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Trace element abundances in major minerals of Late Permian coals from southwestern Guizhou province, China

Fourteen samples of minerals were separated by handpicking from Late Permian coals in southwestern Guizhou province, China. These 14 minerals were nodular pyrite, massive recrystallized pyrite, pyrite deposited from low-temperature hydrothermal fluid and from ground water; clay minerals; and calcite deposited from low-temperature hydrothermal fluid and from ground water. The mineralogy, elemental composition, and distribution of 33 elements in these samples were studied by optical microscopy, scanning electron microscope equipped with energy-dispersive X-ray spectrometer (SEM-EDX), X-ray diffraction (XRD), cold-vapor atomic absorption spectrometry (CV-AAS), atomic fluorescence spectrometry (AFS), inductively coupled-plasma mass spectrometry (ICP-MS), and ion-selective electrode (ISE). The results show that various minerals in coal contain variable amounts of trace elements. Clay minerals have high concentrations of Ba, Be, Cs, F, Ga, Nb, Rb, Th, U, and Zr. Quartz has little contribution to the concentration of trace elements in bulk coal. Arsenic, Mn, and Sr are in high concentrations in calcite. Pyrite has high concentrations of As, Cd, Hg, Mo, Sb, Se, Tl, and Zn. Different genetic types of calcite in coal can accumulate different trace elements; for example Ba, Co, Cr, Hg, Ni, Rb, Sn, Sr, and Zn are in higher concentrations in calcite deposited from low-temperature hydrothermal fluid than in that deposited from ground water. Furthermore, the concentrations of some trace elements are quite variable in pyrite; different genetic types of pyrites (Py-A, B, C, D) have different concentrations of trace elements, and the concentrations of trace elements are also different in pyrite of low-temperature hydrothermal origin collected from different locations. The study shows that elemental concentration is rather uniform in a pyrite vein. There are many micron and submicron mosaic pyrites in a pyrite vein, which is enriched in some trace elements, such as As and Mo. The content of trace element in pyrite vein depends upon the content of mosaic pyrite and of trace elements in it. Many environmentally sensitive trace elements are mainly contained in the minerals in coal, and hence the physical coal cleaning techniques can remove minerals from coal and decrease the emissions of potentially hazardous trace elements. ?? 2002 Elsevier Science B.V. All rights reserved.

International Journal of Coal Geology↗

IUPAC Periodic Table of the Elements and Isotopes (IPTEI) for the education community (IUPAC Technical Report)

The IUPAC (International Union of Pure and Applied Chemistry) Periodic Table of the Elements and Isotopes (IPTEI) was created to familiarize students, teachers, and non-professionals with the existence and importance of isotopes of the chemical elements. The IPTEI is modeled on the familiar Periodic Table of the Chemical Elements. The IPTEI is intended to hang on the walls of chemistry laboratories and classrooms. Each cell of the IPTEI provides the chemical name, symbol, atomic number, and standard atomic weight of an element. Color-coded pie charts in each element cell display the stable isotopes and the relatively long lived radioactive isotopes having characteristic terrestrial isotopic compositions that determine the standard atomic weight of each element. The background color scheme of cells categorizes the 118 elements into four groups: (1) white indicates the element has no standard atomic weight, (2) blue indicates the element has only one isotope that is used to determine its standard atomic weight, which is given as a single value with an uncertainty, (3) yellow indicates the element has two or more isotopes that are used to determine its standard atomic weight, which is given as a single value with an uncertainty, and (4) pink indicates the element has a well-documented variation in its atomic weight, and the standard atomic weight is expressed as an interval. An element-by-element review accompanies the IPTEI and includes a chart of all known stable and radioactive isotopes for each element. Practical applications of isotopic measurements and technologies are included for the following fields: forensic science, geochronology, Earth-system sciences, environmental science, and human health sciences, including medical diagnosis and treatment.

