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A chemical-spectrochemical method for the determination of rare earth elements and thorium in cerium minerals

In a combined chemical-spectrochemical procedure for quantitatively determining rare earth elements in cerium minerals, cerium is determined volumetrically, a total rare earths plus thoria precipitate is separated chemically, the ceria content of the precipitate is raised to 80·0 percent by adding pure ceria, and the resulting mixture is analyzed for lanthanum, praseodymium, neodymium, samarium, gadolinium, yttrium, and thorium spectrochemically by means of the d.c. carbon arc. Spectral lines of singly ionized cerium are used as internal standard lines in the spectrochemical determination which is patterned after Fassel's procedure [1]. Results of testing the method with synthetic mixtures of rare earths and with samples of chemically analyzed cerium minerals show that the coefficient of variation for a quadruplicate determination of any element does not exceed 5·0 (excepting yttrium at concentrations less than 1 percent) and that the method is free of serious systematic error.

Spectrochimica Acta↗

Movement of elements into the atmosphere from coniferous trees in subalpine forests of Colorado and Idaho

Exudates from conifer trees, presumably consisting largely of volatile materials, were sampled at 19 subalpine localitites in Colorado and Idaho where anomalous amounts of several metals were determined in vegetation and mull during previous geochemical testing. The trees sampled were lodgepole pine ( Pinus contorta ), Engelmann spruce ( Picea engelmannii ) and Douglas fir ( Pseudotsuga menziesii ). The condensed exudates were passed through No. 40 Whatman filters, and through 5-micron, 0.45-micron, and 0.05-micron average-pore-diameter membrane filters, evaporated to dryness, and each residue was ashed and analyzed by a semiquantitative spectrographic method. The ashed residues of the exudates contain lithium, beryllium, boron, sodium, magnesium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, gallium, arsenic, strontium, yttrium, zirconium, molybdenum, silver, lead, bismuth, cadmium, tin, antimony, barium, and lanthanum. The presence of these elements suggests that volatile exudates from vegetation are a medium for the transport of elements in the biogeochemical cycle in subalpine environments. Thus, air sampling and analysis of aerosols derived from volatile exudates may be a useful tool in geochemical exploration.

Colorado, Idaho↗

An electric-analog simulation of elliptic partial differential equations using finite element theory

Elliptic partial differential equations can be solved using the Galerkin-finite element method to generate the approximating algebraic equations, and an electrical network to solve the resulting matrices. Some element configurations require the use of networks containing negative resistances which, while physically realizable, are more expensive and time-consuming to construct.

Mathematics and Computers in Simulation↗

Baseline models of trace elements in major aquifers of the United States

Trace-element concentrations in baseline samples from a survey of aquifers used as potable-water supplies in the United States are summarized using methods appropriate for data with multiple detection limits. The resulting statistical distribution models are used to develop summary statistics and estimate probabilities of exceeding water-quality standards. The models are based on data from the major aquifer studies of the USGS National Water Quality Assessment (NAWQA) Program. These data were produced with a nationally-consistent sampling and analytical framework specifically designed to determine the quality of the most important potable groundwater resources during the years 1991-2001. The analytical data for all elements surveyed contain values that were below several detection limits. Such datasets are referred to as multiply-censored data. To address this issue, a robust semi-parametric statistical method called regression on order statistics (ROS) is employed. Utilizing the 90th-95th percentile as an arbitrary range for the upper limits of expected baseline concentrations, the models show that baseline concentrations of dissolved Ba and Zn are below 500 ??g/L. For the same percentile range, dissolved As, Cu and Mo concentrations are below 10 ??g/L, and dissolved Ag, Be, Cd, Co, Cr, Ni, Pb, Sb and Se are below 1-5 ??g/L. These models are also used to determine the probabilities that potable ground waters exceed drinking water standards. For dissolved Ba, Cr, Cu, Pb, Ni, Mo and Se, the likelihood of exceeding the US Environmental Protection Agency standards at the well-head is less than 1-1.5%. A notable exception is As, which has approximately a 7% chance of exceeding the maximum contaminant level (10 ??g/L) at the well head.

