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Determination and prediction of micro scale rare earth element geochemical associations in mine drainage treatment wastes

Acid mine drainage (AMD) has been proposed as a novel source of rare earth elements (REE), a group of elements that includes critical metals for clean energy and modern technologies. REE are sequestered in the Fe–Al–Mn-rich precipitates produced during the treatment of AMD. These AMD solids are typically managed as waste but could be a REE source. Here, results from AMD solids characterization and geochemical modeling are presented to determine the minerals/solid phases that are enriched in REE and identify the mechanism(s) of REE attenuation. AMD solids collected from limestone-based AMD treatment systems were subjected to sequential extraction and synchrotron microprobe analyses to characterize the binding nature of the REE. The results of these analyses indicated REEs were mainly associated with Al or Mn phases. Only selected REE (Gd, Dy) were associated with Fe phases, which were less abundant than Al and Mn phases in analyzed samples. The sequential extractions demonstrated that acidic and/or reducing extractions effectively mobilize REE from the AMD solids evaluated. The observed element associations in solids are consistent with geochemical model results that indicate dissolved REE can be effectively attenuated by adsorption on freshly precipitated Fe, Al, and Mn oxides/hydroxides. The model, which simulates dissolution of CaCO 3 and the precipitation of Fe, Al, and Mn oxides with increased pH, accurately predicts the pH dependent accumulation of dissolved REE with Al, Mn, and Fe oxides/hydroxides in the studied AMD treatment systems. The methods and results presented here can be used to identify conditions favorable for accumulation of REE-enriched AMD solids and possible passive or active treatment(s) to extract REE from AMD. This information can be used to design AMD treatment systems for the recovery of REE and is an opportunity to transform the challenges of addressing polluted mine drainage into an environmental and economic asset.

Pennsylvania

Mercury and trace element distribution in density separates of a South African Highveld (#4) coal: Implications for mercury reduction and preparation of export coal

Eight density separates of Permian Highveld (#4) coal were investigated for partitioning of Hg and trace elements. The separates include float fractions obtained in heavy media having densities of 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, and 2.0 g/cm 3 , and the sink fraction for 2.0 g/cm 3 . Bulk analysis of the separates shows strong (R 2 ≥ 0.80) positive correlations between pyritic sulfur and mercury, and between ash yield and both pyritic sulfur and mercury. Laser ablation (LA) ICP-MS analysis of individual pyrite grains in the separates confirms association of Hg and As with pyrite as indicated by bulk analysis. Other elements detected in pyrite by LA-ICP-MS include Mn, Co, Ni, Tl, and Pb. Results for the separates allow prediction of Hg, trace elements, and ash yields expected in specific South African coal products. These range from 0.06 ppm Hg and an ash yield of 11.5% ash for the export fraction to 0.47 ppm Hg and an ash yield of 60.9% for the discard (stone) fraction (dry basis). Results show pronounced differences expected between coal used for domestic power generation and coal which is exported.

International Journal of Coal Geology

Machine learning and data augmentation approach for identification of rare earth element potential in Indiana Coals, USA

Rare earth elements and yttrium (REYs) are critical elements and valuable commodities due to their limited availability and high demand in a wide range of applications and especially in high-technology products. The increased demand and geopolitical pressures motivate the search for alternative sources of REYs, and coal, coal waste, and coal ash are considered as new sources for these critical elements. This research evaluates the REY potential of coals from Indiana (USA). However, although coal data revealed REY potential, it suffered from sparse samples with complete REY measurements. Therefore, we explore the applicability of machine learning (ML) models and data augmentation techniques to demonstrate their applicability to evaluate REY potential in Indiana, and other areas in coal basins, using selected coal parameters (Al2O3, Fe2O3, C, Ash, S, P, Mo, Zn, and As contents) as covariates (indicators). Due to the relatively small sample size with complete REY data in the Indiana Coal Database, two data augmentation techniques (Random Over-Sampling Examples and Synthetic Minority Over-Sampling Technique) were used. Four machine learning algorithms (linear discriminate analysis, support vector machine, random forest, and artificial neural networks) were applied for modeling REY potential as a classification problem. The results show that application of Synthetic Minority Over-Sampling Technique prior to development of the support vector machine (SVM) models generated the best REY classification with an accuracy of 95%. The encouraging results based on Indiana coal data may suggest that a similar approach can be used for other coal basins for screening the locations with REY potential. Those locations then can be targeted for more detailed geochemical surveys to identify most promising areas and evaluate overall REY resources.

