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Origin of magnetite and pyrrhotite in carbonaceous chondrites

CARBONACEOUS chondrites, although comprising only about 2% of known meteorites, are extremely interesting for scientific investigation. Their mineral constitution, and the correspondence between their bulk chemical composition and the solar abundance of condensable elements, indicate that minimum chemical fractionation and thermal alteration have occurred. The mineral phases observed in these primitive chondrites are sufficiently unique, with respect to other meteorite classes, to have elicited considerable speculation about the physical environment in which they formed 1–7 .

Nature

Stream sediment geochemistry in mineral exploration: A review of fine-fraction, clay-fraction, bulk leach gold, heavy mineral concentrate and indicator mineral chemistry

Stream sediment surveys support early-stage reconnaissance mineral exploration and regional assessment programmes, enhanced by recent improvements in analytical method detection limits, continuously improving mineral chemistry, and new approaches to the interpretation of geochemical data. Sediment surveys may be used to predict catchment basin lithology, mineralization type based on pathfinder geochemistry, and geological features based on indicator mineral chemistry. Sediment surveys that target a finer-fraction sediment sample led to the discovery of the La Colosa gold deposit, Colombia. The Batu Hijau porphyry Cu–Au deposit in Indonesia was discovered based on an anomalous clay-sized fraction sample 12 km downstream. In an arid region with poorly developed drainages and minor topographic relief, the Ag-base-metal Navidad District in Argentina was discovered with clay-fraction sediment geochemistry. Heavy mineral concentrate (HMC) sediment surveys that include mineral chemistry determinations have led to global diamond discoveries. HMC surveys contributed to discovery of the Ring of Fire Ni–Cu–PGE and chromite district, Ontario, Canada. Discoveries and geochemical mapping can assist advancement of the application of stream sediment geochemistry in those global areas for which lithologies and deposits are exposed. Stream sediment surveys continue to be one of the most cost-effective geochemical methods for covering large areas for mineral exploration.

Geochemistry: Exploration, Environment, Analysis

Relation of hydrogeologic characteristics to distribution of radioactivity in ground water, Newark Basin, New Jersey

The distribution of radioactivity in ground water in the Newark Basin is controlled by the lithology of the aquifer and the degree of contact between the water that flows through the fractured strata and the radioactive lithologic units. The primary water-bearing lithologic units of the Newark Basin that contain elevated levels of radioactivity are the arkosic sandstones of the Stockton Formation and the black mudstones of the lower part of the Passaic Formation. Lithologic and hydrogeologic characteristics of these rock aquifers that affect the spatial distribution of radionuclides in the water include the concentration of radioactive minerals in the strata; the continuity of radioactive strata; the orientation, depth, interconnectedness, and continuity of regional and local fracture patterns; and the geochemical environment, which affects radionuclide solubility. The stratigraphic zones of uranium enrichment and the continuity of the radioactive strata differ between the Stockton Formation and the lower part of the Passaic Formation. Uranium enrichment in both formations, however, is identified in permeable sections of strata that have sharp contacts with, or that are enclosed by, less permeable zones. In the Stockton Formation, basal conglomerates overlying fine-grained mudstones are the most radioactive lithology. In interbedded red and black mudstones of the lower part of the Passaic Formation, the uranium-rich zones are the black and white carbonate-rich siltstone and mudstone laminae overlying massive fine-grained mudstones. Most samples of the arkosic sandstones of the Stockton Formation tended to be slightly enriched in uranium relative to thorium, whereas all samples of the black mudstones of the lower part of the Passaic Formation were heavily enriched in uranium with respect to thorium, with a maximum concentration of uranium of 6,200 parts per million (ppm). Spatial orientation of radioactive zones is controlled by the depositional environment of the host lithology. Radioactive strata in the arkosic sandstones of the Stockton Formation, which is deltaic or fluvial/deltaic in origin, arc stratigraphically discontinuous and nonplanar. In contrast, the radioactive lacustrine black mudstones of the lower part of the Passaic Formation are laterally continuous and planar. Geophysical logs of boreholes indicate that the number and depths of probable waterbearing fractures are greater in the arkoses of the Stockton Formation and red mudstones of the lower part of the Passaic Formation than in the interbedded red and black mudstones of the lower part of the Passaic Formation, despite the fact that fracture-density counts in cores indicate that black mudstones are more highly fractured than the other rock types. The total number of fractures is greater and bedding-plane fractures are generally more common in the lower part of the Passaic Formation than in the Stockton Formation. Fractures in the Stockton Formation form a well-connected network consisting of both bedding-plane and several sets of high-angle fractures present on a regional scale. The large-scale continuity of interconnected bedding-plane fractures and high-angle regional fractures may be partly responsible for the higher yields observed for wells in the Stockton Formation than for wells in the Passaic Formation and may facilitate migration of dissolved radionuclides far from their source. The well-connected fracture network may increase the likelihood that circulating water comes in contact with radioactive strata. Water in the black mudstones of the lower part of the Passaic Formation may also contain high levels of radioactivity, primarily as a result of the high frequency of radioactive strata and of fracturing, rather than the presence of a well-connected regional fracture system. Ground-water chemistry is dominated by the calcium cation and the bicarbonate anion, both derived from abundant secondary calcite in the fractures. The concentrations of uranium and radium in water that comes into contact with radioactive rock are controlled by the water chemistry. Uranium is the dominant alpha emitter in the oxidizing waters in the red mudstones of the Passaic Formation, whereas radium-226 (226Ra) is the dominant alpha emitter in the suboxic (reducing) water in the black mudstones of the lower part of the Passaic Formation. Because the lithology of the Stockton Formation and, in places, the lower part of the Passaic Formation varies greatly, wells can intercept multiple fracture zones that can contain oxic or suboxic waters, thereby resulting in the presence of both uranium and radium in detectable quantities in the same water sample.

