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Constraining the onset of carboniferous cyclicity in the Arkoma Basin of the Midcontinent, North America: Implications for calibrating a globally significant latest Bashkirian transgression

Cyclothems are defined by the repeat juxtaposition of littoral and open marine successions over short stratigraphic distances (meters to 10's of meters) and are interpreted to be driven by glacioeustatic forcing of sea level during the late Paleozoic Ice Age. The concept of cyclothems was defined in the Midcontinent region of the United States. However, correlating the Midcontinent region to other cyclic successions is difficult, which is the result of no geochronologic control for the Midcontinent biostratigraphic framework. We present the first high-resolution U Pb zircon CA-ID-TIMS and feldspar 40 Ar/ 39 Ar age control for the onset of Midcontinent cyclothem deposition in the Arkoma Basin, Arkansas USA. Geochronologic control is obtained from a volcaniclastic unit preserved in the newly recovered Dare Creek #1 core. We integrate these data with biostratigraphic, lithostratigraphic and trace element analyses to investigate the timing, stratigraphic and geochemical response to late Paleozoic climate forcing. The lowermost Atoka Formation is associated with the onset of five high frequency transgressive-regressive cycles, which are defined by nearshore sandstones juxtaposed on top of offshore marine mudstones and are associated with changes in salinity and redox conditions. The Trace Creek Member of the lower Atoka Formation hosts a thick, organic-rich black shale, which defines the last and maximum transgression of the lower Atoka Formation in the Arkoma Basin, in the latest Bashkirian. Base-level records from time equivalent stratigraphic successions from Arrow Canyon, Nevada, U.S.A. and the Donets Basin, Ukraine also record a maximum transgression in the latest Bashkirian. The synchroneity of maximum flooding events from multiple basins which span the low latitudes in the latest Bashkirian support that cyclothem deposition was controlled by allostratigraphic forcing mechanisms, likely glacioeustatic forcing resulting from dynamic glaciation in high-latitude Gondwana.

Arkansas, Oklahoma↗

The relation of stream sediment surface area, grain size and composition to trace element chemistry

Intensive studies of 17 geographically and hydrologically diverse stream bed sediments provide information on the relation between grain size, surface area, and operationally defined geochemical phases (e.g. Mn oxides, amorphous Fe oxides) to trace element concentrations. Of the size fractions investigated (<2, <16, <63and<125 μm), the strongest correlation with trace elements occurs with the percent <63 μm or<125 μm fractions. As the proportion of these size fractions increases in the samples, so do the trace element concentrations. When surface area (as defined by nitrogen adsorption and the BET equations) increases, trace element levels also increase. Correlations between bulk sediment chemistry and surface area are as strong as those between sediment chemistry and the proportion of the <63or<125 μm fractions. Surface area appears to serve as a proxy for grain size. The strongest correlations between grain size and surface area are the same as for trace elements and grain size (with the <63or<125 μm fractions). Surface area also is affected by geochemical phase, as are the trace elements associated with sediments. Of the phases considered (carbonates, Mn oxides, reactive Fe, amorphous Fe, organic matter), amorphous Fe oxides appear to exert the greatest control over both surface area and trace element levels. The concentrations of various geochemical phases affect surface area, grain size, and trace element chemistry. However, the effect of phase is grain-size dependent. For material with mean grain sizes in the fine sand range and coarser (> 125 μm), each of the various phases contribute to overall sample surface area. For material having mean grain sizes in the very fine sand range and finer (<125 μm), the same phases act as surface-area inhibitors by cementing fine grains together to form aggregates. This increases the mean grain size of the sample and reduces the surface area. The presence of these aggregates may explain why the <63 μm or<125 μm size fractions are more important to sediment-trace element levels and surface area than other finer fractions.

