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USGS2006

Review of Trace Element Blank and Replicate Data Collected in Ground and Surface Water for the National Water-Quality Assessment Program, 1991-2002

The trace elements Sb, Be, and Tl in ground water and Sb, Be, Co, Mo, and U in surface water are unaffected by contamination. Limited quality control data (blanks) for Li and V in ground water and surface water do not allow for a good assessment on the potential contamination associated with these trace elements. Potential contamination was identified for Al, As, Ba, B, Cd, Cr, Cu, Fe, Pb, Mn, Ni, Se, Ag, Sr, and Zn in ground water and surface water. Evidence of potential contamination was shown for Co, Mo, and U in ground water; potential contamination was shown for T1 in surface water. In comparing the potential contamination for these trace elements with the U.S. Environmental Protection Agency's (USEPA) drinking-water standards, the contamination for most of these trace elements is less than 10 percent of the drinking-water standard; therefore, contamination would have little or no effect when comparing trace element concentrations with the USEPA drinking-water standards. The exceptions are Al, Cd, and possibly Pb in ground water, and As and possibly Pb in surface water. Potential contamination identified for these trace elements is greater than 10 percent of the USEPA drinking-water standard, but affects only 5 percent or less of the As, Cd, and Pb samples. For most trace elements, the level of potential contamination is not large enough to significantly affect the measured concentration of the environmental sample. The exceptions may be Fe in ground water and Al in surface water, which have concentrations for at least 10 percent of the environmental samples that exceeded the USEPA drinking-water standards. Sample variability for some of the trace elements could not be determined because there were either no detected concentrations, or there were less than 10 replicate sets with detected concentrations. These trace elements are Be, Ag, and Tl for ground water and Sb, Be, Cr, Co, Pb, Ag, and Tl for surface water. For most trace elements, sample variability was less than 10 percent, which would have little or no affect on the reported concentrations. The exceptions are Al, Cd, Cu, Pb, Rn (at concentrations less than about 700 picocuries per liter), Se, and Zn in ground water and Cu, Se, and Zn in surface water, all of which have sample variability ranging from 10 to 20 percent. Sample variability should be considered when evaluating the potential error associated with a sample measurement. Collection of additional quality control samples for some of these trace elements to determine bias and variability is probably warranted particularly for those trace elements that the NAWQA Program did not begin sampling until 1998. Results obtained from the analysis of the quality control data can be applied to the interpretation of the environmental data collected from 1991 to 2002 and for water-quality data that are currently being collected as part of the NAWQA Program. More...

Scientific Investigations Report↗

USGS2008

Estimated Loads of Suspended Sediment and Selected Trace Elements Transported through Milltown Reservoir in the Upper Clark Fork Basin, Montana, Water Years 2004-07