New Jersey

Geochemistry and microbiology of iron-related well-screen encrustation and aquifer biofouling in Suffolk County, Long Island, New York

Iron-related well-screen encrustation and aquifer biofouling has decreased the specific capacity of several production wells in Suffolk County, N.Y., and has forced the Suffolk County Water Authority to adopt a costly well-reconditioning and replacement program. The specific-capacity declines are the result of the precipitation of iron oxyhydroxides and the growth of iron bacteria on the well screens and in the pore spaces of the surrounding formation. Mineralogic and chemical analyses indicate that the inorganic part of the encrusting material consists primarily of amorphous ferric hydroxide (Fe(OH)3 ); minor components of the material include goethite (FeOOH), hematite (Fe2 O 3 ), and quartz (SiO 2 ). The weight percent of ferric hydroxide in the material ranged from 32.3 to 98.6 percent and averaged 64.3 percent. Equilibrium modeling indicated that during pumping the well waters were supersaturated with respect to goethite, hematite, magnetite, and quartz and were under-saturated with respect to ferric hydroxide. Theoretical Eh values computed for the ferrous/ferric-iron redox couple and the oxygen/water redox couple averaged 390 millivolts and 810 millivolts, respectively, indicating that the waters were in a state of redox disequilibrium. The disequilibrium condition arises from the mixing of ground water with a low dissolved-oxygen concentration with oxygenated ground water during operation of the well. The low pH of the ground water contributes to the disequilibrium condition by slowing the rate of iron oxidation after the introduction of oxygen. Chemical and mineralogical data indicate that most of the encrusting material in the wells was deposited while the wells were shut down, probably in response to the use of treated water of higher pH to keep pump turbines wet while the wells were not in operation; the increased pH of water in the static water column increases the rate of ferrous-iron oxidation and causes the well water to become increasingly saturated with respect to ferric hydroxide. The median half-time of oxidation in samples of untreated ground water (pH 4-5) was 4.19 days, whereas the average half-time of oxidation in treated water (pH 7-8) was 11.9 minutes Equilibrium modeling indicated that treated waters generally were supersaturated with respect to ferric hydroxide, whereas untreated well waters were not. Field and laboratory data indicate that iron bacteria play an important role in the encrustation and biofouling process in Suffolk County. Filamentous iron bacteria were common in the affected wells. The most common species was Gallionella ferruginea, an effective biofouling agent that prefers water with low, but detectable, dissolved-oxygen concentrations and high dissolved-iron concentrations; this species was more common in biofilm samples from the Magothy aquifer than in those from the upper glacial aquifer. Iron bacteria also were found in sediment cores from several locations in the aquifer and in drilling water. Lignite could act as a carbon source for heterotrophic iron bacteria, which could accelerate the formation of iron-bacteria biofilms in wells screened in some parts of the Magothy aquifer. Iron-bacteria biofilms alter the chemistry of well water by removing iron, manganese, and sulfate from solution and by increasing the pH. Sulfur-reducing bacteria and iron-sulfide mineral phases were observed in some samples of encrusting material, indicating that these bacteria could contribute to well-screen encrustation in some geochemical environments.

