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Mars chronology: Assessing techniques for quantifying surficial processes

Currently, the absolute chronology of Martian rocks, deposits and events is based mainly on crater counting and remains highly imprecise with epoch boundary uncertainties in excess of 2 billion years. Answers to key questions concerning the comparative origin and evolution of Mars and Earth will not be forthcoming without a rigid Martian chronology, enabling the construction of a time scale comparable to Earth's. Priorities for exploration include calibration of the cratering rate, dating major volcanic and fluvial events and establishing chronology of the polar layered deposits. If extinct and/or extant life is discovered, the chronology of the biosphere will be of paramount importance. Many radiometric and cosmogenic techniques applicable on Earth and the Moon will apply to Mars after certain baselines (e.g. composition of the atmosphere, trace species, chemical and physical characteristics of Martian dust) are established. The high radiation regime may pose a problem for dosimetry-based techniques (e.g. luminescence). The unique isotopic composition of nitrogen in the Martian atmosphere may permit a Mars-specific chronometer for tracing the time-evolution of the atmosphere and of lithic phases with trapped atmospheric gases. Other Mars-specific chronometers include measurement of gas fluxes and accumulation of platinum group elements (PGE) in the regolith. Putting collected samples into geologic context is deemed essential, as is using multiple techniques on multiple samples. If in situ measurements are restricted to a single technique it must be shown to give consistent results on multiple samples, but in all cases, using two or more techniques (e.g. on the same lander) will reduce error. While there is no question that returned samples will yield the best ages, in situ techniques have the potential to be flown on multiple missions providing a larger data set and broader context in which to place the more accurate dates. ?? 2004 Elsevier B.V. All rights reserved.

Earth-Science Reviews

Nature's refineries — Metals and metalloids in arc volcanoes

Chemical data for fumaroles and for atmospheric gas and ash plumes from active arc volcanoes provide glimpses of the rates of release of metal and metalloids, such as Tl and Cd, from shallow and mid-crust magmas. Data from copper deposits formed in ancient volcanoes at depths of up to about 1500 m in the fractures below paleo-fumaroles, and at around 2000–4000 m in association with sub-volcanic intrusions (porphyry copper deposits) provide evidence of sub-surface deposition of Cu–Au–Ag–Mo and a range of other minor elements including Te, Se, As and Sb. These deposits, or ‘sinks’, of metals consistently record sustained histories of magmatic gas streaming through volcanic systems interspersed by continuing intrusive and eruptive activity. Here we integrate data from ancient and modern volcanic systems and show that the fluxes of metals and metalloids are controlled by a) the maintenance of fracture permeability in the stressed crust below volcanoes and b) the chemical processes that are triggered as magmatic gas, initially undersaturated with metals and metalloids, expands from lithostatic to very low pressure conditions through fracture arrays. The recognition of gas streaming may also account for the phenomenon of ‘excess degassing’, and defines an integral, but generally understated, component of active volcanic systems – a volcanic gas core – that is likely to be integral to the progression of eruptions to Plinean state. Destabilization of solvated molecular metal and metalloid species in magmatic gas mixtures and changes in their redox state are triggered, as it expands to the surface by abrupt pressure drops, or throttles' in the fracture array that guides expansion to the surface. The electronically harder, low electronegativity metals, such as copper and iron, deposit rapidly in response to expansion followed more slowly by arsenic with antimony as sulfosalts. Heavy, large radius, softer elements such as bismuth, lead, and thallium along with cadmium are strongly fractionated along the way, eventually venting their excess along with SO 2 , CO 2 , and other components of the carrier gas, into the atmosphere. These elements, many of which are toxic, may also be dispersed by mixing with groundwater in the permeable crust below volcanoes and generate potential health risks due to Hg, As, and Se contamination of drinking water resources.

Earth-Science Reviews

User's guide to revised method-of-characteristics solute-transport model (MOC--version 31)