Pure and Applied Chemistry↗

The occurrence of trace elements in bed sediment collected from areas of varying land use and potential effects on stream macroinvertebrates in the conterminous western United States, Alaska, and Hawaii, 1992-2000

As part of the National Water-Quality Assessment Program of the U.S. Geological Survey, this study examines the occurrence of nine trace elements in bed sediment of varying mineralogy and land use and assesses the possible effects of these trace elements on aquatic-macroinvertebrate community structure. Samples of bed sediment and macroinvertebrates were collected from 154 streams at sites representative of undeveloped, agricultural, urban, mined, or mixed land-use areas and 12 intermediate-scale ecoregions within the conterminous western United States, Alaska, and Hawaii from 1992 to 2000. The nine trace elements evaluated during this study—arsenic (As), cadmium (Cd), chromium (Cr), copper (Cu), lead (Pb), mercury (Hg), nickel (Ni), selenium (Se), and zinc (Zn)—were selected on the basis of potential ecologic significance and availability of sediment-quality guidelines. At most sites, the occurrence of these trace elements in bed sediment was at concentrations consistent with natural geochemical abundance, and the lowest concentrations were in bed-sediment samples collected from streams in undeveloped and agricultural areas. With the exception of Zn at sampling sites influenced by historic mining-related activities, median concentrations of all nine trace elements in bed sediment collected from sites representative of the five general land-use areas were below concentrations predicted to be harmful to aquatic macroinvertebrates. The highest concentrations of As, Cd, Pb, and Zn were in bed sediment collected from mined areas. Median concentrations of Cu and Ni in bed sediment were similarly enriched in areas of mining, urban, and mixed land use. Concentrations of Cr and Ni appear to originate largely from geologic sources, especially in the western coastal states (California, Oregon, and Washington), Alaska, and Hawaii. In these areas, naturally high concentrations of Cr and Ni can exceed concentrations that may adversely affect aquatic macroinvertebrates. Generally, Hg concentrations were below the sediment-quality guideline for this trace element but appeared elevated in urbanized areas and at sites contaminated by historic mining practices. Lastly, although there was no distinctive pattern in Se concentrations with land use, median bed-sediment concentrations were slightly elevated in urbanized areas. Macroinvertebrate community structure was influenced by topographic, geologic, climatic, and in-stream characteristics. To account for inherent distribution patterns resulting from these influences, samples of macroinvertebrates were stratified by ecoregion to assess the influence of trace elements on community structure. Cumulative toxic units (CTUs) were used to evaluate gradients in trace-element concentrations in mixture. Correlation analyses among the trace elements under different land-use conditions indicate that trace-element mixtures vary among bed sediment and can have a marked influence on CTU composition. Macroinvertebrate response to bed-sediment trace-element exposure was evident only at the most highly contaminated sites, notably at sites classified as contaminated by the Comprehensive Environmental Response, Compensation, and Liability Act (CERCLA) as a result of historic mining activities. Results of this study agree with the findings of other studies evaluating trace-element exposure to in-stream macroinvertebrate community structure in that generally lower richness metrics and taxa dominance occur in streams where high trace-element enrichment occurs; however, not all streams in all areas have the same characterizing taxa. In the mountain and xeric ecosystems, the mayfly, Baetis sp.; the Diptera, Simulium sp.; caddisflies in the family Hydropsychiidae; midges in the family Orthocladiinae; and the worms belonging to Turbellaria and Naididae all demonstrated resilience to trace-element exposure and, in some cases, possible changes in physical habitat within stream ecosystems. The taxa characteristics within the Ozark Highland ecoregion were different than other ecoregions as evidenced by generally more diverse mayfly populations. In addition, Baetis sp. was common and dominated many of the mayfly populations found in the Rocky Mountain streams within the Mountain Southern Rockies and Mountain Northern Rockies ecoregions; however, within the Ozark Highland ecoregion, Tricorythodes sp. appeared to be more common than Baetis sp.