The purpose of this report is to present estimated daily and annual loads of suspended sediment and selected trace elements for water years 2004-07 at two sites upstream and one site downstream from Milltown Reservoir. Milltown Reservoir is a National Priorities List Superfund site in the upper Clark Fork basin of western Montana where sediments enriched in trace elements from historical mining and ore processing have been deposited since the construction of Milltown Dam in 1907. The estimated loads were used to quantify annual net gains and losses (mass balance) of suspended sediment and trace elements within Milltown Reservoir before and after June 1, 2006, which was the start of Stage 1 of a permanent drawdown of the reservoir in preparation for removal of Milltown Dam. This study was done in cooperation with the U.S. Environmental Protection Agency. Daily loads of suspended sediment were estimated for water years 2004-07 by using either high-frequency sampling as part of daily sediment monitoring or regression equations relating suspended-sediment discharge to streamflow. Daily loads of unfiltered-recoverable arsenic, cadmium, copper, iron, lead, manganese, and zinc were estimated by using regression equations relating trace-element discharge to suspended-sediment discharge. Regression equations were developed from data for eriodic water-quality samples collected during water years 2004-07. The equations were applied to daily records of either streamflow or suspended-sediment discharge to produce estimated daily loads. Variations in daily suspended-sediment and trace-element loads generally coincided with variations in streamflow. For most of the period before June 1, 2006, differences in daily loads transported to and from Milltown Reservoir were minor or indicated small amounts of deposition; however, losses of suspended sediment and trace elements from the reservoir occurred during temporary drawdowns in July-August 2004 and October-December 2005. After the start of Stage 1 of the permanent drawdown on June 1, 2006, losses of suspended sediment and trace elements from the reservoir persisted for all streamflow conditions during the entire interval of the Stage 1 drawdown (June 1, 2006-September 30, 2007) within the study period. Estimated daily loads of suspended sediment and trace elements were summed for each year to produce estimated annual loads used to determine the annual net gains (deposition) or losses (erosion) of each constituent within Milltown Reservoir during water years 2004-07. During water year 2004, there was an annual net gain of suspended sediment in the reservoir. The annual net gains and losses of trace elements were inconsistent in water year 2004, with gains occurring for arsenic ad iron, but losses occurring for cadmium, copper, lead, manganese, and zinc. In water year 2005, there were annual net gains of suspended sediment and all the trace elements within the reservoir. In water year 2006, there were annual net losses of all constituents from the reservoir, likely as the result of sediment erosion from the reservoir during both a temporary drawdown in October-December 2005 and Stage 1 of the permanent drawdown that continued after June 1, 2006. In water year 2007, when the Stage 1 drawdown was in effect for the entire year, there were large annual net losses of suspended sediment and trace elements from the reservoir. The annual net losses of constituents from Milltown Reservoir in water year 2007 were the largest of any year during the 2004-07 study period. In water year 2007, the annual net loss of suspended sediment from the reservoir was 130,000 tons, which was more than double (about 222 percent) the combined inflow to the reservoir. The largest annual net losses of trace elements in water year 2007, in percent of the combined inflow to the reservoir, occurred for cadmium, copper, lead, and zinc-about 190 percent for cadmium, 170 percent for copper, 150 percent for lead, and 238 p

Scientific Investigations Report↗

USGS2011