Water-Resources Investigations Report

Deep-ocean macrofaunal assemblages on ferromanganese and phosphorite-rich substrates in the Southern California Borderland

Mineral-rich hardgrounds, such as ferromanganese (FeMn) crusts and phosphorites, occur on seamounts and continental margins, gaining attention for their resource potential due to their enrichment in valuable metals in some regions. This study focuses on the Southern California Borderland (SCB), an area characterized by uneven and heterogeneous topography featuring FeMn crusts, phosphorites, basalt, and sedimentary rocks that occur at varying depths and are exposed to a range of oxygen concentrations. Due to its heterogeneity, this region serves as an optimal setting for investigating the relationship between mineral-rich hardgrounds and benthic fauna. This study characterizes the density, diversity, and community composition of macrofauna (>300 μm) on hardgrounds as a function of substrate type and environment (depth and oxygen ranges). Rocks and their macrofauna were sampled quantitatively using remotely operated vehicles (ROVs) during expeditions in 2020 and 2021 at depths above, within, and below the oxygen minimum zone (OMZ). A total of 3,555 macrofauna individuals were counted and 416 different morphospecies (excluding encrusting bryozoans and hydrozoans) were identified from 82 rocks at depths between 231 and 2,688 m. Average density for SCB macrofauna was 11.08 ± 0.87 ind. 200 cm −2 and mean Shannon-Wiener diversity per rock (H′ [loge] ) was 2.22 ± 0.07. A relationship was found between substrate type and macrofaunal communities. Phosphorite rocks had the highest H′ of the four substrates compared on a per-rock basis. However, when samples were pooled by substrate, FeMn crusts had the highest H′ and rarefaction diversity. Of all the environmental variables examined, water depth explained the largest variance in macrofaunal community composition. Macrofaunal density and diversity values were similar at sites within and outside the OMZ. This study is the first to analyze the macrofaunal communities of mineral-rich hardgrounds in the SCB, which support deep-ocean biodiversity by acting as specialized substrates for macrofaunal communities. Understanding the intricate relationships between macrofaunal assemblages and mineral-rich substrates may inform effects from environmental disruptions associated with deep-seabed mining or climate change. The findings contribute baseline information useful for effective conservation and management of the SCB and will support scientists in monitoring changes in these communities due to environmental disturbance or human impact in the future.

California

Geology and Mineral Resources of the East Mojave National Scenic Area, San Bernardino County, California