Applied Geochemistry↗

The potential of mid- and near-infrared diffuse reflectance spectroscopy for determining major- and trace-element concentrations in soils from a geochemical survey of North America

In 2004, soils were collected at 220 sites along two transects across the USA and Canada as a pilot study for a planned soil geochemical survey of North America (North American Soil Geochemical Landscapes Project). The objective of the current study was to examine the potential of diffuse reflectance (DR) Fourier Transform (FT) mid-infrared (mid-IR) and near-infrared (NIRS) spectroscopy to reduce the need for conventional analysis for the determination of major and trace elements in such continental-scale surveys. Soil samples (n = 720) were collected from two transects (east-west across the USA, and north-south from Manitoba, Canada to El Paso, Texas (USA), n = 453 and 267, respectively). The samples came from 19 USA states and the province of Manitoba in Canada. They represented 31 types of land use (e.g., national forest, rangeland, etc.), and 123 different land covers (e.g., soybeans, oak forest, etc.). The samples represented a combination of depth-based sampling (0-5 cm) and horizon-based sampling (O, A and C horizons) with 123 different depths identified. The set was very diverse with few samples similar in land use, land cover, etc. All samples were analyzed by conventional means for the near-total concentration of 49 analytes (C total , C carbonate and C organic , and 46 major and trace elements). Spectra were obtained using dried, ground samples using a Digilab FTS-7000 FT spectrometer in the mid- (4000-400 cm -1 ) and near-infrared (10,000-4000 cm -1 ) at 4 cm -1 resolution (64 co-added scans per spectrum) using a Pike AutoDIFF DR autosampler. Partial least squares calibrations were develop using: (1) all samples as a calibration set; (2) samples evenly divided into calibration and validation sets based on spectral diversity; and (3) samples divided to have matching analyte concentrations in calibration and validation sets. In general, results supported the conclusion that neither mid-IR nor NIRS would be particularly useful in reducing the need for conventional analysis of soils from this continental-scale geochemical survey. The extreme sample diversity, likely caused by the widely varied parent material, land use at the site of collection (e.g., grazing, recreation, agriculture, etc.), and climate resulted in poor calibrations even for C total , C organic and C carbonate . The results indicated potential for mid-IR and NIRS to differentiate soils containing high concentrations (>100 mg/kg) of some metals (e.g., Co, Cr, Ni) from low-level samples (<50 mg/kg). However, because of the small number of high-level samples, it is possible that differentiation was based on factors other than metal concentration. Results for Mg and Sr were good, but results for other metals examined were fair to poor, at best. In essence, it appears that the great variation in chemical and physical properties seen in soils from this continental-scale survey resulted in each sample being virtually unique. Thus, suitable spectroscopic calibrations were generally not possible.

Applied Geochemistry↗

Weathering of the New Albany Shale, Kentucky, USA: I. Weathering zones defined by mineralogy and major-element composition

Comprehensive understanding of chemical and mineralogical changes induced by weathering is valuable information when considering the supply of nutrients and toxic elements from rocks. Here minerals that release and fix major elements during progressive weathering of a bed of Devonian New Albany Shale in eastern Kentucky are documented. Samples were collected from unweathered core (parent shale) and across an outcrop excavated into a hillside 40 year prior to sampling. Quantitative X-ray diffraction mineralogical data record progressive shale alteration across the outcrop. Mineral compositional changes reflect subtle alteration processes such as incongruent dissolution and cation exchange. Altered primary minerals include K-feldspars, plagioclase, calcite, pyrite, and chlorite. Secondary minerals include jarosite, gypsum, goethite, amorphous Fe(III) oxides and Fe(II)-Al sulfate salt (efflorescence). The mineralogy in weathered shale defines four weathered intervals on the outcrop-Zones A-C and soil. Alteration of the weakly weathered shale (Zone A) is attributed to the 40-a exposure of the shale. In this zone, pyrite oxidization produces acid that dissolves calcite and attacks chlorite, forming gypsum, jarosite, and minor efflorescent salt. The pre-excavation, active weathering front (Zone B) is where complete pyrite oxidation and alteration of feldspar and organic matter result in increased permeability. Acidic weathering solutions seep through the permeable shale and evaporate on the surface forming abundant efflorescent salt, jarosite and minor goethite. Intensely weathered shale (Zone C) is depleted in feldspars, chlorite, gypsum, jarosite and efflorescent salts, but has retained much of its primary quartz, illite and illite-smectite. Goethite and amorphous FE(III) oxides increase due to hydrolysis of jarosite. Enhanced permeability in this zone is due to a 14% loss of the original mass in parent shale. Denudation rates suggest that characteristics of Zone C were acquired over 1 Ma. Compositional differences between soil and Zone C are largely attributed to illuvial processes, formation of additional Fe(III) oxides and incorporation of modern organic matter.

