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USGS1994

The geochemical cycling of trace elements in a biogenic meromictic lake

The geochemical processes affecting the behavior and speciation of As, Co, Cr, Cu, Fe, Mn, Mo, Ni, Pb, V, and Zn in Hall Lake, Washington, USA, are assessed by examining dissolved and acid soluble particulate profiles of the elements and utilizing results from thermodynamic calculations. The water column of this meromictic lake is highly stratified and contains distinctive oxic, suboxic, and anoxic layers. Changes in the redox state of the water column with depth affect the distribution of all the elements studied. Most noticeable are increases in dissolved Co, Cr, Fe, Mn, Ni, Pb, and Zn concentrations across the oxic-suboxic boundary, increases in dissolved As, Co, Cr, Fe, Mn, and V concentrations with depth in the anoxic layer, significant decreases in dissolved Cu, Ni, Pb, and Zn concentrations in the anoxic region below the sulfide maximum, and large increases in acid soluble particulate concentrations of As, Cr, Cu, Fe, Mo, Ni, Pb, V, and Zn in the anoxic zone below the sulfide maximum. Thermodynamic calculations for the anoxic region indicate that all redox sensitive elements exist in their reduced forms, the primary dissolved forms of Cu, Ni, Pb, and Zn are metal sulfide solution complexes, and solid sulfide phases of Cu, Fe, Mo, and Pb are supersaturated. Calculations using a vertical diffusion and reaction model indicate that the oxidation rate constant for Mn(II) in Hall Lake is estimated to be 0.006 d-1 and is at the lower end of the range of microbial oxidation rates observed in other natural systems. The main geochemical processes influencing the distribution and speciation of trace elements in Hall Lake appear to be transformations of dissolved elements between their oxidation states (As, Cr, Cu, Fe, Mn, V), cocycling of trace elements with Mn and Fe (As, Co, Cr, Cu, Mo, Ni, Pb, V, Zn), formation of soluble metal sulfide complexes (Co, Cu, Ni, Pb, Zn), sorption (As, Co, Cr, Ni, V), and precipitation (Cu, Fe, Mn, Mo, Pb, Zn).

Geochimica et Cosmochimica Acta↗

USGS1989

Chemistry and origin of minor and trace elements in vitrinite concentrates from a rank series from the eastern United States, England, and Australia

A rank series consisting of twelve vitrinite concentrates and companion whole-coal samples from mined coal beds in the eastern United States, England, and Australia were analyzed for C, H, N, O, ash, and 47 trace and minor elements by standard elemental, instrumental neutron activation analysis (INAA), and direct-current-arc spectrographic (DCAS) techniques. The reflectance of vitrinite, atomic H:C and O:C, and ash-free carbon data were used to determine ranks that range from high-volatile C bituminous coal to meta-anthracite. A van Krevelen (atomic H:C vs. O:C) diagram of the vitrinite concentrates shows a smooth curve having its lowest point at H:C = 0.18 and O:C = 0.01. This improves the van Krevelen diagram by the addition of our vitrinite concentrate from meta-anthracite from the Narragansett basin of New England. Boron content (400–450 ppm) in two Illinois basin vitrinite concentrates was about an order of magnitude higher than B contents in other concentrates analyzed. We attribute this to marine origin or hydrothermal activity. The alkaline-earth elements Ca, Mg and Ba (DCAS) have higher concentrations in our vitrinite concentrates from bituminous coals of the Appalachian basin, than they do in vitrinite concentrates from the marine-roofed bituminous coals of the Illinois basin; therefore, a nonmarine origin for these alkaline-earth elements is postulated for the Appalachian basin coals. An ion-exchange mechanism due to high concentrations of these elements as ions in diagenetic water, but probably not recent ground water, may be responsible for the relatively high values of these elements in Appalachian concentrates. Higher concentrations of Ni and Cr in one of the English vitrinite concentrates and of Zr in the Australian concentrate probably indicate organic association and detrital influence, respectively.

