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Minor-element composition and organic carbon content of marine and nonmarine shales of Late Cretaceous age in the western interior of the United States

The composition of nonmarine shales of Cretaceous age that contain less than 1 per cent organic carbon is assumed to represent the inherited minor-element composition of clayey sediments delivered to the Cretaceous sea that occupied the western interior region of North America. Differences in minor-element content between these samples and samples of 1. (a) nonmarine carbonaceous shales (1 to 17 per cent organic carbon), 2. (b) nearshore marine shales (less than 1 per cent organic carbon), and 3. (c) offshore marine shales (as much as 8 per cent organic carbon), all of the same age, reveal certain aspects of the role played by clay minerals and organic materials in affecting the minor-element composition of the rocks. The organic carbon in the nonmarine rocks occurs in disseminated coaly plant remains. The organic carbon in the marine rocks occurs predominantly in humic material derived from terrestrial plants. The close similarity in composition between the organic isolates from the marine samples and low-rank coal suggests that the amount of marine organic material in these rocks is small. The minor-element content of the two kinds of nonmarine shales is the same despite the relatively large amount of organic carbon in the carbonaceous shales. The nearshore marine shales, however, contain larger median amounts of arsenic, boron, chromium, vanadium and zinc than do the nonmarine rocks; and the offshore marine shales contain even larger amounts of these elements. Cobalt, molybdenum, lead and zirconium show insignificant differences in median content between the nonmarine and marine rocks, although as much as 25 ppm molybdenum is present in some offshore marine samples. The gallium content is lower in the marine than in the nonmarine samples. Copper and selenium contents of the two kinds of nonmarine rocks and the nearshore marine samples are the same, but those of the offshore samples are larger. In general, arsenic, chromium, copper, molybdenum, selenium, vanadium and zinc are concentrated in those offshore marine samples having the largest amounts of organic carbon, but samples with equal amounts of vanadium, for instance, may differ by a factor of 3 in their amount of organic carbon. Arsenic and molybdenum occur in some samples chiefly in syngenetic pyrite but also are present in relatively large amounts in samples that contain little pyrite. The data on nonmarine carbonaceous shales indicate that organic matter of terrestrial origin in marine shales contributes little to the minor-element content of such rocks. It is possible that marine organic matter, even though seemingly small in amount in marine shales, contributes to the minor-element composition of the shales. In addition to any such contribution, however, the great effectiveness in sorption processes of humic materials in conjunction with clay minerals suggests that such processes must have played an important role as these materials moved from the relatively dilute solutions of the nonmarine environment to the relatively concentrated solution of sea water. The volumes of sea water sufficient to supply for sorption the amounts of most minor elements in the offshore marine samples are insignificant compared to the volumes of water with which the clay and organic matter were in contact during their transportation and sedimentation. Consequently, the chemical characteristics of the environment in which the clay minerals and organic matter accumulated and underwent diagenesis probably were the most important factors in controlling the degree to which sorption processes and the formation of syngenetic minerals affected the final composition of the rocks.

Geochimica et Cosmochimica Acta

Enrichment of trace elements in garnet amphibolites from a paleo-subduction zone: Catalina Schist, southern California

