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By-products of porphyry copper and molybdenum deposits

Porphyry Cu and porphyry Mo deposits are large to giant deposits ranging up to >20 and 1.6 Gt of ore, respectively, that supply about 60 and 95% of the world’s copper and molybdenum, as well as significant amounts of gold and silver. These deposits form from hydrothermal systems that affect 10s to >100 km 3 of the upper crust and result in enormous mass redistribution and potential concentration of many elements. Several critical elements, including Re, Se, and Te, which lack primary ores, are concentrated locally in some porphyry Cu deposits, and despite their low average concentrations in Cu-Mo-Au ores (100s of ppb to a few ppm), about 80% of the Re and nearly all of the Se and Te produced by mining is from porphyry Cu deposits. Rhenium is concentrated in molybdenite, whose Re content varies from about 100 to 3,000 ppm in porphyry Cu deposits, ≤150 ppm in arc-related porphyry Mo deposits, and ≤35 ppm in alkali-feldspar rhyolite-granite (Climax-type) porphyry Mo deposits. Because of the relatively small size of porphyry Mo deposits compared to porphyry Cu deposits and the generally low Re contents of molybdenites in them, rhenium is not recovered from porphyry Mo deposits. The potential causes of the variation in Re content of molybdenites in porphyry deposits are numerous and complex, and this variation is likely the result of a combination of processes that may change between and within deposits. These processes range from variations in source and composition of parental magmas to physiochemical changes in the shallow hydrothermal environment. Because of the immense size of known and potential porphyry Cu resources, especially continental margin arc deposits, these deposits likely will provide most of the global supply of Re, Te, and Se for the foreseeable future. Although Pd and lesser Pt are recovered from some deposits, platinum group metals are not strongly enriched in porphyry Cu deposits and PGM resources contained in known porphyry deposits are small. Because there are much larger known PGM resources in deposits in which PGMs are the primary commodities, it is unlikely that porphyry deposits will become a major source of PGMs. Other critical commodities, such as In and Nb, may eventually be recovered from porphyry Cu and Mo deposits, but available data do not clearly define significant resources of these commodities in porphyry deposits. Although alkali-feldspar rhyolite-granite porphyry Mo deposits and their cogenetic intrusions are locally enriched in many rare metals (such as Li, Nb, Rb, Sn, Ta, and REEs) and minor amounts of REEs and Sn have been recovered from the Climax mine, these elements are generally found in uneconomic concentrations. As global demand increases for critical elements that are essential for the modern world, porphyry deposits will play an increasingly important role as suppliers of some of these metals. The affinity of these metals and the larger size and greater number of porphyry Cu deposits suggest that they will remain more significant than porphyry Mo deposits in supplying many of these critical metals.

Book chapter↗

Evaluation of the extent of contaminated sediments in the west branch of the Grand Calumet river, Indiana-Illinois, USA

The extent of contamination in river sediments is often not rigorously evaluated. In many cases, only surface sediment samples are taken. In other cases, entire sediment cores are composited for analysis, an approach that limits the ability to identify discrete zones of contamination. In addition, few studies include information on the rate of sedimentation. Composited sediment cores, subsamples of cores made at discrete intervals, and surface samples were obtained from locations in the West Branch of the Grand Calumet River. The organic carbon content and concentrations of up to 26 major, minor, and trace elements were determined. Sedimentation rates at the ten locations were estimated using 137Cs. The mean concentrations of metals in the surface samples were considerably higher than concentrations in samples obtained by the two coring approaches. Only by analyzing discrete subsamples was it possible to plot the concentrations by depth and location. This approach was used to demonstrate that high levels of organic carbon and trace elements are confined between river miles 5 and 7.5. Sedimentation rate information combined with chemical analyses of the same cores indicate that contamination of this part of the river began in the 1930s.The extent of contamination in river sediments is often not rigorously evaluated. In many cases, only surface sediment samples are taken. In other cases, entire sediment cores are composited for analysis, an approach that limits the ability to identify discrete zones of contamination. In addition, few studies include information on the rate of sedimentation. Composited sediment cores, subsamples of cores made at discrete intervals, and surface samples were obtained from locations in the West Branch of the Grand Calumet River. The organic carbon content and concentrations of up to 26 major, minor, and trace elements were determined. Sedimentation rates at the ten locations were estimated using 137Cs. The mean concentrations of metals in the surface samples were considerably higher than concentrations in samples obtained by the two coring approaches. Only by analyzing discrete subsamples was it possible to plot the concentrations by depth and location. This approach was used to demonstrate that high levels of organic carbon and trace elements are confined between river miles 5 and 7.5. Sedimentation rate information combined with chemical analyses of the same cores indicate that contamination of this part of the river began in the 1930s.