International Journal of Coal Geology↗

USGS1976

The zonal distribution of selected elements above the Kalamazoo porphyry copper deposit, San Manuel district, Pinal County, Arizona

There may be many as-yet-undiscovered porphyry copper deposits that exist as blind deposits deep within exposed rock bodies. The Kalamazoo porphyry copper-molybdenum deposit is a blind deposit present at depths up to at least 1,000 m (about 3,200 ft) that contains zoning features common to many of the known porphyry copper deposits found in western North and South America. As the preliminary phase in a geochemical study of the Kalamazoo deposit, whole-rock samples of core and cuttings from two drill holes have been analyzed for 60 different elements. Each hole represents a different major rock unit and each has penetrated completely through all the existing alteration zones and the ore zone. Plots of concentration vs. depth for 17 selected elements show distinct high- or low-concentration zones that are spatially related to the ore zone. For most of the ore-related elements no significant correlation with the two lithologies is apparent. The spatial distribution and abundance of elements such as Co, Cu, S, Se, Mn, Tl, Rb, Zn, B, and Li may be useful in determining the direction for exploration to proceed to locate a blind deposit. Trace element studies should be valuable in evaluating areas containing extensive outcrops of rocks with disseminated pyrite. Elemental zoning should be at least as useful as alteration-mineralization zoning for evaluating rock bodies thought to contain blind deposits similar to the Kalamazoo deposit.

Journal of Geochemical Exploration↗

USGS2009

A water-leach procedure for estimating bioaccessibility of elements in soils from transects across the United States and Canada

An objective of the North American Soil Geochemical Landscapes Project is to provide relevant data concerning bioaccessible concentrations of elements in soil to government and other institutions undertaking environmental studies. A protocol was developed that employs a 1-g soil sample agitated overnight with 40 mL of reverse-osmosis de-ionized water for 20 h, and determination of 63 elements following three steps of centrifugation by inductively coupled plasma–atomic emission spectrometry and inductively coupled plasma–mass spectrometry the following day. Statistical summaries are presented for those 48 elements (Ag, Al, As, B, Ba, Be, Br, Ca, Cd, Ce, Co, Cr, Cs, Cu, Dy, Er, Eu, Fe, Ga, Gd, Ge, Hf, Ho, I, K, La, Li, Lu, Mg, Mn, Mo, Na, Nb, Nd, Ni, P, Pb, Pr, Rb, Re, S, Sb, Si, Sm, Sn, Sr, Tb, Ti, Tl, Tm, U, V, W, Y, Yb, Zn, Zr, and pH) for which <20% of their data were reported as below the detection limit. The resulting data set contains analyses for 161 A-horizon soils collected along two transects, one along the 38th parallel across the USA and the other from northern Manitoba to the USA–Mexico border. The spatial distribution of three selected elements (Ca, Cu, and Pb) along the two transects is discussed in this paper both as absolute amounts liberated by the leach and expressed as a percentage of the total, or near-total, amounts determined for the elements. The Ca data reflect broad trends in soil parent materials, their weathering, and subsequent soil development. Calcium concentrations are generally found to be lower in the older soils of the eastern USA. The Cu data are higher in the eastern half of the USA, correlating with soil organic C, with which it is sequestered. The Pb data exhibit little regional variability due to natural sources, but are influenced by anthropogenic sources. Based on the Pb results, the percentage water-extractable data demonstrate promise as a tool for identifying anthropogenic components. The soil–water partition (distribution) coefficients, K d s (L/kg), were determined and their relevance to estimating bioaccessible amounts of elements to soil fauna and flora is discussed. Finally, a possible link between W concentrations in human urine and water-extractable W levels in Nevada soils is discussed.

Applied Geochemistry↗

USGS2011

Effects of human-induced alteration of groundwater flow on concentrations of naturally-occurring trace elements at water-supply wells

The effects of human-induced alteration of groundwater flow patterns on concentrations of naturally-occurring trace elements were examined in five hydrologically distinct aquifer systems in the USA. Although naturally occurring, these trace elements can exceed concentrations that are considered harmful to human health. The results show that pumping-induced hydraulic gradient changes and artificial connection of aquifers by well screens can mix chemically distinct groundwater. Chemical reactions between these mixed groundwaters and solid aquifer materials can result in the mobilization of trace elements such as U, As and Ra, with subsequent transport to water-supply wells. For example, in the High Plains aquifer near York, Nebraska, mixing of shallow, oxygenated, lower-pH water from an unconfined aquifer with deeper, confined, anoxic, higher-pH water is facilitated by wells screened across both aquifers. The resulting higher-O2, lower-pH mixed groundwater facilitated the mobilization of U from solid aquifer materials, and dissolved U concentrations were observed to increase significantly in nearby supply wells. Similar instances of trace element mobilization due to human-induced mixing of groundwaters were documented in: (1) the Floridan aquifer system near Tampa, Florida (As and U), (2) Paleozoic sedimentary aquifers in eastern Wisconsin (As), (3) the basin-fill aquifer underlying the California Central Valley near Modesto (U), and (4) Coastal Plain aquifers of New Jersey (Ra). Adverse water-quality impacts attributed to human activities are commonly assumed to be related solely to the release of the various anthropogenic contaminants to the environment. The results show that human activities including various land uses, well drilling, and pumping rates and volumes can adversely impact the quality of water in supply wells, when associated with naturally-occurring trace elements in aquifer materials. This occurs by causing subtle but significant changes in geochemistry and associated trace element mobilization as well as enhancing advective transport processes.

