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USGS1993

SPECtrum Processing Routines User's Manual Version 3 (program SPECPR)

Introduction The SPECtrum Processing Routines (SPECPR) is a large-scale interactive program for general one-dimensional array processing and optimized for reflectance spectroscopy data and analysis. The program processes one-dimensional arrays up to 4852 data points and the operations include addition, subtraction, multiplication, division, trigonometric functions, logarithmic and exponential functions, and many more specialized routines. The Specpr user interface is a menu driven, character command system with all user input entered as ascii characters to the program. User commands are thoroughly checked for the context in which they will be used. This provides for essentially all user input mistakes to be caught and appropriate error messages to be issued. The user interface also allows for command aliasing, variable substitutions, command history and batch command processing to occur at any point in the program. The user can also control his or her own variables, increment and decrement them, and monitor certain internal variables. This flexibility allows for sophisticated programming, e.g. from specific computations, to management of a database. All arrays are treated as one dimensional lists of numbers, each with an appropriate header for identification and history. Any array can be plotted versus another array, and each axis labeled appropriately. For example, you may plot a reflectance spectrum versus wavelength or wavelength versus reflectance. The array type is simply a label, so data like temperature versus time can be treated just as easily as a reflectance spectrum. Some routines are specific to certain purposes, however. For example, the Planck black body generator is specific to intensity versus wavelength, whereas a smoothing routine could operate equally on reflectance versus wavelength or temperature versus time. Each array element can have an error bar associated with it and errors are propagated through all appropriate routines. Data points can be marked deleted and deleted points are tracked appropriately. These features allow the program to be effectively used on real world data. This philosophy has resulted in a flexible system for which a user can manipulate data arrays efficiently. The program was designed for analysis of laboratory, field, telescopic, and spacecraft spectroscopic data, and although general in nature, there are biases built in. For example, horizontal axis labels default to wavelength in micrometers, but the defaults can be changed. Because of the orientation in Specpr to process planetary and terrestrial data, and the need to access such data, Specpr has been extended to have access to non-Specpr default file types. In particular, Specpr can "skewer" an 3-dimensional (3D) data file along any of the three axes. Further, block skewers can be done with the standard deviation of the mean computed for each channel in the block. Currently, Specpr can access any of the standard file types common in the terrestrial and planetary remote sensing communities. Details on 3D file I/O are given in Chapter 6. Specpr has multiple record types available within a single Specpr data file. Currently defined record types are data and text. In a data record, a standard one-dimensional array is held, along with its header information. The header information includes a title, history, dates and time of data acquisition and when the data were last processed, the user who processed the data, information typical of a spectrum like temperature and viewing geometry, as well as pointers to wavelengths, resolution, and text. If a spectrum is more than 256 channels in length, then the data gets put in succeeding records in the file, and the following records are continuation records. The second record type is the text, where a title and a block of text (up to 19 kbytes) can be stored. This record type is typically used for a description of samples, experiments, instruments, or data processing for a particular data set. It could also store the actual commands used to create a spectrum. The commands for a complicated plot for a publication might be stored in a text record. That way, you can easily regenerate the plot, or even write the commands to a non-Specpr file, modify them with any editor and re-execute them. The file types, text and command processing, combined with the math and special functions, provide for very powerful and general analysis tool. These facilities also provide the framework for database management.

Open-File Report↗

USGS1998

Analytical results for forty-two fluvial tailings cores and seven stream sediment samples from High Ore Creek, northern Jefferson County, Montana

Metal-mining related wastes in the Boulder River basin study area in northern Jefferson County, Montana have been implicated in their detrimental effects on water quality with regard to acid-generation and toxic-metal solubility. Sediments, fluvial tailings and water from High Ore Creek have been identified as significant contributors to water quality degradation of the Boulder River below Basin, Montana. A study of 42 fluvial tailings cores and 7 stream sediments from High Ore Creek was undertaken to determine the concentrations of environmentally sensitive elements (i.e. Ag, As, Cd, Cu, Pb, Zn) present in these materials, and the mineral phases containing those elements. Two sites of fluvial deposition of mine-waste contaminated sediment on upper High Ore Creek were sampled using a one-inch soil probe. Forty-two core samples were taken producing 247 subsamples. The samples were analyzed by ICP-AES (inductively coupled-plasma atomic emission spectroscopy) using a total mixed-acid digestion. Results of the core analyses show that the elements described above are present at very high concentrations (to 22,000 ppm As, to 460 ppm Ag, to 900 ppm Cd, 4,300 ppm Cu, 46,000ppm Pb, and 50,000 ppm Zn). Seven stream-sediment samples were also analyzed by ICP-AES for total element content and for leachable element content. Results show that the sediment of High Ore Creek has elevated levels of ore-related metals throughout its length, down to the confluence with the Boulder River, and that the metals are, to a significant degree, contained in the leachable phase, namely the hydrous amorphous iron- and manganese-hydroxide coatings on detrital sediment particles.

