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USGS2015

Assessment of general health of fishes collected at selected sites in the Great Lakes Basin In 2012

During the past decade, there has been a substantive increase in the detection of “emerging contaminants”, defined as a new substance, chemical, or metabolite in the environment; or a legacy substance with a newly expanded distribution, altered release, or a newly recognized effect (such as endocrine disruption). Emerging contaminants include substances such as biogenic hormones (human and animal), brominated flame retardants, pharmaceuticals, personal care products, plasticizers, current use pesticides, detergents, and nanoparticles. These contaminants are frequently not regulated or inadequately regulated by state or Federal water quality programs. Information about the toxicity of these substances to fish and wildlife resources is generally limited, compared to more highly regulated contaminants, and some classes have been shown to cause affects (for example feminization of male fish, immunomodulation) that are not evaluated via traditional toxicity testing protocols. As a result, these compounds may pose a substantial, but currently poorly documented threat to aquatic ecosystems. Failure to identify and understand the impacts of these emerging contaminants on fish and wildlife resources may result in deleterious impacts to Great Lakes resources that can result in adverse ecological, economic and recreational consequences. The U. S. Fish and Wildlife Service received funding through the Great Lakes Restoration Initiative (GLRI) for an Early Warning Program to detect and identify emerging contaminants and to evaluate the effects of these contaminants on fish and wildlife. The U.S. Geological Survey (WV Cooperative Fish and Wildlife Research Unit and National Fish Health Research Laboratory, Leetown Science Center) developed and implemented a biological effects monitoring protocol to assist in this program. Fish collections and measurements of biomarkers of exposure in Fall 2010 and Spring 2011 occurred at individual sites within select Areas of Concern (AOCs). They provided an assessment of the utility of the suite of biomarkers and also identified sites for more in-depth analyses. Selected areas are characterized as areas with known emerging contaminants, sensitive or listed species, areas downstream from municipal wastewater discharges or receiving waters for industrial facilities, and/or areas susceptible to agricultural or urban contamination, or harbors or ports. The results of the 2010- 2011 studies were summarized in Blazer et al. 2014 a, b, c; Braham et al. in review and Blazer et al. in review.

Great Lakes↗

USGS2019

Late Quaternary paleohydrology of desert wetlands and pluvial lakes in the Soda Lake basin, central Mojave Desert, California (USA)

Sediment cores taken near extant springs along the western margin of Soda Lake playa, as well as from the playa center, reveal dramatic hydrologic changes that occurred in the central Mojave Desert during the late Quaternary. Results of stratigraphic, chronologic, physical, chemical, and microfossil analyses of seven cores, ranging in length from 5 to 23 m, help refine the timing and character of the final stages of pluvial Lake Mojave during the late Pleistocene and define distinct periods of wetland development in the early and late Holocene. Evidence shows that an incipient lake occupied the central Soda Lake basin by at least 25.0 ka (ka = thousands of calibrated 14 C years before present), and a fully developed Lake Mojave was present between 20.5 and 12.8 ka, before receding and ultimately yielding to playa conditions by 11.0 ka. Organic-rich “black mats” appear in several cores along the playa margin between 10.7 and 9.0 ka, suggesting that spring-fed wetlands persisted in this area long after the lake had regressed. The basin remained relatively dry throughout most of the Holocene until wetland ecosystems expanded along the margins between 0.73 and 0.18 ka, coincident with part of the Medieval Climate Anomaly and Little Ice Age. Overall, our results demonstrate that buried sediments surrounding extant and extinct springs can be used to reconstruct past hydrologic conditions in desert environments on a variety of spatial and temporal scales, and provide important baseline information for effective management of limited desert resources.

California↗

USGS2002

Holocene multidecadal and multicentennial droughts affecting Northern California and Nevada

Continuous, high-resolution δ 18 O records from cored sediments of Pyramid Lake, Nevada, indicate that oscillations in the hydrologic balance occurred, on average, about every 150 years (yr) during the past 7630 calendar years (cal yr). The records are not stationary; during the past 2740 yr, drought durations ranged from 20 to 100 yr and intervals between droughts ranged from 80 to 230 yr. Comparison of tree-ring-based reconstructions of climate change for the past 1200 yr from the Sierra Nevada and the El Malpais region of northwest New Mexico indicates that severe droughts associated with Anasazi withdrawal from Chaco Canyon at 820 cal yr BP (calendar years before present) and final abandonment of Chaco Canyon, Mesa Verde, and the Kayenta area at 650 cal yr BP may have impacted much of the western United States.During the middle Holocene (informally defined in this paper as extending from 8000 to 3000 cal yr BP), magnetic susceptibility values of sediments deposited in Pyramid Lake's deep basin were much larger than late–Holocene (3000–0 cal yr BP) values, indicating the presence of a shallow lake. In addition, the mean δ 18 O value of CaCO 3 precipitated between 6500 and 3430 cal yr BP was 1.6‰ less than the mean value of CaCO 3 precipitated after 2740 cal yr BP. Numerical calculations indicate that the shift in the δ 18 O baseline probably resulted from a transition to a wetter (>30%) and cooler (3–5°C) climate. The existence of a relatively dry and warm middle-Holocene climate in the Truckee River–Pyramid Lake system is generally consistent with archeological, sedimentological, chemical, physical, and biological records from various sites within the Great Basin of the western United States. Two high-resolution Holocene-climate records are now available from the Pyramid and Owens lake basins which suggest that the Holocene was characterized by five climatic intervals. TIC and δ 18 O records from Owens Lake indicate that the first interval in the early Holocene (11,600–10,000 cal yr BP) was characterized by a drying trend that was interrupted by a brief (200 yr) wet oscillation centered at 10,300 cal yr BP. This was followed by a second early-Holocene interval (10,000–8000 cal yr BP) during which relatively wet conditions prevailed. During the early part of the middle Holocene (8000–6500 cal yr BP), high-amplitude oscillations in TIC in Owens Lake and δ 18 O in Pyramid Lake indicate the presence of shallow lakes in both basins. During the latter part of the middle Holocene (6500–3800 cal yr BP), drought conditions dominated, Owens Lake desiccated, and Lake Tahoe ceased spilling to the Truckee River, causing Pyramid Lake to decline. At the beginning of the late Holocene (∼3000 cal yr BP), Lake Tahoe rose to its sill level and Pyramid Lake increased in volume.

