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At least 91 records · Page 5Linked to original sources

Quantification of colloidal and aqueous element transfer in soils: The dual-phase mass balance model

Mass balance models have become standard tools for characterizing element gains and losses and volumetric change during weathering and soil development. However, they rely on the assumption of complete immobility for an index element such as Ti or Zr. Here we describe a dual-phase mass balance model that eliminates the need for an assumption of immobility and in the process quantifies the contribution of aqueous versus colloidal element transfer. In the model, the high field strength elements Ti and Zr are assumed to be mobile only as suspended solids (colloids) and can therefore be used to distinguish elemental redistribution via colloids from redistribution via dissolved aqueous solutes. Calculations are based upon element concentrations in soil, parent material, and colloids dispersed from soil in the laboratory. We illustrate the utility of this model using a catena in South Africa. Traditional mass balance models systematically distort elemental gains and losses and changes in soil volume in this catena due to significant redistribution of Zr-bearing colloids. Applying the dual-phase model accounts for this colloidal redistribution and we find that the process accounts for a substantial portion of the major element (e.g., Al, Fe and Si) loss from eluvial soil. In addition, we find that in illuvial soils along this catena, gains of colloidal material significantly offset aqueous elemental loss. In other settings, processes such as accumulation of exogenous dust can mimic the geochemical effects of colloid redistribution and we suggest strategies for distinguishing between the two. The movement of clays and colloidal material is a major process in weathering and pedogenesis; the mass balance model presented here is a tool for quantifying effects of that process over time scales of soil development.

Geochimica et Cosmochimica Acta

Kinetics of elemental sulfur reduction by petroleum hydrocarbons and the implications for hydrocarbon thermal chemical alteration

Although sulfur-containing compounds are known to play a significant role in the diagenic and catagenic processes that generate oil and gas, relatively little is known about the kinetics of reactions between elemental S and petroleum hydrocarbons. To investigate this subject, a series of closed-system pyrolysis experiments using paraffin, a low-sulfur oil, and a high-sulfur oil with and without elemental S were conducted, and first-order chemical kinetics were fit to the experimental results. The average value for the activation energy required to reduce elemental S to H 2 S and to thermochemically alter higher molecular weight hydrocarbons to methane was calculated to be 193 kJ mol -1 (46 kcal mol -1 ). The results of this study demonstrate that under typical geologic conditions the rate of reduction of elemental S to H 2 S by petroleum hydrocarbons is quite rapid. The maximum time for substantial amounts of elemental S to persist in contact with petroleum hydrocarbons is estimated to be no more than a few million years in cool reservoirs (e.g., <80 °C), and in hotter reservoirs (e.g., >120 °C) the half-life of elemental S may be as short as hundreds of years. Additionally, the presence of elemental S substantially lowers the onset temperature of hydrocarbon thermal chemical alteration (TCA). The activation energy for TCA of a low-sulfur oil to generate methane is estimated to be lowered by 92 kJ mol -1 (22 kcal mol -1 ) due to the presence of elemental sulfur. Consequently, the presence of elemental S in petroleum reservoirs is expected to lower the thermal stability of oil and decrease the maximum depth at which oil occurs within a basin (thermal deadline). The observed acceleration of hydrocarbon TCA is possibly due to organic sulfur compounds (e.g., thiols and sulfides) that form through the reaction of H 2 S or polysulfides with hydrocarbons and subsequently thermally degrade leading to the formation of sulfur radicals that in turn enhance TCA reactions.

Geochimica et Cosmochimica Acta

Geothermal elements in lichens of Yellowstone National Park, USA

Geothermal features (e.g. geysers, fumaroles, vents, and springs) emit gaseous mercury, sulfur and heavy metals and therefore, are natural sources of these elements in the atmosphere. Field studies of heavy metals in lichens in Italy have detected elevated concentrations near geothermal power plants, and have determined that the origin of mercury is from soil degassing, not soil particles. We studied this phenomenon in a geothermal area without power plants to determine the natural levels of mercury and other elements. Two common and abundant species of epiphytic lichens, Bryoria fremontii and Letharia vulpina , were collected at six localities in Yellowstone National Park, USA in 1998 and analyzed for 22 chemical elements. Thirteen elements differed significantly between species. Some elements were significantly higher in the southern part of the park, while others were higher in the north. Levels of most elements were comparable with those in other national parks and wilderness areas in the region, except Hg, which was unusually high. The most likely sources of this element are the geothermal features, which are known emitters of Hg. Multivariate analyses revealed strong positive associations of Hg with S, and negative associations with soil elements, providing strong evidence that the Hg in the lichens is the result of soil degassing of elemental Hg rather than particulate Hg directly from soils. Average Hg levels in the lichens were 140 p.p.b. in Bryoria and 110 p.p.b. in Letharia , but maxima were 291 and 243 p.p.b., respectively. In spite of this, both species were healthy and abundant throughout the park.

