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Concentrations of trace elements in Great Lakes fishes

The concentration of 15 trace elements was determined by activation analysis of samples of whole fish and fish livers from three of the Great Lakes: Michigan, Superior, and Erie. The average concentrations of 7 elements in 19 whole fish from 3 species were as follows: uranium, 3ppb (parts per billion); thorium, 6ppb; cobalt, 28ppb; cadmium, 94ppb; arsenic, 16ppb; chromium, 1ppm; and copper, 1.3ppm. The average concentrations of 8 elements in 40 liver samples from 10 species of fish were as follows: uranium, 2ppb; thorium, 2ppb; cobalt, 40ppb; copper, 9ppm; zinc, 30ppm; bromine, 0.4ppm; arsenic, 30ppb; and cadmium, 0.4ppm. Other elements observed in most of the samples were: antimony, 5100ppb; gold, 25ppb; lanthanum, 120ppb; rhenium, 0.55ppb; rubidium, 0.064ppm; and selenium, 0.12ppb.Trace element concentrations varied with species and lake. Uranium and thorium varied with species, but not for the same species from different lakes. The levels of copper, cobalt, zinc, and bromine varied little between species and lakes. The concentration of cadmium, arsenic, and chromium varied between species and with species between lakes.

Great Lakes

Intensity of quartz cathodoluminescence and trace-element content in quartz from the porphyry copper deposit at Butte, Montana

Textures of hydrothermal quartz revealed by cathodoluminescence using a scanning electron microscope (SEM-CL) reflect the physical and chemical environment of quartz formation. Variations in intensity of SEM-CL can be used to distinguish among quartz from superimposed mineralization events in a single vein. In this study, we present a technique to quantify the cathodoluminescent intensity of quartz within individual and among multiple samples to relate luminescence intensity to specific mineralizing events. This technique has been applied to plutonic quartz and three generations of hydrothermal veins at the porphyry copper deposit in Butte, Montana. Analyzed veins include early quartz-molybdenite veins with potassic alteration, pyrite-quartz veins with sericitic alteration, and Main Stage veins with intense sericitic alteration. CL intensity of quartz is diagnostic of each mineralizing event and can be used to fingerprint quartz and its fluid inclusions, isotopes, trace elements, etc., from specific mineralizing episodes. Furthermore, CL intensity increases proportional to temperature of quartz formation, such that plutonic quartz from the Butte quartz monzonite (BQM) that crystallized at temperatures near 750 ??C luminesces with the highest intensity, whereas quartz that precipitated at ???250 ??C in Main Stage veins luminesces with the least intensity. Trace-element analyses via electron microprobe and laser ablation-ICP-MS indicate that plutonic quartz and each generation of hydrothermal quartz from Butte is dominated by characteristic trace amounts of Al, P, Ti, and Fe. Thus, in addition to CL intensity, each generation of quartz can be distinguished based on its unique trace-element content. Aluminum is generally the most abundant element in all generations of quartz, typically between 50 and 200 ppm, but low-temperature, Main Stage quartz containing 400 to 3600 ppm Al is enriched by an order of magnitude relative to all other quartz generations. Phosphorous is present in abundances between 25 and 75 ppm, and P concentrations in quartz show little variation among quartz generations. Iron is the least abundant of these elements in most quartz types and is slightly enriched in CL-dark quartz in pyrite-quartz veins with sericitic alteration. Titanium is directly correlated with both temperature of quartz precipitation, and intensity of quartz luminescence, such that BQM quartz contains hundreds of ppm Ti, whereas Main Stage quartz contains less than 10 ppm Ti. Our results suggest that Ti concentration in quartz is controlled by temperature of quartz precipitation and that increased Ti concentrations in quartz may be responsible for increased CL intensities.

American Mineralogist

Trace elements in coal ash

Coal ash is a residual waste product primarily produced by coal combustion for electric power generation. Coal ash includes fly ash, bottom ash, and flue-gas desulfurization products (at powerplants equipped with flue-gas desulfurization systems). Fly ash, the most common form of coal ash, is used in a range of products, especially construction materials. A new Environmental Protection Agency ruling upholds designation of coal ash as a non-hazardous waste under Subtitle D of the Resource Conservation and Recovery Act, allowing for the continued beneficial use of coal ash and also designating procedures and requirements for its storage. In this fact sheet, the form, distribution, and behavior of trace elements of environmental interest in samples of coal fly ash were investigated in response to concerns about element mobility in the event of an ash spill. The study includes laboratory-based leaching experiments to examine the behavior of trace elements, such as arsenic (As) and chromium (Cr), in response to key environmental factors including redox conditions (degree of oxygenation), which are known to vary with depth within coal ash impoundments and in natural ecosystems. The experiments show that As dissolves from samples of coal fly ash into simulated freshwater under both oxic (highly oxygenated) and anoxic (poorly oxygenated) conditions, whereas dissolved Cr concentrations are very redox dependent. This U.S. Geological Survey research helps define the distribution of elements such as As in coal ash and shows that element mobility can vary considerably under different conditions expected in the environment.

