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USGS2002

Compilation of minimum and maximum isotope ratios of selected elements in naturally occurring terrestrial materials and reagents

Documented variations in the isotopic compositions of some chemical elements are responsible for expanded uncertainties in the standard atomic weights published by the Commission on Atomic Weights and Isotopic Abundances of the International Union of Pure and Applied Chemistry. This report summarizes reported variations in the isotopic compositions of 20 elements that are due to physical and chemical fractionation processes (not due to radioactive decay) and their effects on the standard atomic weight uncertainties. For 11 of those elements (hydrogen, lithium, boron, carbon, nitrogen, oxygen, silicon, sulfur, chlorine, copper, and selenium), standard atomic weight uncertainties have been assigned values that are substantially larger than analytical uncertainties because of common isotope abundance variations in materials of natural terrestrial origin. For 2 elements (chromium and thallium), recently reported isotope abundance variations potentially are large enough to result in future expansion of their atomic weight uncertainties. For 7 elements (magnesium, calcium, iron, zinc, molybdenum, palladium, and tellurium), documented isotope-abundance variations in materials of natural terrestrial origin are too small to have a significant effect on their standard atomic weight uncertainties. This compilation indicates the extent to which the atomic weight of an element in a given material may differ from the standard atomic weight of the element. For most elements given above, data are graphically illustrated by a diagram in which the materials are specified in the ordinate and the compositional ranges are plotted along the abscissa in scales of (1) atomic weight, (2) mole fraction of a selected isotope, and (3) delta value of a selected isotope ratio. There are no internationally distributed isotopic reference materials for the elements zinc, selenium, molybdenum, palladium, and tellurium. Preparation of such materials will help to make isotope ratio measurements among laboratories comparable. The minimum and maximum concentrations of a selected isotope in naturally occurring terrestrial materials for selected chemical elements reviewed in this report are given below: Isotope Minimum mole fraction Maximum mole fraction -------------------------------------------------------------------------------- 2H 0 .000 0255 0 .000 1838 7Li 0 .9227 0 .9278 11B 0 .7961 0 .8107 13C 0 .009 629 0 .011 466 15N 0 .003 462 0 .004 210 18O 0 .001 875 0 .002 218 26Mg 0 .1099 0 .1103 30Si 0 .030 816 0 .031 023 34S 0 .0398 0 .0473 37Cl 0 .240 77 0 .243 56 44Ca 0 .020 82 0 .020 92 53Cr 0 .095 01 0 .095 53 56Fe 0 .917 42 0 .917 60 65Cu 0 .3066 0 .3102 205Tl 0 .704 72 0 .705 06 The numerical values above have uncertainties that depend upon the uncertainties of the determinations of the absolute isotope-abundance variations of reference materials of the elements. Because reference materials used for absolute isotope-abundance measurements have not been included in relative isotope abundance investigations of zinc, selenium, molybdenum, palladium, and tellurium, ranges in isotopic composition are not listed for these elements, although such ranges may be measurable with state-of-the-art mass spectrometry. This report is available at the url: http://pubs.water.usgs.gov/wri014222.

Water-Resources Investigations Report↗
USGS2002

Organochlorine compounds and trace elements in fish tissue and streambed sediment in the Mobile River Basin, Alabama, Mississippi, and Georgia, 1998

During the summer of 1998, as part of the National Water-Quality Assessment Program, a survey was conducted to determine which organochlorine compounds and trace elements occur in fish tissues and streambed sediments in the Mobile River Basin, which includes parts of Alabama, Mississippi, Georgia, and Tennessee. The data collected were compared to guidelines related to wildlife, land use, and to 1991 and 1994 National Water-Quality Assessment Program Study-Unit data. Twenty-one sites were sampled in subbasins of the Mobile River Basin. The subbasins ranged in size from about 9 to 22,000 square miles and were dominated by either a single land use or a combination of land uses. The major land-use categories were urban, agriculture, and forest. Organochlorine compounds were widespread spatially in the Mobile River Basin. At least one organochlorine compound was reported at the majority of sampling sites (84 percent) and in a majority of whole-fish (80 percent) and streambed-sediment (52 percent) samples. Multiple organochlorine compounds were reported at 75 percent of the sites where fish tissues were collected and were reported at many of the streambed-sediment sampling sites (45 percent). The majority of concentrations reported, however, were less than 5 micrograms per kilogram in fish-tissue samples and less than 1 microgram per kilogram in streambed-sediment samples. The majority of trace elements analyzed in fish-liver tissue (86 percent) and streambed-sediment (98 percent) samples were reported during this study. Multiple trace elements were reported in all samples and at all sites. Based on comparisons of concentrations of organochlorine compounds and trace elements in fish-tissue and streambed-sediment samples in relation to National Academy of Science and National Academy of Engineering and Canadian tissue guidelines, probable-effects concentrations, and mean probable-effects concentration quotients for streambed sediment, the potential exists for adverse effects to wildlife at 15 (72 percent) of the sites sampled. The potential for adverse effects at these sites is because of the presence of residues or breakdown products related to polychlorinated biphenyls (PCB’s), chlordane, dichlorodiphenyltrichloroethane (DDT), chromium, lead, and zinc. The majority of compounds reported (65 percent) were chlordane, DDT, and PCB’s, or their breakdown products. Concentrations of chlordane and heptachlor epoxide in whole-fish tissue were positively correlated to the amount of urban land use in a basin. Total DDT concentrations in whole-fish tissues were positively correlated to agriculture. The relation of trace elements to land use is not as clear as the relation of organochlorine compounds to land use. This lack of clarity may be due to the possibility of geologic sources of trace elements in the Mobile River Basin and to the ubiquitous nature of many of these trace elements. However, there may be a correlation between the amount of urban land use and concentrations of antimony, cadmium, lead, and zinc in streambed-sediment samples from the Mobile River Basin. Fewer organochlorine compounds and trace elements were reported in samples from the Mobile River Basin than in samples collected during the 1991 and 1994 National Water-Quality Assessment Program studies. Of the organochlorine compounds analyzed nationally, 57 percent were reported in whole-fish tissue samples collected locally and 41 percent were reported in streambed-sediment samples collected locally, whereas 96 percent and 86 percent, respectively, were reported nationally. Of trace elements analyzed nationally, 86 percent were reported in fish-liver tissue locally and 95 percent were reported in streambed-sediment samples locally, whereas 95 percent and 98 percent, respectively, were reported nationally. In general, concentrations of organochlorine compounds and trace elements and the frequency with which they were reported in the Mobile River Basin are similar to or less than those reported by 1991 and 1994 Study Units; however, exceptions do exist to this generality. Exceptions are the higher reporting frequency of heptachlor epoxide, p,p' -DDT, and PCB’s in whole-fish samples, higher quartile concentrations of heptachlor epoxide and p,p' -DDT in whole-fish samples, the higher maximum concentration of heptachlor epoxide in whole-fish samples, and the higher maximum concentration and reporting frequency of trans -chlordane in streambed-sediment samples in the Mobile River Basin. In addition, aluminum, barium, chromium, cobalt, nickel, and strontium were reported more frequently in fish-liver samples locally than nationally, boron concentrations were consistently higher in fish-liver samples locally than nationally, and mercury, silver, and ytterbium were reported more frequently in streambed-sediment samples from the Mobile River Basin than nationally. The higher reporting frequencies and concentrations of heptachlor epoxide, p,p' -DDT, and trans-chlordane in samples from the Mobile River Basin are probably due to the greater use of these compounds locally than nationally. The reason for the higher reporting frequency of PCB’s is less clear, but may be due to the production of these compounds within the basin. The higher frequency with which some trace elements were reported in fish-liver tissue and streambed-sediment samples in the Mobile River Basin may be due to geology or anthropomorphic activities. Higher boron concentrations locally are probably due to anthropomorphic activities, because there are no major geological sources for boron in the Mobile River Basin. Potential sources locally for most of these trace elements include irrigation drain water (mercury), coal combustion (mercury and nickel), metallurgy (barium, boron, chromium, and nickel), soaps (boron), and the wood and pulp industry (barium and chromium). Other sources that could enrich samples from the Mobile River Basin are the Black Warrior coal fields (aluminum and mercury) in the northwestern quarter of the basin, which are known to have elevated levels of mercury, and barite deposits (barium) in east-central Alabama.

