deposits in the Cordillera Central of Puerto Rico contained maximum dissolved concentrations of 110 ppm sulfate, 15.9 ppm iron, 0.56 ppm aluminum, 0.13 ppm copper, and 0.04 ppm zinc. The pH was high (7.7 to 8.6). Fey and others (2008) documented surface-water pH values of between 4.1 and 7.3 in the vicinity of the Pebble deposit in southwestern Alaska. Alkalinity ranged between 0 and 100 ppm calcium carbonate (CaCO3 ) equivalent; sulfate, between 1 and 85 ppm; and hardness of water, between 2 and 130 ppm CaCO3 equivalent. Dissolved trace element concentrations showed a range of values for, in decreasing order of maximum concentration, iron 20 to 4,260 ppb), copper 0.5 to 688 ppb), zinc 0.5 to 68 ppb), arsenic (<1 to 36.2 ppb), molybdenum 2 to 21.9 ppb), lead 0.05 to 18.8 ppb), and cadmium 0.2 to 11.6 ppb). Leybourne and Cameron (2006, 2008) documented high salinity in groundwaters associated with the undeveloped Spence deposit where the salinity reached 10,000 to 55,000 ppm, with one outlier sample at 145,000 ppm. The pH of the groundwaters varied widely, between 4.7 and 9.2. Dissolved sulfate concentrations in groundwaters were between 5,000 and 10,000 ppm. Dissolved trace element concentrations showed a range of values for, in decreasing order of maximum concentration, iron (4 to 54,454 ppb), copper (9 to 28,991 ppb), zinc (5 to 1,344 ppb), molybdenum (2 to 475 ppb), arsenic (<10 to 160.9 ppb), and lead (0.025 to 23.8 ppb). Environmental baseline characterization studies of sediment-hosted copper deposits are more limited than those for porphyry copper deposits. For sedimentary-hosted copper deposits, soil and stream sediments may contain anomalous abundances of copper, lead, silver, and possibly arsenic, mercury, and zinc in the vicinity of the deposits (Lindsey and others, 1995). Stream-sediment samples collected in the Kafue River (Zambia) upstream from sediment-hosted copper deposits contained copper in concentrations of between 15 and 146 ppm, some of which were just below the stream-sediment criterion (that is, the probable effects concentration, or the concentration at which toxic effects would be expected for aquatic organisms) of 149 ppm (MacDonald and others, 2000; Pettersson and others, 2000; Pettersson and Ingri, 2001). Also, soil and sediment associated with some sandstone deposits in Montana contained anoma lous copper (up to 2,000 ppm), lead (greater than 150 ppm), and silver (greater than 0.5 ppm), as reported by Cazes and others (1981) and Wells and others (1981). In contrast to some of the sediment and soils that have anomalous metal concentrations, surface water in the Kafue River upstream from the mining area in Zambia contains low levels of copper (up to 3 ppm) and other trace elements (Norrgren and others, 2000; Pettersson and Ingri, 2001). The draft environmental impact statement for the Montanore Project, which is a proposed mine in the Rock CreekMontanore deposit in Montana, describes the surface-water quality in streams and lakes near the proposed mine as being "excellent," which presumably means that all trace elements meet environmental criteria. The concentrations of total suspended solids, total dissolved solids, major ions, nutrient concentrations, and metal concentrations are generally low and frequently at or below detection limits. The surface waters generally contain iron, copper, and silver in low concen trations that are well below environmental guidelines. The surface waters tend to be slightly acidic (U.S. Department of Agriculture, Forest Service, and others, 2009). Mine Waste Characteristics The amount of mine waste associated with porphyry copper and sediment-hosted deposits varies with the size of the deposit. Porphyry copper deposits range from 30 million metric tons to more than 20 billion metric tons with a median size of 250 million metric tons. Because copper grades are typically less than 1 percent copper (median grade of 0.44 percent copper), more than 95 percent of the material mined ends up as solid mine waste of one form or another. The solid mine waste typically falls into one or more of the following three types: tailings, waste rock, and leach-pad waste. Tailings and waste rock are usually found at all mines, whereas leach-pad waste is found only at those mines where the ores are amenable to a copper extraction method known as solvent extraction-electrowinning (SX-EW). SX-EW is viable only for deposits that have been subject to prolonged periods of weathering, which has produced a zone near the surface where sulfide minerals have been oxidized to copper oxide or copper carbonate minerals. The oxide zone will overlie an unweathered sulfide zone. The oxide ore is mined and crushed to a coarse grain size and placed on lined pads. The piles are leached with a sulfuric acid solution, which is recovered to collect the leached copper. Oxide zones are not universally present at porphyry copper deposits, so this type of mine waste is not always present at porphyry copper deposits.
P22 Critical Mineral Resources of the United States— Rhenium Tailings are produced when the ore is crushed to a sand or silt size to facilitate the separation of the copper sulfide and other metal-sulfide ore minerals from gangue minerals (minerals of no value) using a technique known as froth flotation. After separation of gangue minerals, the tailings are discarded as a slurry or trucked dry to a tailings storage facility. Tailings storage facilities are typically impoundments surrounded by a retaining dam. The other type of solid waste is waste rock. Because of their large size and low grade, porphyry copper deposits are commonly mined by open pit methods. Waste rock is uneco nomic rock that must be removed (stripped) to access the ore. Waste rock is disposed of on site. It can also be used for construction on site if tests determine that it will not generate acid-rock drainage when it is exposed to the atmosphere and water. For open pit porphyry copper mines, waste-to-ore (stripping) ratios commonly can exceed 2:1, which means that for each ton of ore mined, two tons of waste rock must be removed (Porter and Bleiwas, 2003). Porphyry copper deposits at depth can also be mined by block caving. A vertical shaft or spiral decline is built to the base of the orebody, and the orebody is mined from below, leaving a large, unsupported cavity where the ore was removed. With this type of mining, the amount of waste rock is less than that in open pit mining and the waste material is dominated by tailings. The size of sediment-hosted copper deposits depends upon their subtype (reduced type, red bed, or sandstone) and is smaller than most porphyry copper deposits. The volume of mine waste and tailings produced from a deposit depends on the deposit size, depth, geometry, ore grade, and mining method. Sediment-hosted copper deposits can be mined by underground or open pit methods. The reduced-facies-type deposits are generally high tonnage (the median tonnage is 33 million metric tons) with a high copper grade (the median grade is 2.3 percent) (Lindsey and others, 1995; Cox and others, 2003). Red-bed deposits are generally low tonnage (the median tonnage is 1.2 million metric tons), have an intermediate copper grade (the median grade is 1.2 percent), and are mined either by open pit or underground methods. Sandstone deposits are intermediate tonnage (the median tonnage is 14 million metric tons) but they have lower copper grades (the median grade is 0.79 percent). Because of the low copper grades, most of the mined rock is waste. Copper can be separated by froth flotation of finely ground ore or by SX-EW recovery from oxidized ores. The mineralogy of the ore and waste in porphyry copper and sediment-hosted copper mines determines the environmental characteristics of these deposits. In terms of both ecological risks and human health risks, the mineralogy dictates the acid-generating potential of the ores and wastes and the mobility of trace elements. In porphyry copper deposits, sulfide minerals, such as bornite, chalcopyrite, enargite, galena, molybdenite, pyrite, and sphalerite, are the main hosts of the trace elements that are of environmental concern; in total, they typically constitute less than 5 percent of the ore (John and others, 2010). In sediment-hosted copper deposits, the sulfide minerals are dominated by, in general order of decreasing abundance, chalcocite, digenite, bornite, chalcopyrite, pyrite, and subordinate galena and sphalerite (Hayes and others, 2015). The trace element geochemistry of tailings and waste dumps reflects the mineralogy of the waste. For porphyry copper deposits, tailings typically contain significant concentrations of copper (475 to 5,100 ppm), manganese (67 to 700 ppm), molybdenum (12 to 235 ppm), zinc (40 to 210 ppm), and arsenic (3.5 to 136 ppm) (John and others, 2010). Tailings from sediment-hosted copper deposits generally contain 1 to 4 weight percent iron, 0.1 to 0.3 weight percent copper, and 300 to 800 ppm cobalt (Hayes and others, 2015). Approaches for managing solid waste depend upon its acid-generating potential. Acid generation can be considered a "master variable" for aqueous risks. Metals and many other trace elements tend to be more soluble at low pH (acidic) than at neutral or high pH (alkaline). Therefore, the acid-generating or acid-neutralizing potentials of the waste rock, tailings, and other solid waste material are of prime importance in identifying the potential environmental risks associated with mining and ore beneficiation. The acid-generating potential of mine waste is expressed in terms of the amount of calcium carbonate it would take to neutralize it; it is measured in kilograms of calcium carbonate per metric ton of mine waste (kg CaCO3/t) (Price, 2009; International Network for Acid Prevention, 2011). The acid-generating potential resides primarily in pyrite. Mine waste can also have acid-neutralizing potential, which resides in carbonate minerals, such as calcite, and in some silicate minerals, such as feldspars. The rocks associated with porphyry copper deposits, in general, tend to straddle the boundary between having net acid-generating potential and not having net acid-generating potential. During mining and processing of porphyry copper deposits, a variety of materials with differing acid-base accounts may be encountered and produced, and each type must be managed according to its acid-generating potential. Net alkaline waste does not require any special handling and can be used for construction purposes, whereas net acid waste has to be managed to mitigate acid-mine drainage problems. As an example, the net neutralizing potentials for the hypogene and supergene ores from Morenci, Arizona, range from dominantly net acid to slightly net alkaline (-257.0 to 1.1 kg CaCO3/t) (Enders and others, 2006). The net acid-neutralization potentials reported in the literature for tailings from several porphyry copper deposits in Chile are net acid generating, ranging from -101.6 to -18.2 kg CaCO3/t (Dold and Fontboté, 2001). Tailings derived from metal lurgical testing on an exploratory drill core from the Pebble deposit in southwestern Alaska have net neutralization potentials ranging from -110 to 27.2 kg CaCO3/t (Pebble Partnership, 2011).