Alaska, Arizona, California, Colorado, Hawai'i, Id↗

Trace elements in streambed sediments of small subtropical streams on O'ahu, Hawai'i: Results from the USGS NAWQA program

Data are presented for trace element concentrations determined in the <63 ??m fraction of streambed sediment samples collected at 24 sites on the island of O'ahu, Hawai'i. Sampling sites were classified as urban, agricultural, mixed (urban/agricultural), or forested based on their dominant land use, although the mixed land use at selected sampling sites consisted of either urban and agricultural or forested and agricultural land uses. Forest dominated sites were used as reference sites for calculating enrichment factors. Trace element concentrations were compared to concentrations from studies conducted in the conterminous United States using identical methods and to aquatic-life guidelines provided by the Canadian Council of Ministers of the Environment. A variety of elements including Pb, Cr, Cu and Zn exceeded the aquatic-life guidelines in selected samples. All of the Cr and Zn values and 16 of 24 Cu values exceeded their respective guidelines. The potential toxicity of elements exceeding guidelines, however, should be considered in the context of strong enrichments of selected trace elements attributable to source rocks in Hawai'i, as well as in the context of the abundance of fine-grained sediment in the streambed of O'ahu streams. Statistical methods including cluster analysis, Kruskal-Wallis non-parametric test, correlation analysis, and principal component analysis (PCA) were used to evaluate differences and elucidate relationships between trace elements and sites. Overall, trace element distributions and abundances can be correlated to three principal sources of elements. These include basaltic rocks of the volcanic edifice (Fe, Al, Ni, Co, Cr, V and Cu), carbonate/seawater derived elements (Mg, Ca, Na and Sr), and elements enriched owing to anthropogenic activity (P, Sn, Cd, Sn, Ba and Pb). Anthropogenic enrichment gradients were observed for Ba, Cd, Pb, Sn and Zn in the four streams in which sediments were collected upstream and downstream. The findings of this study are generally similar to but differ slightly from previous work on sediments and suspended particulate matter in streams, from two urban watersheds of O'ahu, Hawai'i. Inter-element associations in the latter were often stronger and indicated a mixture of anthropogenic, agricultural and basaltic sources of trace elements. Some elements fell into different statistical categories in the two studies, owing in part to differences in study design and the hydrogeological constraints on the respective study areas.

Applied Geochemistry↗

Weathering of the New Albany Shale, Kentucky: II. Redistribution of minor and trace elements

During weathering, elements enriched in black shale are dispersed in the environment by aqueous and mechanical transport. Here a unique evaluation of the differential release, transport, and fate of Fe and 15 trace elements during progressive weathering of the Devonian New Albany Shale in Kentucky is presented. Results of chemical analyses along a weathering profile (unweathered through progressively weathered shale to soil) describe the chemically distinct pathways of the trace elements and the rate that elements are transferred into the broader, local environment. Trace elements enriched in the unweathered shale are in massive or framboidal pyrite, minor sphalerite, CuS and NiS phases, organic matter and clay minerals. These phases are subject to varying degrees and rates of alteration along the profile. Cadmium, Co, Mn, Ni, and Zn are removed from weathered shale during sulfide-mineral oxidation and transported primarily in aqueous solution. The aqueous fluxes for these trace elements range from 0.1 g/ha/a (Cd) to 44 g/ha/a (Mn). When hydrologic and climatic conditions are favorable, solutions seep to surface exposures, evaporate, and form Fe-sulfate efflorescent salts rich in these elements. Elements that remain dissolved in the low pH (<4) streams and groundwater draining New Albany Shale watersheds become fixed by reactions that increase pH. Neutralization of the weathering solution in local streams results in elements being adsorbed and precipitated onto sediment surfaces, resulting in trace element anomalies. Other elements are strongly adsorbed or structurally bound to solid phases during weathering. Copper and U initially are concentrated in weathering solutions, but become fixed to modern plant litter in soil formed on New Albany Shale. Molybdenum, Pb, Sb, and Se are released from sulfide minerals and organic matter by oxidation and accumulate in Fe-oxyhydroxide clay coatings that concentrate in surface soil during illuviation. Chromium, Ti, and V are strongly correlated with clay abundance and considered to be in the structure of illitic clay. Illite undergoes minimal alteration during weathering and is concentrated during illuvial processes. Arsenic concentration increases across the weathering profile and is associated with the succession of secondary Fe(III) minerals that form with progressive weathering. Detrital fluxes of particle-bound trace elements range from 0.1 g/ha/a (Sb) to 8 g/ha/a (Mo). Although many of the elements are concentrated in the stream sediments, changes in pH and redox conditions along the sediment transport path could facilitate their release for aqueous transport.