Alabama, Georgia, Mississippi, Tennessee↗
USGS1954

U.S. Geological Survey Trace Elements and related reports through 1953

This report combines and brings up-to-date the information previously given in Trace Elements Investigations Report 325, "Numerical list of U.S. Geological Survey Trace Elements Reports to April 30, 1953," and Trace Elements Investigations Report 301, "Topical index and bibliography of U.S. Geological Survey Trace Elements and related reports." Part I is a numerical list of U.S. Geological Survey Trace Elements Investigations and Memorandum reports. It supersedes TEI-325. This part lists not only reports (followed by a date) that have been transmitted to the U.S. Atomic Energy Commission, but also reports in preparation (followed by an asterisk) for which tentative titles were available on December 31, 1953. Reports that have been published are indicated by the abbreviation of the medium of publication. (See also part II.) Part II is a reference guide to Trace Elements and related reports that are available to the public; this part supersedes Part 2 of the TEI-301 (published as Geological survey Circular 281). These reports are grouped according to the type of publication or release. Abstracts published in Nuclear Science Abstracts are not included in Part II, although certain TEI and TEM reports, the abstracts of which have been published in NSA, are so indicated in Part I. Publications in process on December 31, 1953, are designated by an asterisk. Part III is a finding list of states, areas, and subjects. It is based on information derived mostly from the titles of reports and, where titles are of a general nature, from a cursory review of the reports. This list is not a complete index of the information given in Trace Elements and related reports, but is designed to find subjects of major interest. Because of the numerous entries for Colorado and Utah, information has been listed by counties and, where possible, by subject under these states. Other states have county listings only if a county is included in the title of a report; otherwise, areas may be listed separately under the state. Major subjects are listed separately in the index and also where appropriate under states. Analytical methods and subjects related to analytical research are listed under Analytical Methods and Research, but not separately throughout the index. Most mineralogic studies are included under the heading Mineralogy, but are not necessarily listed according to location. Part IV is a finding list of authors. The words “with” and “and” are used to indicate seniority of authorship. For example, a listing of Jones and Brown indicates that Jones is the senior author. A listing of Jones with Brown indicates that Brown is the senior author. In both parts III and IV all Trace Elements reports are listed, as well as other related reports that have not been issued as Trace Elements reports. The following standard abbreviations have been used: TEI, Trace Elements Investigations report; TEM, Trace Elements Memorandum report; P, Professional Paper; B, Bulletin; C, Circular; J, Journal; OF, open file; TIS, Technical Information Service release; NSA, Nuclear Science Abstracts; QM, Quadrangle Map Series; and OM, Oil and Gas map or Mineral Investigations map or report.

Trace Elements Investigations↗
USGS2010

The role of sample preparation in interpretation of trace element concentration variability in moss bioindication studies

Trace element concentrations in plant bioindicators are often determined to assess the quality of the environment. Instrumental methods used for trace element determination require digestion of samples. There are different methods of sample preparation for trace element analysis, and the selection of the best method should be fitted for the purpose of a study. Our hypothesis is that the method of sample preparation is important for interpretation of the results. Here we compare the results of 36 element determinations performed by ICP-MS on ashed and on acid-digested (HNO 3 , H 2 O 2 ) samples of two moss species ( Hylocomium splendens and Pleurozium schreberi ) collected in Alaska and in south-central Poland. We found that dry ashing of the moss samples prior to analysis resulted in considerably lower detection limits of all the elements examined. We also show that this sample preparation technique facilitated the determination of interregional and interspecies differences in the chemistry of trace elements. Compared to the Polish mosses, the Alaskan mosses displayed more positive correlations of the major rock-forming elements with ash content, reflecting those elements’ geogenic origin. Of the two moss species, P. schreberi from both Alaska and Poland was also highlighted by a larger number of positive element pair correlations. The cluster analysis suggests that the more uniform element distribution pattern of the Polish mosses primarily reflects regional air pollution sources. Our study has shown that the method of sample preparation is an important factor in statistical interpretation of the results of trace element determinations.