Environmental Considerations P23 For sediment-hosted copper deposits, the abundance of carbonate minerals and slightly less reactive minerals, principally chlorite- and epidote-group minerals, determine the acid-neutralizing capacity, whereas the acid-generating poten tial is determined by the abundance of sulfides, such as pyrite and chalcopyrite. Many deposits contain a significant amount of carbonate and (or) silicate minerals in the ore or host rock, which neutralize the acidity generated by sulfide weathering. As for acid-generating sulfides, the ore for all three subtypes contain low pyrite contents. The pyrite content of the host rock for all types of sediment-hosted copper deposits is less than 1 volume percent (Hayes and Einaudi, 1986). Limited acid-base accounting data have been reported in the literature for sediment-hosted copper deposits. For tailings, no acid-generating potential has been detected in samples from the White Pine Mine in Michigan (Williams and others, 2002), whereas high acid-neutralizing capacities and neutral-to-alkaline conditions have been reported in samples from the Zambian copperbelt. For the Zambian tailings, the neutralization potential ratios are between 3.4 and 84; most samples at depth have values of greater than 20, and the highest values are for the leached surface materials (Sracek and others, 2010). The mean net neutralization potentials of ore, waste rock, and tailings from sandstone deposits at Montanore, Rock Creek, and Troy, Montana, were summarized in the environmental impact statement for these projects (U.S. Department of Agriculture, Forest Service, and others, 2009). Ore from the Montanore deposit has a mean net neutralization potential of -4 kg CaCO3/t, with values ranging from -24 to 11 kg CaCO3/t, meaning that its average value has a slight acid-generating potential, but ranges from having a slight excess of acid-generating potential to having a slight excess of acid-neutralizing potential. Values for the Rock Creek and the Troy ore samples average 5 and 8 kg CaCO3/t, respectively, meaning that they have acid-generating potential. The mean net neutralization potentials for the tailings from these sandstone deposits range from 2.8 to 10 kg CaCO3/t. These acid-base accounting results reflect the low amounts of sulfides in the tailings. The mean net neutralization potentials for the mine waste from these deposits range from 3.6 to 15 kg CaCO3/t. Human Health Concerns No information is available for rhenium and its toxic effects on humans, partly (presumably) because of its low natural abundance. The U.S. Agency for Toxic Substances and Disease Registry (://www.atsdr.cdc.gov/toxprofiles/index.asp) does not have a toxicological profile for rhenium nor does the U.S. Environmental Protection Agency have drinking-water standards or soil guidelines for rhenium. Unnatural (not natu rally occurring) radioisotopes of rhenium (188Re and 186Re), however, are being investigated for management of metastatic bone pain in cancer patients (Finlay and others, 2005). Instead, the more significant human health risks associ ated with rhenium production are found with the broader aspects of the mining of porphyry and sediment-hosted copper deposits. Contaminated groundwater plumes associated with tailings impoundments may threaten drinking-water supplies, depending upon the geologic and hydrologic setting and engineering aspects of the mine and the waste piles for both deposit types. Host rocks with higher acid-neutralization potentials, such as carbonate rocks, tend to limit the mobility of metals and related compounds. Hydrologic and climatic settings that have net evaporative loss of water may cause evaporative concentration of solutes that may enter ground water used as drinking-water supplies in the vicinity of mines and waste piles. Improperly constructed water-containment structures may allow contaminated mine waters to enter surrounding groundwater. For both porphyry copper deposits and sediment-hosted deposits, elements or compounds with the greatest likelihood of causing problems for drinking-water sources include aluminum, arsenic, copper, iron, manganese, sulfate, and zinc. The U.S. Environmental Protection Agency has primary drinking-water standards, meant to protect human health, for arsenic, cadmium, copper, and lead, and none forceable secondary standards meant to protect the cosmetic and aesthetic qualities of water (skin or tooth discoloration, taste, odor, and color) for aluminum, cadmium, iron, lead, manganese, sulfate, and zinc (U.S. Environmental Protection Agency, 2009a). The potential for groundwater contamination depends upon the waste and water management practices at any given mine. An additional human health risk associated with porphyry copper and sediment-hosted copper deposits is from the smelting of ore concentrates. Historically, it was more common for each mine or mining district to operate its own smelter. In contrast, modern mines typically ship ore concentrates to smelters that may be far away from the mines. Therefore, smelter sites are not a necessary feature of a proposed mine. Smelters may emit carbon monoxide, hydrocarbons, metals, nitrogen oxide, particulates, and sulfur dioxide, which can contaminate surrounding soils, although in the United States, these emissions are currently regulated to protect the environment. For example, numerous studies on the soil surrounding the Glogów and the Legnica smelters in Poland, which serve sediment-hosted copper mines, reported high metal concentrations, especially of, in decreasing order of maximum concentration, lead (90 to 18,000 ppm), copper (250 to 10,000 ppm), zinc (55 to 4,000 ppm), and cadmium (0.3 to 10.9 ppm), that vary with the dominant wind direction and distance from the smelter (Roszyk and Szerszen, 1988; Helios Rybicka and Jędrzejczyk, 1995; Karczewska, 1996; Pilc and others, 1999; Grzebisz and others, 2001; Kabala and Singh, 2001). The concentrations of cadmium and lead in groundwater and surface waters in the vicinity of the two smelters (Pilc and others, 1999) exceed the World Health Organization (WHO) guidelines for drinking water (World Health Organization, 2006).
P24 Critical Mineral Resources of the United States— Rhenium Ecological Health Concerns No information is available for rhenium and its toxic effects on aquatic or terrestrial ecosystems, presumably because of its low crustal abundances. Therefore, as with human health risks, the more significant ecosystem risks associated with rhenium production are found with the broader aspects of the mining of porphyry and sediment-hosted copper deposits. Many of the ecological risks associated with both porphyry copper deposits and sediment-hosted deposits focus on the ability of mine wastes to generate acid, and the ability of the resulting acid-mine drainage to carry metals and other inorganic contaminants. As described above with respect to mine-waste characteristics, the acid-generating potential of mine waste is primarily found in its pyrite content, and it may be offset by the acid-neutralizing potential found in carbonate or less significantly silicate (chlorite and epidote group) minerals. Residual ore minerals in the waste material are the primary hosts of many metals and arsenic in mine drainage. Silicate minerals are common sources of aluminum, iron, and manganese in mine drainage. Sound waste manage ment practices can mitigate these effects. Tailings are prone to being transported by waters, especially in the case of a tailings dam failure, and wind, because of the sand- to silt-size grains. Thus, they present additional potential risks to aquatic organisms through sediment contamination. Mine-drainage data are available for porphyry copper deposits in British Columbia, Canada (Day and Rees, 2006); the Globe mining district in Arizona (Eychaner, 1991; Stollenwerk, 1994; Brown and others, 1998; Lind and others, 1998; Conklin and others, 2001); the Morenci mining district, Arizona (Enders and others, 2006); and Iran (Khorasanipour and others, 2011). Many of the values exceed relevant waterquality guidelines for the protection of aquatic ecosystems (U.S. Environmental Protection Agency, 2009b). In British Columbia, Canada, Day and Rees (2006) documented mine waters with pH values ranging from 2.0 to 8.5, and sulfate was the dominant anionic species (1 to 30,000 ppm). The concen trations of trace elements varied widely: aluminum ranged from 0.001 to 1,000 ppm; copper, 0.0005 to 1,000 ppm; iron, 0.005 to 1,000 ppm; manganese, 0.001 to 100 ppm; and zinc, 0.001 to 100 ppm. Khorasanipour and others (2011) found similar geochemical trends, but in a more arid environ ment, for drainage associated with waste-rock dumps at the Sar Cheshmeh Mine in Kermān Province, southeastern Iran. The pH values ranged from 3.1 to 6.3, and the concentration of sulfates was between 365 and 1,590 ppm. The concentrations of aluminum ranged from less than 0.05 to 60 milligrams per liter (mg/L); manganese, from 14.6 to 95.8 ppm; copper, 2.15 to 70 ppm; and zinc, 2.4 to 27.4 ppm. In the Globe mining district in Arizona, a stream was blocked by mill tailings, causing a lake to form. Water from this lake entered an alluvial aquifer by seepage, and the aquifer and a stream to the north were contaminated (Eychaner, 1991; Stollenwerk, 1994; Brown and others, 1998; Lind and others, 1998; Conklin and others, 2001). The most contaminated groundwater in the aquifer had a pH of 3.3 and contained about 9,600 ppm sulfate, 2,800 ppm iron, 300 ppm aluminum, and 190 ppm copper. As the plume traveled north through the aquifer, the concentration of constituents decreased as the plume interacted with carbonate-bearing alluvium and was diluted by uncontaminated water (including groundwater flowing upward from lower basin fill, water in uncontami nated streams that join the contaminated wash, and surface rainwater). Enders and others (2006) reported analyses of seeps and springs in the Morenci district of Arizona, which had pH values of between 2.6 and 4.6. Sulfate concentra tions were between 550 and 4,300 ppm; copper, between 0.46 and 960 ppm; iron, between 15 and 420 ppm; aluminum, between 0.48 and 370 ppm; and zinc, between 0.8 and 159 ppm. Pit lakes, particularly in porphyry copper mining districts that have extensive historical underground mine workings, such as the