Indiana

Distribution of rare earth and other critical elements in lignites from the Eocene Jackson Group, Texas

Coal is increasingly evaluated as a source of rare earth elements (REEs) in the United States to address the overreliance on imported REEs. The objective of this study was to assess the distribution of REEs in lignites from selected mining areas in the Texas Gulf Coastal Plain region. Thirty-one archived lignite and rock samples previously collected by the U.S. Geological Survey were analyzed for their rare earth element and critical mineral content. These include samples from one core (5400 and 5500 lignite horizons) and two opencast lignite mines (Gibbons Creek 3500 and 4500 horizons, and San Miguel horizons A to D) in the Eocene Jackson Group of the Texas Gulf of Mexico Coastal Plain. Some lithologies in the Gibbons Creek 3500 and 4500 lignite-bearing sections have high total rare earth, yttrium (Y), and scandium (Sc) (REYSc) values, up to 7800 ppm (ash basis) REYSc. The lignite lithologies show an enrichment in rare earths, [samarium (Sm) through gadolinium (Gd)]. The basal Gibbons Creek 3500 lignite bench shows a heavy rare earth element enrichment pattern resembling that often seen in peats through high volatile A bituminous coals. The 5500 lignite sequence, overlying the latter lignite sections, shows a light rare earth enrichment. The San Miguel lignite benches have heavy rare earth enrichments with a negative europium (Eu) anomaly.

Texas

Role of manganese oxides in the exposure of mute swans (Cygnus olor) to Pb and other elements in the Chesapeake Bay, USA

The aims of this study are to estimate exposure of waterfowl to elements in contaminated sediments in the Chesapeake Bay and to consider the potential role of Mn in influencing bioavailability and exposure. Metal concentrations were measured in livers and digesta taken from mute swans living on the Aberdeen Proving Ground, whose sediment had elevated concentrations of Cu, S, Se, Zn, As, Co, Cr, Hg and Pb. Concentrations of only the first four of these elements were elevated in swan digesta. None of the concentrations detected in the digesta or livers of the swans was considered toxic, although the concentrations of Cu and Se were high compared to concentrations of these elements reported in other waterfowl. Lead was found to be scavenged by Mn and Fe oxides from the water and deposited on the surface of vegetation at a reference site. Under some environmental chemical conditions, this is an important route of exposure to Pb in waterfowl, not previously recognized.

Maryland

Trace elements in olivine fingerprint the source of 2018 magmas and shed light on explosive-effusive eruption cycles at Kīlauea Volcano

Understanding magma genesis and the evolution of intensive parameters (temperature, pressure, composition, degree of melting) in the mantle source of highly active volcanic systems is crucial for interpreting magma supply changes over time and recognizing cyclic behavior to anticipate future volcanic behavior. Major and trace elements in olivine are commonly used to study variations in mantle lithologies and melting conditions (e.g., temperature, pressure, oxygen fugacity) affecting the mantle over time. Here, we track the temporal evolution of primary melts through the most recent cycle of explosive and effusive eruptions at Kīlauea (Hawai‘i), which spans the last ∼500 years. We report major and trace elements in olivine from the last explosive period (∼1500 – early 1820’s Keanakāko‘i Tephra) and the most recent decade of the current effusive period (2018 LERZ, 2015–2018 Pu‘u‘ō‘ō, 2008–2018 lava lake and 2020 eruption in Halema‘uma‘u). Scandium concentrations in olivine allow characterizing changes in mantle source between 1500 and 2018, and suggest that the recent (2015–2018) magma feeding the Pu‘u‘ō‘ō cone did not significantly interact with the magma that erupted in the LERZ in 2018. The evolution of olivine and melt compositions over the past 500 years is not easily reconcilable with variations in mantle potential temperature, pressure of mantle melt pooling and storage, or oxygen fugacity. Instead, Sc, Mn, and Co concentrations and Ni/Mg ratio in high forsterite (Fo >87) olivine advocate for an increase in the proportion of clinopyroxene in the mantle source associated with a slightly higher degree of partial melting from 1500 to 2018. Changes in primitive melt compositions and degrees of mantle melting may well modulate magma supply to the crust and formation-replenishment of steady or ephemeral summit reservoirs, and thereby control transitions between explosive and effusive periods at Kīlauea. Analyzing trace elements in olivine at Kīlauea and elsewhere could therefore provide important clues on subtle changes occurring at the mantle level that might herald changes in volcanic behavior.