Applied Geochemistry↗

Present investigations of radioactive raw materials by the Geological Survey and a recommended program for future work

The Geological Survey's program of investigation of radioactive raw materials is presented herewith under present investigations, plans for future investigations, plan of operation, and cost of operation. This report was prepared at the request of the Atomic Energy Commission. Present investigations are summarized to show the scope of the present Trace Elements program, grouping individual projects into related types of investigations. Plans for future investigations on an expanded scale are outlined. These should provide sufficient data and knowledge of the occurrence and availability of uranium, thorium, and related elements, to permit a more complete evaluation of domestic resources. Reconnaissance projects are designed to discover possible new sources of uranium and thorium and to select areas and materials warranting further investigation. Typical projects leading to the estimation of reserves are the investigation of the carnotite ores of the Colorado Plateau by geologic mapping, exploratory drilling, and related research, and investigation of asphaltic sandstone in Emery County, Utah. Extensive research will be undertaken to establish the principles governing the geological and geochemical relations of uranium, thorium, and associated elements as an essential guide in appraising domestic resources. Particular emphasis will be placed on phosphatic rocks and black shales which offer ultimate resources of uranium far greater than carnotite ores. All the foregoing investigations will be accompanied by chemical, gephysical, and mineralogical research and analytical work. Under plan of operation is discussed the organization of the Trace Elements Unit, space requirements for laboratory and office, the scheduling of investigations, and other related problems. The proposed scheduling of work calls for approximately 109, 173, and 203 man years in fiscal years 1948, 1949, and 1950 respectively. Definite plans have been formulated only for the next three fiscal years, by which time it is assumed the program will reach stable proportions or can be altered as experience dictates. Under cost of operation is set forth the funds available in fiscal year 1947, the status of funds transferred from Atomic Services (14-217/80920), and funds necessary in succeeding fiscal years. The estimate for fiscal year 1948 inclues a non-recurring item of $1,025,000 for establishing adequate laboratories for chemical, physical, spectrographic and mineralogic research and analytical work. The total funds required in fiscal years 1948, 1949, and 1950 to support the proposed program will be $2,440,000, $2,161,000 and $2,198,000 respectively. The Geological survey anticipates contributing from its appropriation in fiscal years 1948, 1949 and 1950 approximately $243,000, $350,000, and $400,000 respectively; the balance of the necessary funds to be contributed by the Atomic Energy Commission in fiscal years 1948, 1949, and 1950 will be approximately $2,196,900, $1,811,000, and $1,798,000 respectively.

Trace Elements Investigations↗

Bathymetric map of Coeur D'Alene Lake, Idaho

The U.S. Geological Survey investigated nutrient and trace-element enrichment in Coeur d'Alene Lake, northern Idaho, during 1991-92. The objectives of the investigation were to characterize limnology, quantify hydrologic and nutrient budgets, and develop a nutrient-load/lake-response model. The model required bathymetric data to compute mass balances of water and nutrients within many depth layers in the lake. A review of historical bathymetric data for the lake (Funk and others, 1973; U.S. Environmental Protection Agency, 1977; Milligan and others, 1983) revealed a need for contoured bathymetric data. Therefore, to augment past studies, the U.S. Geological Survey collected extensive bathymetric data and developed a bathymetric map of Coeur d'Alene Lake.

Idaho↗

Hypolimnetic concentrations of dissolved oxygen, nutrients, and trace elements in Coeur d'Alene Lake, Idaho

A reconnaissance study of Coeur d'Alene Lake, Idaho done from May through November 1987 assessed water quality throughout the lake. Particular emphasis was on hypolimnetic concentrations of dissolved oxygen, nutrients, and trace elements. Study results enabled refinement of the sampling protocol in a U.S. Geological Survey research proposal for a large-scale investigation of nutrient enrichment and trace element contamination problems affecting the 129.5 sq kilometer lake in northern Idaho. Hypolimnetic dissolved-oxygen concentrations as low as 4.1 mg/L in November and the frequent occurrence of supersaturated dissolved-oxygen concentrations during June through August indicated nutrient enrichment. Secchi-disc depths in the lake 's central and southern areas were typical of mesotrophic conditions, whereas oligotrophic conditions prevailed in the northern area. Throughout the study, hypolimnetic concentrations of total recoverable zinc exceeded chronic and acute toxicity criteria for freshwater aquatic life. (USGS)

Water-Resources Investigations Report↗

Stanford-USGS shrimp-RG ion microprobe: A new approach to determining the distribution of trace elements in coal