Butte district in Montana, which has a 140-year mining history, can be problematic. The Berkeley Pit lake at Butte contains more than 100 billion liters of pH-2.5 mine water (Gammons and others, 2005; Gammons and Duaime, 2005). The pit lake has high levels of dissolved solids and elevated concentrations of copper, iron, sulfate, and zinc (Gammons and Duaime, 2005). In contrast, pit lakes in the Yerington and Robinson districts in Nevada have pH values that typically range from 7.0 to 8.5 with a few outliers near 4.7, which have been attributed to discharge from solventextraction operations rather than groundwater-rock interac tions in the vicinity of the pits (Shevenell and others, 1999). In Nevada, the total dissolved solids are generally less than 6,000 ppm, and concentrations of manganese are less than 5 ppm; iron, less than 4.5 ppm; selenium, less than 0.14 ppm; and arsenic, less than 0.05 ppm. Several studies provide insights into the ecosystem risks associated with sediment-hosted copper deposits. Detailed ecological studies have been carried out along the Kafue River in Zambia, which flows through the Zambian Copperbelt Province's mining district. Syakalima and others (2001) analyzed water downstream of the mining-affected areas of two national parks. This study found concentrations of lead in water of between 0.29 and 0.36 ppm compared with the WHO drinking-water guideline of 0.01 ppm. Other studies focused on the toxic effects of metals in the Kafue River on tropical fish. River sediment collected downstream of several mines and near a city that has a major ore-processing facility was significantly more toxic to zebrafish (Pterois volitans) and tilapia (both redbreast tilapia [Tilapia rendalli] and spotted tilapia [Tilapia mariae]) than sediment collected further downstream (Mwase and others, 1998). The toxicity was directly related to the contamination of sediments by the mining activities (Mwase and others, 1998). The results of another study showed that tilapia exposed in situ to Kafue River water for 2 weeks bioaccumulated several trace elements (cadmium, chromium, cobalt, copper, and nickel) for experiments located downstream of mining activities and other industrial point sources (Norrgren and others, 2000).
Acknowledgments P25 The Zambian copperbelt contains both reduced-facies and red-bed-associated deposits, and stream sediments from the Kafue River—an area affected by mining of these deposits— contains up to 0.8 weight percent sulfur, 12,855 ppm copper, and 1,030 ppm cobalt (Pettersson and others, 2000; Pettersson and Ingri, 2001). A study by the mining company to assess the local and long-term effects on Lake Superior from the discharge from the White Pine Mine in Michigan was conducted in 1991. The study indicated that discharge from the mine area was not causing measurable effects based on a lack of observable impact on the benthic community, an insignificant increase in chloride from mine discharges, and a lack of detectable effects on local water intakes (U.S. Environmental Protection Agency, 1994). According to the Surface Water Quality Division of the Michigan Department of Natural Resources, a diverse fish community exists in the nearby river that receives drainage from the mine. According to the U.S. Environmental Protection Agency (1994), the Michigan Department of Natural Resources report did show a reduced macro invertebrate community downstream from the mine drainage compared with upstream in the river. They suggested that this reduction may be owing to major physical and natural stream quality differences in the White Pine area. Several environmental impact statements for sandstone deposits in Montana discuss the mobility of trace elements to surface water. Tailing effluent and mine water chemistries for the Spar Lake (Troy) Mine had concentrations of cadmium, copper, and lead in the tailings outflow that exceed aquatic ecosystem guidelines (U.S. Department of Agriculture, Forest Service, and others, 1992). Carbon Footprint Rhenium extraction through mining does not have a unique carbon footprint beyond the general energy require ments of mining. In terms of its uses, rhenium is most directly linked to the global carbon cycle through its use in platinumrhenium catalysts to produce high-octane, lead-free gasoline (Polyak, 2013). Mine Closure The methods used to close porphyry copper mines and sediment-hosted copper mines depend primarily on the method of mining and the characteristics of the waste material. Open pit mining of either deposit type produces at least three different features after mining: the open pit, tailings storage facilities, and waste rock piles. Backfilling pits is typically not practical for a variety of reasons. If the water table is above the bottom of the pit, the pit will become a lake. The water quality of the lake will depend upon a number of factors, including the characteristics of the wall rock, the extent of underground mine workings that connect to the pit, the water level and volume in the pit, the local hydrology, and climate, among others (Castendyk and Eary, 2009). The long-term fate of tailing storage facilities depends upon the nature of the tailings and the method of construction of the facility. Some tailings storage facilities can be regraded, capped, and revegetated. Others are designed to have a water cover in perpetuity to limit sulfide oxidation. Either type may have seepage that could require some form of water treatment. The long-term fate of waste rock piles typically includes regrading, capping, and revegetation. Depending upon the acid-generating potential of the waste, some piles may also require some form of water treatment. For underground mines, tailings and waste rock may be handled similarly to how they are handled at open pit mines. Some of the tailings may be transferred back into the minedout workings, depending upon how the orebody is mined. The entire volume of tailings cannot be placed back in the mine workings, however, because of the volume expansion associ ated with crushing and milling the ore and the relatively small volume of the mineral commodity that is recovered. Problems and Future Research The lack of published data about the rhenium contents of most deposits, including many deposits from which rhenium is produced, hinders understanding of where additional resources may be located. The many uncertainties in the estimates of rhenium grades and rhenium contents of identified deposits preclude more-detailed analysis of rhenium resources. The geology and geochemistry of rhenium-enriched deposits are not fully understood. Areas of future research will likely include investigating the following: (a) why rhenium is generally more enriched in molybdenite that occurs in porphyry copper deposits (where the rhenium content is in the hundreds to thousands of parts per million) than in molyb denite that occurs in porphyry molybdenum deposits (where the rhenium content ranges from less than one to tens of parts per million) and why molybdenite in gold-rich porphyry copper deposits tends to have higher rhenium concentrations than it does in other subtypes of porphyry copper deposits; (b) where rhenium occurs in sediment-hosted strata-bound copper deposits and in sandstone uranium deposits; (c) the source of rhenium in sediment-hosted strata-bound copper deposits; and (d) the origin of the Merlin molybdenumrhenium deposit. Acknowledgments Peter Vikre, Steve Ludington, and John DeYoung provided helpful reviews. David Sinclair provided unpublished data and a preprint of the Millensifer and others (2014) paper. Keith Labay helped create the deposit location map and Suzanne Nicholson provided additional editorial comments after the technical review was complete.
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[Also available at ://dx.doi.org/10.1016/ j.aca.2004.11.065.] U.S. Department of Agriculture, Forest Service, Kootenai National Forest, Montana Department of State Lands, Montana Department of Health and Environmental Sciences, and Montana Department of Natural Resources, 1992, Montanore project—Final environmental impact statement: Libby, Mont., U.S. Forest Service, Kootenai National Forest, v. 1, 625 p. U.S. Department of Agriculture, Forest Service, Northern Region, Kootenai National Forest, and Montana Depart ment of Environmental Quality, 2009, The draft environ mental impact statement for the Montanore project: Libby, Mont., U.S. Forest Service, Kootenai National Forest, 3 v., 1, 383 p., accessed June 1, 2015, at ://deq.mt.gov/eis/hardrock/Montanore/DraftEIS/ MontanoreProjectDraftEISopt75.pdf. 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U.S. Geological Survey, 1996, Global 30 arc-second elevation (GTOPO30): Reston, Va., U.S. Geological Survey dataset (digital elevation model), accessed June 23, 2014, at ://lta.cr.usgs.gov/GTOPO30. U.S. Geological Survey, 2014, Mineral Resources Data System: U.S. Geological Survey database, accessed July 8, 2014, at ://mrdata.usgs.gov//. Valencia, V.A., Ruiz, J., Barra, F., Geherls, G., Ducea, M., Titley, S.R., and Ochoa-Landin, L., 2005, U-Pb zircon and Re-Os molybdenite geochronology from La Caridad porphyry copper deposit—Insights for the duration of mag matism and mineralization in the Nacozari district, Sonora, Mexico: Mineralium Deposita, v. 40, no. 2, p. 175-191. [Also available at ://dx.doi.org/10.1007/s00126-005-0480-1.] Vaughan, D.J., Sweeney, M.A., Friedrich, G., Diedel, R., and Haranczyk, C., 1989, The Kupferschiefer—An overview with an appraisal of the different types of mineralization: Economic Geology, v. 84, p. 1003-1027. [Also available at ://dx.doi.org/10.2113/gsecongeo.84.5.1003.] Voudouris, P.C., Melfos, Vasilios, Spry, P.G., Bindi, Luca, Kartal, Tamara, Arikas, Kyriakos, Moritz, Robert, and Ortelli, Melissa, 2009, Rhenium-rich molybdenite and rheniite in the Pagoni Rachi Mo-Cu-Te-Ag-Au prospect, northern Greece—Implications for the Re geochemistry of porphyry-style Cu-Mo and Mo mineralization: Canadian Mineralogist, v. 47, no. 5, p. 1013-1036. [Also available at ://dx.doi.org/10.3749/canmin.47.5.1013.] Watanabe, Yasushi, and Stein, H.J., 2000, Re-Os ages for the Erdenet and Tsagaan Suvarga porphyry Cu-Mo deposits, Mongolia, and tectonic implications: Economic Geology, v. 95, p. 1537-1542. [Also available at ://dx.doi.org/ 10.2113/gsecongeo.95.7.1537.]