Applied Geochemistry↗

Mechanisms of water-rock interaction and implications for remediating flooded mine workings elucidated from environmental tracers, stable isotopes, and rare earth elements

Contamination from acid mine drainage affects ecosystems and usability of groundwater for domestic and municipal purposes. The Captain Jack Superfund Site outside of Ward, Boulder County, Colorado, USA, hosts a draining mine adit that was remediated through emplacement of a hydraulic bulkhead to preclude acid mine drainage from entering nearby Lefthand Creek. During impoundment of water within the mine workings in 2020, a diverse and novel dataset of stable isotopes of water, sulfate, and carbon (δ 2 H, δ 18 O H2O , δ 18 O SO4 , δ 34 S, δ 13 C DIC ), rare earth elements, and environmental tracers (noble gases and tritium) were collected to understand groundwater recharge and mixing, mechanisms of sulfide oxidation and water-rock interaction, and the influence of remediation on the hydrologic and geochemical system. Water isotopes indicate that groundwater distal from the mine workings has seasonally variable recharge sources whereas water within the workings has a distinctive composition with minimal temporal variability. Sulfate isotopes indicate that sulfide oxidation occurs both within the mine workings and in adjacent igneous dikes, and that sulfide oxidation may occur under suboxic conditions with ferric iron as the oxidant. Carbon isotopes track the neutralization of acidic waters and the carbon mass budget of the system. Rare earth elements corroborate stable isotopes in indicating groundwater compartmentalization, and additionally illustrate enhanced mineral weathering in the mine workings. Environmental tracers indicate mixing of modern and pre-modern groundwater and inform timelines that active remediation may be needed. Together these datasets provide a useful template for similar investigations of abandoned mine sites where physical mixing processes, sources of solute loading, or remediation timeframes are of importance.

Colorado↗

Interspecies and interregional comparisons of the chemistry of PAHs and trace elements in mosses Hylocomium splendens (Hedw.) B.S.G. and Pleurozium schreberi (Brid.) Mitt. from Poland and Alaska

Comparative biogeochemical studies performed on the same plant species in remote areas enable pinpointing interspecies and interregional differences of chemical composition. This report presents baseline concentrations of PAHs and trace elements in moss species Hylocomium splendens and Pleurozium schreberi from the Holy Cross Mountains (south-central Poland) (HCM) and Wrangell-Saint Elias National Park and Preserve (Alaska) and Denali National Park and Preserve (Alaska). Total PAH concentrations in the mosses of HCM were in the range of 473-2970 ??g kg-1 (dry weight basis; DW), whereas those in the same species of Alaska were 80-3390 ??g kg-1 DW. Nearly all the moss samples displayed the similar ring sequence: 3 > 4 > 5 > 6 for the PAHs. The 3 + 4 ring/total PAH ratios show statistically significant differences between HCM (0.73) and Alaska (0.91). The elevated concentrations of PAHs observed in some sampling locations of the Alaskan parks were linked to local combustion of wood, with a component of vehicle particle- and vapor-phase emissions. In HCM, the principal source of PAH emissions has been linked to residential and industrial combustion of coal and vehicle traffic. In contrast to HCM, the Alaskan mosses were distinctly elevated in most of the trace elements, bearing a signature of??the underlying geology. H.??splendens and P. schreberi showed diverse bioaccumulative capabilities of PAHs in all three study areas. ?? 2008 Elsevier Ltd.

Atmospheric Environment↗

Historical deposition of mercury and selected trace elements to high-elevation National Parks in the Western U.S. inferred from lake-sediment cores