Applied Geochemistry↗

USGS2004

Atmospheric wet deposition of trace elements to a suburban environment, Reston, Virginia, USA

Wet deposition from a suburban area in Reston, Virginia was collected during 1998 and analyzed to assess the anion and trace-element concentrations and depositions. Suburban Reston, approximately 26 km west of Washington, DC, is densely populated and heavily developed. Wet deposition was collected bi-weekly in an automated collector using trace-element clean sampling and analytical techniques. The annual volume-weighted concentrations of As, Cd, and Pb were similar to those previously reported for a remote site on Catoctin Mt., Maryland (70 km northwest), which indicated a regional signal for these elements. The concentrations and depositions of Cu and Zn at the suburban site were nearly double those at remote sites because of the influence of local vehicular traffic. The 1998 average annual wet deposition (μg m −2 yr −1 ) was calculated for Al (52,000), As (94), Cd (54), Cr (160), Cu (700), Fe (23,000), Mn (2000), Ni (240), Pb (440), V (430), and Zn (4100). The average annual wet deposition (meq m −2 yr −1 ) was calculated for H + (74), Cl − (8.5), NO 3 − (33), and SO 4 2− (70). Analysis of digested total trace-element concentrations in a subset of samples showed that the refractory elements in suburban precipitation comprised a larger portion of the total deposition of trace elements than in remote areas.

Virginia↗

USGS2011

Trace and minor element variations and sulfur isotopes in crystalline and colloform ZnS: Incorporation mechanisms and implications for their genesis

Various models have been proposed to explain the formation mechanism of colloform sphalerite, but the origin is still under debate. In order to decipher influences on trace element incorporation and sulfur isotope composition, crystalline and colloform sphalerite from the carbonate-hosted Mississippi-Valley Type (MVT) deposit near Wiesloch, SW Germany, were investigated and compared to sphalerite samples from 52 hydrothermal vein-type deposits in the Schwarzwald ore district, SW Germany to study the influence of different host rocks, formation mechanisms and fluid origin on trace element incorporation. Trace and minor element incorporation in sphalerite shows some correlation to their host rock and/or origin of fluid, gangue, paragenetic minerals and precipitation mechanisms (e.g., diagenetic processes, fluid cooling or fluid mixing). Furthermore, crystalline sphalerite is generally enriched in elements like Cd, Cu, Sb and Ag compared to colloform sphalerite that mainly incorporates elements like As, Pb and Tl. In addition, sulfur isotopes are characterized by positive values for crystalline and strongly negative values for colloform sphalerite. The combination of trace element contents, typical minerals associated with colloform sphalerite from Wiesloch, sulfur isotopes and thermodynamic considerations helped to evaluate the involvement of sulfate-reducing bacteria in water-filled karst cavities. Sulfate-reducing bacteria cause a sulfide-rich environment that leads in case of a metal-rich fluid supply to a sudden oversaturation of the fluid with respect to galena, sphalerite and pyrite. This, however, exactly coincides with the observed crystallization sequence of samples involving colloform sphalerite from the Wiesloch MVT deposit.