Fact Sheet

A compilation of whole-rock and glass major-element geochemistry of Kilauea Volcano, Hawai'i, near-vent eruptive products: January 1983 through September 2001

This report presents major-element geochemical data from 652 glasses (~6,520 analyses) and 795 whole-rock aliquots from 1,002 fresh samples of olivine-tholeiitic lava collected throughout the near-continuous eruption of Kïlauea Volcano, Hawai'i, from January 1983 through September 2001. The data presented herein provide a unique temporal compilation of lava geochemistry that best reflects variations of pre-eruptive magma compositions during prolonged rift-zone eruption. This document serves as a repository for geochemical data referred to in U.S. Geological Survey Professional Paper 1676 (Heliker, Swanson, and Takahashi, eds., 2003) which includes multidisciplinary research papers pertaining to the first twenty years of Puu Oo-Kupaianaha eruption activity. Details of eruption characteristics and nomenclature are provided in the introductory chapter of that volume (Heliker and Mattox, 2003). Geochemical relations among all or portions of this data set are depicted and interpreted by Thornber (2003), Thornber and others (2003) and Thornber (2001). Trace element compositions and Nd, Sr and Pb isotopic analyses of representative samples of this select eruption suite will be provided in a separate and complimentary open file report. From 1983 to October 2001, approximately 2,500 eruption samples were collected and archived by the U.S. Geological Survey’s Hawaiian Volcano Observatory (HVO). Geochemical data for 1,002 of these samples are included here. Previous reports present bulk-lava major- element chemistry for eruption samples collected from 1983 to 1986 and from 1990 to 1994 (Neal and others, 1988 and Mangan and others, 1995, respectively). Major element glass chemistry and thermometry data for samples collected from 1983 to 1994 is reported by Helz and Hearn (1998) and whole-rock and glass chemistry for samples collected from September 1994 to October 2001 is provided by Thornber and others (2002). This report is a compilation of previously published data along with unpublished whole-rock data for the 1986–1990 eruptive interval (episode 48, see Heliker and Mattox, 2003). The geochemical data in this report is mostly limited to well-quenched samples collected at or near their respective vents. The samples include tephra and spatter, in addition to lava dipped from lava lakes, lava tubes, and surface lava flows. The details of sample collection techniques as described by Thornber and others (2002) are generally applicable for this entire sampling interval. Specifically excluded from this database are samples of distal surface flows, many of which were collected for topical studies of emplacement dynamics (for example, Cashman and others, 1999). Samples of sluggish or crystal-laden tube flows collected during eruptive pauses were also excluded, because they bear visual, petrographic and geochemical evidence for crystal accumulation during surface-flow stagnation. In addition, the pre-1992 whole-rock major element data reported here has been corrected to compensate for minor analytical discrepancies between pre- and post-1991 XRF analyses. These discrepancies resulted from a change in instrumentation at the USGS Denver analytical laboratories. This select suite of time-constrained geochemical data is suitable for constructing petrologic models of pre-eruptive magmatic processes associated with prolong rift zone eruption of Hawaiian shield volcanoes.

Hawai'i

Multi-elemental analysis of aqueous geological samples by inductively coupled plasma-optical emission spectrometry

Typically, 27 major, minor, and trace elements are determined in natural waters, acid mine drainage, extraction fluids, and leachates of geological and environmental samples by inductively coupled plasma-optical emission spectrometry (ICP-OES). At the discretion of the analyst, additional elements may be determined after suitable method modifications and performance data are established. Samples are preserved in 1–2 percent nitric acid (HNO3) at sample collection or as soon as possible after collection. The aqueous samples are aspirated into the ICP-OES discharge, where the elemental emission signals are measured simultaneously for 27 elements. Calibration is performed with a series of matrix-matched, multi-element solution standards.