Environmental Chemistry Letters↗
USGS1994

Seawater as the source of minor elements in black shales, phosphorites and other sedimentary rocks

Many of the minor elements in seawater today have a concentration-depth profile similar to that of the biologically essential nutrients, NO-3 and PO3-4. They show a relative depletion in the photic zone and enrichment in the deep ocean. The difference between their surface- and deep-ocean values, normalized to the change in PO3-4, approaches the average of measured minor-element: P ratios in marine plankton, although individual analyses of the latter show extreme scatter for a variety of reasons. Despite this scatter in the minor-element analyses of plankton, agreement between the two sets of data shows unequivocally that an important marine flux of many minor elements through the ocean is in the form of biogenic matter, with a composition approaching that of plankton. This interpretation is further supported by sediment studies, particularly of sediments which accumulate in shelf-slope environments where biological productivity in the photic zone is exceptionally high and organic carbon contents of the underlying sediment elevated. The interelement relations observed for some of these sediments approach the average values of plankton. These same interelement relations are observed in many marine sedimentary rocks such as metalliferous black shales and phosphorites, rocks which have a high content of marine fractions (e.g., organic matter, apatite, biogenic silica and carbonates). Many previous studies of the geochemistry of these rocks have concluded that local hydrothermal activity, and/or seawater with an elemental content different from that of the modern ocean, was required to account for their minor-element contents. However, the similarity in several of the minor-element ratios in many of these formations to minor-element ratios in modern plankton demonstrates that these sedimentary rocks accumulated in environments whose marine chemistry was virtually identical to that seen on continental shelf-slopes, or in marginal seas, of the ocean today. The accumulation of the marine fraction of minor elements on these ancient sea floors was determined largely by the accumulation of organic matter, settling from the photic zone and with a composition of average plankton. A second marine fraction of minor elements in these rocks accumulated through precipitation and adsorption from seawater. The suite of elements in this fraction reflects redox conditions in the bottom water, as determined by bacterial respiration. For example, high Mn, high Cr+V and high Mo concentrations, above those which can be attributed to the accumulation of planktonic matter, characterize accumulation under bottom-water oxidizing, denitrifying and sulfate-reducing conditions, respectively. ?? 1994.

Chemical Geology↗
USGS2020

Making ‘chemical cocktails’ – Evolution of urban geochemical processes across the periodic table of elements

Urbanization contributes to the formation of novel elemental combinations and signatures in terrestrial and aquatic watersheds, also known as ‘chemical cocktails.’ The composition of chemical cocktails evolves across space and time due to: (1) elevated concentrations from anthropogenic sources, (2) accelerated weathering and corrosion of the built environment, (3) increased drainage density and intensification of urban water conveyance systems, and (4) enhanced rates of geochemical transformations due to changes in temperature, ionic strength, pH, and redox potentials. Characterizing chemical cocktails and underlying geochemical processes is necessary for: (1) tracking pollution sources using complex chemical mixtures instead of individual elements or compounds; (2) developing new strategies for co-managing groups of contaminants; (3) identifying proxies for predicting transport of chemical mixtures using continuous sensor data; and (4) determining whether interactive effects of chemical cocktails produce ecosystem-scale impacts greater than the sum of individual chemical stressors. First, we discuss some unique urban geochemical processes which form chemical cocktails, such as urban soil formation, human-accelerated weathering, urban acidification-alkalinization, and Freshwater Salinization Syndrome. Second, we review and synthesize global patterns in concentrations of major ions, carbon and nutrients, and trace elements in urban streams across different world regions and make comparisons with reference conditions. In addition to our global analysis, we highlight examples from watersheds in the Baltimore-Washington DC area, USA, which show increased transport of major ions, trace metals, and nutrients across streams draining a well-defined land-use gradient. Urbanization increased the concentrations of multiple major and trace elements in streams draining human-dominated watersheds compared to reference conditions. Chemical cocktails of major and trace elements were formed over diurnal cycles coinciding with changes in streamflow, dissolved oxygen, pH, and other variables measured by high-frequency sensors. Some chemical cocktails of major and trace elements were also significantly related to specific conductance (p < 0.05), which can be measured by sensors. Concentrations of major and trace elements increased, peaked, or decreased longitudinally along streams as watershed urbanization increased, which is consistent with distinct shifts in chemical mixtures upstream and downstream of other major cities in the world. Our global analysis of urban streams shows that concentrations of multiple elements along the periodic table significantly increase when compared with reference conditions. Furthermore, similar biogeochemical patterns and processes can be grouped among distinct mixtures of elements of major ions, dissolved organic matter, nutrients, and trace elements as chemical cocktails. Chemical cocktails form in urban waters over diurnal cycles, decades, and throughout drainage basins. We conclude our global review and synthesis by proposing strategies for monitoring and managing chemical cocktails using source control, ecosystem restoration, and green infrastructure. We discuss future research directions applying the watershed chemical cocktail approach to diagnose and manage environmental problems. Ultimately, a chemical cocktail approach targeting sources, transport, and transformations of different and distinct elemental combinations is beneficial to more holistically monitor and manage the emerging impacts of chemical mixtures in the world's fresh waters.

Applied Geochemistry↗
USGS2006

Trace element geochemistry and surface water chemistry of the Bon Air coal, Franklin County, Cumberland Plateau, southeast Tennessee