Hawaii

The role of nanoparticles in mediating element deposition and transport at hydrothermal vents

Precipitation processes in hydrothermal fluids exert a primary control on the eventual distribution of elements, whether that sink is in the subseafloor, hydrothermal chimneys, near-field metalliferous sediments, or more distal in the ocean basin. Recent studies demonstrating abundant nanoparticles in hydrothermal fluids raise questions as to the importance of these nanoparticles relative to macro minerals, as well as the fate of such particles in hydrothermal systems. Here we evaluate the particle geochemistry of black smoker fluids from Niua South vent field, including nanoparticles and macro minerals, in order to consider how the processes of mineral precipitation affect mineral size and morphology, and how this mineral precipitation may dictate element sinks as hydrothermal fluids begin to mix with seawater. We find that the Niua vent fluids are dominated by sulfide and sulfate minerals, with the mineralogy of major and minor minerals changing with temperature, degree of mixing with seawater and rate of precipitation. The majority of particles are submicron in size, and sulfide minerals become larger and exhibit more crystalline morphology with increasing seawater content in the fluids. Minor minerals include gold and bismuth tellurides, and nanoparticulate chalcopyrite and nano-zinc sulfide occur. These findings are consistent with major mineral classes and precipitation processes observed in other systems, while providing further insight into the details of mineral precipitation at Niua including the separate and combined influences of boiling, mixing and cooling during hydrothermal fluid transport and initial interactions with seawater. This work demonstrates that boiling and rapid mixing encourages the formation of nanoparticles, whereas conductive cooling encourages particle growth. Further, these data demonstrate that the possible influence of nanoparticles in hydrothermal systems are not restricted to enhancing element transport, but may also include restricting mineral growth and affecting physicochemical properties of hydrothermal chimneys

Geochimica et Cosmochimica Acta

The distribution of selected elements and minerals in soil of the conterminous United States

In 2007, the U.S. Geological Survey initiated a low-density (1 site per 1600 km 2 , 4857 sites) geochemical and mineralogical survey of soil of the conterminous United States as part of the North American Soil Geochemical Landscapes Project. Three soil samples were collected, if possible, from each site; (1) a sample from a depth of 0 to 5 cm, (2) a composite of the soil A-horizon, and (3) a deeper sample from the soil C-horizon or, if the top of the C-horizon was at a depth greater than 100 cm, from a depth of approximately 80–100 cm. The < 2 mm fraction of each sample was analysed for a suite of 45 major and trace elements following near-total multi-acid digestion. The major mineralogical components in samples from the soil A- and C-horizons were determined by a quantitative X-ray diffraction method using Rietveld refinement. Sampling ended in 2010 and chemical and mineralogical analyses were completed in May 2013. Maps of the conterminous United States showing predicted element and mineral concentrations were interpolated from actual soil data for each soil sample type by an inverse distance weighted (IDW) technique using ArcGIS software. Regional- and national-scale map patterns for selected elements and minerals apparent in interpolated maps are described here in the context of soil-forming factors and possible human inputs. These patterns can be related to (1) soil parent materials, for example, in the distribution of quartz, (2) climate impacts, for example, in the distribution of feldspar and kaolinite, (3) soil age, for example, in the distribution of carbonate in young glacial deposits, and (4) possible anthropogenic loading of phosphorus (P) and lead (Pb) to surface soil. This new geochemical and mineralogical data set for the conterminous United States represents a major step forward from prior national-scale soil geochemistry data and provides a robust soil data framework for the United States now and into the future.

Journal of Geochemical Exploration

Paragneiss zircon geochronology and trace element geochemistry, North Qaidam HP/UHP terrane, western China

In the southeastern part of the North Qaidam terrane, near Dulan, paragneiss hosts minor peridotite and UHP eclogite. Zircon geochronology and trace element geochemistry of three paragneiss samples (located within a ???3 km transect) indicates that eclogite-facies metamorphism resulted in variable degrees of zircon growth and recrystallization in the three samples. Inherited zircon core age groups at 1.8 and 2.5 Ga suggest that the protoliths of these rocks may have received sediments from the Yangtze or North China cratons. Mineral inclusions, depletion in HREE, and absence of negative Eu anomalies indicate that zircon U-Pb ages of 431 ?? 5 Ma and 426 ?? 4 Ma reflect eclogite-facies zircon growth in two of the samples. Ti-in-zircon thermometry results are tightly grouped at ???660 and ???600 ??C, respectively. Inclusions of metamorphic minerals, scarcity of inherited cores, and lack of isotopic or trace element inheritance demonstrate that significant new metamorphic zircon growth must have occurred. In contrast, zircon in the third sample is dominated by inherited grains, and rims show isotopic and trace element inheritance, suggesting solid-state recrystallization of detrital zircon with only minor new growth. ?? 2009 Elsevier Ltd.