The U.S. Geological Survey computer model to simulate two-dimensional solute transport and dispersion in ground water (Konikow and Bredehoeft, 1978; Goode and Konikow, 1989) has been modified to improve management of input and output data and to provide progressive run-time information. All opening and closing of files are now done automatically by the program. Names of input data files are entered either interactively or using a batch-mode script file. Names of output files, created automatically by the program, are based on the name of the input file. In the interactive mode, messages are written to the screen during execution to allow the user to monitor the status and progress of the simulation and to anticipate total running time. Information reported and updated during a simulation include the current pumping period and time step, number of particle moves, and percentage completion of the current time step. The batch mode enables a user to run a series of simulations consecutively, without additional control. A report of the model's activity in the batch mode is written to a separate output file, allowing later review. The user has several options for creating separate output files for different types of data. The formats are compatible with many commercially available applications, which facilitates graphical postprocessing of model results. Geohydrology and Evaluation of Stream-Aquifer Relations in the Apalachicola-Chattahoochee-Flint River Basin, Southeastern Alabama, Northwestern Florida, and Southwestern Georgia By Lynn J. Torak, Gary S. Davis, George A. Strain, and Jennifer G. Herndon Abstract The lower Apalachieola-Chattahoochec-Flint River Basin is underlain by Coastal Plain sediments of pre-Cretaceous to Quaternary age consisting of alternating units of sand, clay, sandstone, dolomite, and limestone that gradually thicken and dip gently to the southeast. The stream-aquifer system consism of carbonate (limestone and dolomite) and elastic sediments, which define the Upper Floridan aquifer and Intermediate system, in hydraulic connection with the principal rivers of the basin and other surface-water features, natural and man made. Separate digital models of the Upper Flori-dan aquifer and Intermediate system were constructed by using the U.S. Geological Survey's MODular Finite-Element model of two dimensional ground-water flow, based on concep- tualizations of the stream-aquifer system, and calibrated to drought conditions of October 1986. Sensitivity analyses performed on the models indicated that aquifer hydraulic conductivity, lateral and vertical boundary flows, and pumpage have a strong influence on groundwater levels. Simulated pumpage increases in the Upper Floridan aquifer, primarily in the Dougherty Plain physiographic district of Georgia,. caused significant reductions in aquifer discharge to streams that eventually flow to Lake Seminole and the Apalachicola River and Bay. Simulated pumpage increases greater than 3 times the October 1986 rates caused drying ofsome stream reaches and parts of the Upper Floridan aquifer in Georgia. Water budgets prepared from simulation results indicate that ground- water discharge to streams and recharge by horizontal and vertical flow are the principal mechanisms for moving water through the flow system. The potential for changes in ground-water quality is high in areas where chemical constituents can be mobilized by these mechanisms. Less than 2 percent of ground-water discharge to streams comes from the Intermediate system; thus, it plays a minor role in the hydrodynamics of the stream- aquifer system.

Water-Resources Investigations Report

Fractional crystallization-induced variations in sulfides from the Noril’sk-Talnakh mining district (polar Siberia, Russia)

The distribution of platinum-group elements (PGE) within zoned magmatic ore bodies has been extensively studied and appears to be controlled by the partitioning behavior of the PGE during fractional crystallization of magmatic sulfide liquids. However, other chalcophile elements, especially TABS (Te, As, Bi, Sb, and Sn) have been neglected despite their critical role in forming platinum-group minerals (PGM). TABS are volatile trace elements that are considered to be mobile so investigating their primary distribution may be challenging in magmatic ore bodies that have been somewhat altered. Magmatic sulfide ore bodies from the Noril’sk-Talnakh mining district (polar Siberia, Russia) offer an exceptional opportunity to investigate the behavior of TABS during fractional crystallization of sulfide liquids and PGM formation as the primary features of the ore bodies have been relatively well preserved. In this study, new petrographic (2D and 3D) and whole-rock geochemical data from Cu-poor to Cu-rich sulfide ores of the Noril’sk-Talnakh mining district are integrated with published data to consider the role of fractional crystallization in generating mineralogical and geochemical variations across the different ore types (disseminated to massive). Despite textural variations in Cu-rich massive sulfides (lenses, veins, and breccias), these sulfides have similar chemical compositions, which suggests that Cu-rich veins and breccias formed from fractionated sulfide liquids that were injected into the surrounding rocks. Numerical modeling using the median disseminated sulfide composition as the initial sulfide liquid composition and recent DMSS/liq and DISS/liq predicts the compositional variations observed in the massive sulfides, especially in terms of Pt, Pd, and TABS. Therefore, distribution of these elements in the massive sulfides was likely controlled by their partitioning behavior during sulfide liquid fractional crystallization, prior to PGM formation. Our observations indicate that in the Cu-poor massive sulfides the PGM formed as the result of exsolution from sulfide minerals whereas in the Cu-rich massive sulfides the PGM formed by crystallization from late-stage fractionated sulfide liquids. We suggest that the significant amount of Sn-bearing PGM may be related to crustal contamination from granodiorite, whereas As, Bi, Te, and Sb were likely added to the magma along with S from sedimentary rocks. Large PGM that are scarce and randomly distributed may account for most of the whole-rock Pt budget. Based on our results, we propose a holistic genetic model for the formation of the magmatic sulfide ore bodies of the Noril’sk-Talnakh mining district.

