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Outlining potential biomarkers of exposure and effect to critical minerals: Nutritionally essential trace elements and the rare earth elements

Emerging and low-carbon technologies and innovations are driving a need for domestic sources, sustainable use, and availability of critical minerals (CMs)—those vital to the national and economic security of the United States. Understanding the known and potential health effects of exposures to such mineral commodities can inform prudent and environmentally responsible handling and harvesting. We review the occurrence, use, predominant exposure pathways, and adverse outcome pathways (AOP) for human and fish receptors of those CMs that are nutritionally essential trace metals (specifically, cobalt, chromium, manganese, nickel, and zinc), as well as the rare earth elements. Biological responses to some elements having comparable biogeochemistry can sometimes be similar. Candidate quantifiable biomarkers for assessing potential AOP are conveyed.

Toxics↗

Focus areas for data acquisition for potential domestic resources of 11 critical minerals in Alaska—Aluminum, cobalt, graphite, lithium, niobium, platinum group elements, rare earth elements, tantalum, tin, titanium, and tungsten, chap. C of U.S. Geological Survey, Focus areas for data acquisition for potential domestic sources of critical minerals

Phase 2 of the Earth Mapping Resources Initiative (Earth MRI) focuses on geologic belts that are favorable for hosting mineral systems that may contain select critical minerals. Phase 1 of the Earth MRI program focused on rare earth elements (REE), and phase 2 adds aluminum, cobalt, graphite, lithium, niobium, platinum-group metals, tantalum, tin, titanium, and tungsten. This report describes the methodology and techniques utilized to define focus areas for future data acquisition in Alaska; the conterminous United States are covered in a separate report. Definition of focus areas relies on a mineral systems framework that considers geologic features that may influence or control the formation and preservation of a mineral deposit and links the critical commodities to genetically related processes. Mineral systems are therefore larger than any given deposit. Evaluation of these larger systems allows for a broader understanding of how and where critical minerals may move through geologic systems. Delineation of focus areas in Alaska was informed by statewide geological, geochemical, geophysical, and mineral occurrence datasets that are publicly available. Additionally, previously published prospectivity analyses for six different critical mineral-bearing deposit types help identify focus areas. A total of 74 focus areas prospective for the phase 2 critical minerals that occur in 12 different mineral systems were defined in Alaska. Identified focus areas may be used to guide future geologic, geochemical, and geophysical data in the State of Alaska.

Alaska↗

Mercury and other element exposure in tree swallows nesting at low pH and neutral pH lakes in northern Wisconsin USA

The primary objective of this study was to determine whether tree swallows ( Tachycineta bicolor ) demonstrate similar responses to lake pH and mercury (Hg) contamination in northern Wisconsin as do common loons ( Gavia immer ). Similar to common loons, Hg concentrations in the blood of tree swallow nestlings were higher, Hg concentrations in eggs tended to be higher, and egg size tended to be smaller at low (<6.2) pH lakes. In contrast to common loons, tree swallow nestling production was not lower at low pH lakes. Based on modeling associations, Hg concentrations in tree swallow eggs and nestling blood can be used to predict Hg concentrations in common loons without the invasive or destructive sampling of loons. Mean concentrations of cadmium, manganese, and mercury in nestling livers were higher at low pH lakes than neutral pH lakes. Concentrations of cadmium, chromium, mercury, selenium, and zinc were not at toxic levels.

Wisconsin↗

The future of rare earth elements&mdash;will these high-tech industry elements continue in short supply?

* REE will continue to find increasing use due to their unique properties. * There is a realistic possibility around 2015-2016 of sufficient REE capacity to meet demand under conditions of healthy price competition. * REE supplies will be tight and prices high for a few years. * There is significant downside risk that newly developed mines will not perform as planned.