Montana↗

USGS1999

Analytical results for 35 mine-waste tailings cores and six bed sediment samples, and an estimate of the volume of contaminated materials at Buckeye meadow on upper Basin Creek, northern Jefferson County, Montana

Metal-mining related wastes in the Boulder River basin study area in northern Jefferson County, Montana have been implicated in their detrimental effects on water quality with regard to acid-generation and toxic-metal solubilization. Flotation-mill tailings in the meadow below the Buckeye mine, hereafter referred to as the Buckeye mill-tailings site, have been identified as significant contributors to water quality degradation of Basin Creek, Montana. Basin Creek is one of three tributaries to the Boulder River in the study area; bed sediments and waters draining from the Buckeye mine have also been implicated. Geochemical analysis of 35 tailings cores and six bed-sediment samples was undertaken to determine the concentrations of Ag, As, Cd, Cu, Pb,and Zn present in these materials. These elements are environmentally significant, in that they can be toxic to fish and/or the invertebrate organisms that constitute their food. A suite of one-inch cores of dispersed flotation-mill tailings and underlying premining material was taken from a large, flat area north of Basin Creek near the site of the Buckeye mine. Thirty-five core samples were taken and divided into 204 subsamples. The samples were analyzed by ICP-AES (inductively coupled plasma-atomic emission spectroscopy) using a mixed-acid digestion. Results of the core analyses show that the elements listed above are present at moderate to very high concentrations (arsenic to 63,000 ppm, silver to 290 ppm, cadmium to 370 ppm, copper to 4,800 ppm, lead to 93,000 ppm, and zinc to 23,000 ppm). Volume calculations indicate that an estimated 8,400 metric tons of contaminated material are present at the site. Six bed-sediment samples were also subjected to the mixed-acid total digestion, and a warm (50°C) 2M HCl-1% H 2 O 2 leach and analyzed by ICP-AES. Results indicate that bed sediments of Basin Creek are only slightly impacted by past mining above the Buckeye-Enterprise complex, moderately impacted at the upper (eastern) end of the tailings area, and heavily impacted at the lower (western) end of the area and downstream. The metals are mostly contained in the 2M HCl-1% H 2 O 2 leachable phase, which are the hydrous amorphous iron- and manganese-hydroxide coatings on detrital sediment particles.

Montana↗

USGS1999

Organic compounds and trace elements in the Pocomoke River and tributaries, Maryland

In response to concern about recent blooms of the dinoflagellate, Pfiesteria piscicida, samples of sediment and water were collected from the lower Pocomoke River Basin and were screened for trace elements, pesticides, and other organic compounds. A large group of steroid and fatty acid methyl-ester compounds was detected in streamwater using gas chromatography/mass spectroscopy in scan mode. Some of these steroid compounds have been identified and further quantified in bed-sediment extracts. Spatial patterns of the concentrations of cholesterol suggest that these compounds are linked to the runoff of animal wastes into the river. Many of the organic compounds found in the Pocomoke River sediments have not yet been identified, but at least several are in the class of hormone compounds related to estradiols and have the potential to promote endocrine-disrupting effects in aquatic life. Particulate forms of arsenic and zinc are slightly elevated above normal levels for streams, but the sources for these elements are still undetermined. Several pesticides were found in low, parts-per-trillion concentrations, but were within the ranges commonly found in streams of this region.