Quaternary Science Reviews↗

USGS2003

The behavior of U- and Th-series nuclides in groundwater

Groundwater has long been an active area of research driven by its importance both as a societal resource and as a component in the global hydrological cycle. Key issues in groundwater research include inferring rates of transport of chemical constituents, determining the ages of groundwater, and tracing water masses using chemical fingerprints. While information on the trace elements pertinent to these topics can be obtained from aquifer tests using experimentally introduced tracers, and from laboratory experiments on aquifer materials, these studies are necessarily limited in time and space. Regional studies of aquifers can focus on greater scales and time periods, but must contend with greater complexities and variations. In this regard, the isotopic systematics of the naturally occurring radionuclides in the U- and Th- decay series have been invaluable in investigating aquifer behavior of U, Th, and Ra. These nuclides are present in all groundwaters and are each represented by several isotopes with very different half-lives, so that processes occurring over a range of time-scales can be studied (Table 1 ⇓ ). Within the host aquifer minerals, the radionuclides in each decay series are generally expected to be in secular equilibrium and so have equal activities (see Bourdon et al. 2003 ). In contrast, these nuclides exhibit strong relative fractionations within the surrounding groundwaters that reflect contrasting behavior during release into the water and during interaction with the surrounding host aquifer rocks. Radionuclide data can be used, within the framework of models of the processes involved, to obtain quantitative assessments of radionuclide release from aquifer rocks and groundwater migration rates. The isotopic variations that are generated also have the potential for providing fingerprints for groundwaters from specific aquifer environments, and have even been explored as a means for calculating groundwater ages.

Reviews in Mineralogy and Geochemistry↗

USGS2004

Determining sources of water and contaminants to wells in a carbonate aquifer near Martinsburg, Blair County, Pennsylvania, by use of geochemical indicators, analysis of anthropogenic contaminants, and simulation of ground-water flow

Water supply for the Borough of Martinsburg, Pa., is from two well fields (Wineland and Hershberger) completed in carbonate-bedrock aquifers in the Morrison Cove Valley. Water supply is plentiful; however, waters with high concentrations of nitrate are a concern. This report describes the sources of water and contaminants to the supply wells. A review of previous investigations was used to establish the aquifer framework and estimate aquifer hydraulic properties. Aquifer framework and simulation of ground-water flow in a 25-square-mile area using the MODFLOW model helped to further constrain aquifer hydraulic properties and identify water-source areas in the zone of contribution of ground water to the well fields. Flow simulation identified potential contaminant-source areas. Data on contaminants and geochemical characteristics of ground water at the well fields were compared to the results of flow simulation. The Woodbury Anticline controls the aquifer framework near the well fields and four carbonate-bedrock formations contain the primary aquifers. Three carbonate-bedrock aquifers of Ordovician age overlie the Gatesburg aquifer of Cambrian age on the flanks of the anticline. Fracture, not conduit, permeability was determined to be the dominant water-bearing characteristic of the bedrock. The horizontal hydraulic conductivity of the Gatesburg aquifer is about 36 feet per day. The other carbonate aquifers (Nittany/Stonehenge, Bellefonte/Axemann, and Coburn through Loysburg aquifers) overlying and flanking the Gatesburg aquifer have horizontal hydraulic conductivities of about 1 foot per day. Regional directions of ground-water flow are toward the major streams with Clover Creek as the major discharge point for ground water in the east. Ground-water flow to the well fields is anisotropic with a 5:1 preferential horizontal direction along strike of the axial fold of the anticline. Thus, the zone of contribution of ground water to the well fields is elongate in a north-south direction along the anticline axis, with the majority of the flow to the well fields originating from the south. Human activity in the areal extent of the zone of contribution to the well fields was the source of contaminants. The areal extent of the zone of contribution included both urban areas in the Borough and a large amount of agricultural land. By relating results of flow simulation, natural geochemistry, and analyses of anthropogenic (human-made) contaminants, the source areas for water and contaminants were determined with more confidence than by using only flow simulation. Analysis of natural geochemistry identified water sources from both limestone and dolomite aquifers. Geochemistry results also indicated fractures, not conduits, were the dominant source of water from aquifers; however, quantitative source identification was not possible. Chemical ratios of chloride and bromide were useful to show that all samples of ground water had sources with chemical contributions from land surface. Nitrogen isotope ratio analysis indicated animal manure as the possible primary source of nitrate in most ground water. Some of the nitrate in ground water had chemical fertilizer as a source. At the Wineland well field, chemical fertilizer was likely the source of nitrate. The nitrate in water from the Hershberger well field was from a mixture of fertilizer and animal-manure sources. Human sewage was ruled out as a major source of nitrate in water from the municipal wells by results showing 1) wastewater compounds in sewage were rarely detected and 2) a mass-balance calculation indicating the small contribution of nitrogen that could be attributed to septic systems.