Applied Geochemistry↗

Geochemistry of trace elements in coals from the Zhuji Mine, Huainan Coalfield, Anhui, China

The abundances of nine major elements and thirty-eight trace elements in 520 samples of low sulfur coals from the Zhuji Mine, Huainan Coalfield, Anhui, China, were determined. Samples were mainly collected from 10 minable coal seams of 29 boreholes during exploration. The B content in coals shows that the influence of brackish water decreased toward the top of coal seams; marine transgression and regression occurred frequently in the Lower Shihezi Formation. A wide range of elemental abundances is found. Weighted means of Na, K, Fe, P, Be, B, Co, Ni, Cr, Se, Sb, Ba, and Bi abundances in Zhuji coals are higher, and the remainder elements are either lower or equal to the average values of elements in coals of northern China. Compared to the Chinese coals, the Zhuji coals are higher in Na, K, Be, B, Cr, Co, Se, Sn, Sb, and Bi, but lower in Ti, P, Li, V and Zn. The Zhuji coals are lower only in S, P, V and Zn than average U.S. and world coals. Potassium, Mg, Ca, Mn, Sr, As, Se, Sb and light rare earth elements (LREE) had a tendency to be enriched in thicker coal seams, whereas Fe, Ti, P, V, Co, Ni, Y, Mo, Pb and heavy rare earth elements (HREE) were inclined to concentrate in thinner coal seams. The enrichment of some elements in the Shanxi or Upper Shihezi Formations is related to their depositional environments. The elements are classified into three groups based on their stratigraphic distributions from coal seams 3 to 11-2, and the characteristics of each group are discussed. Lateral distributions of selected elements are also investigated. The correlation coefficients of elemental abundances with ash content show that the elements may be classified into four groups related to modes of occurrence of these elements. ?? 2009 Elsevier B.V. All rights reserved.

International Journal of Coal Geology↗

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

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

Open-File Report↗

Use of an ultra-clean sampling technique with inductively coupled plasma-mass spectrometry to determine trace-element concentrations in water from the Kirkwood-Cohansey Aquifer system, coastal plain, New Jersey