Maryland↗

USGS2006

Constraints on the age and provenance of the Chugach accretionary complex from detrital zircons in the Sitka Graywacke near Sitka, Alaska

The Sitka Graywacke is the westernmost and youngest unit of the Chugach accretionary complex in southeastern Alaska. Using laser-ablation inductively coupled plasma mass spectroscopy, we obtained 492 detrital-zircon ages on seven typical samples of Sitka Graywacke turbidites, which were collected in a transect across much of the unit near Sitka, Alaska. Individual grains range in age from 66 to 1,802 m.y. The youngest peak ages on relative-probability plots of the western four samples (74, 72, 74, and 74 m.y., from west to east) are distinctly younger than the youngest peak ages of the eastern three samples (105, 103, and 97 m.y., from west to east). These youngest peak ages set maximum depositional ages for each sample. We suggest that these peak ages are not significantly older (within ~5 m.y.) than the depositional age of the Sitka Graywacke because the deposits accumulated in a trench along a convergent margin, where magmatic sources likely continuously introduced juvenile zircons. The differences in the youngest cluster of detrital-zircon ages between the eastern and western sample localities is likely due to both a change in provenance and a fault. The similarity of the youngest peak ages in the Sitka Graywacke to fossil ages in the Valdez Group, in Prince William Sound, implies that the western part of the Sitka Graywacke is correlative with the Valdez Group, as previously inferred. However, the eastern part of the Sitka Graywacke has youngest detrital-zircon ages older than fossil ages in the Valdez Group and younger than fossil ages in the McHugh Complex, which in south-central Alaska is the oldest part of the accretionary complex. The age distribution of zircons in the older, eastern sequence suggests sources along the British Columbia margin. The detrital-zircon ages in the younger, western sequence are similar to igneous ages from south-central Alaska to southern British Columbia. Right-lateral strike slip on various fault systems inboard of the Sitka Graywacke implies that it lay to the south when it was deposited and offscraped. Thus, although source areas as far north as the St. Elias Mountains and south-central Alaska are possible, they were most likely in coastal and interior British Columbia.

Professional Paper↗

USGS2007

Integrated geoscience studies in the Greater Yellowstone Area - Volcanic, tectonic, and hydrothermal processes in the Yellowstone geoecosystem

Yellowstone National Park, rimmed by a crescent of older mountainous terrain, has at its core the Quaternary Yellowstone Plateau, an undulating landscape shaped by forces of volcanism, tectonism, and later glaciation. Its spectacular hydrothermal systems cap this landscape. From 1997 through 2003, the United States Geological Survey Mineral Resources Program conducted a multidisciplinary project of Yellowstone National Park entitled Integrated Geoscience Studies of the Greater Yellowstone Area, building on a 130-year foundation of extensive field studies (including the Hayden survey of 1871, the Hague surveys of the 1880s through 1896, the studies of Iddings, Allen, and Day during the 1920s, and NASA-supported studies starting in the 1970s—now summarized in USGS Professional Paper 729 A through G) in this geologically dynamic terrain. The project applied a broad range of scientific disciplines and state-of-the-art technologies targeted to improve stewardship of the unique natural resources of Yellowstone and enable the National Park Service to effectively manage resources, protect park visitors from geologic hazards, and better educate the public on geologic processes and resources. This project combined a variety of data sets in characterizing the surficial and subsurface chemistry, mineralogy, geology, geophysics, and hydrothermal systems in various parts of the park. The sixteen chapters presented herein in USGS Professional Paper 1717, Integrated Geoscience Studies in the Greater Yellowstone Area—Volcanic, Tectonic, and Hydrothermal Processes in the Yellowstone Geoecosystem , can be divided into four major topical areas: (1) geologic studies, (2) Yellowstone Lake studies, (3) geochemical studies, and (4) geophysical studies. The geologic studies include a paper by Ken Pierce and others on the influence of the Yellowstone hotspot on landscape formation, the ecological effects of the hotspot, and the human experience and human geography of the greater Yellowstone ecosystem as influenced by the Yellowstone hotspot. Another paper by Paul Carrara describes the recent movement of a large landslide block dated by tree-ring analyses in the Tower Falls area. The section under Yellowstone Lake studies begins with a classic paper by J. David Love and others on ancestral Lake Yellowstone. Other papers in this section include results and interpretation of the high-resolution bathymetric, seismic reflection, and submersible studies by Lisa Morgan and others. Ken Pierce and others describe results from their studies of shorelines along Yellowstone Lake and their interpretation of inflation-deflation cycles, tilting, and faulting in the Yellowstone caldera. The influence of sublacustrine hydrothermal vent fluids on the geochemistry of Yellowstone Lake is described by Laurie Balistrieri and others. In Pat Shanks and others’ chapter, hydrothermal reactions, stable-isotope systematics, sinter deposition, and spire formation are related to the geochemistry of sublacustrine hydrothermal deposits in Yellowstone Lake. The geochemical studies section considers park-wide geochemical systems in Yellowstone National Park. In Bob Rye and Alfred Truesdell’s paper, the question of recharge to the deep thermal reservoir underlying the geysers and hot springs of Yellowstone National Park is discussed. Irving Friedman and Dan Norton report on the chloride flux emissions from Yellowstone in their paper questioning whether Yellowstone is losing its steam. Wildlife issues as addressed by examining trace-element and stable-isotope geochemistry are discussed in a chapter by Maurice Chaffee and others. In another chapter by Chaffee and others, natural and anthropogenic anomalies and their potential impact on the environment using geochemistry is reported. Pam Gemery-Hill and others present geochemical data for selected rivers, lake waters, hydrothermal vents, and subaerial geysers for the time interval of 1996–2004. The life cycle of gold deposits near the northeast corner of the park is discussed by Brad Van Gosen. Under the geophysical studies segment, Ray Kokaly and others use AVIRIS (Airborne Visible and Infrared Spectroscopy) data to map vegetation cover and microbial communities in Yellowstone National Park. Eric Livo and others report their results using AVIRIS data on hydrothermally altered rock and hot-spring deposits. In his final paper following a half century of scientific research, Irving Friedman presents data on monitoring changes in geothermal activity at Norris Geyser Basin using satellite telemetry. These papers summarize a near-decade-long effort by the USGS from the late 1990s to mid-2000s. In 2001, the USGS in cooperation with the National Park Service (Yellowstone National Park) and the University of Utah established the Yellowstone Volcano Observatory, the 5th volcano observatory in the United States.