Open-File Report↗

Occurrence and distribution of iron, manganese, and selected trace elements in ground water in the glacial aquifer system of the northern United States

Dissolved trace elements, including iron and manganese, are often an important factor in use of ground water for drinking-water supplies in the glacial aquifer system of the United States. The glacial aquifer system underlies most of New England, extends through the Midwest, and underlies portions of the Pacific Northwest and Alaska. Concentrations of dissolved trace elements in ground water can vary over several orders of magnitude across local well networks as well as across regions of the United States. Characterization of this variability is a step toward a regional screening-level assessment of potential human-health implications. Ground-water sampling, from 1991 through 2003, of the National Water-Quality Assessment (NAWQA) Program of the U.S. Geological Survey determined trace element concentrations in water from 847 wells in the glacial aquifer system. Dissolved iron and manganese concentrations were analyzed in those well samples and in water from an additional 743 NAWQA land-use and major-aquifer survey wells. The samples are from monitoring and water-supply wells. Concentrations of antimony, barium, beryllium, cadmium, chromium, cobalt, copper, iron, lead, manganese, molybdenum, nickel, selenium, strontium, thallium, uranium, and zinc vary as much within NAWQA study units (local scale; ranging in size from a few thousand to tens of thousands of square miles) as over the entire glacial aquifer system. Patterns of trace element concentrations in glacial aquifer system ground water were examined by using techniques suitable for a dataset with zero to 80 percent of analytical results reported as below detection. During the period of sampling, the analytical techniques changed, which generally improved the analytical sensitivity. Multiple reporting limits complicated the comparison of detections and concentrations. Regression on Order Statistics was used to model probability distributions and estimate the medians and other quantiles of the trace element concentrations. Strontium and barium were the most frequently detected and usually were present in the highest concentrations. Iron and manganese were the next most commonly detected and next highest in concentrations. Iron concentrations were the most variable with respect to the range of variations (both within local networks and aquifer-wide) and with respect to the disparity between magnitude of concentrations (detections) and the frequency of samples below reporting limits (nondetections). Antimony, beryllium, cadmium, silver, and thallium were detected too infrequently for substantial interpretation of their occurrence or distributions or potential human-health implications. For those elements that were more frequently detected, there are some geographic patterns in their occurrence that primarily reflect climate effects. The highest concentrations of several elements were found in the West-Central glacial framework area (High Plains and northern Plains areas). There are few important patterns for any element in relation to land use, well type, or network type. Shallow land-use (monitor) wells had iron concentrations generally lower than the glacial aquifer system wells overall and much lower than major-aquifer survey wells, which comprise mostly private- and public-supply wells. Unlike those for iron, concentration patterns for manganese were similar among shallow land-use wells and major-aquifer survey wells. An apparent relation between low pH and relatively low concentrations of many elements, except lead, may be more indicative of the relatively low dissolved-solids content in wells in the Northeastern United States that comprise the majority of low pH wells, than of a pH dependent pattern. Iron and manganese have higher concentrations and larger ranges of concentrations especially under more reducing conditions. Dissolved oxygen and well depth were related to iron and manganese concentrations. Redox conditions also affect several trace elements such as arsenic and copper; however, a comparison of redox categories, based in part on iron and manganese concentrations, indicated that the concentrations of many redox-sensitive elements were not significantly different among redox categories. Some of the redox-related patterns were not what would be expected on the basis of solubility constraints. Furthermore, barium is affected by redox conditions in at least one well network even though it is not a redox-sensitive element. Concentrations of barium in portions of the glacial aquifer system are limited by sulfate, which is strongly affected by redox conditions. Few samples had concentrations of any trace element that exceeded drinking-water standards (Maximum Contaminant Levels), for compounds regulated in drinking water or Health-Based Screening Levels for unregulated trace elements. More unregulated trace elements had concentrations greater than benchmarks than regulated trace elements. More samples had manganese concentrations greater its benchmark than any other element in the glacial aquifer system wells. Of the 1,590 wells sampled for manganese, only 556 are for private or public drinking-water supplies, and of those, 9.9 percent (55) exceeded the manganese Lifetime Health Advisory. Concentrations of arsenic, selenium, and uranium less frequently exceeded Maximum Contaminant Levels. There are 29 wells that had 2 element concentrations that exceeded their respective benchmarks. Most concentrations that exceeded a health-based benchmark were from wells in the West-Central area (Iowa, Minnesota, North and South Dakota, Nebraska, and Kansas); however, there is little geographical pattern to the wells with element concentrations of concern.