P36 Critical Mineral Resources of the United States— Rhenium Wells, J.D., Domenico, J.A., Frisken, J.G., and Hopkins, R.T., 1981, Geochemical survey of the Cabinet Mountains Wilderness, Lincoln and Sanders Counties, Montana, in U.S. Geological Survey and U.S. Bureau of Mines, Mineral resources of the Cabinet Mountains Wilderness, Lincoln and Sanders Counties, Montana: U.S. Geological Survey Bulletin 1501, p. 25-51, 2 pls. [Also available at ://pubs.usgs.gov/bul/1501/report.pdf.] Williams, Tom, Schultz-Stoker, Jill, and Duvall, Elizabeth, 2002, Tailings stabilisation at White Pine: Mining Environ mental Management, v. 10, no. 3, p. 6-12. Wodzicki, A., and Piestrzynski, A., 1994, An ore genetic model for the Lubin-Sieroszowice mining district, Poland: Mineralium Deposita, v. 29, no. 1, p. 30-43. Wolfe, W.J., 1995, Exploration and geology of the Quartz Hill molybdenum deposit, southeast Alaska, in Schroeter, T.G., ed., Porphyry deposits of the northwestern cordillera of North America: Montreal, Quebec, Canada, Canadian Institute of Mining, Metallurgy and Petroleum (CIM), Special Volume 46, p. 764-770. World Health Organization, 2006, Guidelines for drinkingwater quality, 3d ed: Geneva, Switzerland, WHO Press, accessed March 28, 2013, at ://www.who.int/ water_sanitation_health/dwq/3rev/en/index.. World Nuclear Association, 2013, In situ leach (ISL) mining of uranium: World Nuclear Association Web page, accessed March 13, 2013, ://www.world-nuclear.org/info/ Nuclear-Fuel-Cycle/Mining-of-Uranium/In-Situ-LeachMining-of-Uranium/#.UUDg7Y6xHWQ. Xie, G.-Q., Mao, J.-W., Li, R.-L., Qu, W.-J., Pirajno, F., and Du, A.-D., 2007, Re-Os molybdenite and Ar-Ar phlogo pite dating of Cu-Fe-Au-Mo (W) deposits in southeastern Hubei, China: Mineralogy and Petrology, v. 90, nos. 3-4, p. 249-270. [Also available at ://dx.doi.org/10.1007/ s00710-006-0176-y.] Xiong, Yongliang, Wood, Scott, and Kruszewski, Jason, 2006, Hydrothermal transport and deposition of rhenium under subcritical conditions revisited: Economic Geology, v. 101, p. 471- 478. [Also available at ://dx.doi.org/10.2113/ gsecongeo.101.2.471.] Zhao, Yiming, Bi, Chengsi, Xiaoqiu, Zou, Yali, Sun, Andao, Du, and Yumin, Zhao, 1997, The Re-Os isotopic age of molyb denite from Duobaoshan and Tongshan porphyry copper (molybdenum) deposits: Acta Geoscientica Sinica, v. 18, no. 1, p. 61- 67. Zheng, Qingdong, Liu, Jianming, Qin, Feng, and Zhang, Zuolun, 2010, Geochronology of the Xiaodonggou porphyry Mo deposit in northern margin of North China craton: Resource Geology, v. 60, no. 2, p. 192-202. [Also available at ://dx.doi.org/10.1111/j.1751-3928.2010.00125.x.] Zientek, M.L., Hayes, T.S., and Hammarstrom, J.M., 2013, Overview of a new descriptive model for sediment-hosted stratabound copper deposits, chap. 1 of Taylor, C.D., Causey, J.D., Denning, P.D., Hammarstrom, J.M., Hayes, T.S., Horton, J.D., Kirschbaum, M.J., Parks, H.L., Wilson, A.B.,Wintzer, N.E., and Zientek, M.L., Descrip tive models, grade-tonnage relations, and databases for the assessment of sediment-hosted copper deposits—With empha sis on deposits in the Central Africa Copperbelt, Democratic Republic of the Congo and Zambia: U.S. Geological Survey Scientific Investigations Report 2010-5090-J, p. 2-16. [Also available at ://pubs.usgs.gov/sir/2010/5090/j/.]
Table P2 and Appendix P1
P38 Critical Mineral Resources of the United States— Rhenium Table P2. Rhenium data for selected porphyry copper and porphyry molybdenum deposits of the world.—Continued [The names, locations, and types of most of the deposits are taken from the U.S. Geological Survey Mineral Resources Data System (MRDS) (U.S. Geological Survey, 2014). The minimum and maximum values are concentrations of rhenium in molybdenite separates; the estimated average is based on mill concentrates. Elements and compound: Au, gold; Cu, copper; Mo, molybdenum; MoS2, molybdenite; Os, osmium; Re, rhenium. Units of measure: g/t, gram per metric ton; Mt, million metric tons; ppm, part per million; t, metric ton; wt. %, weight percent. —, no data; None, no minimum and maximum values are available because only a single analysis was used to calculate the Re grade] Deposit name Country Deposit subtype1 Tectonic setting Grade (wt. % Cu) Grade (wt. % Mo) Grade (g/t Au) Minimum Re in MoS2 (ppm) Maximum Re in MoS2 (ppm) Estimated average Re in MoS2 (ppm) Porphyry copper deposits Agarak Armenia Cu Continental arc 6,310 Ajax West Canada Cu Island arc None None 3,161 Aksug Russia Cu Post-collisional None None Aktogai (or Aktogay) Kazakhstan Cu-Mo Continental arc 2,700 Bagdad United States Cu-Mo Continental arc Berg Canada Cu-Mo Continental arc Bethlehem- Huestis Canada Cu-Mo Island arc None None Bethlehem-Iona Canada Cu-Mo Island arc None None 1,015 Bethlehem-JA Canada Cu-Mo Island arc Bingham United States Cu Post-collisional 2,000 Borly Kazakhstan Cu Continental arc 5,500 3,160 Boschekul Kazakhstan Cu-Mo Island arc 1,500 Brenda Canada Cu-Mo Island arc Bronson Slope Canada Cu-Au Island arc None None Butte United States Cu-Mo Continental arc None None Cananea Mexico Cu Continental arc None None Casino Canada Cu Continental arc — Castle Dome (Pinto Valley) United States Cu-Au Continental arc 1,200 1,750 1,750 Cerro Verde Peru Cu Continental arc — 3,060 3,497 3,280 ChuquicamataRadomiro Tomic Chile Cu-Mo Continental arc Collahuasi Chile Cu-Mo Continental arc Copper Creek United States Cu Continental arc — 2,107 1,165 Cuajone Peru Cu Continental arc — None None
Table P2 P39 Table P2. Rhenium data for selected rhenium porphyry copper and porphyry molybdenum deposits of the world.—Continued [The names, locations, and types of most of the deposits are taken from the U.S. Geological Survey Mineral Resources Data System (MRDS) (U.S. Geological Survey, 2014). The minimum and maximum values are concentrations of rhenium in molybdenite separates; the estimated average is based on mill concentrates. Elements and compound: Au, gold; Cu, copper; Mo, molybdenum; MoS , molybdenite; Os, osmium; Re, rhenium. Units of measure: g/t, gram per metric ton; Mt, million metric tons; ppm, part per million; t, metric ton; wt. %, weight percent. —, no data; None, no minimum and maximum values are available because only a single analysis was used to calculate the Re grade] Number of Re analyses2 Grade3 (g/t Re) Deposit tonnage (Mt) Contained Mo (t) Contained Re (t) Mo:Re ratio Data sources Deposit name Porphyry copper deposits 106, 0, 0 1, 0, 0 0, 0, 1 30, 0, 0 0, 7, 2 4, 0, 0 1, 0, 0 1, 0, 0 4, 0, 0 36, 6, 1 19, 0, 0 23, 0, 0 11, 0, 2 1, 0, 1 1, 0, 0 0, 0, 1 4, 0, 0 3, 0, 2 0, 2, 0 1, 6, 2 0, 3, 0 0, 3, 0 1, 0, 1 2,636 1,600 3,230 1,000 5,220 5,141 1,438 2,528 21,277 3,100 1,630 31,300 18,300 50,600 260,000 160,000 73,800 1,780 44,200 1,710,000 10,400 23,000 67,200 4,740 1,460,000 103,000 140,000 79,090 250,000 8,500,000 1,200,000 3,500 348,800 3,800 1,300 1,200 4,000 1,400 2,700 2,400 5,200 3,300 2,500 3,100 2,300 1,500 1,030 Berzina and others, 2005; Singer and others, 2008 Sinclair and others, 2009 Berzina and others, 2005; Singer and others, 2008 Berzina and others, 2005; Singer and others, 2008 Sutulov, 1974; Nadler, 1997; Barra and others, 2003; Singer and others, 2008 Sinclair and others, 2009 Sinclair and others, 2009 Sinclair and others, 2009 Sinclair and others, 2009 Giles and Schilling, 1972; McCandless and Ruiz, 1993; Chesley and Ruiz, 1998; Singer and others, 2008; Austen and Ballantyne, 2010; J.T. Chesley, Ph.D., written commun., 2013 Berzina and others, 2005; Singer and others, 2008 Singer and others, 2008; Sinclair and others, 2009 Sutulov, 1974; Sinclair and others, 2009; W.D. Sinclair, Ph.D., Geological Survey of Canada, written commun., 2013 Sinclair and others, 2009 Giles and Schilling, 1972; Singer and others, 2008 Giles and Schilling, 1972; Sutulov, 1974; Singer and others, 2008 Sinclair and others, 2009 Giles and Schilling, 1972; Singer and others, 2008 Mathur and others, 2001; Singer and others, 2008 Giles and Schilling, 1972; Sutulov, 1974; Nadler, 1997; Singer and others, 2008; Barra and others, 2013 Mathur and others, 2001; Masterman and others, 2004; Singer and others, 2008 McCandless and Ruiz, 1993; Barra and others, 2005; Singer and others, 2008 Nadler, 1997; Mathur and others, 2001; Singer and others, 2008 Agarak Ajax West Aksug Aktogai (or Aktogay) Bagdad Berg Bethlehem- Huestis Bethlehem-Iona Bethlehem-JA Bingham Borly Boschekul Brenda Bronson Slope Butte Cananea Casino Castle Dome (Pinto Valley) Cerro Verde ChuquicamataRadomiro Tomic Collahuasi Copper Creek Cuajone