The rocks of the East Mojave National Scenic Area (EMNSA) record a history of dynamic geologic events that span more than 1,800 million years (m.y.). These geologic events contributed significantly to development of the spectacular vistas and panoramas present in the area today. The oldest rocks underlie much of the northern part of the EMNSA. These rocks were subjected to extreme pressures and temperatures deep in the Earth's crust about 1,700 million years ago (Ma). They were subsequently intruded by granitic magmas from about 1,695 to 1,650 Ma, by additional granitic magmas at about 1,400 Ma and, later, at about 1,100 Ma, by iron-rich magmas that crystallized to form dark igneous rocks termed diabase. Unusual potassium- and magnesium-rich rocks, emplaced at about 1,400 Ma, crop out in a few places within and near the EMNSA. Their distinctive composition results from very small degrees of partial melting of mantle peridotite that was highly enriched in incompatible trace elements. At Mountain Pass, just outside the northeast boundary of the EMNSA, the potassium- and magnesium-rich rocks are accompanied by a rare type of carbonatite, an igneous rock composed of carbonate minerals, that contains high-grade rare earth element mineralization. Subsequent to these igneous-dominated events, sedimentary strata began to be deposited at about 1,000 Ma; mostly sandstone and shale were deposited initially in marine and, less commonly, in continental environments along the west edge of the core of the North American continent. Sedimentation eventually culminated in the widespread deposition of thick marine limestones from about 400 to about 245 Ma. These limestones represent a continental-shelf environment where shallow-water limestone formed to the east and deeper water limestone formed to the west. The end of the formation of these sedimentary deposits probably was caused by uplift of the shelf, which marked the beginning of a long period of tectonic upheaval. At about 170 Ma, widespread emplacement of coarse-grained granitic magmas began again in the region; some of these magmas also erupted as volcanic rocks. Additional episodes of magmatism took place at about 100 Ma and at 75 Ma. Most of the metallic-mineral occurrences in the EMNSA are associated with the igneous rocks that range in age from 170 to 75 Ma. During each of these magmatic events, the previously deposited sedimentary strata were buckled and broken as the entire region, part of a continental-scale fold and thrust belt, underwent crustal shortening and compression. A period of tectonic quiescence characterized the region from about 65 Ma to about 20 Ma. The quiet period ended abruptly with widespread volcanism along the southern and eastern parts of the EMNSA. The major gold deposits in the Castle Mountains are associated with this episode of volcanism. During this volcanic outburst, the crust extended laterally in several areas that border the EMNSA: along the lower Colorado River 65 km to the east, in the Kingston Range 20 km to the north, and in the central Mojave Desert 75 km to the southwest. This extensional deformation is characterized by the superposition of upper-crustal rocks over midcrustal rocks along large flat-lying faults, several of which project beneath rocks now exposed at the surface in the EMNSA. The near-surface rocks of the EMNSA, however, apparently escaped much of this intense extensional deformation. High-angle faults, which cut several of the mountain ranges, possibly have undergone several periods of movement, which date back to approximately 70 to 100 Ma. Some faults are of local importance to the physiographic development of the mountain ranges and intervening basins, and, in places, the faults seem to have localized various kinds of ore bodies and mineral occurrences. Volcanism and extensional deformation waned from 14 to 11 Ma. By approximately 10 Ma, widespread erosion had produced broad erosional dome-shaped mountains in the n

Bulletin

Nitrogen dynamics across silvicultural canopy gaps in young forests of western Oregon

Silvicultural canopy gaps are emerging as an alternative management tool to accelerate development of complex forest structure in young, even-aged forests of the Pacific Northwest. The effect of gap creation on available nitrogen (N) is of concern to managers because N is often a limiting nutrient in Pacific Northwest forests. We investigated patterns of N availability in the forest floor and upper mineral soil (0-10 cm) across 6-8-year-old silvicultural canopy gaps in three 50-70-year-old Douglas-fir forests spanning a wide range of soil N capital in the Coast Range and Cascade Mountains of western Oregon. We used extractable ammonium (NH 4 + ) and nitrate (NO 3 - ) pools, net N mineralization and nitrification rates, and NH 4 + and NO 3 - ion exchange resin (IER) concentrations to quantify N availability along north-south transects run through the centers of 0.4 and 0.1 ha gaps. In addition, we measured several factors known to influence N availability, including litterfall, moisture, temperature, and decomposition rates. In general, gap-forest differences in N availability were more pronounced in the mineral soil than in the forest floor. Mineral soil extractable NH 4 + and NO 3 - pools, net N mineralization and nitrification rates, and NH 4 + and NO 3 - IER concentrations were all significantly elevated in gaps relative to adjacent forest, and in several cases exhibited significantly greater spatial variability in gaps than forest. Nitrogen availability along the edges of gaps more often resembled levels in the adjacent forest than in gap centers. For the majority of response variables, there were no significant differences between northern and southern transect positions, nor between 0.4 and 0.1 ha gaps. Forest floor and mineral soil gravimetric percent moisture and temperature showed few differences along transects, while litterfall carbon (C) inputs and litterfall C:N ratios in gaps were significantly lower than in the adjacent forest. Reciprocal transfer incubations of mineral soil samples between gap and forest positions revealed that soil originating from gaps had greater net nitrification rates than forest samples, regardless of incubation environment. Overall, our results suggest that increased N availability in 6-8-year-old silvicultural gaps in young western Oregon forests may be due more to the quality and quantity of litterfall inputs resulting from early-seral species colonizing gaps than by changes in temperature and moisture conditions caused by gap creation.