Water samples were collected during 1993 from 22 public supply wells screened in the Kirkwood-Cohansey aquifer system; concentrations of 18 trace elements were determined primarily by using inductively coupled plasma-mass spectrometry (ICP-MS) techniques, though graphite furnace atomic adsorption, hydride generation, and cold- vapor flameless atomic adsorption techniques were used for thallium, arsenic, and mercury, respectively, at the U.S. Geological Survey (USGS) National Water Quality Laboratory (NWQL). In addition, laboratory measurements of alkalinity and turbidity were made. The ground-water samples were collected by using ultra-clean sampling protocols developed by the USGS for collecting ground-water samples in areas with water containing low concentrations of trace elements. This technique is based on recently gained experience in sampling surface water for these elements. Field parameters (water temperature, specific conductance, pH, and dissolved-oxygen concentration) were monitored prior to sample collection. Three equipment blanks were collected to ensure that low-level trace-element contamination did not occur during sample collection. One split sample and a commercially- prepared reference standard were submitted to the NWQL o evaluate laboratory precision and accuracy, respectively. Trace-element concentrations in 10 sample splits and one equipment blank were also determined at the Rutgers University Chemistry Department laboratory. Results of the ICP-MS analyses and cold vapor flameless atomic absorption indicated that five trace elements-- cobalt, copper, lead, mercury, and nickel--were detectable in low concentrations (<0.1-29 mg/L) in most of the samples from the 22 wells, and four elements--aluminum, barium, manganese and zinc--were detected in higher concentrations than the other elements (30-710 mg/L for aluminum; 4-180 mg/L for barium, manganese, and zinc). The remaining nine trace elements were present in concentrations consistently lower than the minimum reporting limit. Turbidity was low (less than 1 nephelometric turbidity unit (NTU)), indicating that the trace-element concentrations were present in the dissolved phase and ideally would be reproducible in the absence of highly variable concentrations of particulates. The concentration of lead in one sample exceeded the U.S. Environmental Protection Agency (USEPA) action level of 15 mg/L; concentrations ranged from <1 to 16 mg/L. Mercury was frequently detected; concentrations ranged from <0.1 to 1.1 mg/L but did not exceed the USEPA maximum contaminant level. Results of analyses of the equipment blanks indicated that samples collected by using the new ultra-clean sampling protocols were free of low-level (< 1mg/L) trace-element contamination. The analysis of the split sample sent to the NWQL had a difference of 5 percent or less for all constituents except aluminum, for which the analysis had a difference of 10 percent. Results of ICP-MS analyses of split water samples sent to the Rutgers University Chemistry Department laboratory were, in general, in good agreement (within 10 percent) with those of the NWQL. Results of the analysis of the commercial standard agreed (within 5 percent) with the known concentrations of the trace elements. The quality-assurance data (three blanks, one split sample, and one standard), although not statistically evaluated because of the small data set, indicate that the measured trace-element concentrations are precise and accurate and that the samples were free of contamination at the microgram-per-liter level of contamination.

Open-File Report↗

Kinetic determinations of trace element bioaccumulation in the mussel Mytilus edulis

Laboratory experiments employing radiotracer methodology were conducted to determine the assimilation efficiencies from ingested natural seston, the influx rates from the dissolved phase and the efflux rates of 6 trace elements (Ag, Am, Cd, Co, Se and Zn) in the mussel Mytilus edulis. A kinetic model was then employed to predict trace element concentration in mussel tissues in 2 locations for which mussel and environmental data are well described: South San Francisco Bay (California, USA) and Long Island Sound (New York, USA). Assimilation efficiencies from natural seston ranged from 5 to 18% for Ag, 0.6 to 1% for Am, 8 to 20% for Cd, 12 to 16% for Co, 28 to 34% for Se, and 32 to 41% for Zn. Differences in chlorophyll a concentration in ingested natural seston did not have significant impact on the assimilation of Am, Co, Se and Zn. The influx rate of elements from the dissolved phase increased with the dissolved concentration, conforming to Freundlich adsorption isotherms. The calculated dissolved uptake rate constant was greatest for Ag, followed by Zn > Am = Cd > Co > Se. The estimated absorption efficiency from the dissolved phase was 1.53% for Ag, 0.34% for Am, 0.31% for Cd, 0.11% for Co, 0.03% for Se and 0.89% for Zn. Salinity had an inverse effect on the influx rate from the dissolved phase and dissolved organic carbon concentration had no significant effect on trace element uptake. The calculated efflux rate constants for all elements ranged from 1.0 to 3.0% d-1. The route of trace element uptake (food vs dissolved) and the duration of exposure to dissolved trace elements (12 h vs 6 d) did not significantly influence trace element efflux rates. A model which used the experimentally determined influx and efflux rates for each of the trace elements, following exposure from ingested food and from water, predicted concentrations of Ag, Cd, Se and Zn in mussels that were directly comparable to actual tissue concentrations independently measured in the 2 reference sites in national monitoring programs. Sensitivity analysis indicated that the total suspended solids load, which can affect mussel feeding activity, assimilation, and trace element concentration in the dissolved and particulate phases, can significantly influence metal bioaccumulation for particle-reactive elements such as Ag and Am. For all metals, concentrations in mussels are proportionately related to total metal load in the water column and their assimilation efficiency from ingested particles. Further, the model predicted that over 96% of Se in mussels is obtained from ingested food, under conditions typical of coastal waters. For Ag, Am, Cd, Co and Zn, the relative contribution from the dissolved phase decreases significantly with increasing trace element partition coefficients for suspended particles and the assimilation efficiency in mussels of ingested trace elements; values range between 33 and 67% for Ag, 5 and 17% for Am, 47 and 82% for Cd, 4 and 30% for Co, and 17 and 51% for Zn.