The distribution of Cr and other trace metals of environmental interest in a range of widely used U.S. coals was investigated using the Stanford-USGS SHRIMP-RG ion microprobe . Using the oxygen ion source, concentrations of Cr (11 to 176 ppm), V (23 to 248 ppm), Mn (2 to 149 ppm), Ni (2 to 30 ppm), and 13 other elements were determined in illite/smectite, a group of clay minerals commonly present in coal. The results confirm previous indirect or semi-quantitative determinations indicating illite/smectite to be an important host of these metals. Calibration was achieved using doped aluminosilicate-glass synthetic standards and glasses prepared from USGS rock standards. Grains for analysis were identified optically, and confirmed by 1) precursory electron microprobe analysis and wavelength-dispersive compositional mapping, and 2) SHRIMP-RG major element data obtained concurrently with trace element results. Follow-up investigations will focus on the distribution of As and other elements that are more effectively ionized with the cesium primary beam currently being tested.

ACS Division of Fuel Chemistry, Preprints↗

List of current and planned projects of the trace elements program, U.S. Geological Survey

This summary lists the Geological Survey's current and future investigations of uranium and other elements of related interest. The titles of the investigations are grouped under the headings listed in the table of contents. Entries in each category are listed alphabetically, according to author or project leader, and numbered consecutively.

Trace Elements Investigations↗

Volcanogenic Sulfur on Earth and Io: Composition and Spectroscopy

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

Icarus↗

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↗

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 &ge; 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↗

Geochemical conditions and the occurrence of selected trace elements in groundwater basins used for public drinking-water supply, Desert and Basin and Range hydrogeologic provinces, 2006-11: California GAMA Priority Basin Project