The abundance, P - T stability, solubility, and element-partitioning behavior of minerals such as rutile, garnet, sphene, apatite, zircon, zoisite, and allanite are critical variables in models for mass transfer from the slab to the mantle wedge in deep regions of subduction zones. The influence of these minerals on the composition of subduction-related magmas has been inferred (and disputed) from inverse modelling of the geochemistry of island-arc basalt, or by experiment. Although direct samples of the dehydration + partial-melting region of a mature subduction zone have not been reported from subduction complexes, garnet amphibolites from melanges of circumpacific and Caribbean blueschist terranes reflect high T (>600°C) conditions in shallower regions. Such rocks record geochemical processes that affected deep-seated, high- T portions of paleo-subduction zones. In the Catalina Schist, a subduction-zone metamorphic terrane of southern California, metasomatized and migmatitic garnet amphibolites occur as blocks in a matrix of meta-ultramafic rocks. This mafic and ultramafic complex may represent either slab-derived material accreted to the mantle wedge of a nascent subduction zone or a portion of a shear zone closely related to the slab-mantle wedge contact, or both. The trace-element geochemistry of the complex and the distribution of trace elements among the minerals of garnet amphibolites were studied by INAA, XRF, electron microprobe, and SEM. In order of increasing alteration from a probable metabasalt protolith, three common types of garnet amphibolite blocks in the Catalina Schist are: (1) non-migmatitic, clinopyroxene-bearing blocks, which are compositionally similar to MORB that has lost an albite component; (2) garnet-amphibolite blocks, which have rinds that reflect local interaction between metabasite, metaperidotite, and fluid; and (3) migmatites that are extremely enriched in Th, HFSE, LREE, and other trace elements. These trace-element enrichments are mineralogically controlled by rutile, garnet, sphene, apatite, zircon, zoisite, and allanite. Alkali and alkaline earth elements are much less enriched in the solid assemblage, and thus appear to be decoupled from the other elements in the inferred metasomatic process(es). The compositions of migmatitic garnet amphibolite blocks seem to complement that of “average” island-arc tholeiite. Trace-element metasomatism reflects fluid-solid, rather than melt-solid, interaction. The metasomatic effects indicate that H 2 O-rich fluid, perhaps with a significant component of Na-Al silicate and alkalis, carried Th, U, Sr, REE, and HFSE. Fractionations of LREE in migmatites resemble those of migmatitic metasedimentary rocks underlying the mafic and ultramafic complex. “Exotic” LREE deposited in allanite in migmatites could have been derived from fluids in equilibrium with subducted sediment. If the paleo-subduction zone represented by the mafic and ultramafic complex of the Catalina Schist had continued its thermal and fluid evolution, a selvage of similarly enriched rocks might have been generated along the slab-mantle wedge contact between ~30 and 85 km depth. Rocks affected by “subduction-zone metasomatism,” although rarely recognized at the surface, could be volumetrically significant products of the initiation of subduction and may prove to be geochemical probes of convergent margins that approach the significance of xenoliths in the study of other magmatic environments.

Geochimica et Cosmochimica Acta

Abnormal chemical element concentrations in lichens of Isle Royale National Park

Lichens have been used for many years to monitor changes in deposited airborne chemical elements in many areas, but few studies have focused on areas suspected of experiencing slightly elevated pollution. Detection of subtle patterns of slightly elevated pollutants calls for developing several lines of evidence as opposed to single line studies used in heavily polluted areas. This study of two lichen species, Hypogymnia physodes and Evernia mesomorpha , in Isle Royale National Park, Michigan compares the concentrations and ranks of elements with the concentrations and ranks of the elements in the earth's crust, changes in element concentrations over a nine year period, and the geography of element concentrations in the park. S, Zn, Pb, Cd and Se were elevated in both species and higher in rank compared to the concentrations and ranks in the earth's crust. Toxic elements increased 123% in Hypogymnia and 62% in Evernia over 9 years, compared to increases of 45% and 59% for non-toxic elements in each species, respectively. Geographically, the lichens at certain localities with higher exposures experienced higher than average element concentrations. Finally, tissue concentrations of Mn, S and Se at some localities were above levels known to be either toxic or similar to those found in polluted areas. These four lines of evidence suggest that Isle Royale National Park is experiencing the onset of chronic air pollution stress from a number of sources.

Michigan

Geochemistry of environmentally sensitive trace elements in Permian coals from the Huainan coalfield, Anhui, China

To study the geochemical characteristics of 11 environmentally sensitive trace elements in the coals of the Permian Period from the Huainan coalfield, Anhui province, China, borehole samples of 336 coals, two partings, and four roof and floor mudstones were collected from mineable coal seams. Major elements and selected trace elements were determined by inductively coupled plasma optical emission spectrometry (ICP-OES), inductively coupled plasma mass spectrometry (ICP-MS), and hydride generation atomic absorption spectrometry (HAAS). The depositional environment, abundances, distribution, and modes of occurrence of trace elements were investigated. Results show that clay and carbonate minerals are the principal inorganic constituents in the coals. A lower deltaic plain, where fluvial channel systems developed successively, was the likely depositional environment of the Permian coals in the Huainan coalfield. All major elements have wider variation ranges than those of Chinese coals except for Mg and Fe. The contents of Cr, Co, Ni, and Se are higher than their averages for Chinese coals and world coals. Vertical variations of trace elements in different formations are not significant except for B and Ba. Certain roof and partings are distinctly higher in trace elements than underlying coal bench samples. The modes of occurrence of trace elements vary in different coal seams as a result of different coal-forming environments. Vanadium, Cr, and Th are associated with aluminosilicate minerals, Ba with carbonate minerals, and Cu, Zn, As, Se, and Pb mainly with sulfide minerals.