Open-File Report

A methodology for quantifying trace elements in the exoskeletons of Florida stone crab ( Menippe mercenaria ) larvae using inductively coupled plasma optical emission spectrometry (ICP–OES)

The larvae of the Florida stone crab, Menippe mercenaria , migrate through a variety of habitats as they develop and, therefore, experience a broad range of environmental conditions through ontogeny. Environmental variability experienced by the larvae may result in distinct elemental signatures within the exoskeletons, which could provide a tool for tracking the environmental history of larval stone crab populations. A method was developed to examine trace-element ratios, specifically magnesium-to-calcium (Mg/Ca) and strontium-to-calcium (Sr/Ca) ratios, in the exoskeletons of M. mercenaria larvae. Two developmental stages of stone crab larvae were analyzed—stage III and stage V. Specimens were reared in a laboratory environment under stable conditions to quantify the average ratios of Mg/Ca and Sr/Ca of larval stone crab exoskeletons and to determine if the ratios differed through ontogeny. The elemental compositions (Ca, Mg, and Sr) in samples of stage III larvae (n = 50 per sample) from 11 different broods (mean Sr/Ca = 5.916 ± 0.161 millimole per mole [mmol mol −1 ]; mean Mg/Ca = 218.275 ± 59.957 mmol mol −1 ) and stage V larvae (n = 10 per sample) from 12 different broods (mean Sr/Ca = 6.110 ± 0.300 mmol mol −1 ; mean Mg/Ca = 267.081 ± 67.211 mmol mol –1 ) were measured using inductively coupled plasma optical emission spectrometry (ICP–OES). The ratio of Sr/Ca significantly increased from stage III to stage V larvae, suggesting an ontogenic shift in Sr/Ca ratios between larval stages. The ratio of Mg/Ca did not change significantly between larval stages, but variability among broods was high. The method used to examine the trace-element ratios provided robust, highly reproducible estimates of Sr/Ca and Mg/Ca ratios in the larvae of M. mercenaria , demonstrating that ICP–OES can be used to determine the trace-element composition of chitinous organisms like the Florida stone crab.

Open-File Report

Water-quality, bed-sediment, and invertebrate tissue trace-element concentrations for tributaries in the Clark Fork Basin, Montana, October 2017–September 2018

Water, bed sediment, and invertebrate tissue were sampled in streams from Butte to near Missoula, Montana, as part of a monitoring program in the Clark Fork Basin. The sampling program was completed by the U.S. Geological Survey, in cooperation with the U.S. Environmental Protection Agency, to characterize aquatic resources in the Clark Fork Basin and monitor trace elements associated with historical mining and smelting activities. Sampling sites were on the river and tributaries of the Clark Fork. Water samples were collected periodically at 20 sites from October 2017 through September 2018. Bed-sediment and tissue samples were collected once at 13 sites during August 2018. Water-quality data included concentrations of major ions, dissolved organic carbon, nitrogen (nitrate plus nitrite), trace elements, and suspended sediment. Daily values of turbidity were determined at four sites. Bed-sediment data included trace-element concentrations in the fine-grained (less than 0.063 millimeter) fraction. Biological data included trace-element concentrations in whole-body tissue of aquatic benthic invertebrates. Statistical summaries of water-quality, bed-sediment, and invertebrate tissue trace element data for sites in the Clark Fork Basin were provided for the period of record: March 1985–September 2018.

Montana

Water-quality, bed-sediment, and invertebrate tissue trace-element concentrations for tributaries in the Clark Fork Basin, Montana, October 2018–September 2019

Water, bed sediment, and invertebrate tissue were sampled in streams from Butte to near Missoula, Montana, as part of a monitoring program in the Clark Fork Basin. The sampling program was completed by the U.S. Geological Survey, in cooperation with the U.S. Environmental Protection Agency, to characterize aquatic resources in the Clark Fork Basin and monitor trace elements associated with historical mining and smelting activities. Sampling sites were on the river and tributaries of the Clark Fork. Water samples were collected periodically at 20 sites from October 2018 through September 2019. Bed-sediment and tissue samples were collected once at 13 sites during July 2019. Water-quality data included concentrations of major ions, dissolved organic carbon, nitrogen (nitrate plus nitrite), trace elements, and suspended sediment. Daily values of turbidity were determined at four sites. Bed-sediment data included trace-element concentrations in the fine-grained (less than 0.063 millimeter) fraction. Biological data included trace-element concentrations in whole-body tissue of aquatic benthic invertebrates. Statistical summaries of water-quality, bed-sediment, and invertebrate tissue trace-element data for sites in the Clark Fork Basin were provided for the period of record: March 1985–September 2019.