The geochemical conditions, occurrence of selected trace elements, and processes controlling the occurrence of selected trace elements in groundwater were investigated in groundwater basins of the Desert and Basin and Range (DBR) hydrogeologic provinces in southeastern California as part of the Priority Basin Project (PBP) of the Groundwater Ambient Monitoring and Assessment (GAMA) Program. The GAMA PBP is designed to provide an assessment of the quality of untreated (raw) groundwater in the aquifer systems that are used for public drinking-water supply. The GAMA PBP is being conducted by the California State Water Resources Control Board in collaboration with the U.S. Geological Survey and the Lawrence Livermore National Laboratory. The DBR hydrogeologic provinces consist of 141 defined groundwater basins separated by mountain ranges, faults, and other features. This report presents analyses of data collected from nine study areas within the DBR hydrogeologic provinces: Antelope Valley, Borrego Valley, the Central Desert area, Coachella Valley, Colorado River, Indian Wells Valley, Low-Use Basins of the Mojave and Sonoran Deserts, the Mojave, and Owens Valley. Collectively, these nine study areas are referred to as the DBR study unit. The study unit covers approximately 7,000 square miles and includes the 63 groundwater basins in the DBR hydrogeologic provinces in which groundwater is used for public drinking-water supply. The vast majority of the 223 wells sampled for this study were long-screened production wells used primarily for public supply. Uncorrected carbon-14 ( 14 C) groundwater ages for samples collected in the DBR study unit ranged from less than (<) 100 to 33,700 years before present (BP). Sixty-six percent of sample ages were greater than (>) 100 years BP, and 40 percent were >3,800 years BP. Samples collected from wells located adjacent to mountain-front recharge areas or major surface-water features generally had younger groundwater ages than did samples collected from wells located away from mountain fronts or towards the distal ends of basin groundwater flow paths. Most groundwater sampled in the DBR study unit had alkaline pH: 89 percent of sample pH values ranged from 7.1 to 9.8, with 37 percent greater than or equal to (&ge;) 7.9. Groundwater age was significantly correlated (positively) with pH, likely because silicate weathering is a primary control on groundwater pH and is a slow process. The oxidation-reduction (redox) condition of the groundwater sampled in the DBR study unit was predominantly oxic (71 percent), except in the Colorado River study area where organic-rich fluvial aquifers provide the electron donors necessary to support iron-reducing (anoxic-Fe) redox processes. The cation type of 78 percent of the samples was either sodium- or mixed-type, and the anion type of 83 percent of the samples was either bicarbonate- or mixed-type. Sodium-type groundwaters generally were older and more alkaline than calcium-type groundwaters, consistent with the change in water chemistry expected from cation exchange between groundwater and aquifer sediments over long periods of time. Because of the correlation with young groundwater, calcium-type groundwater was predominantly from wells located adjacent to mountain-front recharge areas. Arsenic (As), boron (B), fluoride (F), molybdenum (Mo), strontium (Sr), uranium (U), and vanadium (V) were selected for assessment in this study because they occurred at concentrations greater than California Department of Public Health or U.S. Environmental Protection Agency regulatory or non-regulatory drinking-water-quality benchmarks in more than 2 percent of the 223 samples collected in the DBR study unit. As and F were detected most commonly (18 and 13 percent, respectively) at concentrations above associated water-quality benchmarks and Sr and V least frequently (both at 3 percent). Given that 14 C groundwater ages are predominantly >100 years BP, land use in the study unit is primarily undeveloped, and chemicals derived from anthropogenic sources, such as volatile organic compounds, were infrequently detected, high concentrations of these trace elements in groundwater were most likely the result of natural factors and not anthropogenic factors. As, F, Mo, and V concentrations showed significant positive correlations to groundwater age and to pH. This relation is partly due to the sources of trace elements likely being the weathering of primary minerals, such as silicate minerals, which is a slow process that takes place over hundreds to thousands of years. This relation also reflects the positive correlation between groundwater age and pH. Geochemical modeling predicted that the dominant species of As, Mo, and V in solution were oxyanions (HAsO 4 2&ndash; , MoO 4 2&ndash; , and H 2 VO 4&ndash; ), which are likely to be mobile in alkaline groundwater because mineral surfaces composing aquifer matrices have a predominantly negative surface charge under alkaline conditions. F also exists predominantly as a negatively charged ion (F &ndash; ). At pH values >7.5, saturation indices generated by the geochemical modeling program PHREEQC indicated that F solubility may be somewhat limited by the precipitation of the mineral fluorapatite [Ca 5 (PO 4 ) 3 F]. Speciation modeling of As in anoxic-Fe groundwater (iron-reducing conditions) showed that samples were supersaturated with orpiment (As 2 S 3 ), indicating that mineral precipitation may be responsible for low As concentrations observed in reducing groundwater. In contrast, U concentrations showed significant negative correlations to groundwater age and to pH. Higher U concentrations generally occurred in samples for which geochemical modeling indicated that the uncharged ternary complex Ca 2 UO 2 (CO 3 ) 3 was the dominant aqueous U species. This uncharged complex is not attracted to the charged surfaces of minerals and thus increases U solubility. Formation of Ca 2 UO 2 (CO 3 ) 3 was greater in younger groundwaters because calcium and uranium concentrations generally were lower in older groundwaters, likely due to cation-exchange processes and precipitation of the mineral calcite as groundwater pH increased. Co-precipitation of U with the calcite (CaCO 3 ) may remove U from the aqueous phase. Saturation indices indicated that the anoxic-Fe groundwaters from the Colorado River study area were supersaturated with the mineral uraninite (UO 2 ), suggesting that UO 2 precipitation may be responsible for the low concentrations of U observed in these samples. Concentrations of strontium, which exists primarily in a cationic form (Sr 2+ ), were not significantly correlated with either groundwater age or pH. Strontium concentrations showed a strong positive correlation with total dissolved solids (TDS). Dissolved constituents, such as Sr, that interact with mineral surfaces through outer-sphere complexation become increasingly soluble with increasing TDS concentrations of groundwater. Boron concentrations also showed a significant positive correlation with TDS, indicating the B may interact to a large degree with mineral surfaces through outer-sphere complexation.