Scientific Investigations Report↗

USGS2017

Formation of Fe-Mn crusts within a continental margin environment

This study examines Fe-Mn crusts that form on seamounts along the California continental-margin (CCM), within the United States 200 nautical mile exclusive economic zone. The study area extends from approximately 30° to 38° North latitudes and from 117° to 126° West longitudes. The area of study is a tectonically active northeast Pacific plate boundary region and is also part of the North Pacific Subtropical Gyre with currents dominated by the California Current System. Upwelling of nutrient-rich water results in high primary productivity that produces a pronounced oxygen minimum zone. Hydrogenetic Fe-Mn crusts forming along the CCM show distinct chemical and mineral compositions compared to open-ocean crusts. On average, CCM crusts contain more Fe relative to Mn than open-ocean Pacific crusts. The continental shelf and slope release both Fe and Mn under low-oxygen conditions. Silica is also enriched relative to Al compared to open-ocean crusts. This is due to the North Pacific silica plume and enrichment of Si along the path of deep-water circulation, resulting in Si enrichment in bottom and intermediate waters of the eastern Pacific. The CCM Fe-Mn crusts have a higher percentage of birnessite than open-ocean crusts, reflecting lower dissolved seawater oxygen that results from the intense coastal upwelling and proximity to zones of continental slope pore-water anoxia. Carbonate fluorapatite (CFA) is not present and CCM crusts do not show evidence of phosphatization, even in the older sections. The mineralogy indicates a suboxic environment under which birnessite forms, but in which pH is not high enough to facilitate CFA deposition. Growth rates of CCM crusts generally increase with increasing water depth, likely due to deep-water Fe sources mobilized from reduced shelf and slope sediments. Many elements of economic interest including Mn, Co, Ni, Cu, W, and Te have slightly or significantly lower concentrations in CCM crusts relative to crusts from the Pacific Prime Crust Zone and other open-ocean basins. However, concentrations of total rare earth elements and yttrium average only slightly lower contents and in the future may be a strategic resource for the U.S.

California↗

USGS2022

Petrogenesis and rare earth element mineralization of the Elk Creek carbonatite, Nebraska, USA

Although carbonatites are the primary source of the world’s rare earth elements (REEs), the processes responsible for ore-grade REE enrichment in carbonatites are still poorly understood. In this study, we present a petrologic, geochemical, and isotopic evaluation of the Elk Creek carbonatite in southeast Nebraska to constrain the origin of REE mineralization. The Elk Creek carbonatite is a multilithologic carbonatite comprised of an early apatite-dolomite carbonatite, a middle/heavy REE-enriched magnetite-dolomite carbonatite, and a late-stage light REE-enriched, barite-dolomite carbonatite, as well as a suite of breccias. Neodymium, strontium, and carbon isotopic data from the early apatite-dolomite carbonatite, ε Nd (T) = 2.3 to 3.4, 87 Sr/ 86 Sr (i) = 0.702704 to 0.702857, and δ 13 C = −3.3 to −3.4, indicate that the parental magma and REEs were derived from the mantle, and textural and chemical data suggest that hydrothermal processes played an important role in reaching ore-grade enrichment. Higher initial 87 Sr/ 86 Sr values (∼0.7041) of REE-mineralized lithologies are evidence that these fluids were derived, in part, from meteoric water that interacted with the country rock. Modeling of the C-O isotopic data reveals that some of the isotopic variation results from closed-system Rayleigh fractionation of an evolving carbonatitic magma between 300 and 500 °C, but an excursion to heavier δ 18 O is likely the result of interaction with H 2 O-CO 2 -fluids at temperatures from 400 to 100 °C. Hydrothermal dolomite has higher 87 Sr/ 86 Sr values than early-formed magmatic dolomite, consistent with metasomatism by fluids derived, in part, from a more radiogenic source such as the Precambrian-age wall rock. Rare earth element mineralization occurs primarily in fine-grained, cavity filling minerals including monazite, bastnäsite, parisite, and synchysite along with barite, dolomite, quartz, and iron oxides. We interpret the LREE enrichment at Elk Creek to be the product of hydrothermal fluids derived from the evolving carbonatite magma and fluids from the wall rock. The REEs likely became enriched in late-stage fluids from the evolving magma as well as being remobilization by the dissolution of earlier formed minerals. Middle/heavy REE-enrichment in the magnetite-dolomite carbonatite is hosted in hydrothermal dolomite and is attributed to variations in the composition of hydrothermal fluids.

Nebraska↗

USGS1996

Hydrogeologic setting and simulation of pesticide fate and transport in the unsaturated zone of a regolith-mantled, carbonate-rock terrain near Newville, Pennsylvania

Physical and chemical data were collected from May 1991 through April 1993 at a 4.5 hectare field site in Cumberland County, Pa., about 5 kilometers southeast of Newville. These data were used to define the hydrogeologic setting of a field site representative of the intensively farmed carbonate valleys of southeastern and south-central Pennsylvania. The environmental processing of commonly used pesticides (herbicides, fungicides, and insecticides) in the unsaturated zone was simulated with a process- oriented digital model to evaluate the environmental fate and transport of pesticides to ground water. Site data and modelling results provide a basis for a discussion of water-quality implications of agricultural best-management practices. The carbonate valleys of Pennsylvania comprise regolith-mantled carbonate-rock terrains that consist of broad undulating upland areas dissected by mostly dry valleys and widely spaced spring-fed creeks. The upland areas are farmed and exhibit possess a doline karst topography with many closed depressions, sinkholes, and bedrock outcrops. Unsaturated materials at the field site consist of an almost continuous soil cover composed of fine-grained residuum underlain by an intermediate vadose zone composed of karstified limestone. Soils are absent on scattered bedrock outcrops and are more than 12 meters thick in other areas of the site. The soil profile stores appreciable quantities of water with a volumetric average of about 36 percent water at field capacity. Organic carbon content of soil materials is about 1.7 percent in the Ap-horizon and from 0.1 to 0.3 percent throughout the full thickness of the B- and C-horizons. Atrazine, metolachlor, simazine, and the atrazine soil metabolites deethylatrazine and deisopropylatrazine were detected at concentrations above 0.05 mg/L in just the upper 0.6 meters of soil materials. However, detectable concentrations of atrazine, simazine, and atrazine soil metabolites were measured in water samples from lysimeters installed in soil materials at depths of 1.2, 2.1, and 3.7 meters and from monitor wells completed in the saturated zone to depths of 122 meters. Data collected from the field site were used to configure a pesticide screening model based on the pesticide version of the leaching estimation and chemistry model (LEACHP) developed by Wagenet and Hutson (1987). Model simulations show that most field-applied pesticides volatilize to the atmosphere, accumulate in soils, degrade in the subsurface environment, or leach to ground water. Model results were used to rank the leaching potentials of 66 pesticides. Eighteen of 32 herbicides, 4 of 9 fungicides, and 10 of 25 insecticides have moderate to large potential for leaching to ground water. A review of available pesticide monitoring data suggests that many compounds given moderate or high leaching potentials have not been tested for in ground water and the presence of pesticides in Pennsylvania's ground water may be underreported. Monitoring data do not exist for more than two-thirds of the pesticide compounds currently used in agricultural, carbonate areas of Pennsylvania. Knowledge of processes that govern fate and transport of pesticides is needed to facilitate development of effective pesticide best-management practices. In addition to comprehensive monitoring for pesticides and pesticide degradation products in ground water downgradient of areas of pesticide use, improved (1) characterization of unsaturated flow and transport through regolith mantled carbonate rocks, (2) estimates of pesticide degradation rates, (3) understanding of soil-property controls on pesticide movement, and (4) management models developed from process-oriented research would aid in understanding the processes.