Montana

Water-quality, bed-sediment, and invertebrate tissue trace-element concentrations for tributaries in the Clark Fork Basin, Montana, October 2019–September 2020

Water, bed sediment, and invertebrate tissue were sampled in streams from Butte to near Missoula, Montana, as part of a monitoring program in the Clark Fork Basin. The sampling program was completed by the U.S. Geological Survey, in cooperation with the U.S. Environmental Protection Agency, to characterize aquatic resources in the Clark Fork Basin and monitor trace elements associated with historical mining and smelting activities. Sampling sites were on the Clark Fork River and a subset of its tributaries. Water samples were collected periodically at 22 sites from October 2019 through September 2020. Bed-sediment and tissue samples were collected once at 12 sites during July 2020. Water-quality data included concentrations of major ions, dissolved organic carbon, nitrogen (nitrate plus nitrite), trace elements, and suspended sediment. Daily values of turbidity were determined at four sites. Bed-sediment data included trace-element concentrations in the fine-grained (less than 0.063 millimeter) fraction. Biological data included trace-element concentrations in whole-body tissue of selected aquatic benthic invertebrates. Statistical summaries of water-quality, bed-sediment, and invertebrate tissue trace-element data for sites in the Clark Fork Basin were provided for the period of record: March 1985–September 2020.

Montana

Select elements of concern in surface water of three hydrologic basins (Delaware River, Illinois River, and Upper Colorado River)—Data screening for the development of spatial and temporal models

The report focuses on the screening of previously published concentration data associated with 12 elements of concern (aluminum, arsenic, cadmium, chromium, copper, iron, mercury, manganese, lead, selenium, uranium, and zinc) measured in stream surface waters of three hydrologic basins (Delaware River Basin, Illinois River Basin, and the Upper Colorado River Basin). The purpose of this analysis is to determine what subsets of the original dataset (containing more than 1,500,000 observations) may be most suitable for each of two types of modeling efforts. The first type of modeling envisions a machine learning approach to determine which geospatial attributes are most significant in describing the spatial distribution of elemental concentrations within a basin. The second type of modeling envisions a stepwise regression approach to develop multivariable models that can be used to determine high resolution time-series estimates of elemental concentrations or loads at discrete U.S. Geological Survey real-time stream surface water sites. These site-specific temporal models are based on continuous measurements of available discharge and (or) in situ sensor data (temperature, pH, turbidity, dissolved oxygen, specific conductance, and (or) fluorescent dissolved organic matter) as the explanatory variables. The data screening for both model types considered historical trends in analytical methods and detection quantitation limits, the extent of censored data, data density, and environmental relevance with respect to three U.S. Environmental Protection Agency water quality thresholds (drinking water guidelines, human health criteria, and aquatic life criteria). The result of this analysis was the production of a final list of potential models deemed suitable for further development based upon the data exclusion (or inclusion) scheme developed herein for each model type. In both cases, the final models included mostly the three crustal elements (iron, manganese, and aluminum) that are found at comparatively high concentrations in surface water, whereas most of the more pernicious elements were excluded from the final model lists owing to various data limitations. The one exception to this was arsenic, for which the existing data were sufficient at three U.S. Geological Survey real-time sites for potential further development of time-series models.

Colorado, Delaware, Illinois, Indiana, Maryland, N

Trace element analysis of marine organisms by anodic stripping voltammetry (ASV)

Trace element analysis of marine organisms has generally been conducted by (1) sophisticated instrumentation (e. g., atomic absorption), (2) complicated cookbook laboratory procedures utilizing a host of chemicals and glassware, or (3) a combination of the above. All these procudures present problems to the investigator. For example, analysis by methods other than instrumentation are unable to detect minute amounts of various trace elements and in general are not extremely accurate. Problems common to all procedures are (1) relatively large amounts of sample (2 grams or more) are required for analyses of even the more common trace elements and (2) contamination of samples is almost a certainty due to complicated sample preparation procedures which include large amounts of glassware, chemicals and excessive handling of the sample. The development of new anodic stripping voltammetry (ASV methods (Matson, 1968) has provided investigators with an instrument which (1) is capable of accurately detecting trace elements in minute quantities, (2) utilizes very small amounts of sample (0.01 mg) , (3) works on a simple operating principle which simplifies sample preparation thereby reducing the possibility of contamination, (4) can be used aboard small boats, and (5) is relatively inexpensive (compared to other instruments used for trace element analysis). Recent ASV literature (Matson, 1968, Fitzgerald, 1970; Bradford, 1972) has dealt exclusively with the analysis of salt water and sediments and does not provide an adequate method for analysis of marine organic matter. This paper reports on an investigation designed to develop the methodology necessary for ASV analysis of organic material from the marine environment.