Wiesloch↗

USGS2012

Leaching of elements from bottom ash, economizer fly ash, and fly ash from two coal-fired power plants

To assess how elements leach from several types of coal combustion products (CCPs) and to better understand possible risks from CCP use or disposal, coal ashes were sampled from two bituminous-coal-fired power plants. One plant located in Ohio burns high-sulfur (about 3.9%) Upper Pennsylvanian Pittsburgh coal from the Monongahela Group of the Central Appalachian Basin; the other in New Mexico burns low-sulfur (about 0.76%) Upper Cretaceous Fruitland Formation coal from the San Juan Basin, Colorado Plateau. The sampled CCPs from the Ohio plant were bottom ash (BA), economizer fly ash (EFA), and fly ash (FA); the sampled CCPs from the New Mexico plant were BA, mixed FA/EFA, FA, and cyclone-separated coarse and fine fractions of a FA/EFA and FA blend. Subsamples of each ash were leached using the long-term leaching (60-day duration) component of the synthetic groundwater leaching procedure (SGLP) or the toxicity characteristic leaching procedure (TCLP, 18-hour duration). These ashes were all alkaline. Leachate concentrations and leachabilities of the elements from the CCPs were similar between corresponding CCP types (BA, EFA, and FA) from each plant. The leachabilities of most elements were lowest in BA (least leachable) and increased from EFA to FA (most leachable). Ca and Sr were leached more from EFA than from either BA or FA. Leachability of most elements also increased as FA particle size decreased, possibly due in part to increasing specific surface areas. Several oxyanion-forming elements (As, Mo, Se, U, and V) leached more under SGLP than under TCLP; the opposite was true for most other elements analyzed.

International Journal of Coal Geology↗

USGS2007

Factors to consider for trace element deposition biomonitoring surveys with lichen transplants

A trace element deposition biomonitoring experiment with transplants of the fruticose lichen Evernia prunastri was developed, aimed at monitoring the effects of different exposure parameters (exposure orientation and direct rain) and to the elements Ti, V, Cr, Co, Cu, Zn, Rb, Cd, Sb and Pb. Accumulations were observed for most of the elements, confirming the ability of Evernia transplants for atmospheric metal deposition monitoring. The accumulation trends were mainly affected by the exposure orientation and slightly less so by the protection from rain. The zonation of the trace elements inside the thallus was also studied. It was concluded that trace element concentrations were not homogeneous in Evernia, thus imposing some cautions on the sampling approach. A nuclear microprobe analysis of an E. prunastri transplanted thallus in thin cross-sections concluded that the trace elements were mainly concentrated on the cortex of the thallus, except Zn, Ca and K which were also present in the internal layers. The size of the particles deposited or entrapped on the cortex surface averaged 7????m. A list of key parameters to ensure the comparability of surveys aiming at observing temporal or spatial deposition variation is presented. ?? 2006 Elsevier B.V. All rights reserved.

Tête Ronde, Gif-sur-Yvette↗

USGS1999

60 Myr records of major elements and Pb-Nd isotopes from hydrogenous ferromanganese crusts: Reconstruction of seawater paleochemistry

We compare the time series of major element geochemical and Pb- and Nd-isotopic composition obtained for seven hydrogenous ferromanganese crusts from the Atlantic, Indian, and Pacific Oceans which cover the last 60 Myr. Average crust growth rates and age-depth relationships were determined directly for the last about 10 Myr using 10Be/9Be profiles. In the absence of other information these were extrapolated to the base of the crusts assuming constant growth rates and constant initial 10Be/9Be ratios due to the lack of additional information. Co contents have also been used previously to estimate growth rates in Co-rich Pacific and Atlantic seamount crusts (Puteanus and Halbach, 1988). A comparison of 10Be/9Be- and Co-based dating of three Co-rich crusts supports the validity of this approach and confirms the earlier chronologies derived from extrapolated 10Be/9Be-based growth rates back to 60 Ma. Our data show that the flux of Co into Co-poor crusts has been considerably lower. The relationship between growth rate and Co content for the Co-poor crusts developed from these data is in good agreement with a previous study of a wider range of marine deposits (Manheim, 1986). The results suggest that the Co content provides detailed information on the growth history of ferromanganese crusts, particularly prior to 10-12 Ma where the 10Be-based method is not applicable. The distributions of Pb and Nd isotopes in the deep oceans over the last 60 Myr are expected to be controlled by two main factors: (a) variations of oceanic mixing patterns and flow paths of water masses with distinct isotopic signatures related to major paleogeographic changes and (b) variability of supply rates or provenance of detrital material delivered to the ocean, linked to climate change (glaciations) or major tectonic uplift. The major element profiles of crusts in this study show neither systematic features which are common to crusts with similar isotope records nor do they generally show coherent relationships to the isotope records within a single crust. Consequently, any interpretation of time series of major element concentrations of a single crust in terms of paleoceanographic variations must be considered with caution. This is because local processes appear to have dominated over more basin-wide paleoceanographic effects. In this study Co is the only element which shows a relationship to Pb and Nd isotopes in Pacific crusts. A possible link to changes of Pacific deep water properties associated with an enhanced northward advection of Antarctic bottom water from about 14 Ma is consistent with the Pb but not with the Nd isotopic results. The self-consistent profiles of the Pb and Nd isotopes suggest that postdepositional diagenetic processes in hydrogenous crusts, including phosphatization events, have been insignificant for particle reactive elements such as Pb, Be, and Nd. Isotope time series of Pb and Nd show no systematic relationships with major element contents of the crusts, which supports their use as tracers of paleo-seawater isotopic composition.