Marine Ecology Progress Series↗

Concentration and distribution of sixty-one elements in coals from DPR Korea

Fifty coal samples (28 anthracite and 22 lignites) were collected from both main and small coal mines in DPR Korea prioritized by resource distribution and coal production. The concentrations of 61 elements in 50 coal samples were determined by several multielement and element-specific techniques, including inductively coupled plasma atomic emission spectrometry (ICP-AES), and inductively coupled plasma mass spectrometry (ICP-MS), ion chromatogram (IC), cold-vapor atomic absorption spectrometry (CV-AAS), and hydride generation atomic absorption spectrometry (HGAAS). The ranges, arithmetic means and geometric means of concentrations of these elements are presented. A comparison with crustal abundances (Clarke values) shows that some potentially hazardous elements in the coals of DPR Korea are highly enriched Li, B, S, Cl, Zn, As, Se, Cd, Sn, Sb, W, Te, Hg, Ag, Pb, and La, Ce, Dy, Tm, Ge, Mo, Cs, Tl, Bi, Th and U are moderately enriched. A comparison of ranges and means of elemental concentrations in DPR Korea, Chinese, and world coals shows the ranges of most elements in DPR Korea coals are very close to the ranges of world coals. Arithmetic means of most elements in DPR Korea coals are close to that of American coals. Most elements arithmetic means are higher in Jurassic and Paleogene coals than coals of other ages. In DPR Korea coals, only seven elements in early Permian coals are higher than other periods: Li, Zn, Se, Cd, Hg, Pb, and Bi. Only five elements B, As, Sr, Mo, W in Neogene coals have arithmetic means higher than others. SiO2 and Al2O 3 in ashes are more than 70% except six samples. The correlation between ash yields and major elements from high to low is in the order of Si>Al>Ti>K>Mg>Fe>Na>Ca>P>S. Most elements have high positive correlation with ash (r>0.5) and show high inorganic affinity. ?? 2005 Elsevier Ltd. All rights reserved.

Fuel↗

Carbonatite and alkaline intrusion-related rare earth element deposits&ndash;A deposit model

The rare earth elements are not as rare in nature as their name implies, but economic deposits with these elements are not common and few deposits have been large producers. In the past 25 years, demand for rare earth elements has increased dramatically because of their wide and diverse use in high-technology applications. Yet, presently the global production and supply of rare earth elements come from only a few sources. China produces more than 95 percent of the world's supply of rare earth elements. Because of China's decision to restrict exports of these elements, the price of rare earth elements has increased and industrial countries are concerned about supply shortages. As a result, understanding the distribution and origin of rare earth elements deposits, and identifying and quantifying our nation's rare earth elements resources have become priorities. Carbonatite and alkaline intrusive complexes, as well as their weathering products, are the primary sources of rare earth elements. The general mineral deposit model summarized here is part of an effort by the U.S. Geological Survey's Mineral Resources Program to update existing models and develop new descriptive mineral deposit models to supplement previously published models for use in mineral-resource and mineral-environmental assessments. Carbonatite and alkaline intrusion-related REE deposits are discussed together because of their spatial association, common enrichment in incompatible elements, and similarities in genesis. A wide variety of commodities have been exploited from carbonatites and alkaline igneous rocks, such as rare earth elements, niobium, phosphate, titanium, vermiculite, barite, fluorite, copper, calcite, and zirconium. Other enrichments include manganese, strontium, tantalum, thorium, vanadium, and uranium.