Water-Resources Investigations Report↗

USGS1993

Guidelines for the processing and quality assurance of benthic invertebrate samples collected as part of the National Water-Quality Assessment Program

Benthic invertebrate samples are collected as part of the U.S. Geological Survey's National Water-Quality Assessment Program. This is a perennial, multidisciplinary program that integrates biological, physical, and chemical indicators of water quality to evaluate status and trends and to develop an understanding of the factors controlling observed water quality. The Program examines water quality in 60 study units (coupled ground- and surface-water systems) that encompass most of the conterminous United States and parts of Alaska and Hawaii. Study-unit teams collect and process qualitative and semi-quantitative invertebrate samples according to standardized procedures. These samples are processed (elutriated and subsampled) in the field to produce as many as four sample components: large-rare, main-body, elutriate, and split. Each sample component is preserved in 10-percent formalin, and two components, large-rare and main-body, are sent to contract laboratories for further processing. The large-rare component is composed of large invertebrates that are removed from the sample matrix during field processing and placed in one or more containers. The main-body sample component consists of the remaining sample materials (sediment, detritus, and invertebrates) and is subsampled in the field to achieve a volume of 750 milliliters or less. The remaining two sample components, elutriate and split, are used for quality-assurance and quality-control purposes. Contract laboratories are used to identify and quantify invertebrates from the large-rare and main-body sample components according to the procedures and guidelines specified within this document. These guidelines allow the use of subsampling techniques to reduce the volume of sample material processed and to facilitate identifications. These processing procedures and techniques may be modified if the modifications provide equal or greater levels of accuracy and precision. The intent of sample processing is to determine the quantity of each taxon present in the semi-quantitative samples or to list the taxa present in qualitative samples. The processing guidelines provide standardized laboratory forms, sample labels, detailed sample processing flow charts, standardized format for electronic data, quality-assurance procedures and checks, sample tracking standards, and target levels for taxonomic determinations. The contract laboratory (1) is responsible for identifications and quantifications, (2) constructs reference collections, (3) provides data in hard copy and electronic forms, (4) follows specified quality-assurance and quality-control procedures, and (5) returns all processed and unprocessed portions of the samples. The U.S. Geological Survey's Quality Management Group maintains a Biological Quality-Assurance Unit, located at the National Water-Quality Laboratory, Arvada, Colorado, to oversee the use of contract laboratories and ensure the quality of data obtained from these laboratories according to the guidelines established in this document. This unit establishes contract specifications, reviews contractor performance (timeliness, accuracy, and consistency), enters data into the National Water Information System-II data base, maintains in-house reference collections, deposits voucher specimens in outside museums, and interacts with taxonomic experts within and outside the U.S. Geological Survey. This unit also modifies the existing sample processing and quality-assurance guidelines, establishes criteria and testing procedures for qualifying potential contract laboratories, identifies qualified taxonomic experts, and establishes voucher collections.

Open-File Report↗

USGS1996

Organic geochemistry applied to environmental assessments of Prince William Sound, Alaska, after the Exxon Valdez oil spill—a review