Huainan coalfield

Chemical element concentrations in four lichens on a transect entering Voyageurs National Park

A three factor transect study was conducted to test the hypothesis that chemical elements from air emissions in the vicinity of International Falls, Minnesota could not be detected in lichens along a 24 km transect reaching into Voyageurs National Park. It was hypothesized that element concentrations in lichens would decline exponentially downwind and would reach background values at a distance before the park boundary. Four species ( Cladina rangiferina, Evernia mesomorpha, Hypogymnia physodes , and Parmelia sulcata ) were sampled at ten sites for 3 years and 17 chemical elements were measured. The most notable result was a curvilinear geographic trend for many elements, which decreased from International Falls and then increased towards the park. This trend was significant for many anthropogenic elements, including S, Hg, Cd, and Cr, and for all four species. This type of distribution pattern has been observed in Hypogymnia physodes in other studies downwind of a steel mill and an oil refinery. Cladina , a ground-dwelling lichen, generally had lower tissue concentrations of the elements than the three epiphytic species. Tissue concentrations over the 3 years of sampling declined an average of 12%. Sufficient evidence exists to conclude that lichen tissue element concentrations in the vicinity of International Falls may be related to local air emissions, and that an exponential decline of element concentrations downwind of the sources does not apply to this situation.

Minnesota

Water–rock interaction and the concentrations of major, trace, and rare earth elements in hydrocarbon-associated produced waters of the United States

Studies of co-produced waters from hydrocarbon extraction across multiple energy-producing basins have generally focused on major ions or a few select tracers, and studies that examine trace elements and involve laboratory experiments have generally been basin specific. Here, new perspective is sought through a broad analysis of concentration data for 26 elements from three hydrocarbon well types using the U.S. Geological Survey National Produced Waters Geochemical Database (v2.3). Those data are compared to leachates (water, hydrochloric acid, and artificial brine) from 12 energy-resource related shales from across the United States. Both lower pH and higher ionic strength were associated with greater concentrations of many trace elements in produced waters. However, individual effects were difficult to distinguish because higher ionic strengths drive decreases in pH. Water–rock interactions in the leaching experiments generally replicated produced water concentrations for trace elements including Al, As, Cd, Co, Cu, Mo, Ni, Pb, Sb, Si, and Zn. Enhanced middle rare earth element (REE) mobilization relative to shale REE content occurred with low pH leachates. Produced water concentrations of Li, Sr, and Ba were not replicated by the leaching experiments. Patterns of high Li, Sr, and Ba concentrations and ratios relative to other elements across produced waters types indicate controls on these elements in many settings related to pore space pools of salts, brines, and ion-exchange sites affected by diagenetic processes. The size of those pools is diluted and masked by other water–rock interaction processes at the water–rock ratios necessitated by laboratory experiments. The results broadly link water–rock interaction processes and environmental patterns across a wide variety of produced waters and host formations and thus provide context for trace element data from other environmental and laboratory studies of such waters.