Conference Paper↗

Factors controlling the geochemical evolution of fumarolic encrustations, Valley of Ten Thousand Smokes, Alaska

Factor and canonical correlation analysis of geochemical data from eight fossil fumaroles suggest that six major factors controlled the formation and evolution of fumarolic encrustations on the 1912 ash-flow sheet in the Valley of Ten Thousand Smokes (VTTS). The six-factor solution model explains a large proportion (low of 74% for Ni to high of 99% for Si) of the individual element data variance. Although the primary fumarolic deposits have been degraded by secondary alteration reactions and up to 75 years of weathering, the relict encrustations still preserve a signature of vapor-phase element transport. This vapor-phase transport probably occurred as halide or oxyhalide species and was significant for As, Sb and Br. At least three, and possibly four, varied temperature leaching events affected the fumarolic deposits. High-temperature gases/liquids heavily altered the ejecta glass and mineral phases adjacent to the fumarolic conduit. As the fumaroles cooled. Fe-rich acidic condensate leached the ejecta and primary fumarolic deposits and resulted in the subsequent precipitation of Fe-hydroxides and/or Fe-oxides. Low- to ambient-temperature leaching and hydration reactions generated abundant hydrated amorphous phases. Up to 87% of the individual element data variance is apparently controlled by the chemistry of the ejecta on which the relict encrustations are found. This matrix chemistry factor illustrates that the primary fumarolic minerals surrounding the active VTTS vents observed by earlier workers have been effectively removed by the dissolution reactions. Element enrichment factors calculated for the VTTS relict encrustations support the statistical factor interpretations. On the average, the relict encrustations are enriched, relative to visibly unaltered matrix protolith, in As, Br, Cr, Sb, Cu, Ni, Pb, Fe, and LOI (an indirect measure of sample H2O content). ?? 1993.

Journal of Volcanology and Geothermal Research↗

Structural fabrics, mineralization and Lamaride kinematics of the Idaho Springs-Ralston shear zone, Colorado mineral belt and central Front Range uplift

The Idaho Springs and Central City mining districts form the central portion of a structurally controlled hydrothermal precious- and base-metal vein system in the Front Range of the northeast-trending Colorado Mineral Belt. Three new 40Ar/39Ar plateau ages on hydrothermal sericite indicate the veins formed during the Laramide orogeny between 65.4??1.5 - 61.9??1.3 Ma. We compile structural geologic data from surface geological maps, subsurface mine maps, and theses for analysis using modern graphical methods and integration into models of formation of economic mineral deposits. Structural data sets, produced in the 1950s and 1960s by the U.S. Geological Survey, are compiled for fabric elements, including metamorphic foliations, fold axial trends, major brittle fault zones, quartz and precious- and base-metal veins and fault veins, Tertiary dikes, and joints. These fabric elements are plotted on equal-area projections and analyzed for mean fabric orientations. Strike-slip fault-vein sets are mostly parallel or sub-parallel, and not conjugate as interpreted by previous work; late-stage, normal-slip fault veins possibly show a pattern indicative of triaxial strain. Fault-slip kinematic analysis was used to model the trend of the Laramide maximum horizontal stress axis, or compression direction, and to determine compatibility of opening and shear motions within a single stress field. The combined-model maximum compression direction for all strike slip fault veins is ???068??, which is consistent with published Laramide compression directions of ???064?? (mean of 23 regional models) and ???072?? for the Front Range uplift. The orientations of fabric elements were analyzed for mechanical and kinematic compatibility with opening, and thus permeability enhancement, in the modeled regional east-northeast, Laramide compression direction. The fabric orientation analysis and paleostress modeling show that structural permeability during mineralization was enhanced along pre-existing metamorphic foliations and fold axial planes. Large orientation dispersion in most fabric elements likely caused myriad potential pathways for permeability. The dominant orientations of opening and shear mode structures are consistent with a sub-parallel network of structures that formed in the Laramide east-northeast compression direction. The results presented demonstrate the importance of using mechanical and kinematic theory integrated with contemporary ideas of permeability structure to better understand the coupled nature of fluid flow, mineral deposition, stress, and strain. Further, the results demonstrate that there is significant internal strain within this basement-cored uplift that was localized by optimally oriented pre-existing structures in a regional stress field.

Mountain Geologist↗

Potential metal recovery from waste streams

‘Waste stream’ is a general term that describes the total flow of waste from homes, businesses, industrial facilities, and institutions that are recycled, burned or isolated from the environment in landfills or other types of storage, or dissipated into the environment. The recovery and reuse of chemical elements from waste streams have the potential to decrease U.S. reliance on primary resources and imports, and to lessen unwanted dispersion of some potentially harmful elements into the environment. Additional benefits might include reducing disposal or treatment costs and decreasing the risk of future environmental liabilities for waste generators. Elemental chemistry and mineralogical residences of the elements are poorly documented for many types of waste streams.