Journal of Asian Earth Sciences

Tracing water and suspended matter in Raritan and Lower New York Bays using dissolved and particulate elemental concentrations

Geochemical tracers were used to examine the mixing of water and particles in Lower New York and Raritan Bays in August 1999 during low-flow conditions. Four brackish water masses (20 &le; S &le; 28) originating in the Raritan and Shrewsbury Rivers, Arthur Kill, and Upper New York Bay were characterized by their dissolved metals concentrations. The mixing lines of dissolved Cu, Ni, and Pb in Lower New York Bay were similar to those in Upper New York Bay, the source of most of the freshwater to the system. Dissolved Cd and Mn seemed to have been removed by particles in several regions of the study. Dissolved Cu, Ni and Pb in the Raritan River fell below the mixing lines of the Lower New York Bay. In contrast, the concentrations of dissolved Co and Mn in the Raritan River were distinctly higher than those in the Lower New York Bay, while dissolved Cu and Ni were elevated in the Arthur Kill. A plot of dissolved Co versus dissolved Ni clearly differentiated among three water masses: (1) Upper and Lower New York Bays and Sandy Hood Bay, (2) the Raritan River, and (3) Arthur Kill&ndash;Raritan Bay&ndash;Shrewsbury River. The concentrations of 22 elements also were measured in the suspended matter of Raritan and Lower New York Bays and brackish water sources. The elemental composition of the suspended matter in surface and bottom waters was correlated with Fe concentrations, which ranged between 50 and 900 &mu;mol g &minus; 1 . Statistical differences among the geographical regions were detected in the relationships of Ti, Ni, Co, As, and U with Fe, with particulate As being an especially strong geochemical indicator of Raritan River particles. The geochemical signatures of Lower New York Bay particles were similar to those of Upper New York Bay. The geochemical signatures of Raritan River particles were distinctly different than those of the Upper New York Bay, but the influence of Raritan River particles appeared to be limited to only inner Raritan Bay. This study illustrates the utility of trace elements for characterization of physical processes in complex estuaries.

Marine Chemistry

Major- and trace-element characterization, expanded distribution, and a new chronology for the latest Pleistocene Glacier Peak tephras in western North America

The Glacier Peak tephra beds are among the most widespread and arguably some of the most important late Pleistocene chronostratigraphic markers in western North America. These beds represent a series of closely-spaced Plinian and sub-Plinian eruptions from Glacier Peak, Washington. The two most widespread beds, Glacier Peak 'G' and 'B', are reliably distinguished by their glass major and trace element abundances. These beds are also more broadly distributed than previously considered, covering at least 550,000 and 260,000??km2, respectively. A third bed, the Irvine bed, known only from southern Alberta, is similar in its major-element composition to the Glacier Peak G bed, but it shows considerable differences in trace element concentrations. The Irvine bed is likely considerably older than the G and B tephras and probably records an additional Plinian eruption, perhaps also from Glacier Peak but from a different magma than G through B. A review of the published radiocarbon ages, new ages in this study, and consideration in a Bayesian framework suggest that the widespread G and B beds are several hundred years older than widely assumed. Our revised age is about 11,600??14C yr BP or a calibrated age (at 2 sigma) of 13,710-13,410??cal yr BP. ?? 2008 University of Washington.

Quaternary Research

Toxicity of selenium and other elements in food organisms to razorback sucker larvae