Scientific Investigations Report↗

A deposit model for carbonatite and peralkaline intrusion-related rare earth element deposits

Carbonatite and alkaline intrusive complexes, as well as their weathering products, are the primary sources of rare earth elements. A wide variety of other commodities have been exploited from carbonatites and alkaline igneous rocks including niobium, phosphate, titanium, vermiculite, barite, fluorite, copper, calcite, and zirconium. Other elements enriched in these deposits include manganese, strontium, tantalum, thorium, vanadium, and uranium. Carbonatite and peralkaline intrusion-related rare earth element deposits are presented together in this report because of the spatial, and potentially genetic, association between carbonatite and alkaline rocks. Although these rock types occur together at many locations, carbonatite and peralkaline intrusion-related rare earth element deposits are not generally found together. Carbonatite hosted rare earth element deposits are found throughout the world, but currently only five are being mined for rare earth elements: Bayan Obo, Daluxiang, Maoniuping, and Weishan deposits in China and the Mountain Pass deposit in California, United States. These deposits are enriched in light rare earth elements, including lanthanum, cerium, praseodynium, and neodynium. The principal rare earth element-minerals associated with carbonatites are fluocarbonates (bastn&auml;site, parisite, and synchysite), hydrated carbonates (ancylite), and phosphates (monazite) with bastn&auml;site being the primary ore mineral. Calcite and dolomite are the primary gangue minerals. At present, the only rare earth element production from a peralkaline intrusion-related deposit is as a byproduct commodity at the Lovozero deposit in Russia. Important rare earth element minerals found in various deposits include apatite, eudialyte, loparite, gittinsite, xenotime, gadolinite, monazite, bastn&auml;site, kainosite, mosandrite, britholite, allanite, fergusonite, and zircon, and these minerals tend to be enriched in heavy rare earth elements. Carbonatite and alkaline intrusive complexes are derived from partial melts of mantle material, and neodymium isotopic data are consistent with the rare earth elements being derived from the parental magma. Deposits and these associated rock types tend to occur within stable continental tectonic units, in areas defined as shields, cratons, and crystalline blocks; they are generally associated with intracontinental rift and fault systems. Protracted fractional crystallization of the magma leads to enrichment in rare earth elements and other incompatible elements. Rare earth element mineralization associated with carbonatites can occur as either primary mineral phases or as mineralization associated with late stage orthomagmatic fluids. Rare earth element mineralization associated with alkaline intrusive complexes may occur as primary phases in magmatic layered complexes or as late-stage dikes and veins. The greatest environmental challenges associated with carbonatite and peralkaline intrusion-related rare earth element deposits center on the associated uranium and thorium. Considerable uncertainty exists around the toxicity of rare earth elements and warrants further investigation. The acid-generating potential of carbonatites and peralkaline intrusion-related deposits is low due to the dominance of carbonate minerals in carbonatite deposits, the presence of feldspars and minor calcite within the alkaline intrusion deposits, and only minor quantities of potentially acid-generating sulfides. Therefore, acid-drainage issues are not likely to be a major concern associated with these deposits. Uranium has the potential to be recovered as a byproduct, which would mitigate some of its environmental effects. However, thorium will likely remain a waste-stream product that will require management since progress is not being made towards the development of thorium-based nuclear reactors in the United States or other large scale commercial uses. Because some deposits are rich in fluorine and beryllium, these elements may be of environmental concern in certain locations.