Mean contents of trace elements and ash in channel, bench-column, and dump samples of the abandoned Bon Air coal (Lower Pennsylvanian) in Franklin County, Tennessee are similar to Appalachian COALQUAL mean values, but are slightly lower for As, Fe, Hg, Mn, Na, Th, and U, and slightly higher for ash, Be, Cd, Co, Cr, REEs, Sr, and V, at the 95% confidence level. Compared to channel samples, dump sample means are slightly lower in chalcophile elements (As, Cu, Fe, Ni, Pb, S, Sb, and V) and slightly higher in clay or heavy-mineral elements (Al, K, Mn, REEs, Th, Ti, U, and Y), but at the 95% confidence level, only As and Fe are different. Consistent abundances of clay or heavy-mineral elements in low-Br, high-S, high-ash benches that are relatively enriched in quartz and mire-to-levee species like Paralycopodites suggest trace elements are largely fluvial in origin. Factor analysis loadings and correlation coefficients between elements suggest that clays host most Al, Cr, K, Ti, and Th, significant Mn and V, and some Sc, U, Ba, and Ni. Heavy accessory minerals likely house most REEs and Y, lesser Sc, U, and Th, and minor Cr, Ni, and Ti. Pyrite appears to host As, some V and Ni, and perhaps some Cu, but Cu probably exists largely as chalcopyrite. Data suggest that organic debris houses most Be and some Ni and U, and that Pb and Sb occur as Pb-Sb sulfosalt(s) within organic matrix. Most Hg, and some Mn and Y, appear to be hosted by calcite, suggesting potential Hg remobilization from original pyrite, and Hg sorption by calcite, which may be important processes in abandoned coals. Most Co, Zn, Mo, and Cd, significant V and Ni, and some Mn probably occur in non-pyritic sulfides; Ba, Sr, and P are largely in crandallite-group phosphates. Selenium does not show organic or "clausthalite" affinities, but Se occurrence is otherwise unclear. Barium, Mn, Ni, Sc, U, and V, with strongly divided statistical affinities, likely occur subequally in multiple modes. For study area surface waters, highest levels of most trace elements occur in mine-adit or mine-dump drainage. Effluent flow rates strongly affect both acidity and trace element levels. Adit drainages where flow is only a trickle have the most acidic waters (pH 3.78-4.80) and highest trace element levels (up to two orders of magnitude higher than in non-mine site waters). Nonetheless, nearly all surface waters have low absolute concentrations of trace elements of environmental concern, and all waters sampled meet U.S. EPA primary drinking water standards and aquatic life criteria for all elements analyzed. Secondary drinking water standards are also met for all parameters except Al, pH, Fe, and Mn, but even in extreme cases (mine waters with pH as low as 3.78 and up to 1243 ppb Al, 6280 ppb Fe, and 721 ppb Mn, and non-mine dam-outflow waters with up to 18,400 ppb Fe and 1540 ppb Mn) downslope attenuation is apparently rapid, as down-drainage plateau-base streams show background levels for all these parameters. ?? 2005 Elsevier B.V. All rights reserved.

International Journal of Coal Geology↗
USGS2017

Trace element contamination in feather and tissue samples from Anna’s hummingbirds

Trace element contamination (17 elements; Be, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, As, Se, Mo, Cd, Ba, Hg, Tl, and Pb) of live (feather samples only) and deceased (feather and tissue samples) Anna's hummingbirds ( Calypte anna ) was evaluated. Samples were analyzed using inductively coupled plasma-mass spectrometry (ICP-MS; 17 elements) and atomic absorption spectrophotometry (Hg only). Mean plus one standard deviation (SD) was considered the benchmark, and concentrations above the mean + 1 SD were considered elevated above normal. Contour feathers were sampled from live birds of varying age, sex, and California locations. In order to reduce thermal impacts, minimal feathers were taken from live birds, therefore a novel method was developed for preparation of low mass feather samples for ICP-MS analysis. The study found that the novel feather preparation method enabled small mass feather samples to be analyzed for trace elements using ICP-MS. For feather samples from live birds, all trace elements, with the exception of beryllium, had concentrations above the mean + 1 SD. Important risk factors for elevated trace element concentrations in feathers of live birds were age for iron, zinc, and arsenic, and location for iron, manganese, zinc, and selenium. For samples from deceased birds, ICP-MS results from body and tail feathers were correlated for Fe, Zn, and Pb, and feather concentrations were correlated with renal (Fe, Zn, Pb) or hepatic (Hg) tissue concentrations. Results for AA spectrophotometry analyzed samples from deceased birds further supported the ICP-MS findings where a strong correlation between mercury concentrations in feather and tissue (pectoral muscle) samples was found. These study results support that sampling feathers from live free-ranging hummingbirds might be a useful, non-lethal sampling method for evaluating trace element exposure and provides a sampling alternative since their small body size limits traditional sampling of blood and tissues. The results from this study provide a benchmark for the distribution of trace element concentrations in feather and tissue samples from hummingbirds and suggests a reference mark for exceeding normal. Lastly, pollinating avian species are minimally represented in the literature as bioindicators for environmental trace element contamination. Given that trace elements can move through food chains by a variety of routes, our study indicates that hummingbirds are possible bioindicators of environmental trace element contamination.

Ecological Indicators↗
USGS2003

Elemental chemistry of four lichen species from the Apostle Islands, Wisconsin, 1987, 1995 and 2001

Four lichen species sampled three times over a 15-year time span at four of the Apostle Islands, Wisconsin were analyzed for 16 chemical elements in order to determine time trends and spatial patterns. Factor analyses of the data revealed that elements associated with soils (Al, Cr, Fe, Na, Ni and S) have increased over the study period, while nutrient and pollutant elements (Cu, K, P, Pb and Zn) have decreased. Four other elements (Ca, Cd, Mg and Mn) were unchanged over time. Cladina rangiferina , a terricolous species, contained the lowest concentrations of all elements, while the corticolous species Evernia mesomorpha was highest in soil elements, Hypogymnia physodes was highest in Ca, Cd, Mg and Mn, and Parmelia sulcata was highest in the nutritional elements. Lichens on islands within 3–4 km of the mainland were highest in soil elements, which decreased with distance from the mainland. Elements that were 18–43% greater on the nearest islands were significantly different between near and far islands. Eight elements (Al, Ca, Cd, K, Mg, Mn, P and S) exceeded enrichment levels for Hypogymnia physodes , suggesting possible contamination problems for this species. Although Pb has decreased significantly over the time period, other elements have increased in the lichens while decreasing in the atmosphere, suggesting that accumulation in the environment is continuing.