Open-File Report↗

Tin and related elements in sediments and beach sands from Afghanistan, Iran, and Turkey

Sixty samples of sediments from stream beds, outwash plains, and beaches were collected in Afghanistan, Iran, and Turkey by Fred L. Klinger, U.S. Bureau of Mines, as part of the field work undertaken by the National Geographic-Smithsonian Pyrotechnological Expedition of 1968. Facilities for the analysis of the samples for tin and other metals were not immediately available, but in 1973 arrangements were made for analyses to be made on a time-permitting basis in the U.S. Geological Survey. The original purpose in collecting the samples was to determine whether tin was present in amounts indicative of sources for tin ores used in antiquity for the manufacture of bronze. The results of the analyses not only permitted an evaluation of the potential for tin in the localities sampled, but also afforded chemical and mineralogical data that were interpretable in the context of regional potential for other elements of current industrial use. These include gold, base metals, ferro-alloy metals, beryllium, rare earths, and barium. The original 60 samples of sand were sieved to make three size fraction (>0.707 mm, <O.707->O.177 mm, and <0.177 mm) for spectrographic and chemical analysis. Splits of these fractions were used for replicate analyses to permit evaluation of the precision of the analytical procedures. Further splitting of the <0.707->0.177 mm sand gave fractions from each sample that were separated in bromoform. Concentrates from the heavy-liquid separations were divided magnetically into six parts from most magnetic to least magnetic. These concentrates were analyzed spectrographically. The precision of the spectrographic analyses is well within the limits of precision expected from semiquantitative procedures. Such precision allows semiquantitative spectrographic procedures to be used with confidence as a valuable tool for reconnaissance investigations in which multi-element analyses are necessary. The analyses of the various fractions of sediments and sediment concentrates indicate the sample media in which an element was most likely to occur. Tin exhibited no preferential concentration into any particular medium. However, many elements with which tin is associated, and other elements of industrial use, do concentrate into one or more of the sample media. This indication of a preferred medium permits interpretation of the analyses as to the best sample medium for a particular element in the environment of western Asia. Cassiterite and/or tin were detected in many samples from Afghanistan, Iran, and Turkey, but in most of the samples the tin was present in normal crustal abundance. Sixteen samples, including seven from Afghanistan, eight from Iran, and one from Turkey contain unusually large amounts of tin. The most notable areas of anomalous tin are near Mirzaka, Qala-i-Asad, and Shah Agha in Afghanistan; near Meshed, Shir Kuh, Natanz, Nodus, and Talmesi in Iran; and on the shore of the Balck Sea just west of Trabzon in Turkey. Even in these localities the tin appears to be a minor element associated with other ores. The most common association of tin is with copper at known mineralized areas. This relation may have historical significance in the context of the development of bronze. The results of the analyses provided geochemical data on the distribution of other elements of industrial use and clearly identified nine of the ten known mineral deposits represented by the samples. The known metallization at the reported deposits may be only a part of more complex groups of metals. In Afghanistan an array of anomalous elements at the known gold placers around Mirzaka and along the Anguri River signals the presence of complex ore deposits. These elements are silver, arsenic, gold, bismuth, cadmium, copper, mercury, indium, molybdenum, lead, antimony, tin, thallium, tungsten, and zinc. They may indicate a Carlin-type gold deposit in which the wall-rocks are enriched in micron-sized particles of gold. Other localities in Afghanistan signalled by the results of the analyses to be anomalous and to merit further geochemical exploration are: (1) a reach of the Panjshir River for beryllium, lead, zinc, chromium and nickel; (2) the area near Bamian for beryllium; (3) the Siakhak village area for gold and copper; (4) around Qala-i-Asad and Shah Agha for lead, zinc, gold, and tungsten. Some attention to the distribution of monazite around Siakhak, Shahjui, Qala-i-Asad, and Shah Agha is justified to determine if this ore mineral for the rare earths and thorium is enriched over its normally expectable trace as an accessory mineral in granitic rocks, pelitic schists, and gneisses. In Iran, the pluton of granodiorite porphyry near Sar Cheshmeh, an area where a huge porphyry copper deposit was being investigated by the Geological Survey of Iran when the present samples were collected in 1968, shows as a strong geochemical anomaly for copper and molybdenum. The granitic area near Meshed is geochemically enriched persistently in beryllium, tin, and barium, and locally in gold, lanthanum, niobium, yttrium, and other elements. This area deserves a thorough regional geochemical survey for beryl and nonberyl sources of beryllium, for fluorite, and for the ores of niobium, tin, barium, the rare earths, and thorium. Other localities in Iran that merit geochemical exploration on the basis of these data are: ;1) the areas between Tabas and Deyhuk, east of Naiband, and south of Naiband for barium and zinc; (2) a locality about midway between Kerman and Sirdjan for barium, lanthanum, strontium, and zinc; (4) the Meskani copper mine area for mercury, lead, and nickel as well as copper; (5) the Talmesi copper mine area for such other elements as barium, cobalt, mercury, strontium, and zinc; (6) a small pluton of granodiorite north of Natanz for tungsten and base metals; (7) the vicinity of Zendjan for auriferous polymetallic sufide deposits; (8) gold in the gorge 15 km east of Miyaneh; and (9) the area near Nodus for gold, base metals, molybdenum, and niobium, and possibly uranium. The Harsit River basin in Turkey appears to be a suitable target for geochemical exploration for gold and low-temperature hydrothermal deposits of base metals, barium, and mercury.