Forest Ecology and Management

New zircon (U-Th)/He and U/Pb eruption age for the Rockland tephra, western USA

Eruption ages of a number of prominent Quaternary volcanic deposits remain inaccurately and/or imprecisely constrained, despite their importance as regional stratigraphic markers in paleo-environment reconstruction and as evidence of climate-altering eruptions. Accurately dating volcanic deposits presents challenging analytical considerations, including poor radiogenic yield, scarcity of datable minerals, and contamination of crystal populations by magma, eruption, and transport processes. One prominent example is the Rockland tephra, which erupted from the Lassen Volcanic Center in the southern Cascade arc. Despite a range in published eruption ages from 0.40 to 0.63 Ma, the Rockland tephra is extensively used as a marker bed across the western United States. To more accurately and precisely constrain the age of the Rockland tephra-producing eruption, we report U/Pb crystallization dates from the outermost ∼2 μm of zircon crystal faces (surfaces) using secondary ion mass spectrometry (SIMS). Our new weighted mean 238 U/ 206 Pb age for Rockland tephra zircon surfaces is 0.598 ± 0.013 Ma (2σ) and MSWD = 1.11 (mean square weighted deviation). As an independent test of the accuracy of this age, we obtained new (U-Th)/He dates from individual zircon grains from the Rockland tephra, which yielded a weighted mean age of 0.599 ± 0.012 Ma (2σ, MSWD = 5.13). We also obtained a (U-Th)/He age of 0.628 ± 0.014 Ma (MSWD = 1.19) for the Lava Creek Tuff member B, which was analyzed as a secondary standard to test the accuracy of the (U-Th)/He technique for Quaternary tephras, and to evaluate assumptions made in the model-age calculation. Concordance of new U/Pb and (U-Th)/He zircon ages reinforces the accuracy of our preferred Rockland tephra eruption age, and confirms that zircon surface dates sample zircon growth up to the time of eruption. We demonstrate the broad applicability of coupled U/Pb zircon-surface and single-grain zircon (U-Th)/He geochronology to accurate dating of Quaternary tephra, and highlight the challenges and opportunities of this technique.

Quaternary Science Reviews

Bottom sediments of Saginaw Bay, Michigan

Saginaw Bay is a southwest extension of Lake Huron on the east shore of the Southern Peninsula of Michigan. It is a shallow-water derivative of the Pleistocene Lake Saginaw. Sixty-one bottom samples were collected on a semigrid pattern and analyzed physically. Findings were treated statistically. Sediments range in size from large pebbles to clay. Medium- to fine-grained clear quartz sand is common to all parts of the bay. Currents and wave action are primarily responsible for both median diameter and sorting distribution patterns. Only a very general correlation can be established between depth and median diameter. Heavy minerals occur in abundance locally and show an affinity to shallow-water areas subject to prevailing currents. Shape also locally determines heavy mineral concentrations. Only general conclusions can be established from roundness and sphericity and acid-soluble content. Increased organic content is correlative with quiet water environments. The shallow-water, heterogeneous nature of Saginaw Bay is not conducive to the recognition of sedimentary criteria suitable for correlations in other than a local environment.