Siberia

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

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

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

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

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

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

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

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

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

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

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

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

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 &delta;-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&ndash;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&ndash;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

Mercury and methylmercury in reservoirs in Indiana

Mercury (Hg) is an element that occurs naturally, but evidence suggests that human activities have resulted in increased amounts being released to the atmosphere and land surface. When Hg is converted to methylmercury (MeHg) in aquatic ecosystems, MeHg accumulates and increases in the food web so that some fish contain levels which pose a health risk to humans and wildlife that consume these fish. Reservoirs unlike natural lakes, are a part of river systems that are managed for flood control. Data compiled and interpreted for six flood-control reservoirs in Indiana showed a relation between Hg transport, MeHg formation in water, and MeHg in fish that was influenced by physical, chemical, and biological differences among the reservoirs. Existing information precludes a uniform comparison of Hg and MeHg in all reservoirs in the State, but factors and conditions were identified that can indicate where and when Hg and MeHg levels in reservoirs could be highest. As part of a statewide monitoring network for Hg and MeHg in Indiana streams, 66 water samples were collected from four reservoir tailwater sites (downstream near the dams) on a quarterly schedule for 5 years. The reservoirs were Brookville Lake, Cagles Mill Lake, J. Edward Roush Lake, and Mississinewa Lake. Particulate-bound Hg concentrations were significantly lower in tailwater samples than in samples from free-flowing streams in the statewide network. (Free-flowing streams were not affected by dams and were not upstream from these reservoirs.) These data indicated the reduced flow velocity of water upstream from dams was allowing particulate-bound Hg to settle out of the water in the reservoir pools. The concentration ratios of MeHg to Hg were significantly higher in the tailwater samples than in samples from free-flowing streams, and the MeHg to Hg ratios were significantly higher in summer than in other seasons. To evaluate the conditions related to MeHg formation, pools of three reservoirs (Brookville Lake, Monroe Lake, and Patoka Lake) were investigated during summer hydrologic conditions. Water temperature and dissolved oxygen were measured from the water surface to the lake bottom at 10 to 17 transects across each reservoir to identify three thermal strata, defined by water temperature, dissolved oxygen concentration, and depth. Depth-specific water samples were collected from these thermal strata throughout each reservoir, from the headwaters to the dam and from the tailwater. Mercury concentrations higher than 0.04 nanogram per liter (ng/L) were detected in all 53 samples, and MeHg concentrations higher than 0.04 ng/L were detected in 53 percent of the samples. The investigation found a zone of water below 8 or 9 meters, with temperatures less than 18 degrees Celsius and dissolved oxygen less than 3.5 milligrams per liter, extending through nearly half the reservoir area in Monroe Lake and Patoka Lake. This zone had abundant dissolved MeHg and concentration ratios of dissolved MeHg to Hg that ranged from 25 to 82 percent. This zone also had water with pH less than 7 and decreased dissolved sulfate, conditions indicating sulfate reduction by microorganisms that promoted a high potential for the conversion of Hg to MeHg. Reservoir outflow came from this zone at Monroe Lake and contributed to a tailwater concentration ratio for dissolved MeHg to Hg of 56 percent. Reservoir outflow at Patoka Lake was not from this zone, and dissolved MeHg was not detected in the tailwater. In contrast, samples from the summer pool at Brookville Lake had no MeHg detections even though Hg was detected, probably because the water pH higher than 7 inhibited sulfate reduction and did not promote the conversion of Hg to MeHg. Mercury and MeHg concentrations and the concentration ratios of MeHg to Hg in water varied among the six reservoirs in Indiana, and the differences were related to a combination of factors that could apply to other reservoirs. In areas with moderate to high rates of atmospheric Hg wet and dry deposition, Hg runoff and transport to streams and reservoirs was potentially highest for reservoirs with heavily forested watersheds in steep terrains of near-surface bedrock. Methylmercury concentrations and concentration ratios of MeHg to Hg were highest for reservoirs with the longest summer pools and highest inflow-to-outflow retention times, where water-chemistry conditions favoring sulfate reduction promoted conversion of Hg to MeHg. Methylmercury (reported as Hg) in fish-tissue samples collected for the State fish consumption advisory program was used to describe MeHg food-web accumulation and magnification in the reservoirs. The highest percentages of fish-tissue samples with Hg concentrations that exceeded the criterion of 0.30 milligram per kilogram for protection of human health were from Monroe Lake (38 percent) and Patoka Lake (33 percent). A review of the number and size of fish species caught from these two reservoirs resulted in two implications for fish consumption by humans. First, the highest numbers of fish harvested for potential human consumption were species more likely to have MeHg concentrations lower than the human-health criterion (crappie, bluegill, and catfish). Second, although largemouth bass were likely to have MeHg concentrations higher than the human-health criterion, they were caught and released more often than they were harvested. However, the average size largemouth bass (in both reservoirs) and above-average size walleye (in Monroe Lake) that were harvested for potential human consumption were likely to have MeHg concentrations higher than the human-health criterion.

Indiana