Conference Paper↗

An orientation soil survey at the Pebble Cu-Au-Mo porphyry deposit, Alaska

Soil samples were collected in 2007 and 2008 along three traverses across the giant Pebble Cu-Au-Mo porphyry deposit. Within each soil pit, four subsamples were collected following recommended protocols for each of ten commonly-used and proprietary leach/digestion techniques. The significance of geochemical patterns generated by these techniques was classified by visual inspection of plots showing individual element concentration by each analytical method along the 2007 traverse. A simple matrix by element versus method, populated with a value based on the significance classification, provides a method for ranking the utility of methods and elements at this deposit. The interpretation of a complex multi-element dataset derived from multiple analytical techniques is challenging. An example of vanadium results from a single leach technique is used to illustrate the several possible interpretations of the data.

Alaska↗

In-situ arsenic removal during groundwater recharge through unsaturated alluvium

OBJECTIVES The purpose of this study was to determine the feasibility and sustainability of in-situ removal of arsenic from water infiltrated through unsaturated alluvium. BACKGROUND Arsenic is naturally present in aquifers throughout the southwestern United States and elsewhere. In January 2006, the U.S. Environmental Protection Agency (EPA) lowered the Maximum Contaminant Level (MCL) for arsenic from 50 to 10 micrograms per liter (g/L). This raised concerns about naturally-occurring arsenic in groundwater. Although commercially available systems using sorbent iron or aluminum oxide resins are available to treat high-arsenic water, these systems are expensive to build and operate, and may generate hazardous waste. Iron and aluminum oxides occur naturally on the surfaces of mineral grains that compose alluvial aquifers. In areas where alluvial deposits are unsaturated, these oxides may sorb arsenic in the same manner as commercial resins, potentially providing an effective low-cost alternative to commercially engineered treatment systems. APPROACH The Antelope Valley within the Mojave Desert of southern California contains a shallow water-table aquifer with arsenic concentrations of 5 g/L, and a deeper aquifer with arsenic concentrations of 30 g/L. Water was pumped from the deep aquifer into a pond and infiltrated through an 80 m-thick unsaturated zone as part of field-scale and laboratory experiments to treat high-arsenic groundwater and recharge the shallow water table aquifer at the site. The field-scale recharge experiment included the following steps: 1) construction of a recharge pond 2) test drilling for sample collection and instrument installation adjacent to the pond 3) monitoring downward migration of water infiltrated from the pond 4) monitoring changes in selected trace-element concentrations as water infiltrated through the unsaturated zone Data from instruments within the borehole adjacent to the pond were supplemented with borehole and surface geophysical data to evaluate the lateral spreading of water as it moved downward through the unsaturated zone. Three laboratory studies were undertaken. Sequential extraction was used to evaluate the abundance of iron, aluminum, and manganese oxides and selected trace elements on operationally defined sites on the surfaces of mineral grains collected before and after infiltration from the pond. Secondly, radio-labeled arsenic-73 microcosm experiments evaluated the potential for incorporation of arsenic sorbed to exchange sites on mineral grains into less reactive crystalline mineral structures with time. Finally, column studies evaluated arsenic sorption and the pH dependence of sorption for selected unsaturated zone materials. RESULTS/CONCLUSIONS Between December 2010 and July 2012, more than 120,000 cubic meters (m3 ) (about 97 acre-feet) of high-arsenic groundwater was pumped from the deep aquifer into a 0.11 hectare (about 0.27 acres) pond and infiltrated though an 80-meter (about 260 feet) thick unsaturated zone to recharge a water-table aquifer. Arsenic concentrations were lowered from 30 to 2 g/L as water infiltrated though the unsaturated zone at the site. Some uranium, possibly associated with past agricultural land use at the site, was mobilized to concentrations as high as 66 g/L within the unsaturated zone during the experiment. Uranium was resorbed and the high uranium concentrations did not reach the water table at the site. Concentrations of other trace elements, including antimony, chromium, vanadium, and selenium were low throughout the study. Infiltration rates from the pond were as high as 0.4 meters per day (1.1 feet per day, ft/d), and the wetting front moved downward about 25 centimeters per day (cm/d) (0.8 ft/d) to a depth of about 50 m (about 165 feet). Clay layers at that depth slowed the downward movement of the wetting front to about 5 cm/d (0.16 ft/d). Lateral movement of the wetting front was monitored using sequential direct-current (DC) surface and sequential electromagnetic (EM) and DC borehole resistivity. Most lateral movement occurred on a clay layer about 50 m (about 165 feet) below land surface. Infiltrated water reached the water table in January 2013. At the water table, the “wetted footprint” of water infiltrated from the pond, indicated by surface resistivity data, was about 13 hectares (about 32 acres). On the basis of data collected at the site, there is enough sorbent material to operate this pond and treat groundwater having an arsenic concentration of 30 g/L to 2 g/L for about 500 years. Toxicity Characteristic Leaching Procedure (TCLP) data showed arsenic concentrations to be below hazardous levels beneath the pond after the experiment. Pond maintenance may be required to keep infiltration rates high, and prevent accumulation of organic material on the pond bottom, although organic material on the pond bottom may increase removal of other trace elements in infiltrated water including chromium, selenium, and vanadium. Laboratory results are consistent with the field data and show sorption of arsenic in 10 cm (0.3 feet) columns to about 2 g/L over a pH range of 6 to 8, and at influent arsenic concentrations as high as 300 g/L, without breakthrough in 50 pore volumes. Column results suggest that the insitu treatment may remove arsenic in a range of hydrogeologic settings, and would not necessarily be restricted to alkaline alluvial aquifers common throughout the southwestern United States. Radiolabeled arsenic-73 experiments show that although arsenic is initially weakly sorbed (and potentially mobile), with time arsenic is incorporated into amorphous materials. One year after sorption onto surface exchange sites, most sorbed arsenic is incorporated into crystalline oxide minerals on the surfaces of primary mineral grains and is less mobile. Results of the study suggest that long-term land use restrictions on sites used for in-situ treatment of arsenic may not be needed to control water applied to surface materials. This minimizes some regulatory concerns about future land use at sites used for in-situ arsenic treatment. However, future land uses that may alter reduction-oxidation conditions in the subsurface should be avoided, such as infiltration of stormwater recharge or recharge with other water having high organic carbon concentrations (including unsewered residential land use, dairy or other confined animal operations).