P40 Critical Mineral Resources of the United States— Rhenium Table P2. Rhenium data for selected porphyry copper and porphyry molybdenum deposits of the world.—Continued [The names, locations, and types of most of the deposits are taken from the U.S. Geological Survey Mineral Resources Data System (MRDS) (U.S. Geological Survey, 2014). The minimum and maximum values are concentrations of rhenium in molybdenite separates; the estimated average is based on mill concentrates. Elements and compound: Au, gold; Cu, copper; Mo, molybdenum; MoS , molybdenite; Os, osmium; Re, rhenium. Units of measure: g/t, gram per metric ton; Mt, million metric tons; ppm, part per million; t, metric ton; wt. %, weight percent. —, no data; None, no minimum and maximum values are available because only a single analysis was used to calculate the Re grade] Deposit name Country Deposit subtype1 Tectonic setting Grade (wt. % Cu) Grade (wt. % Mo) Grade (g/t Au) Minimum Re in MoS (ppm) Maximum Re in MoS (ppm) Estimated average Re in MoS (ppm) Porphyry copper deposits—Continued Cuatro Hermanos Mexico Cu Continental arc — None None Cumobabi Mexico Cu-Mo Continental arc — Dastakert Armenia Cu Continental arc — Duobaoshan China Cu Island arc Elatsite (or Bulgaria Elatzite) El Salvador Chile Cu Cu Continental arc Continental arc None 2,740 None 1,250 El Teniente Chile Cu-Mo Continental arc 1,154 Ely United States Cu Continental arc 1,250 2,840 1,600 Erdenet (Erdene- Mongolia tuin-Obo) Gibraltar Canada Cu Cu Post-collisional Island arc — Granisle (or Bell) Canada Cu Continental arc Highmont Canada West Pit Cu-Mo Island arc Huckleberry Canada Hushamu Canada Cu Cu-Au Continental arc Island arc None None 3,140 Ingerbelle (or Canada Similco) Island Copper Canada Cu-Au Cu Island arc Island arc None 1,654 None 1,863 1,620 1,730 Kadjaran Armenia (Kadzharan) Kalmakyr Uzbekistan (Almalyk) Kemess South Canada Cu Cu-Au Cu-Au Continental arc Continental arc Island arc 3,106 2,620 2,000 4,609 1,500 3,858 Kounrad Kazakhstan Cu Continental arc 4,050 1,540
Table P2 P41 Table P2. Rhenium data for selected rhenium porphyry copper and porphyry molybdenum deposits of the world.—Continued [The names, locations, and types of most of the deposits are taken from the U.S. Geological Survey Mineral Resources Data System (MRDS) (U.S. Geological Survey, 2014). The minimum and maximum values are concentrations of rhenium in molybdenite separates; the estimated average is based on mill concentrates. Elements and compound: Au, gold; Cu, copper; Mo, molybdenum; MoS , molybdenite; Os, osmium; Re, rhenium. Units of measure: g/t, gram per metric ton; Mt, million metric tons; ppm, part per million; t, metric ton; wt. %, weight percent. —, no data; None, no minimum and maximum values are available because only a single analysis was used to calculate the Re grade] Number of Re analyses2 Grade3 (g/t Re) Deposit tonnage (Mt) Contained Mo (t) Contained Re (t) Mo:Re ratio Data sources Deposit name Porphyry copper deposits—Continued 0, 1, 0 0, 2, 0 8, 0, 1 0, 8, 0 19, 0, 0 1, 0, 2 1, 14, 2 4, 0, 1 2, 1, 1 3, 0, 1 0, 0, 5 2, 0, 0 2, 0, 0 1, 0, 0 1, 0, 0 0, 0, 11 237, 0, 1 20, 0, 1 2, 0, 0 20, 0, 1 3,836 20,731 1,780 1,700 2,000 81,600 66,000 17,000 152,000 35,000 844,000 3,940,000 75,000 445,000 56,100 8,560 10,300 46,900 1,600 52,800 935,000 120,000 17,000 70,100 2,760 1,300 2,100 2,700 1,070 1,020 1,430 5,810 1,360 1,100 3,800 2,378 2,140 Barra and others, 2005; Singer and others, 2008 Barra and others, 2005; Singer and others, 2008 Sutulov, 1974; Berzina and others, 2005; Global Metals (ARM) Ltd., 2015 Zhao and others, 1997; Singer and others, 2008; Deng and others, 2013 Singer and others, 2008; Sinclair and others, Giles and Schilling, 1972; Sutulov, 1974; Nadler, 1997; Singer and others, 2008 Giles and Schilling, 1972; Sutulov, 1974; Nadler, 1997; Maksaev and others, 2004; Cannell, 2004; Klemm and others, 2007; Singer and others, 2008 Giles and Schilling, 1972; Sutulov, 1974; Singer and others, 2008 Watanabe and Stein, 2000; Berzina and others, 2005; Singer and others, 2008 Sinclair and others, 2009; W.D. Sinclair, Ph.D., Geological Survey of Canada, written commun., 2013 Sinclair and others, 2009; W.D. Sinclair, Ph.D., Geological Survey of Canada, written commun., 2013 Sinclair and others, 2009 Sinclair and others, 2009 Giroux and Casselman, 2012 Sinclair and others, 2009 Sinclair and others, 2009; W.D. Sinclair, Ph.D., Geological Survey of Canada, written commun., 2013 Nadler, 1997; Berzina and others, 2005; Singer and others, 2008 Sutulov, 1974; Singer and others, 2008; Pašava and others, 2010 Sinclair and others, 2009 Sutulov, 1974; Berzina and others, 2005; Singer and others, 2008 Cuatro Hermanos Cumobabi Dastakert Duobaoshan Elatsite (or Elatzite) El Salvador El Teniente Ely Erdenet (Erdenetuin-Obo) Gibraltar Granisle (or Bell) Highmont West Pit Huckleberry Hushamu Ingerbelle (or Similco) Island Copper Kadjaran (Kadzharan) Kalmakyr (Almalyk) Kemess South Kounrad
P42 Critical Mineral Resources of the United States— Rhenium Table P2. Rhenium data for selected porphyry copper and porphyry molybdenum deposits of the world.—Continued [The names, locations, and types of most of the deposits are taken from the U.S. Geological Survey Mineral Resources Data System (MRDS) (U.S. Geological Survey, 2014). The minimum and maximum values are concentrations of rhenium in molybdenite separates; the estimated average is based on mill concentrates. Elements and compound: Au, gold; Cu, copper; Mo, molybdenum; MoS , molybdenite; Os, osmium; Re, rhenium. Units of measure: g/t, gram per metric ton; Mt, million metric tons; ppm, part per million; t, metric ton; wt. %, weight percent. —, no data; None, no minimum and maximum values are available because only a single analysis was used to calculate the Re grade] Deposit name Country Deposit subtype1 Tectonic setting Grade (wt. % Cu) Grade (wt. % Mo) Grade (g/t Au) Minimum Re in MoS (ppm) Maximum Re in MoS (ppm) Estimated average Re in MoS (ppm) Porphyry copper deposits—Continued La Caridad Mexico Cu Continental arc — La Escondida Chile Cu-Au Continental arc 1,805 Lomex Canada Cu-Mo Island arc Los BroncesRio Blanco (Andina) Los Pelambres Chile Chile Cu-Mo Cu-Mo Continental arc Continental arc — Machangqing China Cu-Au Collision belt(?) Maggie Canada Cu-Mo Continental arc — None None Majdanpek Serbia Cu-Au Continental arc 2,320 3,550 2,770 Medet Bulgaria Cu Continental arc None None Miami United States Cu-Mo Continental arc None None Mineral Park (Ithaca Peak) Mission-Pima United States United States Cu Cu Continental arc Continental arc — — None None Mitchell (Sulphurets) Morenci Canada United States Cu-Au Cu-Mo Island arc Continental arc 7,012 8,170 7,590 Mt. Tolman United States Cu-Mo Continental arc — None None OK Canada Cu Continental arc — None None Pebble United States Cu Post-collisional 2,070 1,100 Qulong China Cu-Mo Post-collisional — Ray United States Cu Continental arc — 1,500 San ManuelKalamazoo United States Cu-Mo Continental arc 1,200 Santa Rita United States Cu Continental arc 1,200