Geochimica et Cosmochimica Acta↗

USGS2000

Distribution of trace elements in selected pulverized coals as a function of particle size and density

Trace elements in coal have diverse modes of occurrence that will greatly influence their behavior in many coal utilization processes. Mode of occurrence is important in determining the partitioning during coal cleaning by conventional processes, the susceptibility to oxidation upon exposure to air, as well as the changes in physical properties upon heating. In this study, three complementary methods were used to determine the concentrations and chemical states of trace elements in pulverized samples of four US coals: Pittsburgh, Illinois No. 6, Elkhorn and Hazard, and Wyodak coals. Neutron Activation Analysis (NAA) was used to measure the absolute concentration of elements in the parent coals and in the size- and density-fractionated samples. Chemical leaching and X-ray absorption fine structure (XAFS) spectroscopy were used to provide information on the form of occurrence of an element in the parent coals. The composition differences between size-segregated coal samples of different density mainly reflect the large density difference between minerals, especially pyrite, and the organic portion of the coal. The heavy density fractions are therefore enriched in pyrite and the elements associated with pyrite, as also shown by the leaching and XAFS methods. Nearly all the As is associated with pyrite in the three bituminous coals studied. The sub-bituminous coal has a very low content of pyrite and arsenic; in this coal arsenic appears to be primarily organically associated. Selenium is mainly associated with pyrite in the bituminous coal samples. In two bituminous coal samples, zinc is mostly in the form of ZnS or associated with pyrite, whereas it appears to be associated with other minerals in the other two coals. Zinc is also the only trace element studied that is significantly more concentrated in the smaller (45 to 63 ??m) coal particles.

Fuel Processing Technology↗

USGS2002

Spatial and temporal variability of trace element concentrations in an urban subtropical watershed, Honolulu, Hawaii

Trace metal concentrations in soils and in stream and estuarine sediments from a subtropical urban watershed in Hawaii are presented. The results are placed in the context of historical studies of environmental quality (water, soils, and sediment) in Hawaii to elucidate sources of trace elements and the processes responsible for their distribution. This work builds on earlier studies on sediments of Ala Wai Canal of urban Honolulu by examining spatial and temporal variations in the trace elements throughout the watershed. Natural processes and anthropogenic activity in urban Honolulu contribute to spatial and temporal variations of trace element concentrations throughout the watershed. Enrichment of trace elements in watershed soils result, in some cases, from contributions attributed to the weathering of volcanic rocks, as well as to a more variable anthropogenic input that reflects changes in land use in Honolulu. Varying concentrations of As, Cd, Cu, Pb and Zn in sediments reflect about 60 a of anthropogenic activity in Honolulu. Land use has a strong impact on the spatial distribution and abundance of selected trace elements in soils and stream sediments. As noted in continental US settings, the phasing out of Pb-alkyl fuel additives has decreased Pb inputs to recently deposited estuarine sediments. Yet, a substantial historical anthropogenic Pb inventory remains in soils of the watershed and erosion of surface soils continues to contribute to its enrichment in estuarine sediments. Concentrations of other elements (e.g., Cu, Zn, Cd), however, have not decreased with time, suggesting continued active inputs. Concentrations of Ba, Co, Cr, Ni, V and U, although elevated in some cases, typically reflect greater proportions attributed to natural sources rather than anthropogenic input. ?? 2002 Elsevier Science Ltd. All rights reserved.