Idaho, Montana, Wyoming

Trace element geochemistry of altered volcanic ash layers (tonsteins) in late Permian coal-bearing formations of eastern Yunnan and western Guizhou Provinces, China

Trace element compositions were determined (by instrumental neutron activation analysis; INAA) in 30 samples of synsedimentary volcanic ash-derived tonsteins and detrital claystones from coal seams within the late Permian coal-bearing formation of eastern Yunnan and western Guizhou Provinces, China. The characteristics of trace-element geochemistry in the tonsteins can be distinguished from those of detrital claystones because of the former's unique volcanic-ash origin. The detrital claystones are characterized by their relatively high content of V, Ti, Sc, Cr, Co and Ni, relatively low content of Th and U, Th/U ratio, and small negative Eu anomaly (Eu/Eu* 0.63-0.93). Overall, these trace element characteristics are consistent with a mafic source similar to the composition of basalt rocks in the erosional region on the western edge of the study area. In contrast, the tonsteins are low in V, Ti, Sc, Cr, Co and Ni contents and have a high Th/U ratio with a distinct negative Eu anomaly (Eu/Eu* normally in the range of 0.2-0.4), consistent with a silicic magmatic source. Within the group of tonsteins, those from the lower section (P2.1) of the coal-bearing formation are relatively high in Ti, Zr, Hf, Nb, Ta and rare earth elements (REE), as compared to those from the middle and upper sections (P2.2+3). In trace-element discrimination diagrams (scatter plots) of Hf-Ta, Ti-Ta, Ti-V, Hf-Sc, Lu-Hf and Lu-Th, tonsteins from the P2.1 horizon always fall in isolated distribution areas, separate from the tonsteins of the P2.2+3 horizon. These results suggest that the source materials of tonsteins from the two separate horizons were probably derived from volcanic ash falls of two distinctly different natures. Based on a comparison of the concentrations and assemblages of trace elements between various magmatic rocks, the source materials of tonsteins from P2.1 horizon were mostly composed of calc-alkalic, silica-poor volcanic ash (similar to rhyodacitic magma), whereas those from P2.+3 were apparently more siliceous and K-rich (rhyolitic magma). Thus, tonsteins from the two different horizons are characterized by unique geochemical properties, which remain constant over a wide lateral extent. Integration of trace-elemental compositions with mineralogical and textural observations makes possible the establishment of tonstein stratigraphy, thus, facilitating more precise and reliable coal-seam correlations. (C) 2000 Elsevier Science B.V. All rights reserved.Trace element compositions were determined in 30 samples of synsedimentary volcanic ash-derived tonsteins and detrital claystones from coal seams within the late Permian coal-bearing formation of eastern Yunnan and western Guizhou Provinces, China. The characteristics of trace-element geochemistry in the tonsteins can be distinguished from those of detrital claystones because of the former's unique volcanic-ash origin. The detrital claystones are characterized by their relatively high content of V, Ti, Sc, CR, Co and Ni, relatively low content of Th and U, Th/U ratio, and small negative Eu anomaly.

International Journal of Coal Geology

Discrimination of lichen genera and species using element concentrations

The importance of organic chemistry in the classification of lichens is well established, but inorganic chemistry has been largely overlooked. Six lichen species were studied over a period of 23 years that were growing in 11 protected areas of the northern Great Lakes ecoregion, which were not greatly influenced by anthropogenic particulates or gaseous air pollutants. The elemental data from these studies were aggregated in order to test the hypothesis that differences among species in tissue element concentrations were large enough to discriminate between taxa faithfully. Concentrations of 16 chemical elements that were found in tissue samples from Cladonia rangiferina, Evernia mesomorpha, Flavopunctelia flaventior, Hypogymnia physodes, Parmelia sulcata, and Punctelia rudecta were analyzed statistically using multivariate discriminant functions and CART analyses, as well as t-tests. Genera and species were clearly separated in element space, and elemental discriminant functions were able to classify 91-100 of the samples correctly into species. At the broadest level, a Zn concentration of 51 ppm in tissues of four of the lichen species effectively discriminated foliose from fruticose species. Similarly, a S concentration of 680 ppm discriminated C. rangiferina and E. mesomorpha , and a Ca concentration of 10 436 ppm discriminated H. physodes from P. sulcata . For the three parmelioid species, a Ca concentration >32 837 ppm discriminated Punctelia rudecta from the other two species, while a Zn concentration of 56 ppm discriminated Parmelia sulcata from F. flaventior . Foliose species also had higher concentrations than did fruticose species of all elements except Na. Elemental signatures for each of the six species were developed using standardized means. Twenty-four mechanisms explaining the differences among species are summarized. Finally, the relationships of four species based on element concentrations, using additive-trees clustering of a Euclidean-distance matrix, produced identical relationships as did analyses based on secondary product chemistry that used additive-trees clustering of a Jaccard similarity matrix. At least for these six species, element composition has taxonomic significance, and may be useful for discriminating other taxa.