Environmental Science: Processes & Impacts

Global resorption efficiencies of trace elements in leaves of terrestrial plants

Leaf nutrient resorption is a critical nutrient conservation strategy. Previous studies focus mainly on resorption patterns of macronutrients, but resorption patterns of trace elements remain poorly understood. A meta-analysis was conducted to explore the general patterns of the leaf resorption of eight trace elements [i.e. copper (Cu), molybdenum (Mo), zinc (Zn), boron (B), manganese (Mn), sodium (Na), aluminium (Al) and iron (Fe)], and a macronutrient [i.e. sulphur (S)] using data collected from 53 published studies. Sulphur (49.6%) had the highest average resorption efficiency followed by Cu (30.3%), Mo (29.5%), Zn (19.5%) and B (17.6%). Two structural elements, Na and Mn, were not resorbed, whereas two potentially toxic elements, Al (−55.6%) and Fe (−25.4%), were accumulated in senesced leaves. Both climatic factors and growth types affected leaf nutrient resorption efficiency, but the magnitudes and directions of the effects differed greatly between S and the trace elements. The resorption efficiencies of S, Cu, Mo and Zn decreased as leaf nutrient concentrations increased, but the structural or potentially toxic elements (i.e. B, Mn, Na, Fe and Al) presented no response or opposite trends. Our results provide global mean resorption efficiencies of trace elements for the first time, and highlight that structural and potentially toxic elements have relatively lower or no leaf resorption, which should be fully considered in biogeochemical models.

Functional Ecology

Trace element characterisation of MAD‐559 zircon reference material for ion microprobe analysis

We document the composition of a natural zircon gemstone sourced from Madagascar, MAD‐559 – a new reference material for calibrating trace element mass fractions in zircon measured by SIMS. The composition of MAD‐559 was quantified by calibration relative to the well‐documented zircon reference material 91500, for which we compiled existing published data (Mg, Al, Y, rare earth elements, Hf, U, Th) and performed new measurements to characterise the mass fraction of less commonly measured elements (Li, Be, B, F, Na, P, K, Ca, Sc, Ti, Fe, Nb). Measurement results of SL13, CZ3 and MAD‐1 zircons and NIST SRM glasses were performed as quality control materials to test measurement bias and repeatability. We show the intermediate precision for most trace element measurement results of MAD‐559 to be between ± 3% and ± 5% RSD based on 139 measurements by SIMS on twenty‐five individual polished zircon chips measured during a 24‐h period, as well as repeat measurements performed over five separate analytical sessions. Trace element mass fractions were also measured by LA‐ICP‐MS in two different laboratories, and major element compositions measured by electron microprobe, to compare with results measured by SIMS. Based on laser Raman and hyperspectral cathodoluminescence spectroscopy, we show MAD‐559 to have high crystal disorder due to radiation damage relative to crystalline zircon (e.g., SL13 and 91500 zircon). Although the high cumulative alpha dose of MAD‐559 zircon makes it a poor reference material for geochronology, the consistency of the trace element mass fraction results measured in multiple sessions and by various measurement methods shows that it is an ideal reference material for microanalytical trace element mass fraction quantification of zircon.

Geostandards and Geoanalytical Research

Change in field turbidity and trace element concentrations during well purging

Various physical and chemical properties were monitored sequentially in the field during well purging as indicators of stabilization of the composition of the water in the well. Turbidity was monitored on site during purging of oxic water from three wells with screened intervals open to an unconfined aquifer system in the Coastal Plain of southern New Jersey to determine if stabilization of turbidity is a reliable indicator of the optimum purge time required to collect unbiased trace element samples. Concurrent split (one filtered, one unfiltered) samples collected during purging of the wells were analyzed for concentrations of trace elements so that the relationships between trace element concentrations and turbidity could be compared. Turbidity correlated with the whole water recoverable (WWR) concentration of trace element species, such as iron (Fe), aluminum (Al), and manganese (Mn) in the oxic ground water. Turbidity appeared to be independent of other field-measured characteristics of water such as conductivity, pH, temperature, and dissolved oxygen. The WWR concentration of lead and copper, considered to be hydrophobic, correlated significantly with the sum of the WWR concentration of Fe, Al, and Mn. High values of field-measured turbidity were a key indicator of an overestimate of ambient hydrophobic trace element WWR concentrations. Stabilization of turbidity was a better indicator of stable, unfiltered trace element concentrations than were the other commonly measured field characteristics. At one well, turbidity was a better indicator of stable, filtered trace element concentrations than the other commonly measured field characteristics. As analytical methods for trace elements improve resulting in smaller MRLs (method reporting levels) and better precision, turbidity of ground water at values of less than 10 NTU (nepheiometric turbidity units) will become important in interpreting the significance of both unfiltered and filtered sample results.