Open-File Report

Major and trace element data with partition coefficients for lava flows from the San Francisco volcanic field

Major and trace element data from San Francisco Mountain (a stratovolcano), as well as major element data from representative flows of the surrounding volcanic field (figure 1), are presented in this report. Also included are conventional and normalized partition coefficients for trace elements in each of the coexisting mineral phases and mesostasis from San Francisco Mountain lavas. The San Francisco Mountain lavas are from the upper portion of the southeast slope of Humphreys Peak which is composed of three petrographically distinct types: (1) a lower series of hornblende pyroxene andesites, (2) a middle group of hypersthene dacites, and (3) an upper series of olivine andesites. The sequence of volcanic flows was measured and analyzed for the major elements and fifteen trace elements Sc, V, Cr, Cq Ni, Cu, Zn, Ga, Sr, Y, Zr, Ba, La, Ce, and Yb) in each of the coexisting mineral phases, groundmass and bulk rock. The constituent mineral phases (not all are present in every sample) are plagioclase, hypersthene, augite, hornblende, olivine, magnetite, and ilmenite/hematite.

Arizona

Organochlorine compounds and trace elements in fish tissue and ancillary data for the Connecticut, Housatonic, and Thames river basins study unit, 1992-94

Concentrations of organochlorine compounds and trace elements were assayed in fish tissue collected from the Connecticut, Housatonic, and Thames River Basins Study Unit, 1992-94. These data were collected to determine the occurrence and distribution of organochlorine compounds and trace elements in the study unit. Ancillary data included are land-use categories by percentage of the sampling-site basins and the size, gender, and age of the individual fish collected for this study. Concentrations of 28 organochlorine compounds in composited whole fish samples were measured at 32 sites, and concentrations of 22 trace elements in composited fish liver samples were measured at 14 of the 32 sites. Most frequently detected organochlorines were DDT related compounds at 31 sites, total PCBs at 28 sites, and chlordane related compounds at 25 sites. Concentrations of total PCBs in fish tissue were generally higher at the large river sites than at the smaller tributary sites. Concentrations of chlordane-related compounds in fish tissue were higher at sites from more urbanized basins than at sites from predominately agriculture and forested basins. Concentrations of the DDT related compounds were undifferentiated among sites comprising different land uses. Trace elements detected at all 14 sites included boron, copper, iron, manganese, molybdenum, selenium, and zinc. Trace elements detected at 10 or more sites included arsenic, mercury, silver, strontium, and vanadium. Antimony, beryllium, and uranium were not detected at any site.

Open-File Report

Methods of analysis by the U.S. Geological Survey National Water Quality Laboratory - Determination of elements in whole-water digests using inductively coupled plasma-optical emission spectrometry and inductively coupled plasma-mass spectrometry

Inductively coupled plasma-optical emission spectrometry (ICP-OES) and inductively coupled plasma-mass spectrometry (ICP-MS) can be used to determine 26 elements in whole-water digests. Both methods have distinct advantages and disadvantages--ICP-OES is capable of analyzing samples with higher elemental concentrations without dilution, however, ICP-MS is more sensitive and capable of determining much lower elemental concentrations. Both techniques gave accurate results for spike recoveries, digested standard reference-water samples, and whole-water digests. Average spike recoveries in whole-water digests were 100 plus/minus 10 percent, although recoveries for digests with high dissolved-solid concentrations were lower for selected elements by ICP-MS. Results for standard reference-water samples were generally within 1 standard deviation of hte most probable values. Statistical analysis of the results from 43 whole-water digest indicated that there was no significant difference among ICP-OES, ICP-MS, and former official methods of analysis for 24 of the 26 elements evaluated.