Report↗

GIS methodology for geothermal play fairway analysis: Example from the Snake River Plain volcanic province

Play fairway analysis in geothermal exploration derives from a systematic methodology originally developed within the petroleum industry and is based on a geologic and hydrologic framework of identified geothermal systems. We are tailoring this methodology to study the geothermal resource potential of the Snake River Plain and surrounding region. This project has contributed to the success of this approach by cataloging the critical elements controlling exploitable hydrothermal systems, establishing risk matrices that evaluate these elements in terms of both probability of success and level of knowledge, and building automated tools to process results. ArcGIS was used to compile a range of different data types, which we refer to as ‘elements’ (e.g., faults, vents, heatflow…), with distinct characteristics and confidence values. Raw data for each element were transformed into data layers with a common format. Because different data types have different uncertainties, each evidence layer had an accompanying confidence layer, which reflects spatial variations in these uncertainties. Risk maps represent the product of evidence and confidence layers, and are the basic building blocks used to construct Common Risk Segment (CRS) maps for heat, permeability, and seal. CRS maps quantify the variable risk associated with each of these critical components. In a final step, the three CRS maps were combined into a Composite Common Risk Segment (CCRS) map for analysis that reveals favorable areas for geothermal exploration. Python scripts were developed to automate data processing and to enhance the flexibility of the data analysis. Python scripting provided the structure that makes a custom workflow possible. Nearly every tool available in the ArcGIS ArcToolbox can be executed using commands in the Python programming language. This enabled the construction of a group of tools that could automate most of the processing for the project. Currently, our tools are repeatable, scalable, modifiable, and transferrable, allowing us to automate the task of data analysis and the production of CRS and CCRS maps. Our ultimate goal is to produce a toolkit that can be imported into ArcGIS and applied to any geothermal play type, with fully tunable parameters that will allow for the production of multiple versions of the CRS and CCRS maps in order to better test for sensitivity and to validate results.

Idaho↗

Geochemistry of amphibolites from the central Beartooth Mountains, Montana-Wyoming

Trends of variation of major- and minor-element contents in amphibolites from the central Beartooth Mountains strongly suggest that these rocks of andesitic composition are derived from a tholeiitic, mafic igneous parent and not from a sedimentary parent. Discriminant functions based on minor-element content also indicate igneous parentage, whereas functions based on major-element content indicate a sedimentary parent, suggesting that the general assumption that the regional metamorphism is isochemical may not be entirely valid. Furthermore, chemical data on the amphibolites do not fit the fractionation curves of average Beartooth metadolerites, the most likely precursor. If, however, it is assumed that regional metamorphism and formation of amphibolites were accompanied by potassium metasomatism, then the higher concentrations of SiO 2 , Al 2 O 3 , K 2 O, and potassium-related minor elements in the amphibolites relative to metadolerite can be explained.