Scientific Investigations Report↗

Organic contaminants, trace and major elements, and nutrients in water and sediment sampled in response to the Deepwater Horizon oil spill

Beach water and sediment samples were collected along the Gulf of Mexico coast to assess differences in contaminant concentrations before and after landfall of Macondo-1 well oil released into the Gulf of Mexico from the sinking of the British Petroleum Corporation's Deepwater Horizon drilling platform. Samples were collected at 70 coastal sites on the Gulf of Mexico between May 7 and July 7, 2010, to document baseline, "pre-landfall" conditions. A subset of these sites was resampled during October 4 to 14, 2010, after oil had made landfall on the Gulf of Mexico coast ("post-landfall") to determine if actionable concentrations of oil were present along shorelines. Few organic contaminants were detected in water; their detection frequencies were generally low and similar in pre-landfall and post-landfall samples. Only one organic contaminant, toluene, had significantly higher concentrations in post-landfall than pre-landfall water samples. No samples exceeded any human-health benchmarks, and only one sample exceeded an aquatic-life benchmark-the toxic-unit benchmark for polycyclic aromatic hydrocarbons (PAH) mixtures was exceeded in one post-landfall water sample from Louisiana. No exceedance was observed in the corresponding pre-landfall water sample at this site. In sediment, several PAHs were detected at over 20 percent of sites. Concentrations of 3 parent PAHs and 17 alkylated PAH groups were significantly higher in post-landfall samples than pre-landfall samples. One pre-landfall sample from Texas exceeded the sediment toxic-unit benchmark for PAH mixtures; this site was not sampled during the post-landfall period, so no comparison between sampling periods could be made. Twenty-seven percent of sediment samples exceeded empirical sediment-quality benchmarks (upper screening values) for PAHs, indicating these samples are in the probable-effect range. A higher percentage of post-landfall samples exceeded upper screening-value benchmarks (37 percent) than did pre-landfall samples (22 percent), but there was no significant difference in the proportion of samples exceeding one or more benchmarks between paired pre-landfall and post-landfall samples. Seven sites had the largest concentration differences between post-landfall and pre-landfall samples for fifteen alkylated PAHs. Five of these seven sites (1 site in Louisiana, 1 in Mississippi, and 3 in Alabama) were identified on the basis of diagnostic geochemical biomarkers as containing Macondo-1 oil in post-landfall sediments and tarballs, as described in a companion report by Rosenbauer and others (2010). For trace and major elements in water, analytical reporting levels for several elements were highly variable; after censoring to a common reporting threshold, concentrations were significantly different between pre-landfall and post-landfall samples for a few elements, all of which are elements in seawater. No human-health benchmarks were exceeded, although these were available for only two elements. Aquatic-life benchmarks for trace elements were exceeded in almost 50 percent of water samples. Post-landfall samples exceeded one or more acute benchmarks in 21 percent, and chronic benchmarks in 93 percent of samples, compared to 1 percent (acute) and 39 percent (chronic) for pre-landfall samples. The elements responsible for the most exceedances in post-landfall samples were boron (48 samples), copper (22), and manganese (12). Nickel and vanadium, which U.S. Environmental Protection Agency specifically identified as relevant to the oil spill, were responsible for exceedances in only one of the fifty-two post-landfall samples with exceedances. These results represent the minimum number of exceedances for several trace elements because a substantial number of samples could not be compared with benchmarks because the element was determined during only one sampling period (boron and vanadium) or the reporting level for the sample was higher than the applicable benchmark value (for example, cobalt, copper, lead, and nickel). The high and variable reporting levels for trace elements in water also precluded the statistical comparison between sampling periods of the proportion of samples exceeding benchmarks. For trace elements in whole (unsieved) sediment, 47 percent of samples exceeded empirical upper screening-value benchmarks, indicating these samples are in the probable-effect range. However, there was no significant difference in the proportion of samples exceeding one or more benchmarks between paired pre-landfall post-landfall samples. Benchmark exceedance frequencies could be conservatively high, because they are based on measurements of total trace-element concentrations, including the sediment matrix. In fine sediment (the less than 63-micrometer sediment fraction), one or more trace or major elements were anthropogenically enriched relative to national baseline values for U.S. streams for almost all sediment samples (123 of 124). Sixteen percent of sediment samples exceeded upper screening-value benchmarks for, and were enriched in, one or more of the element(s) barium (in 14 samples), vanadium (5), aluminum (3), manganese (3), arsenic (2), chromium (2), and cobalt (1). These samples, collected from Louisiana and Texas, were evenly divided between the pre-landfall (9 samples) and post-landfall (10 samples) periods. Considering all the information evaluated in this report, there were significant differences between pre-landfall and post-landfall samples for PAH concentrations in sediment. Pre-landfall and post-landfall samples did not differ significantly in concentrations or benchmark exceedances for most organics in water or trace elements in sediment. For trace elements in water, aquatic-life benchmarks were exceeded in almost 50 percent of samples, but the high and variable analytical reporting levels precluded statistical comparison of benchmark exceedances between sampling periods. Concentrations of several PAH compounds in sediment were significantly higher in post-landfall samples than pre-landfall samples, and five of seven sites with the largest differences in PAH concentrations also had diagnostic geochemical evidence of Deepwater Horizon Macondo-1 oil from Rosenbauer and others (2010).