Open-File Report

Assessment of Energetic Compounds, Semi-volatile Organic Compounds, and Trace Elements in Streambed Sediment and Stream Water from Streams Draining Munitions Firing Points and Impact Areas, Fort Riley, Kansas, 2007-08

An assessment of energetic compounds (explosive and propellant residues) and associated semi-volatile organic compounds (SVOCs) and trace elements in streambed sediment and stream water from streams draining munitions firing points and impact areas at Fort Riley, northeast Kansas, was performed during 2007-08 by the U.S. Geological Survey (USGS) in cooperation with the U.S. Army. Streambed sediment from 16 sampling sites and stream-water samples from 5 sites were collected at or near Fort Riley and analyzed for as many as 17 energetic compounds, 65 SVOCs, and 27 trace elements. None of the energetic compounds or SVOCs were detected in streambed sediment collected from sites within the Fort Riley Military Reservation. This may indicate that these compounds either are not transported from dispersal areas or that analytical methods are not sensitive enough to detect the small concentrations that may be transported. Concentrations of munitions-associated trace elements did not exceed sediment-quality guidelines recommended by the U.S. Environmental Protection Agency (USEPA) and are not indicative of contamination of streambed sediment at selected streambed sampling sites, at least in regards to movement from dispersal areas. Analytical results of stream-water samples provided little evidence of contamination by energetic compounds, SVOCs, or associated trace elements. Perchlorate was detected in 19 of 20 stream-water samples at concentrations ranging from an estimated 0.057 to an estimated 0.236 ug/L (micrograms per liter) with a median concentration of an estimated 0.114 ug/L, substantially less than the USEPA Interim Health Advisory criterion (15 ug/L), and is in the range of documented background concentrations. Because of these small concentrations and possible natural sources (precipitation and groundwater), it is likely that the occurrence of perchlorate in stream water is naturally occurring, although a definitive identification of the source of perchlorate in stream water at Fort Riley is difficult. The only SVOCs detected in stream-water samples were bis(2-ethylhexyl) phthalate and di-n-butyl phthalate but at concentrations substantially less than the most stringent aquatic-life criteria established by the Kansas Department of Health and Environment. All trace element concentrations in stream-water samples were less than the most stringent aquatic-life criteria. The implication of these stream-water results is that contamination arising from firing-range activities, if it exists, is so small as to be nondetectable with current analytical methods or is not distinguishable from background concentrations for constituents that also are naturally occurring. Overall, the munitions-related constituents analyzed in streambed sediment and stream water, when detected, were at concentrations that were less than regulatory criteria

Scientific Investigations Report

The principal rare earth elements deposits of the United States: A summary of domestic deposits and a global perspective

The rare earth elements (REE) are fifteen elements with atomic numbers 57 through 71, from lanthanum to lutetium ('lanthanides'), plus yttrium (39), which is chemically similar to the lanthanide elements and thus typically included with the rare earth elements. Although industrial demand for these elements is relatively small in tonnage terms, they are essential for a diverse and expanding array of high-technology applications. REE-containing magnets, metal alloys for batteries and light-weight structures, and phosphors are essential for many current and emerging alternative energy technologies, such as electric vehicles, energy-efficient lighting, and wind power. REE are also critical for a number of key defense systems and other advanced materials. Section 843 of the National Defense Authorization Act for Fiscal Year 2010, Public Law 111-84, directs the Comptroller General to complete a report on REE materials in the defense supply chain. The Office of Industrial Policy, in collaboration with other U.S. Government agencies, has initiated (in addition to this report) a detailed study of REE. This latter study will assess the Department of Defense's use of REE, as well as the status and security of domestic and global supply chains. That study will also address vulnerabilities in the supply chain and recommend ways to mitigate any potential risks of supply disruption. To help conduct this study, the Office of Industrial Policy asked the U.S. Geological Survey (USGS) to report on domestic REE reserves and resources in a global context. To this end, the enclosed report is the initial USGS contribution to assessing and summarizing the domestic REE resources in a global perspective. In 2009, the Mineral Resources Program of the USGS organized a new project under the title Minerals at Risk and For Emerging Technologies in order to evaluate mineral resource and supply issues of rare metals that are of increasing importance to the national economy. Leaders and members of this project, with the assistance of the USGS National Minerals Information Center, prepared the enclosed USGS report on domestic REE resources. The USGS Mineral Resources Program has investigated domestic and selected foreign REE resources for many decades, and this report summarizes what has been learned from this research. The USGS National Minerals Information Center (formerly Minerals Information Team) has monitored global production, trade, and resources for an equally long period and is the principal source of statistics used in this report. The objective of this study is to provide a nontechnical overview of domestic reserves and resources of REE and possibilities for utilizing those resources. At the present time, the United States obtains its REE raw materials from foreign sources, almost exclusively from China. Import dependence upon a single country raises serious issues of supply security. In a global context, domestic REE resources are modest and of uncertain value; hence, available resources in traditional trading partners (such as Canada and Australia) are of great interest for diversifying sources of supply. This report restates basic geologic facts about REE relevant to assessing security of supply, followed by a review of current United States consumption and imports of REE, current knowledge of domestic resources, and possibilities for future domestic production. Further detail follows in a deposit-by-deposit review of the most significant domestic REE deposits (see index map). Necessary steps to develop domestic resources are discussed in a separate section, leading into a review of current domestic exploration and a discussion of the value of a future national mineral resource assessment of REE. The report also includes an overview of known global REE resources and discusses the reliability of alternative foreign sources of REE.