New Jersey

Element partitioning in magnetite under low-grade metamorphic conditions – A case study from the Proterozoic Belt Supergroup, USA

The distribution and partitioning of elements in igneous rocks is well established for various melt –(fluid) –solid pairs and provides important insights into the petrogenesis of these rocks. Studies of the partitioning behavior of elements under metamorphic conditions are scarce and commonly focus on high-grade metamorphic facies. Little is known about the partitioning behavior of elements under low-grade metamorphic conditions. Greenschist-facies metasedimentary rocks of the North American Belt Supergroup host magnetite that displays equilibrium features with co-existing mineral phases such as quartz and carbonate. Magnetite is an ideal target for geochemical investigations because it can incorporate a large number of cations and is sensitive to changes in temperature, oxygen fugacity, pressure, whole-rock composition, and cooling trends. Whole-rock major and trace element analyses have been undertaken on representative samples from Belt Supergroup metasedimentary rocks using X-ray luorescence. Electron microprobe and laser ablation ICP-MS were used to obtain major and trace element concentrations for magnetite hosted in these rocks. Stable-isotope geothermometry of magnetite–quartz and magnetite–carbonate pairs constrain metamorphic temperatures to ca. 390°C. Partition coefficients (D) for magnetite–matrix pairs presumably reflect equilibrium at these low-grade metamorphic conditions. Except for Mn and Ni, which show comparable partition coefficients, the calculated values are one to two orders of magnitude lower than those for igneous magnetite. Aluminum displays the lowest calculated partition coefficient with a value of 0.006 and Ni and Fe the highest values with 6.3 and 20.9, respectively. Of the elements that commonly occur in spinel-group minerals, two groups can be distinguished: (1) elements that preferentially partition into the host rock (D<1): Al, Mg, Pb, and Ti and (2) elements that show a preference to partition into magnetite (D>1): Zn, Mn, Cr, V, Ni, and Fe.

European Journal of Mineralogy

Trace element content of gossans at four mines in the West Shasta massive sulfide district

We evaluated the trace element content of gossans at four mines in the West Shasta Cu-Zn mining district in California. We found little difference in trace element content between the chipped rock rind and whole-rock gossan samples. Gossans derived from disseminated sulfides were found to have a lower trace element content as well as a narrower range of values than did gossans derived from massive sulfides. Extreme differences in trace element concentrations in field duplicates of both chip and whole-rock gossan samples due to variations within the gossan bodies prevented use of the data at individual sampling sites for areal pattern studies. A computer program (REM), which uses a cell concept and groups the analysis of gossan at each mine, was used to characterize the trace element content. The gossan at the Mammoth mine had the highest anomaly magnitude and the highest element magnitudes for the most elements. Gossan at the Spread Eagle mine had a much different assemblage of elements relative to the other mines studied and had the lowest anomaly magnitude.

Economic Geology

Visualizing trace element distribution in quartz using cathodoluminescence, electron microprobe, and laser ablation-inductively coupled plasma-mass spectrometry

Cathodoluminescent (CL) textures in quartz reveal successive histories of the physical and chemical fluctuations that accompany crystal growth. Such CL textures reflect trace element concentration variations that can be mapped by electron microprobe or laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS). Trace element maps in hydrothermal quartz from four different ore deposit types (Carlin-type Au, epithermal Ag, porphyry-Cu, and MVT Pb-Zn) reveal correlations among trace elements and between trace element concentrations and CL textures. The distributions of trace elements reflect variations in the physical and chemical conditions of quartz precipitation. These maps show that Al is the most abundant trace element in hydrothermal quartz. In crystals grown at temperatures below 300 &deg;C, Al concentrations may vary by up to two orders of magnitude between adjacent growth zones, with no evidence for diffusion. The monovalent cations Li, Na, and K, where detectable, always correlate with Al, with Li being the most abundant of the three. In most samples, Al is more abundant than the combined total of the monovalent cations; however, in the MVT sample, molar Al/Li ratios are ~0.8. Antimony is present in concentrations up to ~120 ppm in epithermal quartz (~200&ndash;300 &deg;C), but is not detectable in MVT, Carlin, or porphyry-Cu quartz. Concentrations of Sb do not correlate consistently with those of other trace elements or with CL textures. Titanium is only abundant enough to be mapped in quartz from porphyry-type ore deposits that precipitate at temperatures above ~400 &deg;C. In such quartz, Ti concentration correlates positively with CL intensity, suggesting a causative relationship. In contrast, in quartz from other deposit types, there is no consistent correlation between concentrations of any trace element and CL intensity fluctuations.