Open-File Report↗

Major and trace element geochemistry and background concentrations for soils in Connecticut

Soil samples were collected throughout Connecticut (CT) to determine the relationship of soil chemistry with the underlying geology and to better understand background concentrations of major and trace elements in soils. Soil samples were collected (1) from the upper 5 cm of surficial soil at 100 sites, (2) from the A horizon at 86 of these sites, and (3) from the deeper horizon, typically the C horizon, at 79 of these sites. The <2-millimeter fraction of each sample was analyzed for 44 elements by methods that yield the total or near-total elemental content. Sample sites were characterized by glacial setting, underlying bedrock geology, and soil type. These spatial data were used with element concentrations in the C-horizon to relate geologic factors to soil chemistry. Concentrations of elements in C-horizon soils varied with grain size in surficial glacial materials and with underlying rock types, as determined using nonparametric statistical procedures. Concentrations of most elements in C-horizon soils showed a positive correlation with silt and (or) clay content and were higher in surficial materials mapped as till, thick till, and (or) fines. Element concentrations in C-horizon soils showed significant differences among the underlying geologic provinces and were highest overlying the Grenville Belt and (or) the Grenville Shelf Sequence Provinces in western CT. These rocks consist mainly of carbonates and the relatively high element concentrations in overlying soils likely result from less influence of dilution by quartz compared to other provinces. Element concentrations in C-horizon soils in CT were compared with those in samples from other New England states overlying similar lithologic bedrock types. The upper range of As concentrations in C-horizon soils overlying the New Hampshire-Maine (NH-ME) Sequence in CT was 15 mg/kg, lower than the upper range of 24 mg/kg in C-horizon soils overlying the same sequence in ME. In CT, U concentration means were significantly higher in C-horizon soils overlying Avalonian granites, and U concentrations ranged as high as 14 mg/kg, compared to those in C-horizon soil samples collected from other New England states, which ranged as high as 6.1 mg/kg in a sample in NH overlying the NH-ME Sequence. Element concentrations in C-horizon soils in CT were compared with those in samples collected from shallower depths. Concentrations of most major elements were highest in C-horizon soil samples, including Al, Ca, Fe, K, Na, and Ti, but element concentrations showed a relatively similar pattern in A-horizon and surficial soil samples among the underlying geologic provinces. Trace element concentrations, including Ba, W, Ga, Ni, Cs, Rb, Sr, Th, Sc, and U, also were higher in C-horizon soil samples than in overlying soil samples. Concentrations of Mg, and several trace elements, including Mn, P, As, Nb, Sn, Be, Bi, Hg, Se, Sb, La, Co, Cr, Pb, V, Y, Cu, Pb, and Zn were highest in some A-horizon or surficial soils, and indicate possible contributions from anthropogenic sources. Because element concentrations in soils above the C horizon are more likely to be affected by anthropogenic factors, concentration ranges in C-horizon soils and their spatially varying geologic associations should be considered when estimating background concentrations of elements in CT soils.