Professional Paper↗

USGS2008

Chlorine degassing during the lava dome-building eruption of Mount St. Helens, 2004-2005

Remote measurements of volcanic gases from the Mount St. Helens lava dome were carried out using OpenPath Fourier-Transform Infrared spectroscopy on August 31, 2005. Measurements were performed at a site ~1 km from the lava dome, which was used as a source of IR radiation. On average, during the period of measurement, the volcanic gas contained 99 mol percent H 2 O, 0.78 percent CO 2 , 0.095 percent HCl, 0.085 percent SO 2 , 0.027 percent HF, 4.8×10 -4 percent CO, and 2.5×10 -4 percent COS close to the active vent. The fluxes of these species, constrained by synchronous measurements of SO 2 flux, were 7,200 t/d H 2 O, 140 t/d CO 2 , 22 t/d SO 2 , 14 t/d HCl, 2.0 t/d HF, 54 kg/d CO, and 59 kg/d COS, ±20 percent. Observations of H 2 O/Cl in the vapor and melt are compared to models of closed- and open-system degassing and to models where a closed system dominates to depths as shallow as ~1 km, and gases are then allowed to escape through a permeable bubble network. Although several features are consistent with this model--for example, (1) H 2 O/Cl in the gases emitted from stagnant parts of the lava dome, (2) the concentration of Cl in the matrix glass of erupted dacite, and (3) the glass H 2 O/Cl--the gases emitted from the active part of the lava dome have much higher H 2 O/ Cl than expected. These higher H 2 O/Cl levels result from a combination of two factors (1) the addition of substantial amounts of ground water or glacier-derived H 2 O to the gases at shallow depths, such that only ~10 mol percent of the measured H 2 O is magmatic, and (or) (2) some Cl present as alkali chloride (NaCl and KCl) in the gas phase. The mean molar Cl/S is similar to gases measured at other silicic subductionzone volcanoes during effusive activity; this may be due to the influence of Cl in the vapor on S solubility in the melt, which produces a solubility maximum for S at vapor Cl/S ~1.