Great Lakes

Exposure, sensitivity, or adaptive capacity? Reviewing assessments that use only two of three elements of climate change vulnerability

As climate change accelerates, understanding which species are most vulnerable and why they are vulnerable will be vital to inform conservation action. Climate change vulnerability assessments (CCVAs) are tools to assess species' responses to climate change, detect drivers of vulnerability, and inform conservation planning. CCVAs are commonly composed of three elements: exposure, sensitivity, and adaptive capacity. Incorporating all three elements can be challenging, and including only two of the three elements may be a more feasible approach in many systems. Although two-element CCVA approaches have become more common, their utility and procedures remain poorly documented. We conducted a literature review to explore the scope, methods, and rationale of CCVAs that use a two-element approach to assess vertebrate vulnerability. Despite the potential to expand CCVAs into understudied systems, two-element assessments had similar geographic and taxonomic biases as those previously detected in CCVAs in general. Methods varied, yet we found that variables used in two-element studies could be condensed into standardized categories to enhance comparability. Finally, limitations in data availability and computational resources were common rationales for using a two-element approach. By clarifying the purposes, opportunities, and limitations of two-element assessment, this review can aid in selecting appropriate methods for CCVAs.

Conservation Science and Practice

Review of footnotes and annotations to the 1949–2013 tables of standard atomic weights and tables of isotopic compositions of the elements (IUPAC Technical Report)

The Commission on Isotopic Abundances and Atomic Weights uses annotations given in footnotes that are an integral part of the Tables of Standard Atomic Weights to alert users to the possibilities of quite extraordinary occurrences, as well as sources with abnormal atomic-weight values outside an otherwise acceptable range. The basic need for footnotes to the Standard Atomic Weights Table and equivalent annotations to the Table of Isotopic Compositions of the Elements arises from the necessity to provide users with information that is relevant to one or more elements, but that cannot be provided using numerical data in columns. Any desire to increase additional information conveyed by annotations to these Tables is tempered by the need to preserve a compact format and a style that can alert users, who would not be inclined to consult either the last full element-by-element review or the full text of a current Standard Atomic Weights of the Elements report. Since 1989, the footnotes of the Tables of Standard Atomic Weights and the annotations in column 5 of the Table of Isotopic Compositions of the Elements have been harmonized by use of three lowercase footnotes, “g”, “m”, and “r”, that signify geologically exceptionally specimens (“g”), modified isotopic compositions in material subjected to undisclosed or inadvertent isotopic fractionation (“m”), and the range in isotopic composition of normal terrestrial material prevents more precise atomic-weight value being given (“r”). As some elements are assigned intervals for their standard atomic-weight values (applies to 12 elements since 2009), footnotes “g” and “r” are no longer needed for these elements.

Pure and Applied Chemistry

Concentrations of elements in sediments and selective fractions of sediments, and in natural waters in contact with sediments from Lake Roosevelt, Washington, September 2004

Twenty-eight composite and replicate sediment samples from 8 Lake Roosevelt sites were collected and analyzed for 10 alkali and alkaline earth elements, 2 non-metals, 20 metals, and 4 lanthanide and actinide elements. All elements were detected in all sediment samples except for silver (95 percent of the elements detected for 1,008 analyses), which was detected only in 4 samples. Sequential selective extraction procedures were performed on single composite samples from the eight sites. The percentage of detections for the 31 elements analyzed ranged from 76 percent for the first extraction fraction using a weak extractant to 93 percent for the four-acid dissolution of the sediments remaining after the third sequential selective extraction. Water samples in various degrees of contact with the sediment were analyzed for 10 alkali and alkaline earth elements, 5 non-metals, 25 metals, and 16 lanthanide and actinide elements. The filtered water samples included 10 samples from the reservoir water column at 8 sites, 32 samples of porewater, 55 samples from reservoir water overlying sediments in 8 cores from the site incubated in a field laboratory, and 24 water samples that were filtered after being tumbled with sediments from 8 sites. Overall, the concentrations of only 37 percent of the 6,776 analyses of the 121 water samples were greater than the reporting limit. Selenium, bismuth, chromium, niobium, silver, and zirconium were not detected in any water samples. The percentage of concentrations for the water samples that were above the reporting limit ranged from 14 percent for the lanthanide and actinide elements to 77 percent for the alkali and alkaline earth elements. Concentrations were greater than reporting limits in only 23 percent of the analyses of reservoir water and 29 percent of the analyses of reservoir water overlying incubation cores. In contrast, 47 and 48 percent of the concentrations of porewater and water samples tumbled with sediments, respectively, were greater than the reporting limit.