Connecticut↗

Potential sources of analytical bias and error in selected trace element data-quality analyses

Potential sources of analytical bias and error associated with laboratory analyses for selected trace elements where concentrations were greater in filtered samples than in paired unfiltered samples were evaluated by U.S. Geological Survey (USGS) Water Quality Specialists in collaboration with the USGS National Water Quality Laboratory (NWQL) and the Branch of Quality Systems (BQS). Causes for trace-element concentrations in filtered samples to exceed those in associated unfiltered samples have been attributed to variability in analytical measurements, analytical bias, sample contamination either in the field or laboratory, and (or) sample-matrix chemistry. These issues have not only been attributed to data generated by the USGS NWQL but have been observed in data generated by other laboratories. This study continues the evaluation of potential analytical bias and error resulting from matrix chemistry and instrument variability by evaluating the performance of seven selected trace elements in paired filtered and unfiltered surface-water and groundwater samples collected from 23 sampling sites of varying chemistries from six States, matrix spike recoveries, and standard reference materials. Filtered and unfiltered samples have been routinely analyzed on separate inductively coupled plasma-mass spectrometry instruments. Unfiltered samples are treated with hydrochloric acid (HCl) during an in-bottle digestion procedure; filtered samples are not routinely treated with HCl as part of the laboratory analytical procedure. To evaluate the influence of HCl on different sample matrices, an aliquot of the filtered samples was treated with HCl. The addition of HCl did little to differentiate the analytical results between filtered samples treated with HCl from those samples left untreated; however, there was a small, but noticeable, decrease in the number of instances where a particular trace-element concentration was greater in a filtered sample than in the associated unfiltered sample for all trace elements except selenium. Accounting for the small dilution effect (2 percent) from the addition of HCl, as required for the in-bottle digestion procedure for unfiltered samples, may be one step toward decreasing the number of instances where trace-element concentrations are greater in filtered samples than in paired unfiltered samples. The laboratory analyses of arsenic, cadmium, lead, and zinc did not appear to be influenced by instrument biases. These trace elements showed similar results on both instruments used to analyze filtered and unfiltered samples. The results for aluminum and molybdenum tended to be higher on the instrument designated to analyze unfiltered samples; the results for selenium tended to be lower. The matrices used to prepare calibration standards were different for the two instruments. The instrument designated for the analysis of unfiltered samples was calibrated using standards prepared in a nitric:hydrochloric acid (HNO 3 :HCl) matrix. The instrument designated for the analysis of filtered samples was calibrated using standards prepared in a matrix acidified only with HNO 3 . Matrix chemistry may have influenced the responses of aluminum, molybdenum, and selenium on the two instruments. The best analytical practice is to calibrate instruments using calibration standards prepared in matrices that reasonably match those of the samples being analyzed. Filtered and unfiltered samples were spiked over a range of trace-element concentrations from less than 1 to 58 times ambient concentrations. The greater the magnitude of the trace-element spike concentration relative to the ambient concentration, the greater the likelihood spike recoveries will be within data control guidelines (80–120 percent). Greater variability in spike recoveries occurred when trace elements were spiked at concentrations less than 10 times the ambient concentration. Spike recoveries that were considerably lower than 90 percent often were associated with spiked concentrations substantially lower than what was present in the ambient sample. Because the main purpose of spiking natural water samples with known quantities of a particular analyte is to assess possible matrix effects on analytical results, the results of this study stress the importance of spiking samples at concentrations that are reasonably close to what is expected but sufficiently high to exceed analytical variability. Generally, differences in spike recovery results between paired filtered and unfiltered samples were minimal when samples were analyzed on the same instrument. Analytical results for trace-element concentrations in ambient filtered and unfiltered samples greater than 10 and 40 μg/L, respectively, were within the data-quality objective for precision of ±25 percent. Ambient trace-element concentrations in filtered samples greater than the long-term method detection limits but less than 10 μg/L failed to meet the data-quality objective for precision for at least one trace element in about 54 percent of the samples. Similarly, trace-element concentrations in unfiltered samples greater than the long-term method detection limits but less than 40 μg/L failed to meet this data-quality objective for at least one trace-element analysis in about 58 percent of the samples. Although, aluminum and zinc were particularly problematic, limited re-analyses of filtered and unfiltered samples appeared to improve otherwise failed analytical precision. The evaluation of analytical bias using standard reference materials indicate a slight low bias for results for arsenic, cadmium, selenium, and zinc. Aluminum and molybdenum show signs of high bias. There was no observed bias, as determined using the standard reference materials, during the analysis of lead.