Organic geochemistry played a major role in the environmental assessments conducted following the Exxon Valdez oil spill, which occurred on March 24, 1989, and released about 258,000 bbls (41 million liters) of Alaska North Slope crude oil into Prince William Sound. Geochemical analyses of more than 15,000 sediment, tar, and biological samples and about 5000 water samples provide the largest database yet collected on oil-spill chemistry, and we review the results here. The marine environment of the Sound has a complex background of petrogenic, pyrogenic, and biogenic hydrocarbons from natural and anthropogenic sources. Geochemical evaluation of the fate and effects of the spilled oil required that this oil and its residues be distinguished from the background. A variety of molecular and isotopic techniques were employed to identify various hydrocarbon sources and to distinguish quantitatively among mixed sources in the samples. Although the specific criteria used to distinguish multiple sources in the region affected by the Exxon Valdez spill are not necessarily applicable to all spill situations, the principles that governed their selection are. Distributions of polycyclic aromatic hydrocarbons (PAH) and dibenzothiophenes distinguish Exxon Valdez oil and its weathered residues from background hydrocarbons in benthic sediments. Ratios of C 2 -dibenzothiophene C 2 -phenanthrene "> C 2 -dibenzothiopheneC 2 -phenanthrene and C 3 -dibenzothiophene C 3 -phenanthrene "> C 3 -dibenzothiopheneC 3 -phenanthrene were particularly useful. Carbon isotopes and terpane distributions distinguished Exxon Valdez residues found on shorelines from tars from other sources. Diesel and diesel soot were identified by the absence of alkylated chrysenes and a narrow distribution of n -alkanes, whereas pyrogenic products were distinguished by the dominance of 4- to 6-ring PAH over 2- to 3-ring PAH and by the dominance of non-alkylated over alkylated homologues of each PAH series. The presence of 18α(H)-oleanane in benthic sediments, coupled with its absence in Exxon Valdez oil and its residues, confirm another petrogenic source. Results of geochemical studies suggest that the petrogenic component in the background of benthic sediments is derived from oil seeps in the eastern Gulf of Alaska. In 1990 and 1991, Exxon Valdez residues, generally forming a small increment to the pre-spill background, were found to be only sporadically distributed in some shallow, near shore sediments adjacent to shorelines that had been heavily oiled in 1989. In 1994, occurrences of Exxon Valdez tars on shoreline surfaces were rare, although residues could be found buried in shoreline sediments at some isolated locations along the spill path where they were protected from wave action. Spilled oil residues collected 16 months after the spill were degraded, on average, by nearly 50%. Shoreline residues from sources other than the spill were also identified and are widespread throughout the Sound. These residues include (1) geochemically distinct tars and oils imported from California oil fields to Alaska for fuel and construction purposes prior to the discovery of the Cook Inlet and North Slope oil fields, (2) diesel and diesel soot, and (3) more highly refined products. Of the more than 2700 chemical analyses of biological samples of higher life forms (fish, birds, and mammals) about 150 (6%) indicate recognizable residues of Exxon Valdez oil, which were identified by their distribution of polycyclic aromatic hydrocarbons (PAH). Most of these samples (138) were collected in 1989 and most were associated with external surfaces or the gastrointestinal tract. Rarely do internal tissues or fluids contain recognizable fingerprints of spilled oil. This observation includes samples from marine mammals that were visibly oiled externally. Other hydrocarbon sources, including diesel and a non-petroleum artifact that occurs when concentrations of individual PAH are at or near their method detection limit, are also identified in biological samples.

Alaska↗

USGS2015

Characterizing toxicity of metal-contaminated sediments from mining areas

This paper reviews methods for testing the toxicity of metals associated with freshwater sediments, linking toxic effects with metal exposure and bioavailability, and developing sediment quality guidelines. The most broadly applicable approach for characterizing metal toxicity is whole-sediment toxicity testing, which attempts to simulate natural exposure conditions in the laboratory. Standard methods for whole-sediment testing can be adapted to test a wide variety of taxa. Chronic sediment tests that characterize effects on multiple endpoints (e.g., survival, growth, and reproduction) can be highly sensitive indicators of adverse effects on resident invertebrate taxa. Methods for testing of aqueous phases (pore water, overlying water, or elutriates) are used less frequently. Analysis of sediment toxicity data focuses on statistical comparisons between responses in sediments from the study area and responses in one or more uncontaminated reference sediments. For large or complex study areas, a greater number of reference sediments is recommended to reliably define the normal range of responses in uncontaminated sediments – the ‘reference envelope’. Data on metal concentrations and effects on test organisms across a gradient of contamination may allow development of concentration-response models, which estimate metal concentrations associated with specified levels of toxic effects (e.g. 20% effect concentration or EC20). Comparisons of toxic effects in laboratory tests with measures of impacts on resident benthic invertebrate communities can help document causal relationships between metal contamination and biological effects. Total or total-recoverable metal concentrations in sediments are the most common measure of metal contamination in sediments, but metal concentrations in labile sediment fractions (e.g., determined as part of selective sediment extraction protocols) may better represent metal bioavailability. Metals released by the weak-acid extraction of acid-volatile sulfide (AVS), termed simultaneously-extracted metals (SEM), are widely used to estimate the ‘potentially-bioavailable’ fraction of metals that is not bound to sulfides (i.e., SEM-AVS). Metal concentrations in pore water are widely considered to be direct measures of metal bioavailability, and predictions of toxicity based on pore-water metal concentrations may be further improved by modeling interactions of metals with other pore-water constituents using Biotic Ligand Models. Data from sediment toxicity tests and metal analyses has provided the basis for development of sediment quality guidelines, which estimate thresholds for toxicity of metals in sediments. Empirical guidelines such as Probable Effects Concentrations or (PECs) are based on associations between sediment metal concentrations and occurrence of toxic effects in large datasets. PECs do not model bioavailable metals, but they can be used to estimate the toxicity of metal mixtures using by calculation of probable effect quotients (PEQ = sediment metal concentration/PEC). In contrast, mechanistic guidelines, such as Equilibrium Partitioning Sediment Benchmarks (ESBs) attempt to predict both bioavailability and mixture toxicity. Application of these simple bioavailability models requires more extensive chemical characterization of sediments or pore water, compared to empirical guidelines, but may provide more reliable estimates of metal toxicity across a wide range of sediment types.

Applied Geochemistry↗

USGS2010

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↗

USGS2022

Contrasting Common Era climate and hydrology sensitivities from paired lake sediment dinosterol hydrogen isotope records in the South Pacific Convergence Zone