Washington

Review of rare earth element concentrations in oil shales of the Eocene Green River Formation

Concentrations of the lanthanide series or rare earth elements and yttrium were determined for lacustrine oil shale samples from the Eocene Green River Formation in the Piceance Basin of Colorado and the Uinta Basin of Utah. Unprocessed oil shale, post-pyrolysis (spent) shale, and leached shale samples were examined to determine if oil-shale processing to generate oil or the remediation of retorted shale affects rare earth element concentrations. Results for unprocessed Green River oil shale samples were compared to data published in the literature on reference materials, such as chondritic meteorites, the North American shale composite, marine oil shale samples from two sites in northern Tibet, and mined rare earth element ores from the United States and China. The Green River oil shales had lower rare earth element concentrations (66.3 to 141.3 micrograms per gram, &mu;g g -1 ) than are typical of material in the upper crust (approximately 170 &mu;g g -1 ) and were also lower in rare earth elements relative to the North American shale composite (approximately 165 &mu;g g -1 ). Adjusting for dilution of rare earth elements by organic matter does not account for the total difference between the oil shales and other crustal rocks. Europium anomalies for Green River oil shales from the Piceance Basin were slightly lower than those reported for the North American shale composite and upper crust. When compared to ores currently mined for rare earth elements, the concentrations in Green River oil shales are several orders of magnitude lower. Retorting Green River oil shales led to a slight enrichment of rare earth elements due to removal of organic matter. When concentrations in spent and leached samples were normalized to an original rock basis, concentrations were comparable to those of the raw shale, indicating that rare earth elements are conserved in processed oil shales.

Utah;Colorado;Wyoming

Organic Compounds and Trace Elements in Fish Tissue and Bed Sediment in the Delaware River Basin, New Jersey, Pennsylvania, New York, and Delaware, 1998-2000

As part of the National Water-Quality Assessment (NAWQA) program activities in the Delaware River Basin (DELR), samples of fish tissue from 21 sites and samples of bed sediment from 35 sites were analyzed for a suite of organic compounds and trace elements. The sampling sites, within subbasins ranging in size from 11 to 600 square miles, were selected to represent 5 main land-use categories in the DELR -forest, low-agricultural, agricultural, urban, and mixed use. Samples of both fish tissue and bed sediment were also collected from 4 'large-river' sites that represented drainage areas ranging from 1,300 to 6,800 square miles, areas in which the land is used for a variety of purposes. One or more of the organochlorine compounds-DDT and chlordane metabolites, polychlorinated biphenyls (total PCBs), and dieldrin- were detected frequently in samples collected over a wide geographic area. One or more of these compounds were detected in fish-tissue samples from 92 percent of the sites and in bed-sediment samples from 82 percent of the sites. Concentrations of total DDT, total chlordanes, total PCBs, and dieldrin in whole white suckers and in bed sediment were significantly related to urban/industrial basin characteristics, such as percentage of urban land use and population density. Semi-volatile organic compounds (SVOCs)-total polycyclic aromatic hydrocarbons (PAHs), total phthalates, and phenols- were detected frequently in bed-sediment samples. All three types of SVOCs were detected in samples from at least one site in each land-use category. The highest detection rates and concentrations typically were in samples from sites in the urban and mixed land-use categories, as well as from the large-river sites. Concentrations of total PAHs and total phthalates in bed-sediment samples were found to be statistically related to percentages of urban land use and to population density in the drainage areas represented by the sampling sites. The samples of fish tissue and bed sediment collected throughout the DELR were analyzed for a large suite of trace elements, but results of the analyses for eight elements-arsenic, cadmium, chromium, copper, lead, nickel, mercury, and zinc- that are considered contaminants of concern are described in this report. One or more of the eight trace elements were detected in samples from every fish tissue and bed-sediment sampling site, and all of the trace elements were detected in samples from 97 percent of the bed-sediment sites. The concentrations of organic compounds and trace elements in the DELR samples were compared to applicable guidelines for the protection of wildlife and other biological organisms. Concentrations of total DDT, total chlordanes, total PCBs, and dieldrin in fish-tissue samples from 14 sites exceeded one or more of the Wildlife Protective Guidelines established by the New York State Department of Environmental Conservation. Concentrations of one or more organic compounds in samples from 16 bed-sediment sites exceeded the Threshold Effects Concentrations (TEC) of the Canadian Sediment Quality Guidelines, and concentrations of one or more of the eight trace elements in samples from 38 bed-sediment sites exceeded the TEC. (The TEC is the concentration below which adverse biological effects in freshwater ecosystems are expected to be rare.) Concentrations of organic compounds in samples from some bed-sediment sites exceeded the Canadian Probable Effects Concentrations (PEC), and concentrations of trace elements in samples from 18 sites exceeded the PEC. (The PEC is the concentration above which adverse effects to biological organisms are expected to occur frequently). Concentrations of organic compounds and trace elements in samples from the DELR were compared to similar data from other NAWQA study units in the northeastern United States and also data from the Mobile River (Alabama) Basin and the Northern Rockies Intermontane Basin study units. Median concentrations of to