Washington↗

USGS2023

Groundwater chemistry and hexavalent chromium

Water samples collected by the U.S. Geological Survey from more than 100 wells between March 2015 and November 2017 in Hinkley and Water Valleys, in the Mojave Desert 80 miles northeast of Los Angeles, California, were analyzed for field parameters, major ions, nutrients, and selected trace elements, including hexavalent chromium, Cr(VI). Water from most wells was alkaline and oxic. The pH ranged from 6.9 in water-table wells near recharge areas along the Mojave River to 9.4 in deeper wells farther downgradient in the northern subarea. Hexavalent chromium concentrations measured by ion chromatography using U.S. Environmental Protection Agency Method 218.6 and a version of that method used for detection of Cr(VI) concentrations as low as 0.06 micrograms per liter (μg/L), produced results comparable to field speciation with subsequent analyses by graphite furnace atomic absorption spectroscopy (coefficient of determination, R 2 , of 0.97). Hexavalent chromium concentrations ranged from less than the study reporting level of 0.10 to 2,500 μg/L. The highest concentrations were within the October–December 2015 (Q4 2015) regulatory Cr(VI) plume downgradient from the Hinkley compressor station. Hexavalent chromium concentrations outside the Q4 2015 regulatory Cr(VI) plume were as high as 11 μg/L. Hexavalent chromium concentrations in water from most wells were distributed in a narrow redox potential and pH band within the overlapping chromate ion, CrO 4 2− (aqueous) , and manganese-3, Mn(III) (solid) , stability fields. The redox potential of water from some wells completed in carbonate-rich mudflat/playa deposits approached the more oxic manganese-4, Mn(IV) (solid) , stability field. However, Cr(VI) concentrations in porewater pressure-extracted from Mn(IV)-containing deposits in the eastern subarea did not exceed 3.3 μg/L, and porewater does not appear to be a source of Cr(VI) concentrations greater than this concentration in water from wells in the eastern subarea. On the basis of comparison with California-wide data, Cr(VI) concentrations at the measured pH were higher than expected for uncontaminated water from wells (1) within the Q4 2015 regulatory Cr(VI) plume, (2) within the eastern subarea nominally crossgradient from the Hinkley compressor station and upgradient from the Q4 2015 regulatory Cr(VI) plume, and (3) from shallow wells in the northern subarea downgradient from the leading edge of the Q4 2015 regulatory Cr(VI) plume. Hexavalent chromium concentrations in alkaline water from wells in the northern subarea of Hinkley Valley and in Water Valley were within ranges expected for uncontaminated water elsewhere in California given their pH and trace-element composition. Hexavalent chromium concentrations were higher than expected on the basis of selected trace-element concentrations that co-occur with Cr(VI) in water from wells within the Q4 2015 regulatory Cr(VI) plume and from wells in the eastern and northern subareas near the plume margins. Hexavalent chromium concentrations did not exceed 4 μg/L in water from domestic wells sampled in Hinkley and Water Valleys and were generally within ranges expected for uncontaminated groundwater given their pH and trace-element composition. Interpretations derived from Cr(VI) and pH, and from Cr(VI) and selected trace-element concentrations collected between March 2015 and November 2017 were used within a summative-scale analysis to determine the Cr(VI) plume extent (chapter G). However, Cr(VI) background concentrations (chapter G) were calculated from regulatory data collected from selected wells between April 2017 and January 2018.

California↗

USGS2004

Microbial and dissolved organic carbon characterization of stormflow in the Santa Ana River at Imperial Highway, Southern California, 1999-2002