Table P2 P43 Table P2. Rhenium data for selected rhenium porphyry copper and porphyry molybdenum deposits of the world.—Continued [The names, locations, and types of most of the deposits are taken from the U.S. Geological Survey Mineral Resources Data System (MRDS) (U.S. Geological Survey, 2014). The minimum and maximum values are concentrations of rhenium in molybdenite separates; the estimated average is based on mill concentrates. Elements and compound: Au, gold; Cu, copper; Mo, molybdenum; MoS , molybdenite; Os, osmium; Re, rhenium. Units of measure: g/t, gram per metric ton; Mt, million metric tons; ppm, part per million; t, metric ton; wt. %, weight percent. —, no data; None, no minimum and maximum values are available because only a single analysis was used to calculate the Re grade] Number of Re analyses2 Grade3 (g/t Re) Deposit tonnage (Mt) Contained Mo (t) Contained Re (t) Mo:Re ratio Data sources Deposit name Porphyry copper deposits—Continued 0, 2, 1 0, 7, 0 2, 0, 20 0, 13, 2 0, 3, 0 0, 0, 5 1, 0, 0 3, 0, 0 22, 0, 1 1, 0, 0 2, 0, 1 0, 1, 1 2, 0, 0 3, 1, 0 0, 0, 1 1, 0, 0 0, 6, 2 0, 4, 0 9, 0, 0 2, 0, 2 8, 0, 1 1,800 11,158 16,816 7,458 1,000 1,591 6,470 2,177 5,940 1,517 1,583 1,390 3,030 444,600 691,800 64,400 3,400,000 1,120,000 31,000 52,600 50,000 24,000 160,000 96,400 135,000 36,700 614,700 1,180,000 10,000 1,443,000 485,000 15,800 153,000 242,000 1,030 1,500 1,120 2,650 1,050 1,728 2,300 1,000 7,429 1,000 2,200 1,000 1,320 3,330 4,770 Nadler, 1997; Valencia and others, 2005; Singer and others, 2008 Mathur and others, 2001; Singer and others, 2008; Romero and others, 2010 Sinclair and others, 2009; W.D. Sinclair, Ph.D., Geological Survey of Canada, written commun., 2013 Mathur and others, 2001; Singer and others, 2008; Deckart and others, 2013 Mathur and others, 2001; Singer and others, 2008 Hou and others, 2006 Sinclair and others, 2009 Todorov and Staikov, 1985; Singer and others, Sutulov, 1974; Berzina and others, 2005; Singer and others, 2008 Berzina and others, 2005; Singer and others, 2008 Giles and Schilling, 1972; Sutulov, 1974; Singer and others, 2008 Sutulov, 1974; McCandless and Ruiz, 1993; Singer and others, 2008 Sinclair and others, 2009 Giles and Schilling, 1972; McCandless and Ruiz, 1993; Singer and others, 2008 Carten and others, 1993; W.D. Sinclair, Ph.D., Geological Survey of Canada, written commun., 2013 Sinclair and others, 2009 Ghaffari and others, 2011; Lang and others, 2013 Singer and others, 2008; Hou and others, 2009 Giles and Schilling, 1972; Singer and others, 2008 Giles and Schilling, 1972; Sutulov, 1974; Nadler, 1997; Singer and others, 2008. Giles and Schilling, 1972; Sutulov, 1974; Singer and others, 2008 La Caridad La Escondida Lomex Los BroncesRio Blanco (Andina) Los Pelambres Machangqing Maggie Majdanpek Medet Miami Mineral Park (Ithaca Peak) Mission-Pima Mitchell (Sulphurets) Morenci Mt. Tolman OK Pebble Qulong Ray San ManuelKalamazoo Santa Rita
P44 Critical Mineral Resources of the United States— Rhenium Table P2. Rhenium data for selected porphyry copper and porphyry molybdenum deposits of the world.—Continued [The names, locations, and types of most of the deposits are taken from the U.S. Geological Survey Mineral Resources Data System (MRDS) (U.S. Geological Survey, 2014). The minimum and maximum values are concentrations of rhenium in molybdenite separates; the estimated average is based on mill concentrates. Elements and compound: Au, gold; Cu, copper; Mo, molybdenum; MoS , molybdenite; Os, osmium; Re, rhenium. Units of measure: g/t, gram per metric ton; Mt, million metric tons; ppm, part per million; t, metric ton; wt. %, weight percent. —, no data; None, no minimum and maximum values are available because only a single analysis was used to calculate the Re grade] Deposit name Country Deposit subtype1 Tectonic setting Grade (wt. % Cu) Grade (wt. % Mo) Grade (g/t Au) Minimum Re in MoS (ppm) Maximum Re in MoS (ppm) Estimated average Re in MoS (ppm) Porphyry copper deposits—Continued Sar Cheshmeh Iran Cu Continental arc Schaft Creek Canada Cu Island arc None None Sierrita- United States Esperanza Cu-Mo Continental arc 1,800 Silver Bell United States Cu-Mo Continental arc Skouriés Greece Cu-Au Post-collisional 1,000 Snowfields Canada Cu-Au Island arc None None 3,600 Sora (Sorsk) Russia Cu Post-collisional? — Tominskoe Russia Cu Island arc None None 1,080 Tongchankou China Cu uncertain — Toquepala Peru Cu-Mo Continental arc — 1,496 Tsagaan-Suvarga Mongolia Cu Continental arc Twin Buttes United States Cu-Mo Continental arc None None Valley Copper Canada Cu-Au Island arc None None Veliki Krivelj Serbia Cu Continental arc None None Wunugetushan China Cu-Mo Post-collisional? — Yulong China Cu-Au Post-collisional? Zuun Mod Mongolia Molybdenum Cu-Mo Continental arc? — Porphyry molybdenum deposits Boss Mountain Canada Arc-related Continental arc — — Carmi Canada Arc-related Continental arc — — Endako Canada Arc-related Continental arc — Glacier Gulch (Davidson) Canada Arc-related Continental arc —
Table P2 P45 Table P2. Rhenium data for selected rhenium porphyry copper and porphyry molybdenum deposits of the world.—Continued [The names, locations, and types of most of the deposits are taken from the U.S. Geological Survey Mineral Resources Data System (MRDS) (U.S. Geological Survey, 2014). The minimum and maximum values are concentrations of rhenium in molybdenite separates; the estimated average is based on mill concentrates. Elements and compound: Au, gold; Cu, copper; Mo, molybdenum; MoS , molybdenite; Os, osmium; Re, rhenium. Units of measure: g/t, gram per metric ton; Mt, million metric tons; ppm, part per million; t, metric ton; wt. %, weight percent. —, no data; None, no minimum and maximum values are available because only a single analysis was used to calculate the Re grade] Number of Re analyses2 Grade3 (g/t Re) Deposit tonnage (Mt) Contained Mo (t) Contained Re (t) Mo:Re ratio Data sources Deposit name Porphyry copper deposits—Continued 15, 0, 5 1, 0, 0 6, 1, 2 18, 1, 0 4, 0, 0 1, 0, 0 9, 0, 0 1, 0, 0 0, 6, 0 1, 2, 2 0, 2, 0 0, 0, 1 0, 0, 1 1, 0, 0 0, 7, 0 0, 0, 2 2, 0, 0 1,200 1,393 2,262 2,203 2,320 360,000 265,000 660,500 34,900 11,400 17,600 174,000 9,640 18,000 930,000 43,200 216,000 53,000 30,000 450,000 176,000 129,000 1,060 1,000 1,020 2,520 1,130 41,000 2,900 1,000 5,100 1,000 2,030 2,000 3,000 1,350 2,190 Singer and others, 2008; Aminzadeh and others, 2011 Sinclair and others, 2009 Giles and Schilling, 1972; Sutulov, 1974; McCandless and Ruiz, 1993; Nadler, 1997; Singer and others, 2008 Giles and Schilling, 1972; Barra and others, 2005; Singer and others, 2008 Singer and others, 2008; Sinclair and others, 2009 Armstrong and others, 2011 Sotnikov and others, 2001; Berzina and others, 2005; Berzina and Korobeinikov, 2007 Singer and others, 2008; Sinclair and others, 2009 Xie and others, 2007; Singer and others, 2008 Giles and Schilling, 1972; Sutulov, 1974; Nadler, 1997; Mathur and others, 2001; Singer and others, 2008 Watanabe and Stein, 2000; Singer and others, 2008 Sutulov, 1974; Singer and others, 2008 Sinclair and others, 2009; W.D. Sinclair, Ph.D., Geological Survey of Canada, written commun., 2013 Singer and others, 2008; Sinclair and others, 2009 Chen and others, 2011 Hou and others, 2006 Clark and Baudry, 2011 Sar Cheshmeh Schaft Creek Sierrita- Esperanza Silver Bell Skouriés Snowfields Sora (Sorsk) Tominskoe Tongchankou Toquepala Tsagaan-Suvarga Twin Buttes Valley Copper Veliki Krivelj Wunugetushan Yulong Zuun Mod Molybdenum Porphyry molybdenum deposits 7, 0, 0 3, 0, 0 14, 12, 1 2, 0, 0 46,600 13,300 420,000 134,000 7,500 10,000 17,000 16,000 Sinclair and others, 2009 Sinclair and others, 2009 Giles and Schilling, 1972; Selby and Creaser, 2001; Sinclair and others, 2009; W.D. Sinclair, Ph.D., Geological Survey of Canada, written commun., 2013 Sinclair and others, 2009 Boss Mountain Carmi Endako Glacier Gulch (Davidson)