Journal of Sedimentary Petrology

The physical hydrogeology of ore deposits

Hydrothermal ore deposits represent a convergence of fluid flow, thermal energy, and solute flux that is hydrogeologically unusual. From the hydrogeologic perspective, hydrothermal ore deposition represents a complex coupled-flow problem—sufficiently complex that physically rigorous description of the coupled thermal (T), hydraulic (H), mechanical (M), and chemical (C) processes (THMC modeling) continues to challenge our computational ability. Though research into these coupled behaviors has found only a limited subset to be quantitatively tractable, it has yielded valuable insights into the workings of hydrothermal systems in a wide range of geologic environments including sedimentary, metamorphic, and magmatic. Examples of these insights include the quantification of likely driving mechanisms, rates and paths of fluid flow, ore-mineral precipitation mechanisms, longevity of hydrothermal systems, mechanisms by which hydrothermal fluids acquire their temperature and composition, and the controlling influence of permeability and other rock properties on hydrothermal fluid behavior. In this communication we review some of the fundamental theory needed to characterize the physical hydrogeology of hydrothermal systems and discuss how this theory has been applied in studies of Mississippi Valley-type, tabular uranium, porphyry, epithermal, and mid-ocean ridge ore-forming systems. A key limitation in the computational state-of-the-art is the inability to describe fluid flow and transport fully in the many ore systems that show evidence of repeated shear or tensional failure with associated dynamic variations in permeability. However, we discuss global-scale compilations that suggest some numerical constraints on both mean and dynamically enhanced crustal permeability. Principles of physical hydrogeology can be powerful tools for investigating hydrothermal ore formation and are becoming increasingly accessible with ongoing advances in modeling software.

Economic Geology

Sulfur, carbon, hydrogen, and oxygen isotope geochemistry of the Idaho cobalt belt

Cobalt-copper ± gold deposits of the Idaho cobalt belt, including the deposits of the Blackbird district, have been analyzed for their sulfur, carbon, hydrogen, and oxygen isotope compositions to improve the understanding of ore formation. Previous genetic hypotheses have ranged widely, linking the ores to the sedimentary or diagenetic history of the host Mesoproterozoic sedimentary rocks, to Mesoproterozoic or Cretaceous magmatism, or to metamorphic shearing. The δ 34 S values are nearly uniform throughout the Blackbird dis- trict, with a mean value for cobaltite (CoAsS, the main cobalt mineral) of 8.0 ± 0.4‰ ( n = 19). The data suggest that (1) sulfur was derived at least partly from sedimentary sources, (2) redox reactions involving sulfur were probably unimportant for ore deposition, and (3) the sulfur was probably transported to sites of ore for- mation as H 2 S. Hydrogen and oxygen isotope compositions of the ore-forming fluid, which are calculated from analyses of biotite-rich wall rocks and tourmaline, do not uniquely identify the source of the fluid; plausible sources include formation waters, metamorphic waters, and mixtures of magmatic and isotopically heavy meteoric waters. The calculated compositions are a poor match for the modified seawaters that form vol- canogenic massive sulfide (VMS) deposits. Carbon and oxygen isotope compositions of siderite, a mineral that is widespread, although sparse, at Blackbird, suggest formation from mixtures of sedimentary organic carbon and magmatic-metamorphic carbon. The isotopic compositions of calcite in alkaline dike rocks of uncertain age are consistent with a magmatic origin. Several lines of evidence suggest that siderite postdated the emplacement of cobalt and copper, so its significance for the ore-forming event is uncertain. From the stable isotope perspective, the mineral deposits of the Idaho cobalt belt contrast with typical VMS and sedimentary exhalative deposits. They show characteristics of deposit types that form in deeper environments and could be related to metamorphic processes or magmatic processes, although the isotopic evidence for magmatic components is relatively weak.

Idaho

Water and Sediment Chemical Data and Data Summary for Samples Collected in 1999 and 2001 in the Goodpaster River Basin, Big Delta B-2 Quadrangle, Alaska

We report the chemical analysis for water and sediment collected from the Big Delta B-2 quadrangle. These data are part of a study located in the Big Delta B-2 quadrangle that focused on the integration of geology and bedrock geochemistry on with the biogeochemistry of water, sediments, soil, and vegetation. The discovery of the Pogo lode gold deposit in the northwest corner of the quadrangle was the impetus for this study. The study objectives were to create a geologic map, evaluate the bedrock geochemical influence on the geochemical signature of the surficial environment, and define landscape-level predevelopment geochemical baselines. Important to baseline development is an evaluation of what, if any, geochemical difference exists between the mineralized and non-mineralized areas within a watershed or between mineralized and non-mineralized watersheds. The analytic results for the bedrock, soils, and vegetation are reported elsewhere. Presented here, with minimal interpretation, is the analytic data for the water and sediment samples collected in the summers of 1999 and 2001, and a summary statistics of these analyses.