Applied Geochemistry↗

USGS2021

Approach for quantifying rare Earth elements at low keV

The challenges of analyzing bastnaesite (REECO3F) and hydroxylbastnaesite (REECO3OH) include beam sensitivity, quantification of light elements in a heavy element matrix, the presence of elements that cannot be analyzed with EPMA (H), and the use of x-ray lines whose physical constants are not well known. To overcome some of these challenges, Ca, La, Ce, Pr, Nd, and Sm were analyzed at 15 keV accelerating voltage and the light elements (C, O, F) were analyzed at 7 keV accelerating voltage. This approach is ideal for samples that are homogeneous within the volume analyzed. However, for the bastnaesite of interest, this solution is unsatisfactory as backscattered electron imaging reveals chemical variations at scales of less than 1 m (fig. 1). Monte Carlo simulations and wavescans of the REE M family of x-rays were evaluated to determine the best analytical approach. Monte Carlo simulations using Casino v2.42 were ran on a substrate of CeCO3F with a density of 5.00 g/cm3 at 15 keV and 7 kCV accelerating voltage. Depth distribution curves, φ(ρz), reveal x-ray generation at 15 keV for the Ce L shell x-rays approaches 1.0 m whereas the depth of Ce M shell x-ray generation at 7 keV is less than 0.4 m. Similarly, the K shell x-ray generation depth for C, O, and F at 7 keV is also less than 0.4 m. These simulations demonstrate an accelerating voltage of 7 keV or less and use of the REE M x-rays is necessary to acquire chemical information from the same volume of material for the light and heavy elements. Bastnaesite contains all REE and therefore one must consider the energy of the highest x-ray line of interest, namely the Lu M at 1.83 kV, to achieve an overvoltage (Eo/Ec) of over 2. Bastnaesite is also an insulator and requires a conductive coating, therefore 7 keV was used to avoid contributions of the coating material to the analysis given the above constraints. The USNM REE phosphate standards, Edinburgh REE glasses, CeO2, LaB6, and the metals of Sm, Dy, Gd, Er, and Yb were selected to evaluate the peak overlaps of the M family x-ray lines. The materials were coated with ~ 5nm iridium with a Leica ACE600 prior to analysis. Full spectrometer wavescans were collected at 7 keV accelerating voltage, 50 nA beam current, and 20 um beam diameter on a JEOL 8530F Plus using TAP and TAPL crystals. The step size was 0.109 mm along the length of the spectrometer with a dwell of 3 seconds at each step. M and M lines are broad and not individually resolved for the light REE but become more separated and sharper with increasing atomic number. M and M lines for each REE are also present across the spectrometer range further complicating peak interference corrections. The peak positions and overall shape for the Ce M and M lines vary with the coordination of the element. Significant shifts in position and shape were not observed when comparing the Ce M peaks of CeO2 and CePO4. Similar results were seen when comparing the available REE metal to the phosphate (Sm, Dy, Gd, Er, Yb). These wavescans suggest the use of the M or M lines if matrix matched standards are not available.

Microscopy and Microanalysis↗

USGS1999

Trace-element concentrations in streambed sediment across the conterminous United States

Trace-element concentrations in 541 streambed-sediment samples collected from 20 study areas across the conterminous United States were examined as part of the National Water-Quality Assessment Program of the U.S. Geological Survey. Sediment samples were sieved and the <63-μm fraction was retained for determination of total concentrations of trace elements. Aluminum, iron, titanium, and organic carbon were weakly or not at all correlated with the nine trace elements examined: arsenic, cadmium, chromium, copper, lead, mercury, nickel, selenium, and zinc. Four different methods of accounting for background/baseline concentrations were examined; however, normalization was not required because field sieving removed most of the background differences between samples. The sum of concentrations of trace elements characteristic of urban settings - copper, mercury, lead, and zinc - was well correlated with population density, nationwide. Median concentrations of seven trace elements (all nine examined except arsenic and selenium) were enriched in samples collected from urban settings relative to agricultural or forested settings. Forty-nine percent of the sites sampled in urban settings had concentrations of one or more trace elements that exceeded levels at which adverse biological effects could occur in aquatic biota.