American Mineralogist

Trace element, semivolatile organic, and chlorinated organic compound concentrations in bed sediments of selected streams at Fort Gordon, Georgia, February-April 2010

A spatial survey of streams was conducted from February to April 2010 to assess the concentrations of major ions, selected trace elements, semivolatile organic compounds, organochlorine pesticides, and polychlorinated biphenyls associated with the bed sediments of surface waters at Fort Gordon military installation near Augusta, Georgia. This investigation expanded a previous study conducted in May 1998 by the U.S. Geological Survey, in cooperation with the U.S. Department of the Army Environmental and Natural Resources Management Office of the U.S. Army Signal Center and Fort Gordon, that evaluated the streambed sediment quality of selected surface waters at Fort Gordon. The data presented in this report are intended to help evaluate bed sediment quality in relation to guidelines for the protection of aquatic life, and identify temporal trends in trace elements and semivolatile organic compound concentrations at streambed sites previously sampled. Concentrations of 34 major ions and trace elements and 102 semivolatile organic, organochlorine pesticide, and polychlorinated biphenyl compounds were determined in the fine-grained fraction of bed sediment samples collected from 13 of the original 29 sites in the previous study, and 22 additional sites at Fort Gordon. Three of the sites were considered reference sites as they were presumed to be located away from potential sources of contaminants and were selected to represent surface waters flowing onto the fort, and the remaining 32 nonreference sites were presumed to be located within the contamination area at the fort. Temporal trends in trace elements and semivolatile organic compound concentrations also were evaluated at 13 of the 32 nonreference sites to provide an assessment of the variability in the number of detections and concentrations of constituents in bed sediment associated with potential sources, accumulation, and attenuation processes. Major ion and trace element concentrations in fine-grained bed sediment samples from most nonreference sites exceeded concentrations in samples from reference sites at Fort Gordon. Bed sediments from one of the nonreference sites sampled contained the highest concentrations of copper and lead with elevated levels of zinc and chromium relative to reference sites. The percentage change of major ions, trace elements, and total organic carbon that had been detected at sites previously sampled in May 1998 and current bed sediment sites ranged from -4 to 8 percent with an average percentage change of less than 1 percent. Concentrations of major ions and trace elements in bed sediments exceeded probable effect levels for aquatic life (based on the amphipod Hyalella azteca) established by the U.S. Environmental Protection Agency at 46 and 69 percent of the current and previously sampled locations, respectively. The greatest frequency of exceedances for major ions and trace elements in bed sediments was observed for lead. Concentrations of semivolatile organic compounds, organochlorine pesticides, and polychlorinated biphenyls were detected in bed sediment samples at 94 percent of the sites currently sampled. Detections of these organic compounds were reported with greater frequency in bed sediments at upstream sampling locations, when compared to downstream locations. The greatest number of detections of these compounds was reported for bed sediment samples collected from two creeks above a lake. The percentage change of semivolatile organic compounds detected at previously sampled and current bed sediment sites ranged from -68 to 100 percent with the greatest percentage increase reported for one of the creeks above the lake. Concentrations of semivolatile organic compounds and polychlorinated biphenyls in bed sediments exceeded aquatic life criteria established by the U.S. Environmental Protection Agency at three sites. Contaminant compounds exceeding aquatic life criteria included fluoranthene, phenanthrene, anthracene, benzo(a)anthracene

Georgia

Occurrence and distribution of trace elements in snow, streams, and streambed sediments, Cape Krusenstern National Monument, Alaska, 2002-2003