Open-File Report

Uranium content and leachability of some igneous rocks and their geochemical significance

The uranium content and its leachability in 442 igneous rocks if wide variety were measured. Four-gram samples, crushed below 38 mesh, were leached in in 0.05 M HNO 3 for half an hour at 80 to 85° C; the leachate and undissolved residue were analyzed fluorimetrically. This study explored the relation of uranium content and leachability to petrography. With few exceptions, the relations between uranium content, uranium leachability, rock leachability, rock type, and mineral composition seem to be random. Uranium content and leachability in homogeneous outcrops vary erratically, in heterogeneous outcrops the variation appears nonsystematic. Correlations with geologic environment indicate that uranium content and leachability are largely controlled by geologic processes during and after crystallization.

Trace Elements Investigations

A novel non-destructive workflow for examining germanium and co-substituents in ZnS

A suite of complementary techniques was used to examine germanium (Ge), a byproduct critical element, and co-substituent trace elements in ZnS and mine wastes from four mineral districts where germanium is, or has been, produced within the United States. This contribution establishes a comprehensive workflow for characterizing Ge and other trace elements, which captures the full heterogeneity of samples through extensive pre-characterization. This process proceeded from optical microscopy, to scanning electron microscopy and cathodoluminescence (CL) imaging, to electron microprobe analysis, prior to synchrotron-based investigations. Utilizing non-destructive techniques enabled reanalysis, which proved essential for verifying observations and validating unexpected results. In cases where the Fe content was <0.3 wt% in ZnS, cathodoluminescence imaging proved to be an efficient means to qualitatively identify trace element zonation that could then be further explored by other micro-focused techniques. Micro-focused X-ray diffraction was used to map the distribution of the non-cubic ZnS polymorph, whereas micro-focused X-ray fluorescence (μ-XRF) phase mapping distinguished between Ge 4+ hosted in primary ZnS and a weathering product, hemimorphite [Zn 4 Si 2 O 7 (OH) 2 ·H 2 O]. Microprobe data and μ-XRF maps identified spatial relationships among trace elements in ZnS and implied substitutional mechanisms, which were further explored using Ge and copper (Cu) X-ray absorption near-edge spectroscopy (XANES). Both oxidation states of Ge (4+ and 2+) were identified in ZnS along with, almost exclusively, monovalent Cu. However, the relative abundance of Ge oxidation states varied among mineral districts and, sometimes, within samples. Further, bulk XANES measurements typically agreed with micro-focused XANES (μ-XANES) spectra, but unique micro-environments were detected, highlighting the importance of complementary bulk and micro-focused measurements. Some Ge μ-XANES utilized a high energy resolution fluorescence detector, which improved spectral resolution and spectral signal-to-noise ratio. This detector opens new opportunities for exploring byproduct critical elements in complex matrices. Overall, the non-destructive workflow employed here can be extended to other byproduct critical elements to more fully understand fundamental ore enrichment processes, which have practical implications for critical element exploration, resource quantification, and extraction.

Frontiers in Earth Science

Metallogeny of the northeastern Pacific Rim: an example of the distribution of ore deposits along a growing continental margin

The distribution of mineral deposits within northwestern North America (Alaska, Yukon, and northern British Columbia) allows for an in-depth examination of the metallogenic patterns of a growing continental margin. A more complete understanding of the tectonic evolution of this part of the Pacific Rim, achieved over the last 15 to 20 years, now allows for the placement of ore systems into a well-defined plate tectonic framework. Ore deposits older than about 185 Ma represent hydrothermal systems that were active in the platform/shelf environment of ancestral North America's miogeocline or hydrothermal systems developed in oceanic arcs and continental fragments more distal to the craton. These include important SEDEX, VMS, and pre-accretionary porphyry deposits. In contrast, most mineral deposits younger than about 185 Ma were formed within the growing Cordilleran orogen, as terranes were accreted to the continental margin during interactions between the North America and Pacific/Farallon/Kula plates. Such syn- to post-accretionary mineralised systems include many large lode gold and porphyry/skarn systems.