Environmental Science & Technology↗

USGS2016

Geochemistry, Nd-Pb Isotopes, and Pb-Pb Ages of the Mesoproterozoic Pea Ridge Iron Oxide-Apatite–Rare Earth Element Deposit, Southeast Missouri

Iron oxide-apatite and iron oxide-copper-gold deposits occur within ~1.48 to 1.47 Ga volcanic rocks of the St. Francois Mountains terrane near a regional boundary separating crustal blocks having contrasting depleted-mantle Sm-Nd model ages (T DM ). Major and trace element analyses and Nd and Pb isotope data were obtained to characterize the Pea Ridge deposit, improve identification of exploration targets, and better understand the regional distribution of mineralization with respect to crustal blocks. The Pea Ridge deposit is spatially associated with felsic volcanic rocks and plutons. Mafic to intermediate-composition rocks are volumetrically minor. Data for major element variations are commonly scattered and strongly suggest element mobility. Ratios of relatively immobile elements indicate that the felsic rocks are evolved subalkaline dacite and rhyolite; the mafic rocks are basalt to basaltic andesite. Granites and rhyolites display geochemical features typical of rocks produced by subduction. Rare earth element (REE) variations for the rhyolites are diagnostic of rocks affected by hydrothermal alteration and associated REE mineralization. The magnetite-rich rocks and REE-rich breccias show similar REE and mantle-normalized trace element patterns. Nd isotope compositions (age corrected) show that: (1) host rhyolites have ɛ Nd from 3.44 to 4.25 and T DM from 1.51 to 1.59 Ga; (2) magnetite ore and specular hematite rocks display ɛ Nd from 3.04 to 4.21 and T DM from 1.6 to 1.51 Ga, and ɛ Nd from 2.23 to 2.81, respectively; (3) REE-rich breccias have ɛ Nd from 3.04 to 4.11 and T DM from 1.6 to 1.51 Ga; and (4) mafic to intermediate-composition rocks range in ɛ Nd from 2.35 to 3.66 and in T DM from 1.66 to 1.56. The ɛ Nd values of the magnetite and specular hematite samples show that the REE mineralization is magmatic; no evidence exists for major overprinting by younger, crustal meteoric fluids, or by externally derived Nd. Host rocks, breccias, and magnetite ore shared a common origin from a similar source. Lead isotope ratios are diverse: (1) host rhyolite has 206 Pb/ 204 Pb from 24.261 to 50.091; (2) Pea Ridge and regional galenas have 206 Pb/ 204 Pb from 16.030 to 33.548; (3) REE-rich breccia, magnetite ore, and specular hematite rock are more radiogenic than galena; (4) REE-rich breccias have high 206 Pb/ 204 Pb (38.122–1277.61) compared to host rhyolites; and (5) REE-rich breccias are more radiogenic than magnetite ore and specular-hematite rock, having 206 Pb/ 204 Pb up to 230.65. Radiogenic 207 Pb/ 206 Pb age estimates suggest the following: (1) rhyolitic host rocks have ages of ~1.50 Ga, (2) magnetite ore is ~1.44 Ga, and (3) REE-rich breccias are ~1.48 Ga. These estimates are broadly consistent and genetically link the host rhyolite, REE-rich breccia, and magnetite ore as being contemporaneous. Alteration style and mineralogical or textural distinctions among the magnetite-rich rocks and REE-rich breccias do not correlate with different isotopic sources. In our model, magmatic fluids leached metals from the coeval felsic rocks (rhyolites), which provided the metal source reflected in the compositions of the REE-rich breccias and mineralized rocks. This model allows for the likelihood of contributions from other genetically related felsic and intermediate to more mafic rocks stored deeper in the crust. The deposit thus records an origin as a magmatic-hydrothermal system that was not affected by Nd and Pb remobilization processes, particularly if these processes also triggered mixing with externally sourced metal-bearing fluids. The Pea Ridge deposit was part of a single, widespread, homogeneous mixing system that produced a uniform isotopic composition, thus representing an excellent example of an igneous-dominated system that generated coeval magmatism and REE mineralization. Geochemical features suggest that components in the Pea Ridge deposit originated from sources in an orogenic margin. Basaltic magmatism produced by mantle decompression melting provided heat for extracting melts from the middle or lower crust. Continual addition of mafic magmas to the base of the subcontinental lithosphere, in a back-arc setting, remelted calc-alkaline rocks enriched in metals that were stored in the crust. The St. Francois Mountains terrane is adjacent to the regional T DM line (defined at a value of 1.55 Ga) that separates ~1600 Ma basement to the west, from younger basements to the east. Data for Pea Ridge straddle the T DM values proposed for the line. The Sm-Nd isotope system has been closed since formation of the deposit and the original igneous signatures have not been affected by cycles of alteration or superimposed mineralizing events. No evidence exists for externally derived Nd or Sm. The source region for metals within the Pea Ridge deposit had a moderate compositional variation and the REE-rich breccias and mineralized rocks are generally isotopically homogeneous. The Pea Ridge deposit thus constitutes a distinctive isotopic target for use as a model in identifying other mineralized systems that may share the same metal source in the St. Francois Mountains terrane and elsewhere in the eastern Granite-Rhyolite province.