Scientific Investigations Report

Estimated Loads of Suspended Sediment and Selected Trace Elements Transported through the Milltown Reservoir Project Area Before and After the Breaching of Milltown Dam in the Upper Clark Fork Basin, Montana, Water Year 2008

This report presents estimated daily and cumulative loads of suspended sediment and selected trace elements transported during water year 2008 at three streamflow-gaging stations that bracket the Milltown Reservoir project area in the upper Clark Fork basin of western Montana. Milltown Reservoir is a National Priorities List Superfund site where sediments enriched in trace elements from historical mining and ore processing have been deposited since the construction of Milltown Dam in 1907. Milltown Dam was breached on March 28, 2008, as part of Superfund remedial activities to remove the dam and contaminated sediment that had accumulated in Milltown Reservoir. The estimated loads transported through the project area during the periods before and after the breaching of Milltown Dam, and for the entire water year 2008, were used to quantify the net gain or loss (mass balance) of suspended sediment and trace elements within the project area during the transition from a reservoir environment to a free-flowing river. This study was done in cooperation with the U.S. Environmental Protection Agency. Streamflow during water year 2008 compared to long-term streamflow, as represented by the record for Clark Fork above Missoula (water years 1930-2008), generally was below normal (long-term median) from about October 2007 through April 2008. Sustained runoff started in mid-April, which increased flows to near normal by mid-May. After mid-May, flows sharply increased to above normal, reaching a maximum daily mean streamflow of 16,800 cubic feet per second (ft3/s) on May 21, which essentially equaled the long-term 10th-exceedance percentile for that date. Flows substantially above normal were sustained through June, then decreased through the summer and reached near-normal by August. Annual mean streamflow during water year 2008 (3,040 ft3/s) was 105 percent of the long-term mean annual streamflow (2,900 ft3/s). The annual peak flow (17,500 ft3/s) occurred on May 21 and was 112 percent of the long-term mean annual peak flow (15,600 ft3/s). About 81 percent of the annual flow volume was discharged during the post-breach period. Daily loads of suspended sediment were estimated directly by using high-frequency sampling of the daily sediment monitoring. Daily loads of unfiltered-recoverable arsenic, cadmium, copper, iron, lead, manganese, and zinc were estimated by using regression equations relating trace-element discharge to either streamflow or suspended-sediment discharge. Regression equations for estimating trace-element discharge in water year 2008 were developed from instantaneous streamflow and concentration data for periodic water-quality samples collected during all or part of water years 2004-08. The equations were applied to records of daily mean streamflow or daily suspended-sediment loads to produce estimated daily trace-element loads. Variations in daily suspended-sediment and trace-element loads generally coincided with variations in streamflow. Relatively small to moderately large daily net losses from the project area were common during the pre-breach period when low-flow conditions were prevalent. Outflow loads from the project area sharply increased immediately after the breaching of Milltown Dam and during the rising limb and peak flow of the annual hydrograph. Net losses of suspended sediment and trace elements from the project area decreased as streamflow decreased during the summer, eventually becoming small or reaching an approximate net balance between inflow and outflow. Estimated daily loads of suspended sediment and trace elements for all three stations were summed to determine cumulative inflow and outflow loads for the pre-breach and post-breach periods, as well as for the entire water year 2008. Overall, the mass balance between the combined inflow loads from two upstream source areas (upper Clark Fork and Blackfoot River basins) and the outflow loads at Clark Fork above Missoula indicates net losses