Montana, Wyoming↗

Geologic investigations of radioactive deposits, semiannual progress report for June 1 to November 30, 1955

This report is a statement of progress during the six-months period from June 1 to November 30, 1955 on investigations of radioactive materials in the United States and Alaska, undertaken by the U.S. Geological Survey under the sponsorship of the U.S. Atomic Energy Commission. During the period the Geological Survey's program has been directed to an increasing extent toward the understanding of geologic conditions favorable for the concentration of uranium, rather than the search for minable deposits as such. This shift in emphasis is reflected in the decreased amount of exploration drilling during the period, and the accompanying increase in geologic programs of a long-range nature. The program is now directed toward a comprehensive understanding of the many factors involved in uranium geology, and the publication of reports that will make available information on all phases of the uranium program. Many investigations have progressed to the point where final reports are in preparation for future publication with the permission of the Atomic Energy Commission; for other investigations of a continuing nature it will be several years before final reports can be prepared. Formal publications (as distinguished from administrative Trace Elements Reports) published during the period include 10 Geological Survey Bulletins or Bulletin Chapters; 116 Geological Survey maps; 15 reports published in scientific journals; seven Trace Elements Reports sent to the Technical Information Service of the Atomic Energy Commission for distribution and sale to the public; and four Trace Elements reports placed on open file. In addition, a large number •of papers by geologists in the program were presented before scientific societies, and the 61 papers prepared for the United Nations International Conference .on the Peaceful Uses of Atomic Energy during the preceding report period were published by the United Nations.

Trace Elements Investigations↗

Detailed mineral and chemical relations in two uranium-vanadium ores

Channel samples from two mines on the Colorado Plateau have been studied in detail both mineralogically and chemically. A channel sample from the Mineral Joe No. 1 mine, Montrose County, Colo., extends from unmineralized rock on one side, through a zone of variable mineralization, into only weakly mineralized rock. The unmineralized rock is a fairly clean quartz sand cemented with gypsum and contains only minor amounts of clay minerals. One boundary between unmineralized and mineralized rock is quite sharo and is nearly at right angles to the bedding. Vanadium clay minerals, chiefly mixed layered mica-montmorillonite and chlorite-monmorillonite, are abundant throughout the mineralized zone. Except in the dark "eye" of the channel sample, the vanadium clay minerals are accompanied by hewettite, carnotite, tyuyamunite, and probably unidentified vanadates. In the dark "eye," paramontroseite, pyrite, and marcasite are abundant, and bordered on each side by a zone containing abundant corvusite. No recognizable uranium minerals were seen in the paramontroseite zone although uranium is abundant there. Coaly material is recognizable throughout all of the channel but is most abundant in and near the dark "eye." Detailed chemical studies show a general increase in Fe, Al, U, and V, and a decrease in SO 4 toward the "eye" of the channel. Reducing capacity studies indicate that V(IV) and Fe(II) are present in the clay mineral throughout the channel, but only in and near the "eye" are other V(IV) minerals present (paramontroseite and corvusite). The uranium is sexivalent, although its state of combination is conjectural where it is associated with paramontroseite. Where the ore boundary is sharp, the boundary of introduced trace elements is equally sharp. Textural and chemical relations leave no doubt that the "eye: is a partially oxidized remnant of a former lower-valence ore, and the remainder of the channel is a much more fully oxidized remnant. A channel sample from the Virgin No. 3 mine, Montrose County, Colo., extends from weakly mineralized sandstone on both sides through a strongly mineralized central zone. The weakly mineralized zone is a poorly sorted sandstone with common detrital clay partings; chlorite and mixed layer mica-montmorrillonite are abundant interstitial to the quartz grains. No distinct vanadium or uranium minerals are recognizable, although the clay minerals are vanadium bearing. Euherdral pyrite grains and selenian galena are present but rare. The strongly mineralized rock is separated from the weakly mineralized rock by a narrow transition zone which only apporiximates the bedding planes. It contains abundant vanadium-bearing clay minerals (predominantly chlorite) interstitial to the quartz grains, and apparently replacing them. Paramontroseite is common and is intergrown with the clay minerals. Pyrite and marcasite are present, chiefly in or near the abundant blebs and fragments of carbonaceous material. Selenian galena is rarely present, and generally in or near carbonaceous material. Coffinite is the only uranium mineral idenitified; it is extremely fine grained and was identified only in X-ray diffraction patterns of heavy separates. Distribution of trace elements is not clear; some are consistently high in the strongly mineralized rocks, and some are consistently low. The trace element composition of the unmineralized rock is not known. Chemical studies show a very abrupt rise in the total U, V, and Fe from the weakly mineralized to strongly mineralized rock. Reducing-capacity studies indicate that most of the vanadium is present as V(IV), but some is present as V(V); that iron is present as both Fe(II) and Fe(III), the latter believed to have been present in the primary clays of the unmineralized rock; and that come of the uranium is present as U(VI) in addition to the U(IV) in the coffinite. All evidence points to weak oxidation of an ore once having a somewhat lower valence state. The channel samples from both the Mineral Joe No. 1 mine and the Virgin No. 3 mine are believe to have been essentially identical in mineralogy prior to oxidation by weathering: vanadium was present as V(III) in montroseite and V(IV) in the vanadium clays; uranium was present largely as U(IV) in coffinite and/or uraninite. The Mineral Joe No. 1 mine channel sample is now more fully oxidized. Vanadium clays are unquestionably formed abundantly during the primary mineralization, and they persist with a minimum of alteration during much of the weathering. They suggest that the vanadium is carried as V(IV) in the ore-forming fluids; it seems likely too that the uranium is carried as a U(VI) ion.