P46 Critical Mineral Resources of the United States— Rhenium Table P2. Rhenium data for selected porphyry copper and porphyry molybdenum deposits of the world.—Continued [The names, locations, and types of most of the deposits are taken from the U.S. Geological Survey Mineral Resources Data System (MRDS) (U.S. Geological Survey, 2014). The minimum and maximum values are concentrations of rhenium in molybdenite separates; the estimated average is based on mill concentrates. Elements and compound: Au, gold; Cu, copper; Mo, molybdenum; MoS , molybdenite; Os, osmium; Re, rhenium. Units of measure: g/t, gram per metric ton; Mt, million metric tons; ppm, part per million; t, metric ton; wt. %, weight percent. —, no data; None, no minimum and maximum values are available because only a single analysis was used to calculate the Re grade] Deposit name Country Deposit subtype1 Tectonic setting Grade (wt. % Cu) Grade (wt. % Mo) Grade (g/t Au) Minimum Re in MoS (ppm) Maximum Re in MoS (ppm) Estimated average Re in MoS (ppm) Porphyry molybdenum deposits—Continued Kitsault (Lime Canada Creek) Lucky Ship Canada Mount Haskin Canada Nithi Mountain Canada Quartz Hill United States Red Bird Canada Red Mountain Canada Storie Moly Canada Thompson Creek United States Trout Lake Canada (Max) Adanac (Ruby Canada Creek) Climax United States Donggou China Jinduicheng China Questa United States Shapinggou China Urad-Henderson United States Xiaodonggou China Arc-related Continental arc Arc-related Continental arc Arc-related Continental arc Arc-related Continental arc Arc-related Continental arc Arc-related Continental arc Arc-related Continental arc Arc-related Continental arc Arc-related Continental arc Arc-related Continental arc Alk-granite/ Extensional conhybrid? tinental arc Alk-granite Continental rift Alk-granite Collision belt Alk-granite Collision belt Alk-granite Continental rift Alk-granite Collision belt Alk-granite Continental rift Alk-granite Collision belt(?) — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — None None None None None None None None None None None None 1Cox and Singer (1992) porphyry Cu models; Taylor and others (2012) and Ludington and Plumlee (2009) porphyry Mo models. 2Number of analyses of MoS separates, MoS analyzed for Re-Os dating, MoS mill concentrates. Number in bold indicates samples used to calculate Re grade. In cases where no number is bold, average grade of total resources calculated from drilling was used as Re grade. 3Re grade calculated from mean Re content of MoS and Mo grade of deposit.
Table P2 P47 Table P2. Rhenium data for selected rhenium porphyry copper and porphyry molybdenum deposits of the world.—Continued [The names, locations, and types of most of the deposits are taken from the U.S. Geological Survey Mineral Resources Data System (MRDS) (U.S. Geological Survey, 2014). The minimum and maximum values are concentrations of rhenium in molybdenite separates; the estimated average is based on mill concentrates. Elements and compound: Au, gold; Cu, copper; Mo, molybdenum; MoS , molybdenite; Os, osmium; Re, rhenium. Units of measure: g/t, gram per metric ton; Mt, million metric tons; ppm, part per million; t, metric ton; wt. %, weight percent. —, no data; None, no minimum and maximum values are available because only a single analysis was used to calculate the Re grade] Number of Re analyses2 Grade3 (g/t Re) Deposit tonnage (Mt) Contained Mo (t) Contained Re (t) Mo:Re ratio Data sources Deposit name Porphyry molybdenum deposits—Continued 9, 0, 0 1, 0, 0 1, 0, 0 0, 1, 0 0, 0, 1 2, 0, 0 1, 0, 0 3, 0, 0 0, 0, 1 1, 0, 1 4, 0, 0 13, 0, 4 0, 2, 0 0, 7, 0 14, 8, 1 0, 9, 0 2, 0, 2 0, 6, 0 1,600 1,089 1,270 120,000 41,000 11,000 47,900 1,220,000 49,000 190,000 78,400 151,000 51,000 84,800 1,600,000 689,000 1,080,000 640,000 1,600,000 996,000 45,000 8,500 15,000 5,600 7,700 4,030 24,000 19,000 30,000 5,000 11,000 50,000 45,000 145,000 38,000 17,000 126,000 30,000 83,000 Sinclair and others, 2009 Sinclair and others, 2009 Sinclair and others, 2009 Selby and Creaser, 2001; Mosher, 2001 Hudson and others, 1979; Wolfe, 1995; W.D. Sinclair, Ph.D., Geological Survey of Canada, written commun., 2013 Sinclair and others, 2009 Sinclair and others, 2009 Sinclair and others, 2009 Carten and others, 1993; W.D. Sinclair, Ph.D., Geological Survey of Canada, written commun., 2013 Sinclair and others, 2009 Sinclair and others, 2009 Giles and Schilling, 1972; Nadler, 1997; Singer and others, 1993; Sinclair and others, 2009; W.D. Sinclair, Ph.D., Geological Survey of Canada, written commun., 2013 Mao and others, 2011; Deng and others, 2013 Mao and others, 2011; Deng and others, 2013 Giles and Schilling, 1972; Singer and others, 1993; Rosera and others, 2013; W.D. Sinclair, Ph.D., Geological Survey of Canada, written commun., 2013 Mao and others, 2011; Deng and others, 2013 Giles and Schilling, 1972; Nadler, 1997; Seedorff and Einaudi, 2004; Markey and others, 2007; W.D. Sinclair, Ph.D., Geological Survey of Canada, written commun., 2013 Zheng and others, 2010 Kitsault (Lime Creek) Lucky Ship Mount Haskin Nithi Mountain Quartz Hill Red Bird Red Mountain Storie Moly Thompson Creek Trout Lake (Max) Adanac (Ruby Creek) Climax Donggou Jinduicheng Questa Shapinggou Urad-Henderson Xiaodonggou
P48 Critical Mineral Resources of the United States— Rhenium Appendix P1. Rhenium Data Sources and Limitations of Data Used in Rhenium Resource Estimates Kupferschiefer resources in Poland.— Ore reserves in deposits in the Legnica- Glogów copper belt, Poland, which includes the Lubin-Sieroszowice orebody, are estimated to be 1,180 million metric tons (Bartlett and others, 2013) that averages 0.6 ppm rhenium (Smakowski and others, 2010). These tonnage and grade data suggest a rhenium resource of 709 metric tons. Kupferschiefer resources in the Mansfeld-Sangerhausen area, Germany.—Jankowski (1995) reported production of 120 million metric tons of ore from 1200 to 1990 that had an estimated average rhenium grade of 21 grams per metric ton (g/t). This suggests that more than 2,500 metric tons of rhenium was mined (but not recovered). Jankowski (1995) lists a pre-mining resource of 155 million metric tons with an average grade of 21 g/t, which suggests a total pre-mining resource of about 3,300 metric tons of rhenium and that about 800 metric tons of rhenium remains. Jankowski (1995) also reports remaining resources of 35.4 million metric tons of ore with an average rhenium grade of 21 g/t, which suggests that about 740 metric tons of rhenium remains in these deposits. Average rhenium grades and deposit tonnages for the Dzhezhazgan and the Zhaman-Aybat sandstone-type stratabound copper deposits in Kazakhstan are available from Box and others (2013). Rhenium grades for other similar deposits in Kazakhstan are not available. Rhenium contents of some roll-front-type sandstone uranium deposits in Kazakhstan and Uzbekistan are reported by Dahlkamp (2009a, b). For most deposits, however, total contained uranium or total uranium production and ranges of uranium and (or) rhenium concentration data are reported, which precludes calculation of rhenium grades, tonnages, and resources. The estimated tonnage and rhenium grade for the Merlin deposit in Australia is a Canada National Instrument 43-101-compliant estimate of indicated and inferred mineral resources made in April 2012 (Lycopodium Minerals QLD Pty Ltd., 2012). Because of these limitations in the data for known deposits, estimated rhenium resources in table