Scientific Investigations Report

Quantification of trace element loading in the upper Tenmile Creek drainage basin near Rimini, Montana, September 2011

The principle sources of trace elements entering upper Tenmile Creek, Montana, during September 2011, four trace metals and the metalloid arsenic, were identified and quantified by combining and analyzing streamflow data determined from tracer injection with trace-element concentrations and related water-quality data determined from synoptic sampling. The study reach was along upper Tenmile Creek, beginning downstream from the city of Helena’s diversion and extending 5,020 feet downstream. Results from the 2011 study, completed by the U.S. Geological Survey in cooperation with the Montana Department of Environmental Quality, were compared to results from a similar study conducted in 1998 to assess the effectiveness of mine reclamation and remediation work to reduce trace-element loading to upper Tenmile Creek, which has been ongoing throughout the drainage basin. Main-stem concentrations of most trace elements analyzed were generally greater in 1998 than in 2011. However, the State of Montana human-health criteria for total-recoverable cadmium and arsenic were exceeded in parts of upper Tenmile Creek, and concentrations of cadmium and zinc exceeded the acute aquatic-life criteria at all main-stem sites during both studies. Total-recoverable copper concentrations observed in 2011 exceeded the chronic aquatic-life criterion upstream from the Lee Mountain adit, whereas, in 1998, all sites exceeded the acute aquatic-life criteria. Direct comparison of loads from the 1998 and 2011 tracer studies were complicated by the differences in hydrologic conditions. Streamflow in 1998 was about 10 percent of the 2011 streamflow. The Lee Mountain Mine and Susie Lode adit were identified as major contributors of trace elements to upper Tenmile Creek in both studies. However, trace-element loading from the Lee Mountain Mine area was substantially reduced between 1998 and 2011. Total-recoverable loads of all trace elements showed substantial loss in 1998 but increased in 2011 downstream from the Susie Lode adit to the end of the study reach. This reach was one of the primary sources of trace-element loading to upper Tenmile Creek in 2011. This difference indicated that the streambed may act as a sink or a source for trace elements, depending on hydrologic conditions.

Montana

Organochlorine compounds and trace elements in fish tissue and bed sediments in the lower Snake River basin, Idaho and Oregon

Fish-tissue and bed-sediment samples were collected to determine the occurrence and distribution of organochlorine compounds and trace elements in the lower Snake River Basin. Whole-body composite samples of suckers and carp from seven sites were analyzed for organochlorine compounds; liver samples were analyzed for trace elements. Fillets from selected sportfish were analyzed for organochlorine compounds and trace elements. Bed-sediment samples from three sites were analyzed for organochlorine compounds and trace elements. Twelve different organochlorine compounds were detected in 14 fish-tissue samples. All fish-tissue samples contained DDT or its metabolites. Concentrations of total DDT ranged from 11 micrograms per kilogram wet weight in fillets of yellow perch from C.J. Strike Reservoir to 3,633 micrograms per kilogram wet weight in a whole-body sample of carp from Brownlee Reservoir at Burnt River. Total DDT concentrations in whole-body samples of sucker and carp from the Snake River at C.J. Strike Reservoir, Snake River at Swan Falls, Snake River at Nyssa, and Brownlee Reservoir at Burnt River exceeded criteria established for the protection of fish-eating wildlife. Total PCB concentrations in a whole-body sample of carp from Brownlee Reservoir at Burnt River also exceeded fish-eating wildlife criteria. Concentrations of organochlorine compounds in whole-body samples, in general, were larger than concentrations in sportfish fillets. However, concentrations of dieldrin and total DDT in fillets of channel catfish from the Snake River at Nyssa and Brownlee Reservoir at Burnt River, and concentrations of total DDT in fillets of smallmouth bass and white crappie from Brownlee Reservoir at Burnt River exceeded a cancer risk screening value of 10 -6 established by the U.S. Environmental Protection Agency. Concentrations of organochlorine compounds in bed sediment were smaller than concentrations in fish tissue. Concentrations of p,p'DDE, the only compound detected in all three bed-sediment samples, ranged from 1.1 micrograms per kilogram dry weight in C.J. Strike Reservoir to 11 micrograms per kilogram dry weight in Brownlee Reservoir at Burnt River. Data from this study, compared with data collected in the upper Snake River Basin from 1992 to 1994, indicates that, in general, organochlorine concentrations in fish tissue and bed sediment increased from the headwaters of the Snake River in Wyoming downstream to Brownlee Reservoir. The largest trace-element concentrations in fish tissue were in liver samples from carp from Brownlee Reservoir at Burnt River and suckers from the Boise River near Twin Springs. Concentrations of most trace elements were larger in livers than in the sport- fish fillets. However, mercury concentrations were generally larger in the sportfish fillets; they ranged from 0.08 microgram per gram wet weight in yellow perch from C.J. Strike Reservoir to 0.32 microgram per gram wet weight in channel catfish from Brownlee Reservoir at Burnt River. None of the trace-element concentrations in fillets exceeded median international standards or U.S. Food and Drug Administration action levels. Large trace-element concentrations in the upper Snake River Basin were reported in liver samples from suckers from headwater streams, probably a result of historical mining and weathering of metal-rich rocks. Concentrations of most trace elements in the bed-sediment samples were largest in Brownlee Reservoir at Mountain Man Lodge. Concentrations of arsenic, cadmium, chromium, copper, nickel, and zinc in bed sediment from the Mountain Man Lodge site exceeded either the threshold effect level or probable effect level established by the Canadian Government for the protection of benthic life. Arsenic, chromium, copper, and nickel concentrations in bed sediment from Brownlee Reservoir at Burnt River and chromium, copper, and nickel in bed sediment from C.J. Strike Reservoir also exceeded the threshold effect level.