Alaska

Nickel: makes stainless steel strong

Nickel is a silvery-white metal that is used mainly to make stainless steel and other alloys stronger and better able to withstand extreme temperatures and corrosive environments. Nickel was first identified as a unique element in 1751 by Baron Axel Fredrik Cronstedt, a Swedish mineralogist and chemist. He originally called the element kupfernickel because it was found in rock that looked like copper ( kupfer ) ore and because miners thought that "bad spirits" ( nickel ) in the rock were making it difficult for them to extract copper from it. Approximately 80 percent of the primary (not recycled) nickel consumed in the United States in 2011 was used in alloys, such as stainless steel and superalloys. Because nickel increases an alloy's resistance to corrosion and its ability to withstand extreme temperatures, equipment and parts made of nickel-bearing alloys are often used in harsh environments, such as those in chemical plants, petroleum refineries, jet engines, power generation facilities, and offshore installations. Medical equipment, cookware, and cutlery are often made of stainless steel because it is easy to clean and sterilize. All U.S. circulating coins except the penny are made of alloys that contain nickel. Nickel alloys are increasingly being used in making rechargeable batteries for portable computers, power tools, and hybrid and electric vehicles. Nickel is also plated onto such items as bathroom fixtures to reduce corrosion and provide an attractive finish.

Fact Sheet

Attenuation of acid rock drainage by stimulating sulfur-reducing bacteria

Iron-sulfide minerals found in shale formations are stable under anaerobic conditions. However, in the presence of oxygen and water, acid-loving chemolithotrophic bacteria can transform the iron-sulfide minerals into a toxic solution of sulfuric acid and dissolved iron and minerals known as acid rock drainage (ARD). The objective of this study was to disrupt chemolithotrophic bacteria responsible for ARD using chemical treatments and to foster an environment favorable for competing microorganisms to attenuate the biologically induced ARD. Chemical treatments were injected into flow-through microcosms consisting of 501 g of pyrite-rich shale pieces inoculated with ARD bacteria. Three treatments were tested in the microcosms: (1) a sodium hydroxide-bleach mix, (2) a sodium lactate solution, and (3) a sodium lactate-soy infant formula mix. The effectiveness of the treatments was assessed by monitoring pH, dissolved iron, and other geochemical constituents in the discharge waters. The optimal treatment was a sequential injection of 1.5 g sodium hydroxide, followed by 0.75 g lactate and 1.5 g soy formula dissolved in 20 mL water. The pH of the discharge water rose to 6.0 within 10 days, dissolved iron concentrations dropped below 1 mg/L, the median alkalinity increased to 98 mg/L CaCO 3 , and sulfur-reducing and slime-producing bacteria populations were stimulated. The ARD attenuating benefits of this treatment were still evident after 231 days. Other treatments provided a number of ARD attenuating effects but were tempered by problems such as high phosphate concentrations, short longevity, or other shortcomings. The results of these laboratory microcosm experiments were promising for the attenuation of ARD. Additional investigations and careful selection of treatment methods will be needed for field application.

Tennessee

Mineralogy at Meridiani Planum from the Mini-TES experiment on the opportunity rover

The Miniature Thermal Emission Spectrometer (Mini-TES) on Opportunity investigated the mineral abundances and compositions of outcrops, rocks, and soils at Meridiani Planum. Coarse crystalline hematite and olivine-rich basaltic sands were observed as predicted from orbital TES spectroscopy. Outcrops of aqueous origin are composed of 15 to 35% by volume magnesium and calcium sulfates [a high-silica component modeled as a combination of glass, feldspar, and sheet silicates (???20 to 30%)], and hematite; only minor jarosite is identified in Mini-TES spectra. Mini-TES spectra show only a hematite signature in the millimeter-sized spherules. Basaltic materials have more plagioclase than pyroxene, contain olivine, and are similar in inferred mineral composition to basalt mapped from orbit. Bounce rock is dominated by clinopyroxene and is close in inferred mineral composition to the basaltic martian meteorites. Bright wind streak material matches global dust. Waterlain rocks covered by unaltered basaltic sands suggest a change from an aqueous environment to one dominated by physical weathering.

Science