Elevated selenium concentrations documented in water, sediment, and biota in irrigation drain water studies by U.S. Department of the Interior agencies and academia have raised concerns that selenium may be adversely affecting endangered fish in the upper Colorado River basin. The objective of the study was to determine the effects on endangered razorback sucker ( Xyrauchen texanus ) larvae from exposure to selenium and other trace elements in water and zooplankton collected from sites adjacent to the Colorado River near Grand Junction, CO. A 30-day study was initiated with 5-day-old larvae exposed in a 4×4 factor experiment with four food and four water treatments, and the biological endpoints measured were survival, growth, development, and whole-body residues of selenium. Mean selenium concentration in reference water (24-Road) was <0.7 μg/l, in reference food (brine shrimp) was 3.2 μg/g, at Horsethief was 1.6 μg/l in water and 6.0 μg/g in zooplankton, at Adobe Creek was 3.4 μg/l in water and 32 μg/g in zooplankton, and at Walter Walker was 13 μg/l in water and 52 μg/g in zooplankton. Although there were differences in concentrations of inorganic elements in water and biota among the three sites, selenium was apparently the only element elevated to concentrations of concern. Effects on survival were more prominent from dietary exposure compared to waterborne exposure. Selenium concentrations of ≥4.6 μg/g in food organisms adversely affected the survival of razorback sucker larvae. The onset of mortality in larvae exposed to food and water from Walter Walker seemed delayed compared to mortality in larvae exposed to food and water from Horsethief, which has been observed in two other studies. Elevated arsenic in one food source seemed to interact with selenium to reduce the toxic effects of selenium.

Colorado

Rates of As and trace-element mobilization caused by Fe reduction in mixed BTEX–ethanol experimental plumes

Biodegradation of organic matter, including petroleum-based fuels and biofuels, can create undesired secondary water-quality effects. Trace elements, especially arsenic (As), have strong adsorption affinities for Fe(III) (oxyhydr)-oxides and can be released to groundwater during Fe-reducing biodegradation. We investigated the mobilization of naturally occurring As, cobalt (Co), chromium (Cr), and nickel (Ni) from wetland sediments caused by the introduction of benzene, toluene, ethylbenzene, and xylenes (BTEX) and ethanol mixtures under iron- and nitrate-reducing conditions, using in situ push–pull tests. When BTEX alone was added, results showed simultaneous onset and similar rates of Fe reduction and As mobilization. In the presence of ethanol, the maximum rates of As release and Fe reduction were higher, the time to onset of reaction was decreased, and the rates occurred in multiple stages that reflected additional processes. The concentration of As increased from <1 μg/L to a maximum of 99 μg/L, exceeding the 10 μg/L limit for drinking water. Mobilization of Co, Cr, and Ni was observed in association with ethanol biodegradation but not with BTEX. These results demonstrate the potential for trace-element contamination of drinking water during biodegradation and highlight the importance of monitoring trace elements at natural and enhanced attenuation sites.

Environmental Science & Technology

Variations in suspended sediment and associated trace element concentrations in selected riverine cross sections

Detailed sampling and subsequent analyses of riverine suspended sediment obtained from six rivers in the United States indicate substantial differences in suspended sediment concentrations and possibly in some associated trace elements, depending on whether depth- and width-integrated, point, or pumping samples are used. In addition, the data from time-series, depth-integrated sampling indicate that there can be substantial short-term (on the order of 20-30 min) spatial and/or temporal variations in suspended-sediment concentrations. Despite this, major element concentrations are remarkably stable both spatially and temporally. Trace element concentrations are generally stable; however, some spatial and temporal variations may occur.

Environmental Science and Technology

Comparison of streambed sediment and aquatic biota as media for characterizing trace elements and organochlorine compounds in the Willamette Basin, Oregon

During 1992-93, 27 organochlorine compounds (pesticides plus total PCB) and 17 trace elements were analyzed in bed sediment and aquatic biota from 20 stream sites in the Willamette Basin as part of the U.S. Geological Survey's National Water-Quality Assessment Program. Data from each medium were compared to evaluate their relative effectiveness for assessing occurrence (broadly defined as documentation of important concentrations) of these constituents. Except for Cd, Hg, Se, and Ag, trace element concentrations generally were higher in bed sediment than in biota. Conversely, although frequencies of detection for organochlorine compounds in biota were only slightly greater than in bed sediment, actual concentrations in biota (normalized to lipid) were as much as 19 times those in sediment (normalized to organic carbon). Sculpin (Cottus spp.) and Asiatic clams (Corbicula fluminea), found at 14 and 7 sites, respectively, were the most widespread taxa collected during the study. Concentrations of trace elements, particularly As and Cu, were typically greater in Asiatic clams than in sculpin. In contrast, almost half of the organochlorine compounds analyzed were found in sculpin, but only DDT and its degradation products were detected in Asiatic clams; this may be related to the lipid content of sculpin, which was about three times higher than for clams. Thus, the medium of choice for assessing occurrence depends largely on the constituent(s) of interest.

Environmental Monitoring and Assessment

Metals, trace elements, and organochlorine compounds in bottom sediment of Tuttle Creek Lake, Kansas, U.S.A.