Idaho, Oregon

Mineral phase-element associations based on sequential leaching of ferromanganese crusts, Amerasia Basin Arctic Ocean

Ferromanganese (FeMn) crusts from Mendeleev Ridge, Chukchi Borderland, and Alpha Ridge, in the Amerasia Basin, Arctic Ocean, are similar based on morphology and chemical composition. The crusts are characterized by a two- to four-layered stratigraphy. The chemical composition of the Arctic crusts differs significantly from hydrogenetic crusts from elsewhere of global ocean by high mean Fe/Mn ratios, high As, Li, V, Sc, and Th concentrations, and high detrital contents. Here, we present element distributions through crust stratigraphic sections and element phase association using several complementary techniques such as SEM-EDS, LA-ICP-MS, and sequential leaching, a widely employed method of element phase association that dissolves mineral phases of different stability step-by-step: Exchangeable cations and Ca carbonates, Mn-oxides, Fe-hydroxides, and residual fraction. Sequential leaching shows that the Arctic crusts have higher contents of most elements characteristic of the aluminosilicate phase than do Pacific crusts. Elements have similar distributions between the hydrogenetic Mn and Fe phases in all the Arctic and Pacific crusts. The main host phases for the elements enriched in the Arctic crusts over Pacific crusts (Li, As, Th, and V) are the Mn-phase for Li and Fe-phase for As, Th, and V; those elements also have higher contents in the residual aluminosilicate phase. Thus, higher concentrations of Li, As, Th, and V likely occur in the dissolved and particulate phases in bottom waters where the Arctic crusts grow, which has been shown to be true for Sc, also highly enriched in the crusts. The phase distributions of elements within the crust layers is mostly consistent among the Arctic crusts, being somewhat different in element concentrations in the residual phase.

Minerals

Comparison of trace element concentrations in livers of diseased, emaciated and non-diseased southern sea otters from the California coast

Infectious diseases have been implicated as a cause of high rates of adult mortality in southern sea otters. Exposure to environmental contaminants can compromise the immuno-competence of animals, predisposing them to infectious diseases. In addition to organic pollutants, certain trace elements can modulate the immune system in marine mammals. Nevertheless, reports of occurrence of trace elements, including toxic heavy metals, in sea otters are not available. In this study, concentrations of 20 trace elements (V, Cr, Mn, Co, Cu, Zn, Rb, Sr, Mo, Ag, Cd, In, Sn, Sb, Cs, Ba, Hg, Tl, Pb, and Bi) were measured in livers of southern sea otters found dead along the central California coast (n = 80) from 1992 to 2002. Hepatic concentrations of trace elements were compared among sea otters that died from infectious diseases (n = 27), those that died from non-infectious causes (n = 26), and otters that died in emaciated condition with no evidence of another cause of death (n = 27). Concentrations of essential elements in sea otters varied within an order of magnitude, whereas concentrations of non-essential elements varied by two to five orders of magnitude. Hepatic concentrations of Cu and Cd were 10- to 100-fold higher in the sea otters in this study than concentrations reported for any other marine mammal species. Concentrations of Mn, Co, Zn, and Cd were elevated in the diseased and emaciated sea otters relative to the non-diseased sea otters. Elevated concentrations of essential elements such as Mn, Zn, and Co in the diseased/emaciated sea otters suggest that induction of synthesis of metallothionein and superoxide dismutase (SOD) enzyme is occurring in these animals, as a means of protecting the cells from oxidative stress-related injuries. Trace element profiles in diseased and emaciated sea otters suggest that oxidative stress mediates the perturbation of essential-element concentrations. Elevated concentrations of toxic metals such as Cd, in addition to several other organic pollutants, may contribute to oxidative stress-meditated effects in sea otters.