Hydroclimate on ‘Uvea (Wallis et Futuna) is controlled by rainfall associated with the South Pacific Convergence Zone (SPCZ), the southern hemisphere's largest precipitation feature. To extend the short observational precipitation record, the hydrogen isotopic composition of the algal lipid biomarker dinosterol (δ 2 H dinosterol ) was measured in sediment cores from two volcanic crater lakes on ‘Uvea. The modern lakes differ morphologically and chemically but both contain freshwater within the photic zone, support phytoplankton communities inclusive of dinosterol-producing dinoflagellates, and experience identical climate conditions. δ 2 H dinosterol values track lake water isotope ratios, ultimately controlled in the tropics by precipitation amount and evaporative enrichment. However, in 88-m-deep Lac Lalolalo a steadily decreasing trend in sedimentary δ 2 H dinosterol values from −227‰ around year 988 CE to modern values as low as −303‰, suggests this lake's evolution from an active volcanic setting to the present system strongly influenced δ 2 H dinosterol values. Although current hydrology and water isotope systematics may now reflect precipitation and evaporation in this lake, the interaction between these processes and large changes in basin morphology, geochemistry, and hydrology obstruct the recovery of a climate signal from Lac Lalolalo's sedimentary δ 2 H dinosterol records. This work emphasizes the importance of site replication and the use of complementary climate reconstruction tools, especially when using molecular proxies that may be sensitive to more than one environmental parameter. Contrary to its neighbor, duplicate δ 2 H dinosterol records from 23-m-deep Lac Lanutavake varied between −277‰ and −297‰ and indicate slightly drier conditions during the time-period known as the Medieval Climate Anomaly (MCA, 950–1250 CE). The δ 2 H dinosterol signal in Lac Lanutavake was muted compared to published records from ‘Upolu (Samoa) and Efate (Vanuatu) indicating that ‘Uvea's location is not as sensitive to precipitation variability at sites farther from the SPCZ central axis. Lithogenic runoff proxies combined with δ 2 H dinosterol support the interpretation of a relatively dry MCA on ‘Uvea, ‘Upolu, and Efate, potentially due to less intense precipitation, a contracted, or a more zonally oriented SPCZ.

Efate Island, Lac Lalolalo, Lac Lanoto'o, Lac Lanu↗

USGS2002

Flux of dissolved forms of mercury across the sediment-water interface in Lahontan Reservoir, Nevada

Field and laboratory studies were conducted between April 30, 2001 and July 19, 2001 to provide the first direct measurements of the benthic flux of dissolved (0.2-micrometer filtered) mercury species (total and methylated forms) between the bottom sediment and water column at three sites: two in the southern lobe and one in the northern lobe of Lahontan Reservoir, Nevada (Background, Fig. 1). Dissolved-mercury species and predominant ligands (represented by dissolved organic carbon, and sulfides) were the solutes of primary interest. Benthic flux, sometimes referred to as internal recycling, represents the transport of dissolved chemical species between the water column and the underlying sediment. Water-quality managers often assess and prioritize remediation strategies for aquatic systems, in particular Super Fund sites that have been adversely affected by anthropogenic activities. In the case of the Lahontan Reservoir along the Carson River, mercury associated with historic gold and silver extraction has been fluvially transported and accumulated in the bottom sediments. Frequent demands have been made by Super Fund site managers and the general public to quantify the connections between fluxes of contaminants and the health, abundance, and distribution of biological resources (Kuwabara and others, 1999). As part of a comprehensive examination of transport processes affecting mercury dynamics in Lahontan Reservoir, this study focuses on a poorly understood, yet potentially predominant, source of mercury to the reservoir water column, which is internal recycling, or benthic flux of mercury species and associated ligands. Mobilization, flux, and biological availability of mercury into the water column of the reservoir are affected by physical (e.g., advection and diffusion), chemical (i.e., oxidationreduction reactions, complexation and repartitioning) and biological processes (Flegal and others, 1991; Kuwabara and others, 1996; Grenz and others, 2000, Topping and others, 2001). The results described herein followed from the integration of current project studies with information needs identified by the U.S. Environmental Protection Agency, Region 9 (USEPA) to provide initial determinations of dissolved total and methyl-mercury fluxes from the sediments into the water column of Lahontan Reservoir. Recent mercury distribution and transformation studies in the Carson River system by Marvin-Dipasquale and others (2001) indicated the potential importance of sediment-water interactions in describing mercury speciation, its sources and sinks. Quantifying and understanding the magnitude and variability of these interactions are critical to the accurate assessment of contaminant sources and loads as well as to the development of process-integrated water-quality models for this mining-affected system. With a variety of strategies under consideration to determine how to most efficiently improve the water quality in the Carson River system, the primary question posed in this study was, “What processes regulate the fate and transport of mercury species in Lahontan Reservoir? In particular, are sources and sinks of dissolved total and methyl mercury associated with the bottom sediment within Lahontan Reservoir significant relative to major surface-water inputs from the Carson River?” The question was motivated by a number of factors. First, extraction of precious metals up gradient of the reservoir provide a historic source of elemental mercury that continues to be fluvially transported in dissolved and particulate phases (Hoffman and Taylor, 1998; Carroll and others, 2000; Carroll and Warwick, 2001). Elevated total and methyl mercury concentrations into the reservoir have been well documented (Priessler and others, 1999; Jones and others, 1999; Allander and others, 2001, Marvin-Dipasquale and others, 2001). Therefore, determining whether some fraction of this sediment-associated mercury can remobilize for transport to the overlying water and subsequently to down-stream portions of the Carson River is necessary. Second, elevated concentrations of mercury species in reservoir water, sediment, and fish have prompted a compilation, and comparison of dominant contaminant sources so that appropriate remedial strategies can be designed and implemented. Third, changes in oxidizing or reducing (redox) conditions and nutrient availability near the sediment-water interface (e.g., during phytoplankton blooms) can dramatically alter the mobility of metals and ligands associated with the bottom sediment as episodic sources of carbon settle out and accumulate (Thompson and others, 1981). Finally, there is a growing body of evidence from other aquatic systems that benthic flux or internal recycling of contaminants and nutrients is an important process to consider in developing appropriate ecosystem water-quality models (Wood and others, 1995; Kuwabara and others, 2000). The need for more refined numerical and conceptual models for mercury dynamics within the Carson River system thus clearly exists. This report is formatted unconventionally in a pyramid-like structure to effectively serve the needs of diverse parties interested in reviewing or acquiring information at various levels of detail (Appendix 1). The report enables quick transitions between the initial summary information (figuratively at the top of the pyramid) and later details of methods or results (that is, figuratively towards the base) using hyperlinks to supporting figures and tables, and an electronically linked Table of Contents.