Trace elements and radon in groundwater across the United States, 1992-2003

Trace-element concentrations in groundwater were evaluated for samples collected between 1992 and 2003 from aquifers across the United States as part of the U.S. Geological Survey National Water-Quality Assessment Program. This study describes the first comprehensive analysis of those data by assessing occurrence (concentrations above analytical reporting levels) and by comparing concentrations to human-health benchmarks (HHBs). Data from 5,183 monitoring and drinking-water wells representing more than 40 principal and other aquifers in humid and dry regions and in various land-use settings were used in the analysis. Trace elements measured include aluminum (Al), antimony (Sb), arsenic (As), barium (Ba), beryllium (Be), boron (B), cadmium (Cd), chromium (Cr), cobalt (Co), copper (Cu), iron (Fe), lead (Pb), lithium (Li), manganese (Mn), molybdenum (Mo), nickel (Ni), selenium (Se), silver (Ag), strontium (Sr), thallium (Tl), uranium (U), vanadium (V), and zinc (Zn). Radon (Rn) gas also was measured and is included in the data analysis. Climate influenced the occurrence and distribution of trace elements in groundwater whereby more trace elements occurred and were found at greater concentrations in wells in drier regions of the United States than in humid regions. In particular, the concentrations of As, Ba, B, Cr, Cu, Mo, Ni, Se, Sr, U, V, and Zn were greater in the drier regions, where processes such as chemical evolution, ion complexation, evaporative concentration, and redox (oxidation-reduction) controls act to varying degrees to mobilize these elements. Al, Co, Fe, Pb, and Mn concentrations in groundwater were greater in humid regions of the United States than in dry regions, partly in response to lower groundwater pH and (or) more frequent anoxic conditions. In groundwater from humid regions, concentrations of Cu, Pb, Rn, and Zn were significantly greater in drinking-water wells than in monitoring wells. Samples from drinking-water wells in dry regions had greater concentrations of As, Ba, Pb, Li, Sr, V, and Zn, than samples from monitoring wells. In humid regions, however, concentrations of most trace elements were greater in monitoring wells than in drinking-water wells; the exceptions were Cu, Pb, Zn, and Rn. Cu, Pb, and Zn are common trace elements in pumps and pipes used in the construction of drinking-water wells, and contamination from these sources may have contributed to their concentrations. Al, Sb, Ba, B, Cr, Co, Fe, Mn, Mo, Ni, Se, Sr, and U concentrations were all greater in monitoring wells than in drinking-water wells in humid regions. Groundwater from wells in agricultural settings had greater concentrations of As, Mo, and U than groundwater from wells in urban settings, possibly owing to greater pH in the agricultural wells. Significantly greater concentrations of B, Cr, Se, Ag, Sr, and V also were found in agricultural wells in dry regions. Groundwater from dry-region urban wells had greater concentrations of Co, Fe, Pb, Li, Mn, and specific conductance than groundwater from agricultural wells. The geologic composition of aquifers and aquifer geochemistry are among the major factors affecting trace-element occurrence. Trace-element concentrations in groundwater were characterized in aquifers from eight major groups based on geologic material, including (1) unconsolidated sand and gravel; (2) glacial unconsolidated sand and gravel; (3) semiconsolidated sand; (4) sandstone; (5) sandstone and carbonate rock; (6) carbonate rock; (7) basaltic and other volcanic rock; and (8) crystalline rock. The majority of groundwater samples and the largest percentages of exceedences of HHBs were in the glacial and nonglacial unconsolidated sand and gravel aquifers; in these aquifers, As, Mn, and U are the most common trace elements exceeding HHBs. Overall, 19 percent of wells (962 of 5,097) exceeded an HHB for at least one trace element. The trace elements with HHBs included in this summary were Sb, As, Ba, Be, B, Cd, Cr,