Atmospheric deposition of Hg and selected trace elements was reconstructed over the past 150 years using sediment cores collected from nine remote, high-elevation lakes in Rocky Mountain National Park in Colorado and Glacier National Park in Montana. Cores were age dated by 210 Pb, and sedimentation rates were determined using the constant rate of supply model. Hg concentrations in most of the cores began to increase around 1900, reaching a peak sometime after 1980. Other trace elements, particularly Pb and Cd, showed similar post-industrial increases in lake sediments, confirming that anthropogenic contaminants are reaching remote areas of the Rocky Mountains via atmospheric transport and deposition. Preindustrial (pre-1875) Hg fluxes in the sediment ranged from 5.7 to 42 μg m −2 yr −1 and modern (post-1985) fluxes ranged from 17.7 to 141 μg m −2 yr −1 . The average ratio of modern to preindustrial fluxes was 3.2, which is similar to remote lakes elsewhere in North America. Estimates of net atmospheric deposition based on the cores were 3.1 μg m −2 yr −1 for preindustrial and 11.7 μg m −2 yr −1 for modern times. Current-day measurements of wet deposition range from 5.0 to 8.6 μg m −2 yr −1 , which are lower than the modern sediment-based estimate of 11.7 μg m −2 yr −1 , perhaps owing to inputs of dry-deposited Hg to the lakes.

Atmospheric Environment↗

Improved 206Pb/238U microprobe geochronology by the monitoring of a trace-element-related matrix effect; SHRIMP, ID-TIMS, ELA-ICP-MS and oxygen isotope documentation for a series of zircon standards

Precise isotope dilution-thermal ionisation mass spectrometry (ID-TIMS) documentation is given for two new Palaeozoic zircon standards (TEMORA 2 and R33). These data, in combination with results for previously documented standards (AS3, SL13, QGNG and TEMORA 1), provide the basis for a detailed investigation of inconsistencies in 206Pb/238U ages measured by microprobe. Although these ages are normally consistent between any two standards, their relative age offsets are often different from those established by ID-TIMS. This is true for both sensitive high-resolution ion-microprobe (SHRIMP) and excimer laser ablation-inductively coupled plasma-mass spectrometry (ELA-ICP-MS) dating, although the age offsets are in the opposite sense for the two techniques. Various factors have been investigated for possible correlations with age bias, in an attempt to resolve why the accuracy of the method is worse than the indicated precision. Crystallographic orientation, position on the grain-mount and oxygen isotopic composition are unrelated to the bias. There are, however, striking correlations between the 206Pb/238U age offsets and P, Sm and, most particularly, Nd abundances in the zircons. Although these are not believed to be the primary cause of this apparent matrix effect, they indicate that ionisation of 206Pb/238U is influenced, at least in part, by a combination of trace elements. Nd is sufficiently representative of the controlling trace elements that it provides a quantitative means of correcting for the microprobe age bias. This approach has the potential to reduce age biases associated with different techniques, different instrumentation and different standards within and between laboratories. Crown Copyright ?? 2004 Published by Elsevier B.V. All rights reserved.

Chemical Geology↗

The effect of diagenesis and fluid migration on rare earth element distribution in pore fluids of the northern Cascadia accretionary margin

Analytical challenges in obtaining high quality measurements of rare earth elements (REEs) from small pore fluid volumes have limited the application of REEs as deep fluid geochemical tracers. Using a recently developed analytical technique, we analyzed REEs from pore fluids collected from Sites U1325 and U1329, drilled on the northern Cascadia margin during the Integrated Ocean Drilling Program (IODP) Expedition 311, to investigate the REE behavior during diagenesis and their utility as tracers of deep fluid migration. These sites were selected because they represent contrasting settings on an accretionary margin: a ponded basin at the toe of the margin, and the landward Tofino Basin near the shelf's edge. REE concentrations of pore fluid in the methanogenic zone at Sites U1325 and U1329 correlate positively with concentrations of dissolved organic carbon (DOC) and alkalinity. Fractionations across the REE series are driven by preferential complexation of the heavy REEs. Simultaneous enrichment of diagenetic indicators (DOC and alkalinity) and of REEs (in particular the heavy elements Ho to Lu), suggests that the heavy REEs are released during particulate organic carbon (POC) degradation and are subsequently chelated by DOC. REE concentrations are greater at Site U1325, a site where shorter residence times of POC in sulfate-bearing redox zones may enhance REE burial efficiency within sulfidic and methanogenic sediment zones where REE release ensues. Cross-plots of La concentrations versus Cl, Li and Sr delineate a distinct field for the deep fluids (z > 75 mbsf) at Site U1329, and indicate the presence of a fluid not observed at the other sites drilled on the Cascadia margin. Changes in REE patterns, the presence of a positive Eu anomaly, and other available geochemical data for this site suggest a complex hydrology and possible interaction with the igneous Crescent Terrane, located east of the drilled transect.