California↗

The role of shoreland development and commercial cranberry farming in a lake in Wisconsin, USA

Musky Bay in Lac Courte Oreilles, Wisconsin, USA, is currently eutrophic. This large, shallow bay of an oligotrophic lake possesses the densest aquatic plant growth and a floating algal mat. Paleoecological reconstructions encompassing the last 130 years, were based on multiproxy analyses of sediment cores from three coring sites, two within the bay and one in the lake itself. These data were compared to historical records of the construction and expansion of two commercial cranberry bogs and shoreline residential homes to identify temporal and causal relations of eutrophication. The proxies investigated included: minor and trace elements; biogenic silica; and the diatom community. Post-depositional diagenesis of organic carbon, nitrogen, and phosphorus in the upper 30 cm of the core obscured records of historical ambient nutrient concentrations in the bay obviating their usefulness for this purpose. In contrast, calcium, magnesium, and potassium concentration profiles appeared to reflect runoff of soil amendments applied to the cranberry bogs and aerial fertilizer spraying over the eastern bog adjacent to Musky Bay. The increase in aluminum content since about 1930 coincided with the historical trend in shoreland development and construction of the original commercial cranberry farm. The biogenic silica profile recorded a steady increase of nutrients to Musky Bay over the last several decades. Stratigraphic changes in the diatom community indicated that nutrient input began to increase in the 1940s and accelerated in the mid-1990s with the onset of a noxious floating algal mat. The diatom community indicates the bay has possessed a significant macrophyte community for at least the last 200 years, but increased nutrient input was manifested by a change in the composition, and an increase in the density of the epiphytic diatom community. Cranberry farming appeared to be the major source of nutrients because the diatom community changes occurred prior to the significant increase in residential housing.

Journal of Paleolimnology↗

Trace elements and semi-volatile organic compounds in bed sediments from streams and impoundments at Fort Gordon, Georgia

In May 1998, the U.S. Geological Survey, in cooperation with the Environmental and Natural Resources Management Office of the U.S. Army Signal Center and Fort Gordon, investigated the presence and disbursal of trace elements and semi-volatile organic compounds in bed sediments from selected streams and impoundments at the Fort Gordon military installation near Augusta, Georgia. Concentrations of 18 trace elements and total organic carbon, and 66 semi-volatile compounds were determined from analysis of the fine-grained fraction of bed-sediment samples from 29 surface-water deposition locations. Analysis of the bed-sediment data indicates that commercial and industrial land-use areas generally are associated with the highest concentrations of trace elements and semi-volatile organic compounds, and the greatest occurrence and distribution of trace elements and semi-volatile organic compounds in bed sediments at Fort Gordon. Bed sediment collected at sites having drainage areas less than 1.0 square mile and greater than 45 percent commercial and industrial land uses, have the most occurrences and the highest concentrations of trace elements and semi-volatile organic compounds. Sampling sites having less than 2 percent commercial and industrial land uses had the lowest concentrations, regardless of drainage basin size. Relative rankings and evaluation of individual trace element and semi-volatile organic compound concentration data identified two sites that have substantially higher sediment-quality scores than the other sites. This suggests that these sites have the greatest potential risk for adverse effects on aquatic life. The effects of these elevated trace element and semi-volatile organic compound concentrations on aquatic life in these basins may merit further investigation.

Georgia↗

A reactive transport approach to modeling cave seepage water chemistry II: Elemental signatures

Karst systems are useful for examining spatial and temporal variability in Critical Zone processes because they provide a window into the subsurface where waters have interacted with vegetation, soils, regolith, and bedrock across a range of length and timescales. These hydrologic pathways frequently include the precipitation of speleothems, which provide long-term archives of climate and environmental change. Trace element ratios in speleothems (Mg/Ca, Sr/Ca, Ba/Ca) have the potential to provide information about past changes in rainfall and infiltration, but controls on them can be complex and their interpretation must be based on an understanding of the modern cave system. Here we integrate observations of surface conditions, bedrock, soil, and drip water chemistry of Blue Spring Cave in Tennessee, USA with the reactive transport model CrunchTope, which we have calibrated for karst systems to investigate the primary controls on trace element variations in cave seepage waters. We find that measured drip water Mg/Ca and Sr/Ca are captured within the model through variable amounts of limestone dissolution followed by precipitation of secondary calcite that happens within the cave rather than the host limestone. However, strong spatial controls on drip water Mg/Ca and Sr/Ca likely reflect seepage water interactions with variable amounts of diagenetic phases in the host rock. In contrast, Ba/Ca values are consistent across the cave and vary with effective rainfall, suggesting that this parameter may be the most consistent metric for limestone dissolution and prior calcite precipitation and can act as a proxy for rainfall and infiltration in this cave system. Our findings emphasize the importance of evaluating spatial heterogeneity in cave drip waters and outline a novel modeling approach for determining the dominant controls on drip water chemistry in support of the interpretations of paleoclimate records.