Trace Elements Investigations↗

Hind limb malformations in free-living northern leopard frogs (Rana pipiens) from Maine, Minnesota, and Vermont suggest multiple etiologies

Background Reports of malformed frogs have increased throughout the North American continent in recent years. Most of the observed malformations have involved the hind limbs. The goal of this study was to accurately characterize the hind limb malformations in wild frogs as an important step toward understanding the possible etiologies. Methods During 1997 and 1998, 182 recently metamorphosed northern leopard frogs (Rana pipiens) were collected from Minnesota, Vermont, and Maine. Malformed hind limbs were present in 157 (86%) of these frogs, which underwent necropsy and radiographic evaluation at the National Wildlife Health Center. These malformations are described in detail and classified into four major categories: (1) no limb (amelia); (2) multiple limbs or limb elements (polymelia, polydactyly, polyphalangy); (3) reduced limb segments or elements (phocomelia, ectromelia, ectrodactyly, and brachydactyly; and (4) distally complete but malformed limb (bone rotations, bridging, skin webbing, and micromelia). Results Amelia and reduced segments and/or elements were the most common finding. Frogs with bilateral hind limb malformations were not common, and in only eight of these 22 frogs were the malformations symmetrical. Malformations of a given type tended to occur in frogs collected from the same site, but the types of malformations varied widely among all three states, and between study sites within Minnesota. Conclusions Clustering of malformation type suggests that developmental events may produce a variety of phenotypes depending on the timing, sequence, and severity of the environmental insult. Hind limb malformations in free-living frogs transcend current mechanistic explanations of tetrapod limb development.

Maine, Minnesota, Vermont↗

Age of the Lava Creek supereruption and magma chamber assembly at Yellowstone based on 40 Ar/ 39 Ar and U-Pb dating of sanidine and zircon crystals

The last supereruption from the Yellowstone Plateau formed Yellowstone caldera and ejected the >1000 km 3 of rhyolite that composes the Lava Creek Tuff. Tephra from the Lava Creek eruption is a key Quaternary chronostratigraphic marker, in particular for dating the deposition of mid Pleistocene glacial and pluvial deposits in western North America. To resolve the timing of eruption and crystallization history for the Lava Creek magma, we performed (1) 40 Ar/ 39 Ar dating of single sanidine crystals to delimit eruption age and (2) ion microprobe U-Pb and trace-element analyses of the crystal faces and interiors of single zircons to date the interval of zircon crystallization and characterize magmatic evolution. Sanidines from the two informal members composing Lava Creek Tuff yield a preferred 40 Ar/ 39 Ar isochron date of 631.3 ± 4.3 ka. Crystal faces on zircons from both members yield a weighted mean 206 Pb/ 238 U date of 626.5 ± 5.8 ka, and have trace element concentrations that vary with the eruptive stratigraphy. Zircon interiors yield a mean 206 Pb/ 238 U date of 659.8 ± 5.5 ka, and reveal reverse and/or oscillatory zoning of trace element concentrations, with many crystals containing high U concentration cores that likely grew from highly evolved melt. The occurrence of distal Lava Creek tephra in stratigraphic sequences marking the Marine Isotope Stage 16–15 transition supports the apparent eruption age of ∼631 ka. The combined results reveal that Lava Creek zircons record episodic heating, renewed crystallization, and an overall up-temperature evolution for Yellowstone's subvolcanic reservoir in the 10 3 −10 4 year interval before eruption.