Cape Krusenstern National Monument is located in Northwest Alaska. In 1985, an exchange of lands and interests in lands between the Northwest Alaska Native Association and the United States resulted in a 100-year transportation system easement for 19,747 acres in the monument. A road was then constructed along the easement from the Red Dog Mine, a large zinc concentrate producer and located northeast of the monument, through the monument to the coast and a port facility. Each year approximately 1.3 million tonnes of zinc and lead concentrate are transported from the Red Dog Mine via this access road. Concern about the possible deposition of cadmium, lead, zinc and other trace elements in the monument was the basis of a cooperative project with the National Park Service. Concentrations of dissolved cadmium, dissolved lead, and dissolved zinc from 28 snow samples from a 28 mile by 16 mile grid were below drinking water standards. In the particulate phase, approximately 25 percent of the samples analyzed for these trace elements were higher than the typical range found in Alaska soils. Boxplots of concentrations of these trace elements, both in the dissolved and particulate phase, indicate higher concentrations north of the access road, most likely due to the prevailing southeast wind. The waters of four streams sampled in Cape Krusenstern National Monument are classified as calcium bicarbonate. Trace-element concentrations from these streams were below drinking water standards. Median concentrations of 39 trace elements from streambed sediments collected from 29 sites are similar to the median concentrations of trace elements from the U.S. Geological Survey?s National Water-Quality Assessment database. Statistical differences were noted between trace-element concentrations of cadmium, lead, and zinc at sites along the access road and sites north and south of the access road; concentrations along the access road being higher than north or south of the road. When normalized to 1 percent organic carbon, the concentrations of these trace elements are not expected to be toxic to aquatic life when compared to criteria established by the Canadian government and other recent research.

Scientific Investigations Report

Determination of minor elements in water by emission spectroscopy

With the emission spectrograph, the analyst is able to determine many minor elements simultaneously in water samples. Spectrographic methods differ chiefly in techniques of preconcentrating the elements. For waters with dissolved solids of less than 1,000 milligrams per liter, the method of evaporating to dryness and determining the elements in the dried residue is sensitive, precise, and reasonably accurate. The lower limits of detection vary with the quantity of dissolved solids. Twenty-four elements are determined by this method. For waters with more than 1,000 milligrams per liter of dissolved solids, it is necessary to separate the minor elements from the major constituents before spectrographically determining the former, in order to achieve adequate lower limits of detection. Such procedures generally require more time than the residue method. In the first of two such procedures given, 21 of the metallic elements are precipitated with thioacetamide prior to spectrographic determination. In an alternate procedure, 18 elements are precipitated quantitatively with complexing reagents 8-hydroxyquinoline, tannic acid, and thioanlide. This method is faster than the thioacetamide method, but at the sacrifice of some elements. A Fortran IV computer program for processing densitometric data is given in the section 'Computer Program.'

Techniques of Water-Resources Investigations

Areal distribution of selected trace elements, salinity, and major ions in shallow ground water, Tulare Basin, Southern San Joaquin Valley, California

The distribution of salinity and selected trace elements in shallow ground water in the Tulare Basin, California, was assessed to evaluate potential problems related to disposal in evaporation ponds of irrigation drain water containing elevated concentrations of selenium and other trace elements. The constituents of primary concern were selenium, arsenic, and salinity; uranium, boron, and molybdenum also were evaluated. Samples from 117 shallow wells were analyzed, and the results for samples from 110 of the wells were interpreted in relation to surficial geology, sediment depositional environment, soil characteristics, and hydrologic processes to determine the geochemical and hydrologic factors affecting the distribution of these constituents in ground water. In general, shallow ground water in areas where concentrations of salinity and most trace elements are elevated is influenced primarily by sediments derived from marine sedimentary rocks originating in the Coast Range, San Emigdio Mountains, and Tehachapi Mountains, and probably by unusual exposures of similar marine formations in the Sierra Nevada. Ground water in areas where concentrations of salinity and trace elements are significantly lower generally is influenced by igneous and metamorphic rocks exposed in the Sierra Nevada. In addition to sources of sediments, evaporation of shallow ground water, as indicated by isotopic enrichment of oxygen-18 and deuterium, increases salinity and concentrations of conservative trace elements such as selenium (under oxidizing conditions) and boron. Redox conditions affect the oxidation state of all trace elements of concern, except boron, and were found to be a major influence on trace-element solubility. Under oxidized conditions, selenate predominates and behaves conservatively, and arsenate predominates and is affected by sorption reactions that can limit arsenic solubility. Under reduced conditions, selenium is reduced to insoluble elemental selenium and arsenite predominates and generally is more soluble than arsenate. Elevated concentrations of uranium in shallow ground water probably are associated with uranium deposits in Kern County and other parts of the basin where oxidized conditions cause the more soluble uranyl species to predominate. Boron was correlated with salinity and behaved conservatively, whereas adsorption and precipitation of molybdenum minerals probably limited molybdenum solubility. Interrelations among constituents were examined with principal component analysis. The first two principal components explained 50.7 percent of the variance in the data. The first principal component was related to salinity, and the second principal component was related to redox conditions, reflecting two of the major influences on shallow groundwater quality found in this study.