Missouri↗

USGS1986

Platinum-group element resources in podiform chromitites from California and Oregon

Rock samples from about 280 podiform chromite deposits in California and Oregon were analyzed for Pt, Pd, Rh, and Ir by fire assay-atomic absorption and spectrographic techniques to estimate by-product platinum-group element potential of chromite mining. These deposits include ophiolites from the Sierra Nevada, Klamath Mountains, Coast Ranges, and the Canyon Mountain Complex; the deposits vary from Paleozoic to Mesozoic age and vary in size, shape, texture, and degree of metamorphism. The maximum platinum-group element contents (in ppm) measured for chromitites are: Pt, 2.53; Pd, 0.2; Rh, 0.14; Ru, 4.93; and Ir, 2.93.Correlations between Pt and Rh (0.60), Rh and Ir (0.64), Rh and Ru (0.71), and Ir and Ru (0.85) are significant at the 1 percent level. Relatively small but significant differences in platinum-group element content exist between geologic terranes. Chromite production from California and Oregon amounts to about 692,000 metric tons (1914-1985); the mean contained platinum-group element amounts in troy ounces are: Pt, 850; Pd, 100; Rh, 260; Ru, 4200; and Ir, 1,700, using estimated grades. Previous investigators have suggested that relatively few samples can represent the platinum-group element content of a podiform chromite deposit; therefore, these analyses are assumed to approximate "grades." Total world resources of platinum-group elements in podiform chromite deposits are estimated in troy ounces to be: Pt, 210,000; Pd, 25,000; Rh, 64,000; Ru, 1,000,000; and Ir, 420,000.

Economic Geology↗

USGS1980

Four reference soil and rock samples for measuring element availability in the Western Energy Regions

Attaining acceptable precision in extractable element determinations is more difficult than in total element determinations. In total element determinations, dissolution of the sample is qualitatively checked by the clarity of the solution and the absence of residues. These criteria cannot be used for extracts. Possibilities for error are introduced in virtually every step in soil extractions. Therefore, the use of reference materials whose homogeneity and element content are reasonably well known is essential for determination of extractable elements. In this report, estimates of homogeneity and element content are presented for four reference samples. Bulk samples of about 100 kilograms of each sample were ground to pass an 80-mesh sieve. The samples were homogenized and split using a Jones-type splitter. Fourteen splits of each reference sample were analyzed for total content of Ca, Co, Cu, Fe, K, Mg, Mn, Na, and Zn; DTPA-extractable Cd, Co, Cu, Fe, Mn, Ni, Pb, and Zn; exchangeable Ca, Mg, K, and Na; cation exchange capacity water-saturation-extractable Ca, Mg, K, Na, C1, and SO4; soil pH; and hot-water-extractable boron. Error measured between splits was small, indicating that the samples were homogenized adequately and that the laboratory procedure provided reproducible results.

Circular↗

USGS1997

Radioactive Elements in Coal and Fly Ash: Abundance, Forms, and Environmental Significance

Coal is largely composed of organic matter, but it is the inorganic matter in coal—minerals and trace elements— that have been cited as possible causes of health, environmental, and technological problems associated with the use of coal. Some trace elements in coal are naturally radioactive. These radioactive elements include uranium (U), thorium (Th), and their numerous decay products, including radium (Ra) and radon (Rn). Although these elements are less chemically toxic than other coal constituents such as arsenic, selenium, or mercury, questions have been raised concerning possible risk from radiation. In order to accurately address these questions and to predict the mobility of radioactive elements during the coal fuel-cycle, it is important to determine the concentration, distribution, and form of radioactive elements in coal and fly ash.

Fact Sheet↗