Wisconsin↗
USGS1985

The occurrence of extractable elements in soils from the northern Great Plains

The modes of occurrence of extractable elements from 21 A and C horizon samples of uncultivated soils were examined using R-mode factor analysis. The extractants (DTPA, EDTA, HCl, hydroquinone, magnesium nitrate, and ammonium oxalate) cover a wide range of chemical attack. Four major elements (Ca, K, Mg, and Na) and eight trace elements (Cd, Co, Cu, Fe, Mn, Ni, Pb, and Zn) were determined in each extractant solution. A variety of chemical, mineralogical, and physical variables were also determined on each sample. Four varimax factors (clay, organic, Fe and Mn oxides, and soluble-Na) accounted for 74.2% of the total variance of the 90 variables for the A horizon. Seven varimax factors (Fe and Mn oxides, clay, CEC, soluble-Na, organic, Fe and Mn, and plagioclase) accounted for 77.2% of the total variance of the 79 variables for the C horizon. A and C horizon extractable trace elements are most generally related to Fe and Mn oxides, as indicated by loadings on the Fe and Mn oxide factor for both the A and C horizons. Each extractant generally operates on different modes of occurrence of an element in soil. For example, substantial differences occur between the HCl-, oxalate-, and hydroquinone-extractable trace elements. However, the modes of occurrence for trace elements removed by DTPA and EDTA were very similar, suggesting strong relationships between elements dissolved by these two extractants. The modes of occurrence for each individual major element are similar with each of the six extractants. A horizon Ca and Mg, and C horizon K and Mg are strongly related to a clay factor. C horizon Ca and A horizon K are strongly related to the CEC and organic factors, respectively. Both A and C horizon extractable Na are very strongly related to the soluble-Na factor. These results suggest that extractable major elements are water-soluble and are associated with the constituents that are responsible for that factor. Consequently, strong relationships should occur for any individual major element dissolved by any pair of extractants.

northern Great Plains↗
USGS1993

The Effect of mining and related activities on the sediment-trace element geochemistry of Lake Coeur d'Alene, Idaho, U.S.A.; Part II, Subsurface sediments

During the summer of 1990, 12 gravity cores were collected in Lake Coeur d'Alene, Idaho, at various depths and in a variety of depositional environments. All core subsamples were analyzed to determine bulk chemistry and selected subsamples were analyzed for trace-element partitioning and (137)Cs activity. The purpose of these analyses was to determine the trace-element concentrations and distributions in the sediment column and to try to establish a trace-element geochemical history of the lake in relation to mining and mining-related discharge operations in the area. Substantial portions of the near-surface sediments in Lake Coeur d'Alene are markedly enriched in Ag, As, Cd, Hg, Pb, Sb, and Zn, and somewhat enriched in Cu, Fe, and Mn. Variations in the thickness of the trace element- rich sediments suggest that the source of much of this material is the Coeur d'Alene River. Calculated estimates indicate that there are some 75 million metric tons of trace element-rich sediments currently on/in the lakebed. Estimated trace-element masses in excess of those caused by non-mining-related sources, range from a high of 468,000 metric tons of Pb to a low of 260 metric tons of Hg. The similarity between the trace element-rich surface and subsurface sediments as regards their: (1) location; (2) bulk chemistry; (3) interelement relationships; and (4) trace-element partitioning indicate that the sources and/or concentrating mechanisms causing the trace-element enrichment in the lake probably have been the same throughout their depositional history. Based on Mt. St. Helens' ash layer from the 1980 eruption, ages estimated from (137)Cs activity, and the presence of 80 discernible and presumably annual layers in a core collected near the Coeur d'Alene River delta, it appears that deposition rates for the trace element-rich sediments varied from 2.1 to 1.3 cm/yr. These data also indicate that the deposition of trace element-rich sediments began, at least in the Coeur d'Alene River delta, sometime between 1895 and 1910, dates consistent with the onset of mining and ore-processing activities in the area which began in the 1880's.

Open-File Report↗
USGS1979

Environmental implications of element emissions from phosphate-processing operations in southeastern Idaho

In order to assess the contribution to plants and soils of certain elements emitted by phosphate processing, we sampled sagebrush, grasses, and A- and C-horizon soils along upwind and downwind transects at Pocatello and Soda Springs, Idaho. Analyses for 70 elements in plants showed that, statistically, the concentration of 7 environmentally important elements, cadmium, chromium, fluorine, selenium, uranium, vanadium, and zinc, were related to emissions from phosphate-processing operations. Two additional elements, lithium and nickel, show probable relationships. The literature on the effects of these elements on plant and animal health is briefly surveyed. Relations between element content in plants and distance from the phosphate-processing operations were stronger at Soda Springs than at Pocatello and, in general, stronger in sagebrush than in the grasses. Analyses for 58 elements in soils showed that, statistically, beryllium, fluorine, iron, lead, lithium, potassium, rubidium, thorium, and zinc were related to emissions only at Pocatello and only in the A horizon. Moreover, six additional elements, copper, mercury, nickel, titanium, uranium, and vanadium, probably are similarly related along the same transect. The approximate amounts of elements added to the soils by the emissions are estimated. In C-horizon soils, no statistically significant relations were observed between element concentrations and distance from the processing sites. At Soda Springs, the nonuniformity of soils at the sampling locations may have obscured the relationship between soil-element content and emissions from phosphate processing.

Professional Paper↗
USGS1979

Spatial variation in total element concentration in soil within the Northern Great Plains coal region and Regional soil chemistry in Bighorn and Wind River basins, Wyoming and Montana

PART A: To objectively determine the changes in chemical character of an area subjected to mining and reclamation, prior information is needed. This study represents a broadscale inventory of total chemical composition of the surficial materials of the Northern Great Plains coal region (western North and South Dakota, eastern Montana, and northeastern Wyoming); data are given for 41 elements in A and C soil horizons. An unbalanced, nested, analysis-of-variance design was used to quantify variation in total content of elements between glaciated and unglaciated terrains, for four increasingly smaller geographic scales, and to quantify variation due to sample preparation and analysis. From this statistical study, reliable maps on a regional basis (>100 km) were prepared for C, K, and Rb in A and C soil horizons; for N a, Si, Th, D, and Zn in A-horizon soil; and for As, Ca, Ge, and Mg in C-horizon soil. The distribution of variance components for the remaining 29 elements did not permit the construction of reliable maps. Therefore, a baseline value for each of these elements is given as a measure of the total element concentration in the soils of the Northern Great Plains coal region. The baseline is expressed as the 95-percent range in concentration to be expected in samples of natural soils. PART B: A reconnaissance study of total concentrations of 38 elements in samples of soils (0-40 cm deep, composite) from the Bighorn and Wind River Basins of Montana and Wyoming indicates that the geographic variation for most elements occurs locally (5 km or less). However, in the Bighorn Basin, Zn exhibits significant regional variation (between geologic units); and in the Wind River Basin, AI, Cr, K, Mn, Mo, Ni, U, and V exhibit similar variation. For the remaining elements, the lack of regional variation suggests that a single summary statistic can be used to estimate a baseline value that reflects the range in concentration to be expected in samples of soils in each basin. The concentrations of most of these elements in both basins are not much different from those measured independently in the Powder River Basin of Wyoming or in the Western United States. In addition, data from an analysis of variance provide an estimate of the number of random samples within an area of specified size (10 km square, approximately a township) that are needed to prepare a reliable map of total element concentration in soils for each of the elements in each of the basins.