Nebraska↗

USGS2005

Surface water-quality and water-quantity data from selected urban runoff-monitoring sites at the Rocky Mountain Arsenal, Commerce City, Colorado, water years 1988-2004

The U.S. Geological Survey has monitored the quality and quantity of streamflow at the Rocky Mountain Arsenal (RMA) northeast of Denver, Colorado, since the early 1990s in cooperation with the U.S. Army. This report, prepared in cooperation with the U.S. Fish and Wildlife Service, documents existing surface-water-quality conditions on the RMA. All RMA water-quality data for the Irondale Gulch and First Creek Basins adjacent to and on the RMA were reviewed. Where applicable, water-quality data were compared to State standards established by the Colorado Department of Public Health and Environment. At both the Havana Interceptor below 56th Avenue gaging station and the Uvalda Interceptor below 56th Avenue gaging station, all of the dissolved-oxygen concentrations met the State standard requiring at least 5.0 milligrams per liter (mg/L) of dissolved oxygen for the protection of aquatic life. In contrast, the dissolved-oxygen concentrations at the Peoria Interceptor below 56th Avenue gage commonly were less than 5.0 mg/L. Excluding one suspect concentration of 1.6 mg/L, the dissolved-oxygen concentrations for the First Creek Basin ranged from 4.2 to 12.6 mg/L. Excluding the one suspect value, three dissolved-oxygen concentrations failed to meet the State standard of 5.0 mg/L at the First Creek below Buckley Road site. At the Peoria Interceptor below 56th Avenue site, all pH values were within the range specified by the State standard (6.50-8.99). Results of seven sampling events at the Havana Interceptor below 56th Avenue gaging station indicated a pH greater than or equal to 9 (pH values of 9 or greater exceed the upper limit of the standard). No sampling events indicated a pH less than 6.50. Results from one sampling event at the Uvalda Interceptor below 56th Avenue indicated pH values outside the range specified by the State standard. The concentrations obtained for chloride, magnesium, and sodium generally were below 200 mg/L at all three Irondale Gulch monitoring stations for the entire period of record, but there were a few sampling events at each of these sites where much higher concentrations for these analytes were obtained. The median concentrations for calcium, magnesium, and sodium generally were higher at the First Creek below Buckley Road site than in the three Irondale Gulch sites, while the 90th percentile and maximum concentrations for magnesium and sodium generally were higher at the three Irondale Gulch sites than at the First Creek below Buckley Road site. The urban runoff flowing onto the RMA had low concentrations and few, if any, detections for most organic contaminants. Part of the reason for low detections of organic contaminants may be in how the samples are collected. The existing surface-water sampling program was not designed specifically to target storm runoff and therefore does not characterize water quality for all hydrologic regimes, most notably storm runoff. As a result, the existing data may not adequately represent potential contaminant transport onto the RMA. In addition, during stormwater-runoff events, the sites examined for this report frequently are subject to sharp increases in discharge, and just as quickly the discharge rapidly recedes. These types of transient flow events make water-quality sampling difficult, and none of the sites have a safe place to sample the higher flows that occur in any given year. As a result, most of the surface-water-quality samples were collected after the flow had decreased substantially from the peak flow, which may have transported much of the chemical contaminant load through the system. Thus, little is known about the water quality during the critical initial stormwater-runoff period when contaminants are most likely to be mobilized and transported through the stormwater conveyances past the locations where gaging stations are located.

Colorado↗

USGS1976

A review of hydrologic and geologic conditions related to the radioactive solid-waste burial grounds at Oak Ridge National Laboratory, Tennessee

Solid waste contaminated by radioactive matter has been buried in the vicinity of Oak Ridge National Laboratory since 1944. By 1973, an estimated six million cubic feet of such material had been placed in six burial grounds in two valleys. The practice initially was thought of as a safe method for permanently removing these potentially hazardous substances from man's surroundings, but is now que.3tionable at this site because of known leaching of contaminants from the waste, transport in ground water, and release to the terrestrial and fluvial environments. This review attempts to bring together in a single document information from numerous published and unpublished sources regarding the past criteria used for selecting the Oak Ridge burial-ground sites, the historical development and conditions of these facilities as of 1974, the geologic framework of the Laboratory area and the movement of water and water-borne contaminants in that area, the effects of sorption and ion exchange upon radionuclide transport, and a description and evaluation of the existing monitoring system. It is intended to assist Atomic Energy Commission (now Energy Research and Development Administration) officials in the formulation of managerial decisions concerning the burial grounds and present monitoring methods. Sites for the first three burial grounds appear to have been chosen during and shortly after World War II on the basis of such factors as safety, security, and distance from sources of waste origin. By 1950, geologic criteria had been introduced, and in the latter part of that decade, geohydrologic criteria were considered. While no current criteria have been defined, it becomes evident from the historical record that the successful containment of radionuclides below land surface for long periods of time is dependent upon a complex interrelationship between many geologic, hydrologic, and geochemical controls, and any definition of criteria must include consideration of these factors. For the most part, the burial grounds have been developed by a simple cut and fill procedure similar to the operation of a municipal landfill. Low permeability of the residuum, high rainfall, shallow depth to ground water, the excavation of trenches below the water table, and other practices, have contributed to a condition of waste leaching in probably all of the burial grounds. Despite these conditions, only very small concentrations of radionuclides have been found in wells or otherwise attributed to the initial three, small sites in Bethel Valley. This fact, however, may be due in part to the scant extent of site monitoring of those burial grounds for transport of radionuclides in ground water, and to the discharge of liquid radioactive waste to the drainage in concentrations that probably would have masked the presence of contaminants derived from these burial grounds. In comparison to the Bethel Valley sites, larger amounts of radioactive contaminants have been found in wells, seeps, trench overflow, and the drainages that drain Burial Grounds 4 and 5 in Melton Valley. The movement of radionuclides from the trenches to the drainages show that the latter sites are not suitable for the retention of all contaminants under existing conditions, and invalidates the operational concept of long-term or permanent retention of all radionuclides in the geologic environment. The transport of many radioactive ions leached from the waste has been retarded by the very high sorptive and ion exchange capacity of the residuum with which the radionuclides have had contact. Not all radionuclides, though, will be retained in the subsurface by adsorption, absorption, or ion exchange. Among those radioactive contaminants that may be problematical with respect to trench burial at Oak Ridge are tritium and other negatively-charged nuclides, positively-charged radionuclides included in some of the complexed molecules, radioactive ions that have chemical properties si