Wyoming↗

Lake nutrient stoichiometry is less predictable than nutrient concentrations at regional and sub-continental scales

Production in many ecosystems is co-limited by multiple elements. While a known suite of drivers associated with nutrient sources, nutrient transport, and internal processing controls concentrations of phosphorus (P) and nitrogen (N) in lakes, much less is known about whether the drivers of single nutrient concentrations can also explain spatial or temporal variation in lake N:P stoichiometry. Predicting stoichiometry might be more complex than predicting concentrations of individual elements because some drivers have similar relationships with N and P, leading to a weak relationship with their ratio. Further, the dominant controls on elemental concentrations likely vary across regions, resulting in context dependent relationships between drivers, lake nutrients and their ratios. Here, we examine whether known drivers of N and P concentrations can explain variation in N:P stoichiometry, and whether explaining variation in stoichiometry differs across regions. We examined drivers of N:P in ~2,700 lakes at a sub-continental scale and two large regions nested within the sub-continental study area that have contrasting ecological context, including differences in the dominant type of land cover (agriculture vs. forest). At the sub-continental scale, lake nutrient concentrations were correlated with nutrient loading and lake internal processing, but stoichiometry was only weakly correlated to drivers of lake nutrients. At the regional scale, drivers that explained variation in nutrients and stoichiometry differed between regions. In the Midwestern U.S. region, dominated by agricultural land use, lake depth and the percentage of row crop agriculture were strong predictors of stoichiometry because only phosphorus was related to lake depth and only nitrogen was related to the percentage of row crop agriculture. In contrast, all drivers were related to N and P in similar ways in the Northeastern U.S. region, leading to weak relationships between drivers and stoichiometry. Our results suggest ecological context mediates controls on lake nutrients and stoichiometry. Predicting stoichiometry was generally more difficult than predicting nutrient concentrations, but human activity may decouple N and P, leading to better prediction of N:P stoichiometry in regions with high anthropogenic activity.

Ecological Applications↗

A causal partition of trait correlations: using graphical models to derive statistical models from theoretical language

Recent studies hypothesize various causes of species‐level trait covariation, namely size (e.g., metabolic theory of ecology and leaf economics spectrum), pace‐of‐life (e.g., slow‐to‐fast continuum; lifestyle continuum), evolutionary history (e.g., phylogenetic conservatism), and ecological conditions (e.g., stabilizing selection). Various methods have been used in attempts to partition trait correlation among these influences (e.g., univariate analysis, principal components analysis, and factor analysis). However, it is not clear that the implied causal structure assumed by these methods matches the hypothesized causal structure driving trait correlations, a situation that can potentially lead to biased estimates and incorrect partitioning among mechanisms. Here, we propose the application of graphical causal models (GCM) for across‐kingdom synthesis and to aid researchers in their selection of correct analytical strategies. Graphical causal models use causal diagrams (i.e., box‐and‐arrow graphs) to represent expert knowledge of the data‐generating processes to analytically investigate the possibility of identifying hypothesized causal associations. We developed a causal diagram that synthesizes prominent hypotheses of trait covariation. Using the causal diagram, we (1) derived a quantitative expression to partition trait covariance among its hypothesized causal elements (i.e., size, pace‐of‐life, evolutionary history, and ecological conditions) and (2) developed analytic strategies to attribute trait covariance among the hypothesized causal elements under real‐world data availability, namely unobserved variables (i.e., pace‐of‐life) and confounding variables (i.e., evolutionary history and ecological conditions). Finally, we tested each analytic strategy by simulating trait datasets and, after incorporating the data limitations, tested their ability to correctly partition trait covariance. The analytical strategies were able to correctly partition trait covariance into the hypothesized causal elements of size, pace‐of‐life, and the historical effects of evolutionary history and ecological conditions. We demonstrate the efficacy of these strategies by applying them to a widely used trait dataset. Overall, the application of GCM revealed that researchers have used inappropriate measures to represent their theoretical constructs and have relied on analytical strategies that violated their causal assumptions, likely resulting in biased estimates. We discuss how this mismatch between theoretical language and statistical methods is prevalent in species‐level, trait‐based research and call for future studies to address these limitations.

Ecosphere↗

Suspended-sediment sources in an urban watershed, Northeast Branch Anacostia River, Maryland

Fine sediment sources were characterized by chemical composition in an urban watershed , the Northeast Branch Anacostia River , which drains to the Chesapeake Bay. Concentrations of 63 elements and two radionuclides were measured in possible land-based sediment sources and suspended sediment collected from the water column at the watershed outlet during storm events. These tracer concentrations were used to determine the relative quantity of suspended sediment contributed by each source . Although this is an urbanized watershed , there was not a distinct urban signature that can be evaluated except for the contributions from road surfaces. We identified the sources of fine sediment by both physiographic province (Piedmont and Coastal Plain) and source locale (streambanks, upland and street residue) by using different sets of elemental tracers. The Piedmont contributed the majority of the fine sediment for seven of the eight measured storms. The streambanks contributed the greatest quantity of fine sediment when evaluated by source locale. Street residue contributed 13% of the total suspended sediment on average and was the source most concentrated in anthropogenically enriched elements. Combining results from the source locale and physiographic province analyses, most fine sediment in the Northeast Branch watershed is derived from streambanks that contain sediment eroded from the Piedmont physiographic province of the watershed . Sediment fingerprinting analyses are most useful when longer term evaluations of sediment erosion and storage are also available from streambankerosion measurements, sediment budget and other methods.