California

Trace elements and consequent ecological risks in mining- influenced streams of Appalachia

Appalachian coal surface mines fracture geologic materials, causing release of both major ions and trace elements to water via accelerated weathering. When elevated above natural background, trace elements in streams may produce adverse effects to biota via direct exposure from water and sediment and via dietary exposure in food sources. Other studies have found elevated water concentrations of multiple trace elements in Appalachia's mining-influenced streams. Excepting Se, trace-element concentrations in abiotic and biotic media of Appalachian mining-influenced streams are less well-known. We analyzed environmental media of headwater streams receiving alkaline waters from Appalachian coal mines for eight trace elements (Al, As, Cd, Cu, Ni, Sr, V, and Zn) and assessed potential consequent ecological risks. Streamwater, particulate media (sediment, biofilm, leaf detritus) and benthic macroinvertebrates (primary consumers, secondary consumers, crayfish) were sampled from six mining-influenced and three reference streams during low-flow conditions in two seasons. Dissolved Cu, Ni, and Sr were higher in mining-influenced streams than in reference streams; whereas Ni, Sr, and Zn in fine sediments and Ni in macroinvertebrates were also elevated relative to reference-stream levels in samples from mining-influenced streams. Seasonal ratios of mining-influenced stream concentrations to maximum concentrations in reference streams also demonstrated mining-influenced increases for several elements in multiple media. In most media, concentrations of several elements including Ni were correlated positively. All water-column dissolved concentrations were below protective levels, but fine-sediment concentrations of Ni approached or exceeded threshold-effect concentrations in several streams. Further study is warranted for several elements (Cd, Ni, and Zn in biofilms, and V in macroinvertebrates), which approached or exceeded previously established dietary-risk levels.

Virginia, West Virginia

Using laser micro mass spectrometry with the LAMMA-1000 instrument for monitoring relative elemental concentrations in vitrinite

The variation in relative elemental concentrations among a series of coal macerals belonging to the vitrinite maceral group was determined using laser micro mass spectrometry (LAMMS). Variations in Ba, Cr, Ga, Sr, Ti, and V concentrations among the coals were determined using the LAMM A-1000 instrument. LAMMS analysis is not limited to these elements; their selection illustrates the application of the technique. Ba, Cr, Ga, Sr, Ti, and V have minimal site-to-site variance in the vitrinite macerals of the studied coals as measured by LAMMS. The LAMMS data were compared with bulk elemental data obtained by instrumental neutron activation analysis (INAA) and D. C. arc optical emission spectroscopy (DCAS) in order to determine the reliability of the LAMMS data. The complex nature of the ionization phenomena in LAMMS and the lack of standards characterized on a microscale makes obtaining quantitative elemental data within the ionization microvolume difficult; however, we demonstrate that the relative variation of an element among vitrinites from different coal beds in the eastern United States can be observed using LAMMS in a "bulk" mode by accumulating signal intensities over several microareas of each vitrinite. Our studies indicate gross changes (greater than a factor of 2 to 5 depending on the element) can be monitored when the elemental concentration is significantly above the detection limit. "Bulk" mode analysis was conducted to evaluate the accuracy of future elemental LAMMS microanalyses. The primary advantage of LAMMS is the inherent spatial resolution, ~ 20 ??m for coal. Two different vitrite bands in the Lower Bakerstown coal bed (CLB-1) were analyzed. The analysis did not establish any certain concentration differences in Ba, Cr, Ga, Sr, Ti, and V between the two bands. ?? 1988 Springer-Verlag.

Mikrochimica Acta

Minor elements in Keweenawan lavas, Michigan

The distribution of minor elements in three basaltic flows of the Keweenawan series, of Michigan, is related to differentiation in the flows. Thus, nickel is most abundant in the early differentiates; nickel, chromium, and barium are generally deficient in the pegmatites, which formed late; whereas copper, vanadium, yttrium, and other minor elements are concentrated in the pegmatites. The minor-element content of individual minerals in the Greenstone flow varies markedly from one mineral to another and seems to depend primarily on the presence or absence in the minerals of major elements for which the minor elements can substitute. Minor elements have substituted most readily for those major elements with similar ionic radii. Valence and electronegativity also seem to influence the ease of substitution. The distribution of other minor elements in copper-bearing lodes of the Michigan copper district shows no apparent relation to copper mineralization.

Michigan