Open-File Report↗

USGS2020

Holocene paleoclimate change in the western US: The importance of chronology in discerning patterns and drivers

Sediment in lakes and meadows forms a powerful archive that can be used to reconstruct environmental change through time. Reconstructions of lake level, of chemical, biological, and hydrological conditions, and of surrounding vegetation provide detailed information about past climate conditions, both locally and regionally. Indeed, most of our current knowledge of centennial- to millennial-scale climate variability in the arid western United States, where information about past hydroclimate is particularly important, comes from such sediment-based reconstructions. The pressing need for robust, precise predictions of future conditions is a significant motivation for paleoclimate science, and current research questions frequently require Holocene reconstructions to be resolved at sub-centennial timescales. Increasingly, regional syntheses seek to identify synoptic-scale patterns similar to those defined from modern observations (seasonal, interannual, multi-decadal, etc.) or to compare with the output of climate model simulations. However, the age control on existing records, especially those more than about 20 years old, is often sufficient only for millennial-scale interpretation. Here we assess the age control for 84 published and unpublished records from lakes and meadows in the Great Basin, California, and desert southwest, and use Bayesian modeling to evaluate the 95% uncertainty ranges for the 42 best-dated records. In the Late Holocene, about half of the 42 records have <400-year mean uncertainty ranges; however, high-precision age control is especially critical for young records, used to develop an accurate understanding of a proxy’s response to known climate variations. In the Middle Holocene, records vary from 400 to >800-year mean uncertainty and records of the Early Holocene have 600- to >1400-year mean uncertainty ranges. We find that the largest control on modeled uncertainties is dating density, with at least 2 dates/kyr being optimal and suggest obtaining “range-finder” dates at the onset of a study to better predict the total number of dates needed for an adequate age model. Such a density avoids a commonly observed phenomenon of significant peaks in uncertainty arising in gaps between age control points. Analysis of the uncertainties associated with proxy shifts reveal that more than half are >400 years. Although such large uncertainties currently prevent sub-centennial interpretations in most cases, increased dating density, strategic use of limited funds (including budgeting for a 2 date/kyr minimum at the proposal stage), construction of age-depth models with Bayesian methods, and critical evaluation of chronological uncertainty will shed light on past climate variability at finer timescales, enhancing our understanding of global and regional drivers of western U.S. climate.

California, Idaho, Nevada, Oregon, Utah↗

USGS2015

Critical metals in manganese nodules from the Cook Islands EEZ, abundances and distributions

The Cook Islands (CIs) Exclusive Economic Zone (EEZ) encompasses 1,977,000 km 2 and includes the Penrhyn and Samoa basins abyssal plains where manganese nodules flourish due to the availability of prolific nucleus material, slow sedimentation rates, and strong bottom currents. A group of CIs nodules was analyzed for mineralogical and chemical composition, which include many critical metals not before analyzed for CIs nodules. These nodules have varying sizes and nuclei material; however all are composed predominantly of δ-MnO 2 and X-ray amorphous iron oxyhydroxide. The mineralogy, Fe/Mn ratios, rare earth element contents, and slow growth rates (mean 1.9 mm/10 6 years) reflect formation primarily by hydrogenetic precipitation. The paucity of diagenetic input can be explained by low primary productivity at the surface and resultant low organic matter content in seafloor sediment, producing oxic seafloor and sub-seafloor environments. The nodules contain high mean contents of Co (0.41%), Ni (0.38%), Ti (1.20%), and total rare earth elements plus yttrium (REY; 0.167%), and also high contents of Mo, Nb, V, W, and Zr. Compiled data from a series of four cruises by the Japan International Cooperation Agency and the Mining agency of Japan from 1985 to 2000 were used to generate a map that defines the statistical distribution of nodule abundance throughout the EEZ, except the Manihiki Plateau. The abundance distribution map shows a belt of high nodule abundance (19–45 kg/m 2 ) that starts in the southeast corner of the EEZ, runs northwest, and also bifurcates into a SW trending branch. Small, isolated areas contain abundances of nodules of up to 58 kg/m 2 . Six ~ 20,000 km 2 areas of particularly high abundance were chosen to represent potential exploration areas, and maps for metal concentration were generated to visualize metal distribution and to extrapolate estimated metal tonnages within the six sites and the EEZ as a whole. Grades for Mn, Cu, and Ni are low in CIs nodules in areas of high abundance; however, Ti, Co, and REY show high contents where nodule abundances are high. Of the six areas identified to represent a range of metal contents, one at the northern end of the N-S abundance main belt optimizes the most metals and would yield the highest dry metric tons for Mn (61,002,292), Ni (1,247,834), Mo (186,166), V (356,247), W (30,215), and Zr (195,323). When compared with the Clarion–Clipperton Zone, the CIs nodules show higher nodule abundances (> 25 kg/m 2 over ~ 123,844 km 2 ), and are more enriched in the green-tech, high-tech, and energy metals Co, Ti, Te, Nb, REY, Pt, and Zr. The CIs EEZ shows a significant resource potential for these critical metals due to their high prices, high demand, and the high nodule abundance, which will allow for a smaller footprint for a 20-year mine site and therefore smaller environmental impact.

Ore Geology Reviews↗