Montana, North Dakota, Saskatchewan, South Dakota,↗
USGS2002

Trace-element deposition in the Cariaco Basin, Venezuela Shelf, under sulfate-reducing conditions: A history of the local hydrography and global climate, 20 ka to the present

A sediment core from the Cariaco Basin on the Venezuelan continental shelf, which recovered sediment that has been dated back to 20 ka (thousand years ago), was examined for its major-element-oxide and trace-element composition. Cadmium (Cd), chromium (Cr), copper (Cu), molybdenum (Mo), nickel (Ni), vanadium (V), and zinc (Zn) can be partitioned between a siliciclastic, terrigenous-derived fraction and two seawater-derived fractions. The two marine fractions are (1) a biogenic fraction represented by nutrient trace elements taken up mostly in the photic zone by phytoplankton, and (2) a hydrogenous fraction that has been derived from bottom water via adsorption and precipitation reactions. This suite of trace elements contrasts with a second suite of trace elements—barium (Ba), cobalt (Co), gallium (Ga), lithium (Li), the rare-earth elements, thorium (Th), yttrium (Y), and several of the major-element oxides—that has had solely a terrigenous source. The partitioning scheme, coupled with bulk sediment accumulation rates measured by others, allows us to determine the accumulation rate of trace elements in each of the three sediment fractions and of the fractions themselves. The current export of organic matter from the photic zone, redox conditions and advection of bottom water, and flux of terrigenous debris into the basin can be used to calculate independently trace-element depositional rates. The calculated rates show excellent agreement with the measured rates of the surface sediment. This agreement supports a model of trace-element accumulation rates in the subsurface sediment that gives a 20-kyr history of upwelling into the photic zone (that is, primary productivity), bottom-water advection and redox, and provenance. Correspondence of extrema in the geochemical signals with global changes in sea level and climate demonstrates the high degree to which the basin hydrography and provenance have responded to the paleoceanographic and paleoclimatic regimes of the last 20 kyr. The accumulation rate of the marine fraction of Mo increased abruptly at about 14.8 ka (calendar years), from less than 0.5 µg cm -2 yr -1 to greater than 4 µg cm -2 yr -1 . Its accumulation rate remained high but variable until 8.6 ka, when it decreased sharply to 1 µg cm -2 yr -1 . It continued to decrease to 4.0 ka, to its lowest value for the past 15 kyr, before gradually increasing to the present. Between 14.8 ka and 8.6 ka, its accumulation rate exhibited strong maxima at 14.4, 13.0, and 9.9 ka. The oldest maximum corresponds to melt-water pulse IA into the Gulf of Mexico. A relative minimum, centered at about 11.1 ka, corresponds to melt-water pulse IB; a strong maximum occurs in the immediately overlying sediment. The maximum at 13.0 ka corresponds to onset of the Younger Dryas cold event. This pattern to the accumulation rate of Mo (and V) can be interpreted in terms of its deposition from bottom water of the basin, the hydrogenous fraction, under SO 4 2- -reducing conditions, during times of intense bottom-water advection 14.8 ka to 11.1 ka and significantly less intense bottom-water advection 11 ka to the present. The accumulation rate of Cd shows a pattern that is only slightly different from that of Mo, although its deposition was determined largely by the rain rate of organic matter into the bottom water, a biogenic fraction whose deposition was driven by upwelling of nutrient-enriched water into the photic zone. Its accumulation exhibits only moderately high rates, on average, during both melt-water pulses. Its highest rate, and that of upwelling, occurred during the Younger Dryas, and again following melt-water pulse IB. The marine fractions of Cu, Ni, and Zn also have a strong biogenic signal. The siliciclastic terrigenous debris, however, represents the dominant source, and host, of Cu, Ni, and Zn. All four trace elements have a consid-erably weaker hydrogenous signal than biogenic signal. Accumulation rates of the terrigenous fraction, as reflected by accumulation rates of Th and Ga, show strong maxima at 16.2 and 12.7 ka and minima at 14.1 and 11.1 ka. Co, Li, REE, and Y have a similar distribution. The minima occurred during melt-water pulses IA and IB, the maxima during the Younger Dryas and the rise in sea level following the last glacial maximum.

Cariaco Basin↗
USGS2005

Vertical distribution of trace-element concentrations and occurrence of metallurgical slag particles in accumulated bed sediments of Lake Roosevelt, Washington, September 2002