Geochimica et Cosmochimica Acta↗

Distribution of mining-related trace elements in streambed and flood-plain sediment along the middle Big River and tributaries in the Southeast Missouri Barite District, 2012–15

Lead mining first began in the Big River watershed during the 1700s. Lead was the primary metal mined throughout most of the 1700s and early 1800s and it continued to be mined until the mid-1900s. Barite mining began in the middle part of the watershed in the mid- to late 1800s. Although considerable attention has been given to concentrations of miningrelated trace elements (mostly cadmium, lead, and zinc) in the Big River and its tributaries draining the Old Lead Belt, there is less information regarding concentrations of mining-related trace elements in tributaries draining the Barite District in southeast Missouri, which is downstream from the Old Lead Belt, and the contribution of sediment transported from this district to trace elements in lower reaches of the Big River. The purpose of this report is to present results of an investigation of the distribution of mining-related trace elements in sediments in the middle reach of the Big River downstream from the Old Lead Belt and the Big River tributaries that drain a large part of the Barite District. In general, concentrations of cadmium and lead in streambed sediment were largest in samples from the Big River and smallest in Barite District tributary samples. Concentrations of zinc were somewhat similar in the Big River and Barite District tributaries; however, higher concentrations were present in upstream Big River site samples, as well as in samples from one site on Maddin Creek and at another site on Old Mines Creek that drains the Barite District. Barium concentrations were considerably larger in samples from Barite District tributaries compared to samples collected on the Big River. Samples collected downstream from the Barite District on the Big River had considerably larger barium concentrations than samples collected upstream from the Barite District. Flood-plain core samples were collected from 26 cores at 5 transect locations along tributaries in the Barite District. Of the individual 693 bulk (unsieved) samples from these cores analyzed by x-ray fluorescence, the probable effects concentration (PEC) values were exceeded for cadmium (PEC of 4.98 milligrams per kilogram [mg/kg], 218 samples), lead (PEC of 128 mg/kg, 91 samples), nickel (PEC of 48.6 mg/kg, 45 samples), and zinc (PEC of 459 mg/kg, 77 samples). Of the 693 samples, 21 exceeded the U.S. Environmental Protection Agency residential yard cleanup level of 400 mg/kg for lead; 19 of these were samples from a single transect near the mouth of Mineral Fork Creek where its flood plain joins the Big River flood plain. Shortly after the December 2015 flood on the Big River (the third largest flood along the river since the 1950s), 23 samples of fine sediment deposited from the flood were collected from the Big River flood plain upstream and downstream from the Barite District and several tributaries. Overall, the general pattern of barium, lead, and zinc concentrations in the 2015 flood sediment samples was similar to that observed in the streambed-sediment samples. Overall concentrations of barium were larger at Big River sites downstream from the Barite District, and cadmium, lead, and zinc concentrations were generally similar or smaller at sites downstream from the Barite District when compared to sites upstream from the Barite District. These data indicate a substantial influx of barium from the Barite District into the Big River but only a minimal influx of cadmium, lead, and zinc.