Scientific Investigations Report↗

USGS2014

Updated study reporting levels (SRLs) for trace-element data collected for the California Groundwater Ambient Monitoring and Assessment (GAMA) Priority Basin Project, October 2009-March 2013

Groundwater samples have been collected in California as part of statewide investigations of groundwater quality conducted by the U.S. Geological Survey for the Groundwater Ambient Monitoring and Assessment (GAMA) Priority Basin Project (PBP). The GAMA-PBP is being conducted in cooperation with the California State Water Resources Control Board to assess and monitor the quality of groundwater resources used for drinking-water supply and to improve public knowledge of groundwater quality in California. Quality-control samples (source-solution blanks, equipment blanks, and field blanks) were collected in order to ensure the quality of the groundwater sample results. Olsen and others (2010) previously determined study reporting levels (SRLs) for trace-element results based primarily on field blanks collected in California from May 2004 through January 2008. SRLs are raised reporting levels used to reduce the likelihood of reporting false detections attributable to contamination bias. The purpose of this report is to identify any changes in the frequency and concentrations of detections in field blanks since the last evaluation and update the SRLs for more recent data accordingly. Constituents analyzed were aluminum (Al), antimony (Sb), arsenic (As), barium (Ba), beryllium (Be), boron (B), cadmium (Cd), chromium (Cr), cobalt (Co), copper (Cu), iron (Fe), lead (Pb), lithium (Li), manganese (Mn), molybdenum (Mo), nickel (Ni), selenium (Se), silver (Ag), strontium (Sr), thallium (Tl), tungsten (W), uranium (U), vanadium (V), and zinc (Zn). Data from 179 field blanks and equipment blanks collected from March 2006 through March 2013 by the GAMA-PBP indicated that for trace elements that had a change in detection frequency and concentration since the previous review, the shift occurred near October 2009, in conjunction with a change in the capsule filters used by the study. Results for 89 field blanks and equipment blanks collected from October 2009 through March 2013 were evaluated for potential contamination bias by using the same approach developed by Olsen and others (2010). Some data collected by the National Water-Quality Assessment (NAWQA) Program for the Southern California Coastal Drainages study unit were included to supplement the GAMA-PBP data. The detection frequency and upper threshold of potential contamination bias (BD-90/90) were determined from field-blank and equipment-blank data for each trace element. The BD-90/90 is the 90th percentile concentration of potential extrinsic contamination calculated by using the binomial probability distribution for greater than 90 percent confidence. Additionally, data from laboratory blanks and blind blanks analyzed by the National Water Quality Laboratory (NWQL) during water years 2010 through 2013, and compiled by the USGS Branch of Quality Systems (BQS), were considered for each trace element. These results were compared to each constituent’s reporting level to determine whether an SRL was necessary to minimize the potential for detections in the groundwater samples, attributed principally to contamination bias. Results of the evaluation were used to set SRLs for trace-element data for about 1,135 samples of groundwater collected by the GAMA-PBP between October 2009 and March 2013. Ten trace elements analyzed (Sb, As, Be, B, Cd, Li, Se, Ag, Tl, and U) had blank results that did not necessitate establishing SRLs during this review or the review by Olsen and others (2010). Five trace elements analyzed (Al, Ba, Cr, Sr, and V) had blank results that necessitated establishing an SRL during the previous review but did not need an SRL starting October 2009. One trace element (Fe) had field and laboratory-blank results that necessitated keeping the previous SRL (6 micrograms per liter [μg/L]). Two trace elements (Ni and W) had quality-control results that warranted decreasing the previous SRL, and five trace elements (Cu, Pb, Mn, Mo, and Zn) had field, laboratory, or blind blank results that warranted establishing an SRL for the first time or increasing the previous SRL. SRLs for Cu (2.1 μg/L), Pb (0.82 μg/L), Mn (0.66 μg/L), Mo (0.023 μg/L), Ni (0.21 μg/L), W (0.023 μg/L), and Zn (6.2 μg/L) were changed to these levels starting October 2009, based on the BD-90/90 concentration for field blanks or the 99th percentile concentration for laboratory or blind blanks. The SRL for Fe was maintained at 6 μg/L, based on the minimum laboratory reporting level for iron. SRLs for these eight constituents were at least an order of magnitude below the regulatory benchmarks established for drinking water for health and aesthetic purposes; therefore, the practice of reporting concentrations below the SRLs as less than or equal to (≤) the measured value would not prevent the identification of values greater than the drinking-water benchmarks. Co was detected in 99 percent of field blanks, and with a BD-90/90 concentration of 0.38 μg/L, all groundwater results starting October 2009 were coded as “reviewed and rejected.” Co does not currently have a regulatory benchmark for drinking water. The primary sources of contamination for trace elements inferred from this review are the equipment or processes used in the field to collect the samples or in the laboratory. In particular, contamination in field blanks of Co and Mn was attributed to the high-capacity 0.45-micrometer pore-size capsule filters that were in regular use beginning in October 2009 by several USGS programs, including the GAMA-PBP and NAWQA Program, for filtering samples for analysis of trace elements. The SRLs determined in this report are intended to be used for GAMA groundwater-quality data for samples collected October 2009 through March 2013, or for as long as quality-control data indicate contamination similar to what was observed in this report; quality-control data should be continuously reviewed and SRLs re-assessed on at least a study-unit basis.