P1 and shown in figure P4 are likely imprecise, but are accurate enough to allow discussion of some aspects of U.S. and global rhenium resources. Publicly available data for rhenium resources are limited. Of more than 225 porphyry copper deposits with published molybdenum grades and tonnages (Singer and others, 2008), rhenium concentrations are available for only about 80 deposits, several of which are represented by a single rhenium analysis (table P1; John and Taylor, 2016). There are similarly few rhenium data available for porphyry molybdenum deposits. The available rhenium analytical data are a mixture of analyses of (a) small molybdenite separates (for example, Giles and Schilling, 1972; Sinclair and others, 2009), (b) small molybdenite separates used in rhenium-osmium dating studies (for example, McCandless and Ruiz, 1993; Barra and others, 2013), and less commonly, (c) bulk molybdenite mill concentrates (mostly from Sutulov, 1974, and Nadler, 1997). The molybdenite separates and mill concentrates are subject to impurities, and some of the variation in rhenium content within deposits may be the result of variable purity of these molybdenite separates. Electron microprobe analyses of rhenium contents of molybdenites are available for some deposits (Newberry, 1979; McCandless and others, 1993), but these analyses have relatively high detection limits and low precision and were not included in the data compilation. Calculated rhenium resources in porphyry copper and porphyry molybdenum deposits are based on the average concentration of rhenium in molybdenite, the average molyb denum grade for the entire deposit, and the total tonnage of the deposit. The type of analysis used to determine rhenium concentrations in molybdenite is indicated in table P1. Molybdenum grades and tonnages for porphyry copper deposits are mostly from Singer and others (2008) and are subject to the rules specified in their data compilation. For example, average molybdenum grades and the associated tonnages are based on the total production, reserves, and resources at the lowest possible cutoff grade, and all mineralized and altered rock within 2 km are combined into one deposit. Tonnages, therefore, are pre-mining resources. Because many porphyry copper deposits have been mined for decades or longer (for example, the Bingham Canyon deposit has been mined since 1906), remaining tonnages and rhenium resources for these deposits are smaller than indicated in table P1. Rhenium data for strata-bound copper deposits are limited to a few deposits in the Kupferschiefer in Poland and Germany and two deposits in Kazakhstan.
Appendix P1 P49 Appendix P1 References Cited Note: All Web links listed were active as of the access date but may no longer be available. Barra, Fernando, Alcota, Hugo, Rivera, Sergio, Valencia, Victor, Munizaga, Francisco, and Maksaev, Victor, 2013, Timing and formation of porphyry Cu-Mo mineralization in the Chuquicamata district, northern Chile—New constraints from the Toki cluster: Mineralium Deposita, v. 48, no. 5, p. 629-651. [Also available at ://dx.doi.org/10.1007/ s00126-012-0452-1.] Bartlett, S.C., Burgess, Harry, Damjanović, Bogdan, Gowans, R.M., and Lattanzi, C.R., 2013, Technical report on the copper-silver production operations of KGHM Polska Miedź S.A. in the Legnica-Glogów copper belt area of southwestern Poland, NI 43-101 technical report, prepared for KGHM Polska Miedź S.A.: Toronto, Ontario, Canada, Micon International Ltd., 159 p., accessed September 2, 2015, at ://.com/en/technical-reportcopper-silver-production-operations--polska-miedzsa-legnica-glogow-copper-belt. Box, S.E., Syusyura, Boris, Seltmann, Reimar, Creaser, R.A., Dolgopolova, Alla, and Zientek, M.L., 2013, Dzhezkazgan and associated sandstone copper deposits of the Chu-Sarysu basin, central Kazakhstan, in Hedenquist, J.W., Harris, Michael, and Camus, Francisco, eds., Geology and genesis of major copper deposits and districts of the world—A tribute to Richard H. Sillitoe (1st ed.): Littleton, Colo., Society of Economic Geologists Special Publication no. 16, p. 303-328. Dahlkamp, F.J., 2009a, Kazakhstan, in Dahlkamp, F.J., ed., Uranium deposits of the world—Asia: Berlin, Germany, Springer-Verlag, p. 181-189. [Also available at ://dx.doi.org/10.1007/978-3-540-78558-3.] Dahlkamp, F.J., 2009b, Uzbekistan, in Dahlkamp, F.J., ed., Uranium deposits of the world—Asia: Berlin, Germany, Springer-Verlag, p. 397-400. [Also available at ://dx.doi.org/10.1007/978-3-540-78558-3.] Giles, D.L., and Schilling, J.H., 1972, Variation in the rhenium content of molybdenite, in Program—24th International Geological Congress, Montreal, Quebec, Canada, 1972 Proceedings of sec. 10: Ottawa, Ontario, Canada, Interna tional Geological Congress, p. 145-153. Jankowski, Gunter, ed., 1995, Zur geschichte des Mansfelder Kupferschiefer-Bergbaus [The history of the Mansfeld copper shale mining]: Clausthal-Zellerfeld, Germany, Gesellschaft Deutscher Metallhütten- und Bergleute, 370 p., folded page with 2 maps. John, D.A., and Taylor, R.D., 2016, Byproducts of porphyry copper and molybdenum deposits, in Verplanck, P.L., and Hitzman, M.W., eds., Rare earth and critical elements in ore deposits: Reviews in Economic Geology, v. 18, p 137-164. Lycopodium Minerals QLD Pty Ltd., 2012, NI 43-101 technical report, Merlin molybdenum rhenium project, feasibility study, northwest Queensland, Australia: Spring Hill, Queensland, Australia, Lycopodium Minerals QLD Pty Ltd., 302 p., accessed March 14, 2013, at ://www.ivanhoeaustralia.com/i/pdf/NI43-101_ Merlin_Technical_Report.pdf. McCandless, T.E., Ruiz, Joaquin, and Campbell, A.R., 1993, Rhenium behavior in molybdenite in hypogene and nearsurface environments—Implications for Re-Os geochro nometry: Geochimica et Cosmochimica Acta, v. 57, no. 4, p. 889-905. [Also available at ://dx.doi.org/10.1016/
Nadler, H.-G., 1997, Rhenium, in Habashi, Fathi, ed., Handbook of extractive metallurgy—Precious metals, refractory metals, scattered metals, radioactive metals, rare earth metals: New York, N.Y., Wiley-VCH, v. 3, p. 1491-1501. Newberry, R.J., 1979, Polytypism in molybdenite (II)— Relationships between polytypism, ore deposition/alteration stages and rhenium contents: American Mineralogist, v. 64, nos. 7-8, p. 768-775. Sinclair, W.D., Jonasson, I.R., Kirkham, R.V., and Soregaroli, A.E., 2009, Rhenium and other platinum-group metals in porphyry deposits: Geological Survey of Canada Open File 6181, 1 sheet. [Also available at ://dx.doi.org/10.4095/247485.] Singer, D.A., Berger, V.I., and Moring, B.C., 2008, Porphyry copper deposits of the world—Database and grade and ton nage models, 2008 (version 1.0): U.S. Geological Survey Open-File Report 2008-1155, 45 p., accessed April 23, 2015, at ://pubs.usgs.gov/of/2008/1155/. Smakowski, Tadeusz, Ney, Roman, and Galos, Krzysztof, eds., 2010, Minerals yearbook of Poland 2009: Kraków, Poland, Department of Mineral Policy, Mineral and Energy Economy Research Institute, Polish Academy of Sciences, 537 p. [Also available at ://www.min-pan.krakow.pl/ pliki/Minerals_Yearbook_of_Poland_2009.pdf.]
For more information concerning this report, please contact: Mineral Resources Program Coordinator U.S. Geological Survey 913 National Center Reston, VA 20192 Telephone: 703- 648- 6100 Fax: 703- 648- 6057 Email: minerals@usgs.gov Home page: ://minerals.usgs.gov Prepared by the USGS Science Publishing Network Reston Publishing Service Center Edited by J.C. Ishee and Stokely J. Klasovsky Illustrations by Caryl J. Wipperfurth Layout by Caryl J. Wipperfurth and Cathy Y. Knutson Posting by Angela E. Hall
John and others—Critical Mineral Resources of the United States—Rhenium—Professional Paper 1802-P ISSN 2330-7102 (online) ://doi.org/10.3133/pp1802P