Bottom-sediment cores were used to investigate the occurrence of 44 metals and trace elements, and 15 organochlorine compounds in Tuttle Creek Lake, a reservoir with an agricultural basin in northeast Kansas, U.S.A. On the basis of U.S. Environmental Protection Agency sediment-quality guidelines, concentrations of Ag, As, Cr, Cu, Ni, and Zn frequently or typically exceeded the threshold-effects levels for toxic biological effects. Organochlorine compounds either were not detected or were detected at concentrations generally below the threshold-effects levels. Statistically significant positive depositional trends were determined for several elements. However, because the vertical profiles of element concentrations typically indicated a bimodal distribution and much of the variability could be attributable to analytical variance, the statistical trends may not represent actual trends. DDE concentrations reflected the history of DDT use. Substantial increases in grain corn and soybean production, irrigated land, and hog production in the basin have not had a discernible effect on sediment quality in the reservoir. Future research focused on small impoundments throughout the basin may enhance understanding of the effects of human activity on sediment quality within the Tuttle Creek Lake system and elsewhere.

Conference Paper

Evidence of mineral alteration in a salt marsh subterranean estuary: Implications for carbon and trace element cycling

Subterranean estuaries (STE) in salt marshes are biogeochemically active zones where interactions between terrestrial groundwater and seawater drive complex cycling of carbon and trace elements, influenced by mineral dissolution. These systems, characterized by fine-grained organic-rich peat overlying permeable coastal aquifers, play a crucial role as a blue carbon sink, yet their geochemical dynamics remain poorly understood. We investigated dissolved trace elements, carbon, silica, and radium isotopes in a salt marsh STE (Sage Lot Pond, Waquoit Bay, MA) over seasonal and annual cycles. Our results reveal that groundwater and estuarine water circulation through marsh peat and aquifer sediments leads to enrichments of dissolved organic and inorganic carbon (DOC and DIC), Si, Ba, and Mn, with variable source/sink behavior of Fe and net removal of U. Submarine groundwater discharge dominated Ba fluxes, whereas pore water drainage from marsh peat acted as the main sink for U and source of Si. Fe cycling was variable, with terrestrial Fe largely removed as groundwater passed through the STE, consistent with Fe-sulfide and amorphous phase formation. Radium isotope ratios identified two distinct subsurface flow pathways, influenced by metal-oxide cycling and organic matter breakdown. Si production was decoupled from DIC, suggesting Si originates from mineral alteration, whereas DIC results from both mineral weathering and microbial respiration. Silicate mineral alteration, coupled with marsh pore water drainage, accounts for up to 16% of annual DIC exports (66 g C m −2 y −1 ), highlighting the importance of STEs in coastal carbon and trace element cycling, especially as marshes face environmental change.

Massachusetts

Transport and accumulation of radionuclides and stable elements in a Missouri River Reservoir

Several long sediment cores from the Cheyenne River Embayment of Lake Oahe, a 250-km-long Missouri River reservoir in South Dakota, have been analyzed for radionuclides and stable elements. The combination of fine-scale sampling and rapid sedimentation produces radionuclide distributions that can be used to estimate the detailed chronology of particle transport processes in the Oahe reservoir system. A self-consistent and quantitative treatment of the 137 Cs data suggests processes to which characteristic times may be associated. Times that characterize system-wide processes include (1) an integration time of several years reflecting retention of the sediment-bound tracer in regions within or external to the reservoir, (2) a relaxation time of approximately 15 years reflecting a decreasing rate of sediment accumulation ascribed to shoreline stabilization, (3) a time of a few months characterizing the breadth of riverine signatures in cores due to integration effects in the Cheyenne River system and deltaic deposits, and (4) times of a few years associated with propagation of riverine load signatures along the embayment. The distribution of total sedimentary arsenic confirms the validity of the variable sedimentation model. In 1977, a tailings retention facility was built at the Homestake Mine site, and the unrestricted input of As ceased. As a result of this remedial action, the concentration of sedimentary As decreased dramatically. In the upper section of the core, above the depth represented by the year 1976, the concentration of As decreases tenfold. In this same core the distribution of lithologically discriminating chemical elements, calcium and vanadium, relate to major flow events in the Cheyenne River basin. Because there is minimal diagenesis of chemical constituents in these rapidly accumulating sediments, stable element signatures, in addition to radiotracers, may be used to reconstruct hydrologic events in drainage basins that contribute sediment to lakes and reservoirs.

South Dakota