California

Element concentrations in bed sediment of the Yellowstone River basin, Montana, North Dakota, and Wyoming — A retrospective analysis

Chemical data for bed sediment were analyzed as part of the U.S. Geological Survey National Water-Quality Assessment Program investigation of the Yellowstone River Basin in parts of Montana, North Dakota, and Wyoming. The primary data set consisted of about 13,000 samples collected during 1974-79 for the National Uranium Resource Evaluation program. Data were available for 50 elements, although not all samples were analyzed for all elements. Element concentrations varied spatially and were associated with geologic settings or ecoregions. Factor analysis indicated three groups of associated elements: factor 1 elements were strongly correlated with basaltic rocks, factor 2 elements were strongly correlated with granitic rocks, and factor 3 elements were strongly correlated with carbonate rocks. Scores for factor 1 were highest for bed-sediment samples associated with volcanic rocks of Tertiary and Cretaceous age in the Absaroka volcanic field and crystalline rocks of Precambrian age in the Beartooth Mountains. Scores for factor 2 were highest for samples associated with volcanic rocks of Quaternary age on the Yellowstone Plateau, crystalline rocks of Precambrian age, and sedimentary rocks of Tertiary age in the Wyoming Basin ecoregion. Scores for factor 3 were highest in samples associated with sedimentary rocks of Paleozoic age and volcanic rocks of Cretaceous and Tertiary age. Descriptive statistics are presented to serve as a baseline for element concentrations in bed sediment associated with eight geologic settings or ecoregions in the study unit. Some of the concentrations of chromium, copper, lead, nickel, and zinc in bed-sediment samples from areas of crystalline rocks in the Beartooth Mountains and other formations in the western part of the study unit exceeded sediment-quality assessment values associated with toxic effects to aquatic life.

Idaho, Montana, North Dakota, South Dakota, Wyomin

Critical elements in Carlin, epithermal, and orogenic gold deposits

Carlin, epithermal, and orogenic gold deposits, today mined almost exclusively for their gold content, have similar suites of anomalous trace elements that reflect similar low-salinity ore fluids and thermal conditions of metal transport and deposition. Many of these trace elements are commonly referred to as critical or near-critical elements or metals and have been locally recovered, although typically in small amounts, by historic mining activities. These elements include As, Bi, Hg, In, Sb, Se, Te, Tl, and W. Most of these elements are now solely recovered as by-products from the milling of large-tonnage, base metal-rich ore deposits, such as porphyry and volcanogenic massive sulfide deposits. A combination of dominance of the world market by a single country for a single commodity and a growing demand for many of the critical to near-critical elements could lead to future recovery of such elements from select epithermal, orogenic, or Carlin-type gold deposits. Antimony continues to be recovered from some orogenic gold deposits and tellurium could potentially be a primary commodity from some such deposits. Tellurium and indium in sphalerite-rich ores have been recovered in the past and could be future commodities recovered from epithermal ores. Carlin-type gold deposits in Nevada are enriched in and may be a future source for As, Hg, Sb, and/or Tl. Some of the Devonian carbonaceous host rocks in the Carlin districts are sufficiently enriched in many trace elements, including Hg, Se, and V, such that they also could become resources. Thallium may be locally enriched to economic levels in Carlin-type deposits and it has been produced from Carlin-like deposits elsewhere in the world (e.g., Alsar, southern Macedonia; Lanmuchang, Guizhou province, China). Mercury continues to be recovered from shallow-level epithermal deposits, as well as a by-product of many Carlin-type deposits where refractory ore is roasted to oxidize carbon and pyrite, and mercury is then captured in air pollution control devices.

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