Missouri↗

Toxicity of trace element and salinity mixtures to striped bass ( Morone saxatilis ) and Daphnia magna

Acute toxicity tests with reconstituted water were conducted to investigate the relationship between water hardness, salinity, and a mixture of trace elements found in irrigation drain waters entering Stillwater Wildlife Management Area (SWMA), near Fallon, Nevada. The SWMA has been the site of many fish kills in recent years, and previous toxicity studies indicated that one drain water, Pintail Bay, was acutely toxic to organisms acclimated or cultured in fresh water or salt water. This toxicity could reflect both the ionic composition of this saline water and the presence of trace elements. The lowest water salinity tested with Daphnia magna was near the upper salinity tolerance of these organisms; therefore, we were unable to differentiate between the toxic effects of ion composition and those of trace elements. In toxicity tests conducted with striped bass ( Morone saxatilis ), we found that the extent to which salinity was lethal to striped bass depended on the ion composition of that salinity. Survival of striped bass increased as hardness increased. In addition, a trace element mixture was toxic to striped bass, even though the concentrations of individual elements were below expected acutely lethal concentrations. Although salinity is an important water quality characteristic, the ionic composition of the water must be considered when one assesses the hazard of irrigation drain waters to aquatic organisms.

Nevada↗

Water-quality data for selected stations in the East Everglades, Florida

The results of water-quality samples collected from April 1978 through April 1980 from three canal stations, four marsh stations, and two ground-water stations within the East Everglades, Dade County, Florida, are tabulated in 37 tables. The major categories of parameters analyzed are field measurements, physical characteristics, macronutrients (carbon, nitrogen, and phosphorus), major ions, trace elements, and algae. Chemical data for bulk-precipitation stations within and adjacent to the East Everglades are also given. The parameters analyzed include macronutrients, major ions, and trace elements. The period of record for these stations is October 1977 through April 1980. Bottom material at the canal and marsh stations was collected twice during the investigation. These data include analyses for macronutrients, trace elements, and chlorinated-hydrocarbon insecticides.

Florida↗

A Synopsis of Technical Issues of Concern for Monitoring Trace Elements in Highway and Urban Runoff

Trace elements, which are regulated for aquatic life protection, are a primary concern in highway- and urban-runoff studies because stormwater runoff may transport these constituents from the land surface to receiving waters. Many of these trace elements are essential for biological activity and become detrimental only when geologic or anthropogenic sources exceed concentrations beyond ranges typical of the natural environment. The Federal Highway Administration and State Transportation Agencies are concerned about the potential effects of highway runoff on the watershed scale and for the management and protection of watersheds. Transportation agencies need information that is documented as valid, current, and scientifically defensible to support planning and management decisions. There are many technical issues of concern for monitoring trace elements; therefore, trace-element data commonly are considered suspect, and the responsibility to provide data-quality information to support the validity of reported results rests with the data-collection agency. Paved surfaces are fundamentally different physically, hydraulically, and chemically from the natural surfaces typical of most freshwater systems that have been the focus of many traceelement- monitoring studies. Existing scientific conceptions of the behavior of trace elements in the environment are based largely upon research on natural systems, rather than on systems typical of pavement runoff. Additionally, the logistics of stormwater sampling are difficult because of the great uncertainty in the occurrence and magnitude of storm events. Therefore, trace-element monitoring programs may be enhanced if monitoring and sampling programs are automated. Automation would standardize the process and provide a continuous record of the variations in flow and water-quality characteristics. Great care is required to collect and process samples in a manner that will minimize potential contamination or attenuation of trace elements and other sources of bias and variability in the sampling process. Trace elements have both natural and anthropogenic sources that may affect the sampling process, including the sample-collection and handling materials used in many trace-element monitoring studies. Trace elements also react with these materials within the timescales typical for collection, processing and analysis of runoff samples. To study the characteristics and potential effects of trace elements in highway and urban runoff, investigators typically sample one or more operationally defined matrixes including: whole water, dissolved (filtered water), suspended sediment, bottom sediment, biological tissue, and contaminant sources. The sampling and analysis of each of these sample matrixes can provide specific information about the occurrence and distribution of trace elements in runoff and receiving waters. There are, however, technical concerns specific to each matrix that must be understood and addressed through use of proper collection and processing protocols. Valid protocols are designed to minimize inherent problems and to maximize the accuracy, precision, comparability, and representativeness of data collected. Documentation, including information about monitoring protocols, quality assurance and quality control efforts, and ancillary data also is necessary to establish data quality. This documentation is especially important for evaluation of historical traceelement monitoring data, because trace-element monitoring protocols and analysis methods have been constantly changing over the past 30 years.

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