Sediment cores were collected from six locations in Lake Roosevelt to determine the vertical distributions of trace-element concentrations in the accumulated sediments of Lake Roosevelt. Elevated concentrations of arsenic, cadmium, copper, lead, mercury, and zinc occurred throughout much of the accumulated sediments. Concentrations varied greatly within the sediment core profiles, often covering a range of 5 to 10 fold. Trace-element concentrations typically were largest below the surficial sediments in the lower one-half of each profile, with generally decreasing concentrations from the 1964 horizon to the surface of the core. The trace-element profiles reflect changes in historical discharges of trace elements to the Columbia River by an upstream smelter. All samples analyzed exceeded clean-up guidelines adopted by the Confederated Tribes of the Colville Reservation for cadmium, lead, and zinc and more than 70 percent of the samples exceeded cleanup guidelines for mercury, arsenic, and copper. Although 100 percent of the samples exceeded sediment guidelines for cadmium, lead, and zinc, surficial concentrations of arsenic, copper, and mercury in some cores were less than the sediment-quality guidelines. With the exception of copper, the trace-element profiles of the five cores collected along the pre-reservoir Columbia River channel typically showed trends of decreasing concentrations in sediments deposited after the 1964 time horizon. The decreasing concentrations of trace elements in the upper half of cores from along the pre-reservoir Columbia River showed a pattern of decreasing concentrations similar to reductions in trace-element loading in liquid effluent from an upstream smelter. Except for arsenic, trace-element concentrations typically were smaller at downstream reservoir locations along the pre-reservoir Columbia River. Trace-element concentration in sediments from the Spokane Arm of the reservoir showed distinct differences compared to the similarities observed in cores from along the pre-reservoir Columbia River. Particles of slag, which have physical and chemical characteristics of slag discharged to the Columbia River by a lead-zinc smelter upstream of the reservoir at Trail, British Columbia, were found in sediments of Lake Roosevelt. Slag particles are more common in the upstream reaches of the reservoir. The chemical composition of the interior matrix of slag collected from Lake Roosevelt closely approximated the reported elemental concentrations of fresh smelter slag, although evidence of slag weathering was observed. Exfoliation flakes were observed on the surface of weathered slag particles isolated from the core sediments. The concentrations of zinc on the exposed surface of slag grains were smaller than concentrations on interior surfaces. Weathering rinds also were observed in the cross section of weathered slag grains, indicating that the glassy slag material was undergoing hydration and chemical weathering. Trace elements observed in accumulated sediments in the middle and lower reaches of the reservoir are more likely due to the input from liquid effluent discharges compared to slag discharges from the upstream smelter.

Scientific Investigations Report↗
USGS2012

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

Beach water and sediment samples were collected along the Gulf of Mexico coast to assess differences in contaminant concentrations before and after landfall of Macondo-1 well oil released into the Gulf of Mexico from the sinking of the British Petroleum Corporation's Deepwater Horizon drilling platform. Samples were collected at 70 coastal sites between May 7 and July 7, 2010, to document baseline, or "pre-landfall" conditions. A subset of 48 sites was resampled during October 4 to 14, 2010, after oil had made landfall on the Gulf of Mexico coast, called the "post-landfall" sampling period, to determine if actionable concentrations of oil were present along shorelines. Few organic contaminants were detected in water; their detection frequencies generally were low and similar in pre-landfall and post-landfall samples. Only one organic contaminant--toluene--had significantly higher concentrations in post-landfall than pre-landfall water samples. No water samples exceeded any human-health benchmarks, and only one post-landfall water sample exceeded an aquatic-life benchmark--the toxic-unit benchmark for polycyclic aromatic hydrocarbons (PAH) mixtures. In sediment, concentrations of 3 parent PAHs and 17 alkylated PAH groups were significantly higher in post-landfall samples than pre-landfall samples. One pre-landfall sample from Texas exceeded the sediment toxic-unit benchmark for PAH mixtures; this site was not sampled during the post-landfall period. Empirical upper screening-value benchmarks for PAHs in sediment were exceeded at 37 percent of post-landfall samples and 22 percent of pre-landfall samples, but there was no significant difference in the proportion of samples exceeding benchmarks between paired pre-landfall and post-landfall samples. Seven sites had the largest concentration differences between post-landfall and pre-landfall samples for 15 alkylated PAHs. Five of these seven sites, located in Louisiana, Mississippi, and Alabama, had diagnostic geochemical evidence of Macondo-1 oil in post-landfall sediments and tarballs. For trace and major elements in water, analytical reporting levels for several elements were high and variable. No human-health benchmarks were exceeded, although these were available for only two elements. Aquatic-life benchmarks for trace elements were exceeded in 47 percent of water samples overall. The elements responsible for the most exceedances in post-landfall samples were boron, copper, and manganese. Benchmark exceedances in water could be substantially underestimated because some samples had reporting levels higher than the applicable benchmarks (such as cobalt, copper, lead and zinc) and some elements (such as boron and vanadium) were analyzed in samples from only one sampling period. For trace elements in whole sediment, empirical upper screening-value benchmarks were exceeded in 57 percent of post-landfall samples and 40 percent of pre-landfall samples, but there was no significant difference in the proportion of samples exceeding benchmarks between paired pre-landfall and post-landfall samples. Benchmark exceedance frequencies could be conservatively high because they are based on measurements of total trace-element concentrations in sediment. In the less than 63-micrometer sediment fraction, one or more trace or major elements were anthropogenically enriched relative to national baseline values for U.S. streams for all sediment samples except one. Sixteen percent of sediment samples exceeded upper screening-value benchmarks for, and were enriched in, one or more of the following elements: barium, vanadium, aluminum, manganese, arsenic, chromium, and cobalt. These samples were evenly divided between the sampling periods. Aquatic-life benchmarks were frequently exceeded along the Gulf of Mexico coast by trace elements in both water and sediment and by PAHs in sediment. For the most part, however, significant differences between pre-landfall and post-landfall samples were limited to concentrations of PAHs in sediment. At five sites along the coast, the higher post-landfall concentrations of PAHs were associated with diagnostic geochemical evidence of Deepwater Horizon Macondo-1 oil.

Alabama, Arkansas, Florida, Georgia, Louisiana, Te↗
USGS2000

Concentrations of selected trace elements in fish tissue and streambed sediment in the Clark Fork-Pend Oreille and Spokane River basins, Washington, Idaho, and Montana, 1998