Scientific Investigations Report

Groundwater quality and the relation between pH values and occurrence of trace elements and radionuclides in water samples collected from private wells in part of the Kickapoo Tribe of Oklahoma Jurisdictional Area, central Oklahoma, 2011

From 1999 to 2007, the Indian Health Service reported that gross alpha-particle activities and concentrations of uranium exceeded the Maximum Contaminant Levels for public drinking-water supplies in water samples from six private wells and two test wells in a rural residential neighborhood in the Kickapoo Tribe of Oklahoma Jurisdictional Area, in central Oklahoma. Residents in this rural area use groundwater from Quaternary-aged terrace deposits and the Permian-aged Garber-Wellington aquifer for domestic purposes. Uranium and other trace elements, specifically arsenic, chromium, and selenium, occur naturally in rocks composing the Garber-Wellington aquifer and in low concentrations in groundwater throughout its extent. Previous studies have shown that pH values above 8.0 from cation-exchange processes in the aquifer cause selected metals such as arsenic, chromium, selenium, and uranium to desorb (if present) from mineral surfaces and become mobile in water. On the basis of this information, the U.S. Geological Survey, in cooperation with the Kickapoo Tribe of Oklahoma, conducted a study in 2011 to describe the occurrence of selected trace elements and radionuclides in groundwater and to determine if pH could be used as a surrogate for laboratory analysis to quickly and inexpensively identify wells that might contain high concentrations of uranium and other trace elements. The pH and specific conductance of groundwater from 59 private wells were measured in the field in an area of about 18 square miles in Lincoln and Pottawatomie Counties. Twenty of the 59 wells also were sampled for dissolved concentrations of major ions, trace elements, gross alpha-particle and gross beta-particle activities, uranium, radium-226, radium-228, and radon-222 gas. Arsenic concentrations exceeded the Maximum Contaminant Level of 10 micrograms per liter in one sample having a concentration of 24.7 micrograms per liter. Selenium concentrations exceeded the Maximum Contaminant Level of 50 micrograms per liter in one sample having a concentration of 147 micrograms per liter. Both samples had alkaline pH values, 8.0 and 8.4, respectively. Uranium concentrations ranged from 0.02 to 383 micrograms per liter with 5 of 20 samples exceeding the Maximum Contaminant Level of 30 micrograms per liter; the five wells with uranium concentrations exceeding 30 micrograms per liter had pH values ranging from 8.0 to 8.5. Concentrations of uranium and radon-222 and gross alpha-particle activity showed a positive relation to pH, with the highest concentrations and activity in samples having pH values of 8.0 or above. The groundwater samples contained dissolved oxygen and high concentrations of bicarbonate; these characteristics are also factors in increasing uranium solubility. Concentrations of radium-226 and radium-228 (combined) ranged from 0.03 to 1.7 picocuries per liter, with a median concentration of 0.45 picocuries per liter for all samples. Radon-222 concentrations ranged from 95 to 3,600 picocuries per liter with a median concentration of 261 picocuries per liter. Eight samples having pH values ranging from 8.0 to 8.7 exceeded the proposed Maximum Contaminant Level of 300 picocuries per liter for radon-222. Eight samples exceeded the 15 picocuries per liter Maximum Contaminant Level for gross alpha-particle activity at 72 hours (after sample collection) and at 30 days (after the initial count); those samples had pH values ranging from 8.0 to 8.5. Gross beta-particle activity increased in 15 of 21 samples during the interval from 72 hours to 30 days. The increase in gross beta-particle activity over time probably was caused by the ingrowth and decay of uranium daughter products that emit beta particles. Water-quality data collected for this study indicate that pH values above 8.0 are associated with potentially high concentrations of uranium and radon-222 and high gross alpha-particle activity in the study area. High pH values also are associated with potentially high concentrations of arsenic, chromium, and selenium in groundwater when these elements occur in the aquifer matrix along groundwater-flow paths.