Scientific Investigations Report↗

Major and trace elements in Mahogany zone oil shale in two cores from the Green River Formation, piceance basin, Colorado

The Parachute Creek Member of the lacustrine Green River Formation contains thick sequences of rich oil-shale. The richest sequence and the richest oil-shale bed occurring in the member are called the Mahogany zone and the Mahogany bed, respectively, and were deposited in ancient Lake Uinta. The name "Mahogany" is derived from the red-brown color imparted to the rock by its rich-kerogen content. Geochemical abundance and distribution of eight major and 18 trace elements were determined in the Mahogany zone sampled from two cores, U. S. Geological Survey core hole CR-2 and U. S. Bureau of Mines core hole O1-A (Figure 1). The oil shale from core hole CR-2 was deposited nearer the margin of Lake Uinta than oil shale from core hole O1-A. The major- and trace-element chemistry of the Mahogany zone from each of these two cores is compared using elemental abundances and Q-mode factor modeling. The results of chemical analyses of 44 CR-2 Mahogany samples and 76 O1-A Mahogany samples are summarized in Figure 2. The average geochemical abundances for shale (1) and black shale (2) are also plotted on Figure 2 for comparison. The elemental abundances in the samples from the two cores are similar for the majority of elements. Differences at the 95% probability level are higher concentrations of Ca, Cu, La, Ni, Sc and Zr in the samples from core hole CR-2 compared to samples from core hole O1-A and higher concentrations of As and Sr in samples from core hole O1-A compared to samples from core hole CR-2. These differences presumably reflect slight differences in depositional conditions or source material at the two sites. The Mahogany oil shale from the two cores has lower concentrations of most trace metals and higher concentrations of carbonate-related elements (Ca, Mg, Sr and Na) compared to the average shale and black shale. During deposition of the Mahogany oil shale, large quantities of carbonates were precipitated resulting in the enrichment of carbonate-related elements and dilution of most trace elements as pointed out in several previous studies. Q-mode factor modeling is a statistical method used to group samples on the basis of compositional similarities. Factor end-member samples are chosen by the model. All other sample compositions are represented by varying proportions of the factor end-members and grouped as to their highest proportion. The compositional similarities defined by the Q-mode model are helpful in understanding processes controlling multi-element distributions. The models for each core are essentially identical. A four-factor model explains 70% of the variance in the CR-2 data and 64% of the O1-A data (the average correlation coefficients are 0. 84 and 0. 80, respectively). Increasing the number of factors above 4 results in the addition of unique instead of common factors. Table I groups the elements based on high factor-loading scores (the amount of influence each element has in defining the model factors). Similar elemental associations are found in both cores. Elemental abundances are plotted as a function of core depth using a five-point weighted moving average of the original data to smooth the curve (Figure 3 and 4). The plots are grouped according to the four factors defined by the Q-mode models and show similar distributions for elements within the same factor. Factor 1 samples are rich in most trace metals. High oil yield and the presence of illite characterize the end-member samples for this factor (3, 4) suggesting that adsorption of metals onto clay particles or organic matter is controlling the distribution of the metals. Precipitation of some metals as sulfides is possible (5). Factor 2 samples are high in elements commonly associated with minerals of detrital or volcanogenic origin. Altered tuff beds and lenses are prevalent within the Mahogany zone. The CR-2 end-member samples for this factor contain analcime (3) which is an alteration product within the tuff beds of the Green River Formation. Th

Conference Paper↗