Vancouver↗

Utilization of multiple geochronology techniques to constrain the age of laterization and mineralization of the world-class Mount Weld rare earth element deposit, Western Australia

Pervasive chemical weathering on stable cratons may form thick regoliths and elemental enrichment, but constraining the age of regolith formation is challenging. In this study we utilize multiple geochronological techniques on different minerals from the world-class Mount Weld rare earth element (REE) deposit, formed by lateritic weathering of a carbonatite, to constrain the age of formation and provide insight into landscape evolution. The oldest dates, ca. 100 to 38 Ma, are from Lu-Hf dating of churchite [HREE(PO 4 )·2(H 2 O)], a heavy REE phosphate mineral. Growth bands on individual minerals show a younging outwards. 40 Ar/ 39 Ar geochronology of cryptomelane [K(Mn 4+ ,Mn 2+ )₈O₁₆] yielded dates from ca. 40 to 27 Ma. Similarly, (U-Th)/He geochronology of goethite [FeO(OH)] yielded dates ranging from ca. 45 to 19 Ma. Integrating results into regional constraints, suggests 1) churchite formed by mineral saturation in a karst-like setting below the water table from ca. 100 to 40 Ma, 2) with minor uplift and erosion, cryptomelane and goethite formed at or near the water table between ca. 45 and 19 Ma, 3) after ca. 15 to 10 Ma chemical weathering within the profile had ended. Other studies document that the region experienced minimal uplift and a wet, warm climate from ca. 100 Ma to 15 Ma. These conditions and the high carbonate content of the carbonatite promote extensive chemical weathering, a deep weathering profile, and the preservation of the weathered section. This study highlights the use of multiple geochronological techniques utilizing different minerals to provide insight into how laterites form and to constrain the timing and history of the formation of this important mineral deposit.

Western Australia↗

Trace element heterogeneity and crystallization history of the Plesovice zircon: Implications for its use as a U–Pb LA-ICP-MS reference material

Zircon crystals from Plešovice hyperpotassic granulite (HPG) have been widely used as a reference material for LA-ICP-MS dating. Detailed cathodoluminescence (CL) imaging and trace element analysis reveal a complex internal structure of Plešovice zircon linked to extreme chemical heterogeneity, which allows us to distinguish different zircon domains formed during its crystallization: (i) rare low-CL cores enriched in U, Nb, HREE and Y; (ii) dominant sector-zoned to oscillatory-zoned domains, and (iii) CL-bright rims poor in trace elements. Relic fine oscillatory zoned areas are chemically homogeneous, whereas coarsened and blurred areas, and CL-dark replacement domains, are heterogeneous. Based on these data we suggest a complex and protracted zircon evolution: (i) crystallization of metamorphic zircon in anatectic calc-alkaline granulite; (ii) magmatic zircon crystallization at high temperature and pressure in a dry ultrapotassic melt at presence of peritectic garnet; (iii) coupled zircon dissolution-precipitation processes triggered by percolating hydrous residual melt; and (iv) coarsening and replacement of the pre-existing zircon due to prolonged exposure to a reactive fluid/hydrous melt. New CA-ID-TIMS U Pb dates between 337.167 ± 0.080 and 337.840 ± 0.080 Ma confirm crystallization age for HPG zircon at around 337.4 Ma and suggest that previously published dates of 336.37 Ma were biased by non-mitigated lead loss. We thus confirm the U/Pb homogeneity of Plešovice reference zircon despite its chemical heterogeneity. We further discuss the implications of using the chemically extremely heterogeneous Plešovice reference zircon as primary or secondary standard for in-situ LA-ICP-MS geochronology, in particular for quantification of the chemical matrix-dependence of the relative sensitivity factor ( β ) of laser ablation.