Fish tissue and bed sediment samples were collected from 16 stream sites in the Northern Rockies Intermontane Basins study area in 1998 as part of the U.S. Geological Survey National Water-Quality Assessment Program. Bed sediment samples were analyzed for 45 trace elements, and fish livers and sportfish fillets were analyzed for 22 elements to characterize the occurrence and distribution of these elements in relation to stream characteristics and land use activities. Nine trace elements of environmental concern&mdash;arsenic, cadmium, chromium, copper, lead, mercury, nickel, selenium, and zinc&mdash;were detected in bed sediment, but not all of these elements were detected in fish tissue. Trace-element concentrations were highest in bed sediment samples collected at sites downstream from significant natural mineral deposits and (or) mining activities. Arsenic, cadmium, copper, lead, mercury, and zinc in bed sediment at some sites were elevated relative to national median concentrations, and some concentrations were at levels that can adversely affect aquatic biota. Although trace-element concentrations in bed sediment exceeded various guidelines, no concentrations in sportfish fillets exceeded U.S. Environmental Protection Agency screening values for the protection of human health. Correlations between most trace-element concentrations in bed sediment and fish tissue (liver and fillet) were not significant (r<&plusmn;0.50, p>0.05). Concentrations of arsenic, cadmium, copper, lead, mercury, nickel, selenium, and zinc in bed sediment were significantly correlated (r=0.53 to 0.88, p<0.05) with natural mineral deposits and mining activities, but concentrations in fish tissue generally were not correlated with these measures. Regression analysis between mine density and the sum of trace-element concentrations in bed sediment identified two statistically significant relations (r 2 =0.95 and 0.99, p<0.001) that corresponded to trace-element enrichment categories. These strong relations warrant further study using mine density as an explanatory variable to predict trace-element concentrations in bed sediment.

Idaho, Montana, Washington↗
USGS1995

Water-quality assessment of the Kentucky River Basin, Kentucky: Distribution of metals and other trace elements in sediment and water, 1987-90

The U.S. Geological Survey (USGS) National Water-Quality Assessment (NAWQA) Program is designed to provide a nationally consistent description of the current status of water quality, to define water-quality trends, and to relate past and present water-quality conditions to natural features, uses of land and water, and other water-quality effects from human activities. The Kentucky River Basin is one of four NAWQA pilot projects that focused primarily on the quality of surface water. Water, sediment, and bedrock samples were collected in the Kentucky River Basin during 1987-90 for the purpose of (1) describing the spatial distribution, transport, and temporal variability of metals and other trace elements in streams of the basin; (2) estimating mean annual loads, yields, and trends of constituent concentrations and identifying potential causes (or sources) of spatial patterns; (3) providing baseline information for concentrations of metals in streambed and suspended sediments; (4) identifying stream reaches in the Kentucky River Basin with chronic water-quality problems; and (5) evaluating the merits of the NAWQA pilot study-approach for the assessment of metals and other trace elements in a river system. The spatial distribution of metals and other trace elements in streambed sediments of the Kentucky River Basin is associated with regional differences of geology, land use and cover, and the results of human activities. Median concentrations of constituents differed significantly among physiographic regions of the basin because of relations to bedrock geochemistry and land disturbance. Concentrations of potentially toxic metals were large in urban and industrial areas of the basin. Elevated concentrations of certain metals were also found in streambed sediments of the Knobs Region because of the presence of Devonian shale bedrock. Elevated concentrations of lead and zinc found in streambed sediments of the Bluegrass Region are likely associated with urban stormwater runoff, point-source discharges, and waste-management practices. Concentrations of cadmium, chromium, copper, mercury, and silver were elevated in streambed sediments downstream from wastewater-treatment plant discharges. Streambed-sediment concentrations of barium, chromium, and lithium were elevated in streams that receive brine discharges from oil production. Elevated concentrations of antimony, arsenic, molybdenum, selenium, strontium, uranium, and vanadium in streambed sediments of the Kentucky River Basin were generally associated with natural sources. Concentrations of metals and other trace elements in water samples from fixed stations (stations where water-quality samples were collected for 3.5 years) in the Kentucky River Basin were generally related to stream discharge and the concentration of suspended sediment, whereas constituent concentrations in the suspended-sediment matrix were indicative of natural and human sources. Estimated mean annual loads and yields for most metals and other trace elements were associated with the transport of suspended sediment. Land disturbance, such as surface mining and agriculture, contribute to increased transport of sediment in streams, thereby increasing concentrations of metals in water samples during periods of intense or prolonged rainfall and increased stream discharge. Concentrations of many metals and trace elements were reduced during low streamflow. Although total-recoverable and dissolved concentrations of certain metals and trace elements were large in streams affected by land disturbance, concentrations of constituents in the suspendedsediment matrix were commonly large in streams in the Knobs and Eastern Coal Field Regions (because of relations with bedrock geochemistry) and in streams that receive wastewater or oil-well-brine discharges. Concentrations and mean annual load estimates for aluminum, chromium, copper, iron, lead, manganese, and mercury were larger than those obtained from data collected by a State agency, probably because of differences in sample-collection methodology, the range of discharge associated with water-quality samples, and laboratory analytical procedures. However, concentrations, loads, and yields of arsenic, barium, and zinc were similar to those determined from the State data. Significant upward trends in the concentrations of aluminum, iron, magnesium, manganese, and zinc were indicated at one or more fixed stations in the Kentucky River Basin during the past 10 to 15 years. Upward trends for concentrations of aluminum, iron, and manganese were found at sites that receive drainage from coal mines in the upper Kentucky River Basin, whereas upward trends for zinc may be associated with urban sources. Water-quality criteria established by the U.S. Environmental Protection Agency (USEPA) or the State of Kentucky for concentrations of aluminum, beryllium, cadmium, chromium, copper, iron, manganese, nickel, silver, and zinc were exceeded at one or more fixed stations in the Kentucky River Basin. On a qualitative basis, dissolved concentrations of certain metals and trace elements were large during low streamflow at sites where (1) concentrations of these constituents in underlying streambed sediments were large, or (2) dissolvedoxygen concentrations were small. Concentrations of barium, lithium, and strontium were large during low streamflow, which indicates the influence of ground-water baseflows on the quality of surface water during low flow. The effects of point-source discharges, landfills, and other wastemanagement practices are somewhat localized in the Kentucky River Basin and are best indicated by the spatial distribution of metals and other trace elements in streambed sediments and in the suspended-sediment fraction of water samples at stream locations near the source. It was not possible to quantify the contribution of point sources to the total transport of metals and other trace elements at fixed stations because data were not available for wastewater effluents. Quantification of baseline concentrations of metals and other trace elements in streambed sediments provides a basis for the detection of water-quality changes that may result from improvements in wastewater treatment or the implementation of best-management practices for controlling contamination from nonpoint sources in the Kentucky River Basin.

Kentucky↗