California↗

USGS2021

Assessment of diel cycling in nutrients and trace elements in the Eagle River Basin, 2017–18

Diel cycles are known to occur in all types of waters, and increasing studies indicate routine water samples may not provide an accurate snapshot in concentrations of trace elements and nutrients. Diel behavior in neutral to alkaline pH ranges is independent of streamflow variability and concentration. Extensive historical U.S. Geological Survey (USGS) water-quality data have been collected in the Eagle River Basin during daylight hours, which is defined as the period of time between one-half hour prior to sunrise and one-half hour after sunset. However, no USGS data have been collected throughout the nighttime, defined as the time between one-half hour after sunset and one-half hour prior to sunrise, making the evaluation of diel cycles impossible. To assess the importance of diel cycling within the Eagle River Basin, the USGS, in cooperation with Eagle River Watershed Council, developed a study to assess the mechanisms, patterns, and magnitude of change during the diel cycle for selected constituents. Water-quality monitors at five USGS streamgage sites (09065500, Gore Creek at Upper Station, near Minturn, Colorado, 09063000, Eagle River at Red Cliff, Colorado, 09064600, Eagle River near Minturn, Colorado, 09066325, Gore Creek above Red Sandstone Creek at Vail, Colorado, and 394220106431500, Eagle River below Milk Creek near Wolcott, Colorado) were deployed in 2017 to evaluate the water-quality field parameters and to determine if water conditions were favorable for the diel cycling of nutrients and trace elements. Based on the evaluation of water-quality parameters, three of the five sites were sampled for nutrient and trace-element concentrations in 2018 to confirm the presence and magnitude of diel cycling. Historical data were also analyzed to assess the effect of time of day on measured nutrient and trace-element concentrations. An assessment of the effect of land use on diel cycling was also investigated. Measurable nutrients displayed a diel cycle at all three sites with the largest percentage change at the most downstream site (394220106431500), located on the Eagle River. More notable diel cycles at this site include filtered nitrate plus nitrite, which varied 179 percent, with concentrations from 0.24 to 0.67 milligrams per liter (mg/L) and filtered orthophosphate, which varied 71 percent, with concentrations from 0.07 to 0.12 mg/L. Filtered nitrate plus nitrite at site 09066325 varied 57 percent, ranging from 0.14 to 0.22 mg/L. Maximum concentrations occurred prior to noon, decreased through the afternoon (between noon and sunset), and increased during the night (between sunset and sunrise). That pattern is consistent with nutrient uptake in response to daytime (between sunrise and sunset) photosynthesis along with biologically driven denitrification and nitrification cycles. Nutrient concentrations at sites 09064600 and 09066325 were generally low and below laboratory reporting limits, which is the smallest measured concentration that nutrients could be measured by a given analytical method. Trace-element concentrations were detectable at all sites with the largest percentage change at the most downstream site (394220106431500) and exhibited diel concentration variation from 11.6 to 284 percent. Appreciable diel cycles included filtered copper (0.98–1.40 micrograms per liter [µg/L], 42.9 percent), filtered zinc (less than [<] 4.00–5.50 µg/L, greater than [>] 37.5 percent), total manganese (9.70–19.5 µg/L, 101 percent), and total arsenic (0.30–0.40 µg/L, 33.3 percent). The largest percentage change in concentration was filtered manganese (2.84–10.9 µg/L, 284 percent). Diel cycles at site 09064600 ranged from 9.1 to 64.5 percent across the trace elements measured. Dissolved trace elements with appreciable diel cycles during the sampling period include filtered cadmium (0.09–0.12 µg/L, 33.3 percent), filtered copper (0.99–1.40 µg/L, 41.4 percent), and total arsenic (0.20–0.30 µg/L, 50 percent). The largest percentage change was filtered zinc (38.3–63.0 µg/L, 65 percent). Trace-element concentrations at site 09066325 were below laboratory reporting limits for many parameters, and no diel cycle could be assessed for these parameters. However, total recoverable iron, filtered barium, filtered manganese, and filtered selenium exhibited changes in concentrations of <10.0–19.4 µg/L (>94 percent), 115–121 µg/L (5 percent), 1.44–1.72 µg/L (19.4 percent), and 0.25–0.28 µg/L (12 percent), respectively. At sites 09064600 and 394220106431500, maximum trace-element concentrations occurred during nighttime with some variation regarding the timing of the peak. The exceptions to this were filtered copper, total arsenic, and filtered selenium, which had maximum concentrations around noon or as the sun disappeared below the horizon. The timing of minimum concentrations occurred in the afternoon for many trace elements, with filtered copper, total arsenic, and filtered selenium having minimum concentrations in the morning or just prior to the appearance of the sun. Analysis of historical data also showed evidence of diel cycling. Historical samples collected from July through October were used to identify diel cycling in base-flow conditions. The resulting diel pattern in the median concentration for filtered manganese, filtered zinc at water-quality site 09064600, and filtered manganese and filtered nitrate plus nitrite at water-quality site 39422016431500 were consistent with the diel pattern in the September 2018 samples, and indicate time of day can bias sampling results even during daylight hours. Diel cycling in the Eagle River Basin appears to be driven primarily by instream, biological processes. However, land use, particularly human effects downstream from urban areas, mining, and agriculture, may affect these processes. At some locations, diel variations in nutrient and trace-element concentrations are small enough to be of low concern. At other locations, however, variations in concentrations up to 284 percent in the data collected for this study and 214 percent in base-flow historical data, indicate daytime-only sampling, particularly in late afternoon, can underestimate daily average nutrient and trace-element concentrations. When feasible, the potential of diel cycling warrants consideration in sample design to account for the potential of diel cycles, or at a minimum, be recognized as a component of the river dynamic and the potential consequences that diel cycles may have in data interpretation and river management decisions.

Colorado↗

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↗

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↗

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↗