Oklahoma

Occurrence and concentrations of selected trace elements and halogenated organic compounds in stream sediments and potential sources of polychlorinated biphenyls, Leon Creek, San Antonio, Texas, 2012–14

The Texas Department of State Health Services issued fish consumption advisories in 2003 and 2010 for Leon Creek in San Antonio, Texas, based on elevated concentrations of polychlorinated biphenyls (PCBs) in fish tissues. The U.S. Geological Survey (USGS) measured elevated PCB concentrations in stream-sediment samples collected during 2007–9 from Leon Creek at Lackland Air Force Base (now known as Joint Base San Antonio-Lackland; the sampling site at this base is hereinafter referred to as the “Joint Base site”) and sites on Leon Creek downstream from the base. This report describes the occurrence and concentrations of selected trace elements and halogenated organic compounds (pesticides, flame retardants, and PCBs) and potential sources of PCBs in stream-sediment samples collected from four sites on Leon Creek during 2012–14. In downstream order, sediment samples were collected from Leon Creek at northwest Interstate Highway 410 (Loop 410), Rodriguez Park, Morey Road, and Joint Base. The USGS periodically collected streambed-sediment samples during low flow and suspended-sediment samples during high flow. Trace element concentrations were low compared to the consensus-based sediment-quality guidelines (SQGs) for the threshold effect concentration (TEC) and probable effect concentration (PEC). Adverse effects to benthic biota are not expected at concentrations less than the TEC and are expected at concentrations greater than the PEC. No trace element concentrations were greater than the PEC in any of the samples. Trace element concentrations were greatest at the Morey Road and Joint Base sites and exceeded the TECs by 41 and 27 percent, respectively. Trace element concentrations were lowest at the Rodriguez Park and Loop 410 sites and exceeded the TECs by 18 and 14 percent, respectively. Pesticides that have been banned for several decades are commonly detected in Leon Creek stream sediments, particularly the chlordane compounds. Chlordane compounds were detected in 84 percent of the samples and at every sample collection site. The samples collected from the Rodriguez Park site had the most pesticide compounds detected. Only samples collected from the Joint Base site had dichlorodiphenyldichloroethane (DDD), dichlorodiphenyldichloroethylene (DDE), or dichlorodiphenyltrichloroethane (DDT) concentrations greater than the TEC, and a few were also greater than the PEC. Flame retardants were found at every site on Leon Creek where stream sediments were collected; however, a few compounds were frequently detected in the laboratory reagent blanks so their detections in the environmental samples may not be from local sources. Consensus-based SQGs were not available for flame retardants so samples were compared to Environment Canada Federal Environmental Quality Guidelines (FEQGs). The concentrations of flame retardants generally were greater in the suspended-sediment samples than the streambed-sediment samples and greater than the FEQGs in many cases. Eighteen PCB congeners were quantified in the sediment samples collected from Leon Creek. The samples collected from the Joint Base site had the most frequent PCB congener detections. Total PCB concentrations, computed as the sum of the 18 congeners by using the Kaplan-Meier method for left-censored environmental data, were much smaller than the TEC of 59.8 micrograms per kilogram (μg/kg). When detected, the concentrations of total PCBs in the stream-sediment samples collected from Leon Creek during 2012–14 ranged from an estimated 0.2 to 8.7 μg/kg. Sediment samples collected from Leon Creek by the USGS during 2007–9 and 2012–14 at a total of eight sites following identical field and laboratory methods were evaluated to determine if potential PCB sources could be identified. Total PCB concentrations in the sediment samples collected upstream from the Joint Base site were low or nondetections; while concentrations in the samples collected on and downstream from the Joint Base site were greater. Congeners 180 and 138 constituted the greatest proportion of the PCB mixture in samples collected upstream from, on, and downstream from the Joint Base site. Upstream from the Joint Base site, congeners 180 and 138 constituted 50 percent and 35 percent respectively of the PCBs congeners found in the samples. On and downstream from the Joint Base site, congeners 180 and 138 constituted 80 percent and 13 percent respectively of the PCBs congeners found in the samples. Chi-square (C2) tests also indicate that samples collected from the Loop 410 site were statistically different from samples collected from the Joint Base site and sites downstream. The PCB congener pattern in the Leon Creek samples is most like the congener mixture in Aroclor 1260, which is chemically similar to the PCBs detected in the fish samples that resulted in the 2003 fish consumption advisory.

Texas