Maryland↗

Documenting utility of paddlefish otoliths for quantification of metals using inductively coupled plasma mass spectrometry

RATIONALE The otoliths of the inner ear of fishes record the environment of their surrounding water throughout their life. For paddlefish ( Polyodon spathula ), otoliths have not been routinely used by scientists since their detriments were outlined in the early 1940s. We sought to determine if paddlefish otoliths were useful for resolving elemental information contained within. METHODS Adult paddlefish were collected from two wild, self-sustaining populations in Oklahoma reservoirs in the Arkansas River basin. Juveniles were obtained from a hatchery in the Red River basin of Oklahoma. Otoliths were removed and laser ablation, inductively coupled plasma mass spectrometry (ICP-MS) was used to quantify eight elements (Li, Mg, Mn, Rb, Sr, Y, Ba, and Pb) along the core and edge portions, which were analyzed for differences between otolith regions and among paddlefish sources. RESULTS Differences were found among samples for six of the eight elements examined. Otoliths from Red River basin paddlefish born in a hatchery had significantly lower amounts of Mg and Mn, but higher levels of Rb than otoliths from wild paddlefish in the Arkansas River basin. Concentrations of Y, Sr, and Ba were reduced on the edges of adult paddlefish from both reservoirs compared with the cores. CONCLUSIONS This research shows the utility of using an ICP-MS analysis of paddlefish otoliths. Future research that seeks to determine sources of paddlefish production, such as which reservoir tributaries are most important for reproduction or what proportion of the population is composed of wild versus hatchery-produced individuals, appears promising. Published in 2013. This article is a U.S. Government work and is in the public domain in the USA.

Rapid Communications in Mass Spectrometry↗

Volcanogenic Sulfur on Earth and Io: Composition and Spectroscopy

The causes of Io's variegated surface, especially the roles of sulfur, and the geochemical history of sulfur compounds on Io are not well understood. Suspecting that minor impurities in sulfur might be important, we have investigated the major and trace element chemistry and spectroscopic reflectance of natural sulfur from a variety of terrestrial volcanic-hydrothermal environments. Evidence suggests that Io may be substantially coated with impure sulfur. On Earth, a few tenths of a percent to a few percent of chalcophile trace elements (e.g., As and Se) comonly occur in sulfur and appear to stabilize material of yellow, brown, orange, and red hues, which may persist even at low temperatures. Percentage levels of chalcophile impurities are reasonably expected to occur on Io in vapor sublimate deposits and flows derived from such deposits. Such impurities join a host of other mechanisms that might explain Io's reds and yellows. Two-tenths to two percent opaque crystalline impurities, particularly pyrite (FeS2), commonly produces green, gray, and black volcanic sulfur on Earth and might explain areas of Io having deposits of these colors. Pyrite produces a broad absorption near 1 ??m that gradually diminishes out to 1.6 ??m - similar but not identical to the spectrum of Io seen in Galileo NIMS data. Percentage amounts of carbonaceous impurities and tens of percent SiO2 (as silicates) also strongly affect the spectral properties of Earth's sulfur. Io's broad absorption between 0.52 and 0.64 ??m remains unexplained by these data but could be due to sodium sulfides, as suggested previously by others, or to As, Se, or other impurities. These impurities and others, such as P and Cl (which could exist on Io's surface in amounts over 1% that of sulfur), greatly alter the molecular structure of molten and solid sulfur. Minor impurities could impact Io's geology, such as the morphology of sulfur lava flows and the ability of sulfur to sustain high relief. We have not found any natural sulfur containing significant Na beyond that attributable to silicate inclusions. In sum, the unique physical-chemical properties of S-rich systems and the strong affinity of certain elements for S may have broad implications for the appearance, spectroscopic interpretation, and geologic processes of Io. Identification of impurities in sulfur may be helpful in tracing the geochemical evolution of surface deposits on Io. Perhaps foretelling of new areas of investigation, Cl has recently been reported in the Io torus (M. Kueppers and N. M. Schneider 1999, Eos Trans.80, 5207), suggesting the presence on Io of either salts, such as halite, or sulfur chlorides. Further evidence of minor iogenic impurities should be sought in Io's neutral cloud and plasma torus as well as in further scrutiny of Io's reflectance spectra. ?? 1999 Academic Press.

Icarus↗

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