Open-File Report↗

Element concentrations in soils and other surficial materials of Alaska

Mean concentrations of 35 elements, ash yields, and pH have been estimated for samples of sils and other unconsolidated surficial materials from 266 collection locations throughout Alaska. These background values can be applied to studies of environmental geochemistry and health, wildlife management, and soil-forming processes in cold climates and to computation of element abundances on a regional or worldwide scale. Limited data for an additoinal eight elements are also presented. Materials were collected using a one-way, three-level, analysis-of-variance samplling design in which collecting procedures were simplified for the convenience of the many volunteer field workers. The sample collectors were asked to avoid locations of known mineral deposits and obvious contamination, to take samples at a depth of about 20 cm where possible, and to take a replicate sample about 100 m distant from the first sample collected. With more than 60 percent of the samples replicated and 14 percent of the samples split for duplicate laboratory analyses, reliable estimates were made of the variability in element concentrations at two geographic scales and of the error associated with sample handling and laboratory procedures. Mean concentrations of most elements in surficial materials from the state of alaska correspond well with those reported in similar materials from the conterminous United STatess. Most element concentrations and ranges in samples of stream and lake sediments from Alaska, however, as reported in the literature, do not correspond well with those found in surficial materials of this study. This lack of correspondence is attributed to (1) a merger of two kinds ofsediments (stream and lake) for calculating means; (2) elimination from the sediment mean calculations of values below the limit of quantitative determination; (3) analytical methods different from those of the surficial materials study; and (4) most importantly, the inherent differences in chemistry of the materials. The distribution of variability in element concentrations o Alaskan surficial-material samples was, for most elements, largely among sampling locations, with only a samll part of the variability occurring between replicate samples at a location. The geochemical uniformity within sampling locations in Alaska is an expression of uniform geochemical cycling processes within small geographic areas. The concentration values for 35 elements in 266 samples were plotted on maps by symbols representing classes of concentration frequency distributions. These plotted symbols form patterns that may or may not be possible to interpret but nevertheless show differences that are observable at several geographical scales. The largest pattern is one generally low concentrations of many elements in materials from arctic and oceanic tundra regions, as contrasted to their often high concentrations in samples from interior and southeastern Alaska. The patttern for sodium isespecially pronounced. Intermediate-sized patterns are shown, for example, by the generally high values for magnesium and low values for silicon in the coastal forest region of southeastern Alaska. Many elements occur at low concentratoins in samples from the Alaskan peninsula and the Aleutian Islands. The degree of confidence in patterns of element abundance is expected to be in direct proportion to the number of samples included in the area. As the patterns become smaller, the probability increases that the patterns are not reproducible.

Alaska↗

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↗

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↗

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↗

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↗

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↗