The Santa Ana River drains about 2,670 square miles of densely populated coastal southern California, near Los Angeles. Almost all the flow in the river, more than 200,000 acre-feet annually, is diverted to ponds where it infiltrates and recharges underlying aquifers pumped to supply water for more than 2 million people. Base flow in the river is almost entirely treated municipal wastewater discharged from upstream treatment plants and, in the past, stormflow was considered a source of high-quality water suitable for use as a source of ground-water recharge that would dilute poorer quality water recharged during base flow. Stormflow in the Santa Ana River at the Imperial Highway diversion contains total coliform bacteria concentrations as high as 3,400,000 colonies per 100 mL (milliliters). Fecal indicator bacteria concentrations, including fecal coliforms, Escherichia coli, and enterococci, were as high as 310,000, 84,000, and 102,000 colonies per 100 mL, respectively. Although concentrations were high owing to urban runoff during the first stormflow of the rainy season, the highest concentrations occurred during the recessional flows of the first stormflow of the rainy season after streamflow returned to pre-storm conditions. Molecular indicators of microbiological organisms in stormflow, including phospholipid fatty acid (PLFA) and genetic data, show that the diversity of the total microbial population decreases during stormflow while fecal indicator bacteria concentrations increase. This suggests that the source of the bacteria must be poorly diverse and dominated by only a few types of bacteria. Although direct runoff of fecal indicator bacteria from urban areas occurs, this process cannot explain the very high concentrations of fecal indicator bacteria in runoff from upstream parts of the basin characterized by urban, agricultural (including more than 300,000 head of dairy cattle), and other land uses. Although other explanations are possible, fecal indicator bacteria concentrations and molecular microbiological data indicate accumulation and extended survival of bacteria in streambed sediments, and subsequent mobilization of those sediments and associated bacteria during stormflow. Both PLFA and genetic data indicate that water from dairy-waste storage ponds was not present during sampled stormflows. This is consistent with the relatively dry conditions and the absence of large stormflows during the study. Dissolved organic carbon (DOC) concentrations in stormflow ranged from 3 to 15.3 mg/L. In general, concentrations increased during stormflow and were distributed across the stormflow hydrograph in a manner similar to that of fecal indicator bacteria. DOC concentrations typically remained high for several days after flow returned to pre-storm conditions. Ultraviolet absorbance, excitation emission spectroscopy, and sequential fractionation of DOC using XAD-8 and XAD-4 resins showed that the composition of DOC changed rapidly during stormflow. Hydrophobic and hydrophilic acids were the largest fraction of DOC composing between 27 and 45 percent and between 24 and 37 percent of the DOC, respectively. The fraction of DOC composed of hydrophobic acids decreased due to urban runoff and increased during the recession of the first stormflow of the rainy season; the hydrophilic-acid fraction generally decreased throughout the stormflow hydrograph; the transhydrophilic-acid fraction did not vary greatly during stormflow; and the hydrophobic-neutral fraction increased from low values in base flow to almost 30 percent of the DOC after more soluble and more mobile hydrophobic and hydrophilic acids were washed from urban areas. Comparison of ultraviolet absorbance data with data collected during previous studies shows that the optical properties and, presumably, the composition of the DOC were different in this study than DOC collected during wetter periods. Samples of shallow ground water collec

California↗

USGS2005

Remote sensing for environmental site screening and watershed evaluation in Utah Mine lands: East Tintic mountains, Oquirrh mountains, and Tushar mountains

Imaging spectroscopy-a powerful remote-sensing tool for mapping subtle variations in the composition of minerals, vegetation, and man-made materials on the Earth's surface-was applied in support of environmental assessments and watershed evaluations in several mining districts in the State of Utah. Three areas were studied through the use of Landsat 7 ETM+ and Airborne Visible/Infrared Imaging Spectrometer (AVIRIS) data: (1) the Tintic mining district in the East Tintic Mountains southwest of Provo, (2) the Camp Floyd mining district (including the Mercur mine) and the Stockton (or Rush Valley) mining district in the Oquirrh Mountains south of the Great Salt Lake, and (3) the Tushar Mountains and Antelope Range near Marysvale. The Landsat 7 ETM+ data were used for initial site screening and the planning of AVIRIS surveys. The AVIRIS data were analyzed to create spectrally defined maps of surface minerals with special emphasis on locating and characterizing rocks and soils with acid-producing potential (APP) and acid-neutralizing potential (ANP). These maps were used by the United States Environmental Protection Agency (USEPA) for three primary purposes: (1) to identify unmined and anthropogenic sources of acid generation in the form of iron sulfide and (or) ferric iron sulfate-bearing minerals such as jarosite and copiapite; (2) to seek evidence for downstream or downwind movement of minerals associated with acid generation, mine waste, and (or) tailings from mines, mill sites, and zones of unmined hydrothermally altered rocks; and (3) to identify carbonate and other acid-buffering minerals that neutralize acidic, potentially metal bearing, solutions and thus mitigate potential environmental effects of acid generation. Calibrated AVIRIS surface-reflectance data were spectrally analyzed to identify and map selected surface materials. Two maps were produced from each flightline of AVIRIS data: a map of iron-bearing minerals and water having absorption features in the spectral region from 0.35 µ m to 1.35 µ m and a map of minerals (including clays, sulfates, micas, and carbonates) having absorptions in the spectral region from 1.45 µ m to 2.51 µ m. Several methods were used to verify the AVIRIS mapping results, including field checking of selected locations with a portable spectrometer, visual inspection of the AVIRIS reflectance spectra, and X-ray diffraction (XRD) analysis of field samples. The maps of iron-bearing minerals derived from analysis of the visible (VIS) and near-infrared (NIR) regions of the electromagnetic spectrum were shown to be more consistently reliable in indicating the presence of jarosite than were the maps generated from analysis of the short-wave infrared (SWIR) region. When present in abundance, phyllosilicate minerals tend to dominate the SWIR and mask the spectral features of jarosite in that wavelength region. The crystal field absorptions of jarosite in the VIS and NIR spectral regions will commonly be present regardless of whether the Fe-OH absorption feature near 2.27 µ m can be detected. For this reason, the VIS and NIR were preferable to the SWIR for the remote spectroscopic identification of jarosite (and other iron-bearing minerals). Large exposures of unmined hydrothermally altered rocks occur throughout the three study areas. These rocks commonly contain sulfide or sulfate minerals that produce sulfuric acid upon subaerial oxidation. The acid may be introduced into local surface and ground water and thus lower the baseline (that is, the premining) pH for a watershed.