Plešovice quarry↗

Accumulation of As, Cd and selected trace elements in tubers of Scirpus aritimus L. from Doñana marshes (South Spain)

The collapse of a pyrite-mining, tailing dam on 1998 contaminated an area of 4286 ha along the Agrio and Guadiamar river valleys in southern Spain. Over 2700 ha of the Do&ntilde;ana marshes, an important wintering area for wetland European birds, were contaminated. This study reports analyses of the tubers of Scirpus maritimus (an important food for greylag geese, Anser anser ) collected in 2000 in the &ldquo;Entremuros&rdquo; (spill-affected area) and in nearby unaffected Do&ntilde;ana marshes (control areas). In the spill-affected area mean tuber tissue concentrations of Cd (0.25 mg kg &minus;1 ) and Zn (61 mg kg &minus;1 ) were greater than in those tubers from the control area (0.02 mg kg &minus;1 for Cd, and 22 mg kg &minus;1 for Zn); values of Cd and Zn in &ldquo;Entremuros&rdquo; (samples collected two years after the mine spill) were much smaller than those reported only a few months after the accident. Trace elements (As, Fe, Mn and Tl, and to a lesser extent Cd and Pb) showed a preferential accumulation in the outer skin of tubers. Surprisingly, concentrations of As and Fe were greater in tubers from some marsh sites not affected by the mine-spill than in tubers from the &ldquo;Entremuros&rdquo;. We suggest that relic river channels within the Do&ntilde;ana marshes may be contaminated by trace elements from historic mining activities. An exhaustive study of macrophytes and other plant species in this area is recommended to identify potential risks to wildlife.

Chemosphere↗

Abundances and distribution of minerals and elements in high-alumina coal fly ash from the Jungar Power Plant, Inner Mongolia, China

The fly ash from the Jungar Power Plant, Inner Mongolia, China, is unique because it is highly enriched in alumina (Al 2 O 3 >50%). The fly ash mainly consists of amorphous glass and mullite and trace amounts of corundum, quartz, char, calcite, K-feldspar, clay minerals, and Fe-bearing minerals. The mullite content in fly ash is as high as 37.4% because of high boehmite and kaolinite contents in feed coal. Corundum is a characteristic mineral formed during the combustion of boehmite-rich coal.Samples from the economizer were sieved into six size fractions (<120, 120-160, 160-300, 300-360, 360-500, and >500 mesh) and separated into magnetic, mullite+corundum+quartz (MCQ) and glass phases for mineralogical and chemical analysis. The corundum content increases but amorphous glass decreases with decreasing particle size. Fractions of small particle sizes are relatively high in mullite, probably because mullite was formed from fine clay mineral particles under high-temperature combustion condition. Similarly, fine corundum crystals formed in the boiler from boehmite in feed coal. The magnetic phase consists of hematite, magnetite, magnesioferrite, and MgFeAlO 4 crystals. The MCQ phase is composed of 89% mullite, 6.1% corundum, 4.5% quartz, and 0.5% K-feldspar.Overall, the fly ash from the power plant is significantly enriched in Al 2 O 3 with an average of 51.9%, but poor in SiO 2 , Fe 2 O 3 , CaO, MgO, Na 2 O, P 2 O 5 , and As. Arsenic, TiO 2 , Th, Al 2 O 3 , Bi, La, Ga, Ni, and V are high in mullite, and the magnetic matter is enriched in Fe 2 O 3 , CaO, MnO, TiO 2 , Cs, Co, As, Cd, Ba, Ni, Sb, MgO, Zn, and V. The remaining elements are high in the glass fraction. The concentration of K 2 O, Na 2 O, P 2 O 5 , Nb, Cr, Ta, U, W, Rb, and Ni do not clearly vary with particle size, while SiO 2 and Hg decrease and the remaining elements clearly increase with decreasing particle size. ?? 2009 Elsevier B.V.

International Journal of Coal Geology↗

Partitioning of selected trace elements in coal combustion products from two coal-burning power plants in the United States

Samples of feed coal (FC), bottom ash (BA), economizer fly ash (EFA), and fly ash (FA) were collected from power plants in the Central Appalachian basin and Colorado Plateau to determine the partitioning of As, Cr, Hg, Pb, and Se in coal combustion products (CCPs). The Appalachian plant burns a high-sulfur (about 3.9 wt.%) bituminous coal from the Upper Pennsylvanian Pittsburgh coal bed and operates with electrostatic precipitators (ESPs), with flue gas temperatures of about 163 °C in the ESPs. At this plant, As, Pb, Hg, and Se have the greatest median concentrations in FA samples, compared to BA and EFA. A mass balance (not including the FGD process) suggests that the following percentages of trace elements are captured in FA: As (48%), Cr (58%), Pb (54%), Se (20%), and Hg (2%). The relatively high temperatures of the flue gas in the ESPs and low amounts of unburned C in FA (0.5% loss-on-ignition for FA) may have led to the low amount of Hg captured in FA. The Colorado Plateau plant burns a blend of three low-S (about 0.74 wt.%) bituminous coals from the Upper Cretaceous Fruitland Formation and operates with fabric filters (FFs). Flue gas temperatures in the baghouses are about 104 °C. The elements As, Cr, Pb, Hg, and Se have the greatest median concentrations in the fine-grained fly ash product (FAP) produced by cyclone separators, compared to the other CCPs at this plant. The median concentration of Hg in FA (0.0983 ppm) at the Colorado Plateau plant is significantly higher than that for the Appalachian plant (0.0315 ppm); this higher concentration is related to the efficiency of FFs in Hg capture, the relatively low temperatures of flue gas in the baghouses (particularly in downstream compartments), and the amount of unburned C in FA (0.29% loss-on-ignition for FA).

International Journal of Coal Geology↗

Rare-earth elements in the Permian Phosphoria formation: Paleo proxies of ocean geochemistry

The geochemistry of deposition of the Meade Peak Member of the Phosphoria Formation (MPM) in southeast Idaho, USA, a world-class sedimentary phosphate deposit of Permian age that extends over 300,000 km 2 , is ascertained from its rare earth element (REE) composition. Ratios of REE:Al 2 O 3 suggest two sources—seawater and terrigenous debris. The seawater-derived marine fraction identifies bottom water in the Phosphoria Sea as O 2 -depleted, denitrifying (suboxic) most of the time, and seldom sulfate-reducing (anoxic). This interpretation is supported by earlier research that showed progressively greater ratios in the marine sediment fraction of Cr:Ni>V:Ni⪢Mo:Ni, relative to their ratios in seawater; for which marine Cr, V, and Mo can have a dominantly O 2 –depleted bottom-water source and Ni a photic-zone, largely algal, source. The water chemistry was maintained by a balance between bacterial oxidation of organic matter settling through the water column, determined largely by primary productivity in the photic zone, and the flux of oxidants into the bottom water via advection of seawater from the open ocean. Samples strongly enriched in carbonate fluorapatite, the dominant REE host mineral, have variable Er/Sm, Tm/Sm, and Yb/Sm ratios. Their distribution may represent greater advection of seawater between the Phosphoria Sea and open ocean during deposition of two ore zones than a center waste and greater upwelling of nutrient-enriched water into the photic zone. However, the mean rate of deposition of marine Ni, a trace nutrient of algae, and PO 4 3− , a limiting nutrient, indicate that primary productivity was probably high throughout the depositional history. An alternative interpretation of the variable enrichments of Er, Tm, and Yb, relative to Sm, is that they may reflect temporally variable carbonate alkalinity of open-ocean seawater in Permian time. A more strongly negative Ce anomaly for all phosphatic units than the Ce anomaly of modern pelletal phosphate is further indicative of an elevated O 2 concentration in the Permo-Carboniferous open ocean, as proposed by others, in contrast to the depletion of O 2 in the bottom water of the Phosphoria Sea itself. The oceanographic conditions under which the deposit accumulated were likely similar to conditions under which many sedimentary phosphate deposits have accumulated and to conditions under which many black shales that are commonly phosphate poor have accumulated. A shortcoming of several earlier studies of these deposits has resulted from a failure to examine the marine fraction of elements separate from the terrigenous fraction.

Idaho↗

Relationships between hepatic trace element concentrations, reproductive status, and body condition of female greater scaup

We collected female greater scaup ( Aythya marila ) on the Yukon–Kuskokwim Delta, Alaska during two breeding seasons to determine if concentrations of 18 trace elements in livers and eggs were elevated and if hepatic concentrations correlated with body condition or affected reproductive status. Fifty-six percent, 5%, and 42% of females, respectively, had elevated hepatic cadmium (Cd: >3 μg g −1 dry weight [dw]), mercury (Hg: >3 μg g −1 dw), and selenium (Se: >10 μg g −1 dw). Somatic protein and lipid reserves were not correlated with hepatic Cd or Hg, but there was a weak negative correlation between protein and Se. Hepatic Cd, Hg, and Se were similar in females that had and had not initiated egg production. In a sample of six eggs, 33% and 100%, respectively, contained Se and Hg, but concentrations were below embryotoxicity thresholds. We conclude that trace element concentrations documented likely were not adversely impacting this study population.

Environmental Pollution↗