Utah↗

USGS2013

Sources and characteristics of organic matter in the Clackamas River, Oregon, related to the formation of disinfection by-products in treated drinking water

This study characterized the amount and quality of organic matter in the Clackamas River, Oregon, to gain an understanding of sources that contribute to the formation of chlorinated and brominated disinfection by-products (DBPs), focusing on regulated DBPs in treated drinking water from two direct-filtration treatment plants that together serve approximately 100,000 customers. The central hypothesis guiding this study was that natural organic matter leaching out of the forested watershed, in-stream growth of benthic algae, and phytoplankton blooms in the reservoirs contribute different and varying proportions of organic carbon to the river. Differences in the amount and composition of carbon derived from each source affects the types and concentrations of DBP precursors entering the treatment plants and, as a result, yield varying DBP concentrations and species in finished water. The two classes of DBPs analyzed in this study-trihalomethanes (THMs) and haloacetic acids (HAAs)-form from precursors within the dissolved and particulate pools of organic matter present in source water. The five principal objectives of the study were to (1) describe the seasonal quantity and character of organic matter in the Clackamas River; (2) relate the amount and composition of organic matter to the formation of DBPs; (3) evaluate sources of DBP precursors in the watershed; (4) assess the use of optical measurements, including in-situ fluorescence, for estimating dissolved organic carbon (DOC) concentrations and DBP formation; and (5) assess the removal of DBP precursors during treatment by conducting treatability "jar-test" experiments at one of the treatment plants. Data collection consisted of (1) monthly sampling of source and finished water at two drinking-water treatment plants; (2) event-based sampling in the mainstem, tributaries, and North Fork Reservoir; and (3) in-situ continuous monitoring of fluorescent dissolved organic matter (FDOM), turbidity, chlorophyll- a , and other constituents to continuously track source-water conditions in near real-time. Treatability tests were conducted during the four event-based surveys to determine the effectiveness of coagulant and powdered activated carbon (PAC) on the removal of DBP precursors. Sample analyses included DOC, total particulate carbon (TPC), total and dissolved nutrients, absorbance and fluorescence spectroscopy, and, for regulated DBPs, concentrations of THMs and HAAs in finished water and laboratory-based THM and HAA formation potentials (THMFP and HAAFP, respectively) for source water and selected locations throughout the watershed. The results of this study may not be typical given the record and near record amounts of precipitation that occurred during spring that produced streamflow much higher than average in 2010-11. Although there were algal blooms, lower concentrations of chlorophyll- a were observed in the water column during the study period compared to historical data. Concentrations of DBPs in finished (treated) water averaged 0.024 milligrams per liter (mg/L) for THMs and 0.022 mg/L for HAAs; maximum values were about 0.040 mg/L for both classes of DBPs. Although DBP concentrations were somewhat higher within the distribution system, none of the samples collected for this study or for the quarterly compliance monitoring by the water utilities exceeded levels permissible under existing U.S. Environmental Protection Agency (USEPA) regulations: 0.080 mg/L for THMs and 0.060 mg/L for HAAs. DOC concentrations were generally low in the Clackamas River, typically about 1.0-1.5 mg/L. Concentrations in the mainstem occasionally increased to nearly 2.5 mg/L during storms; DOC concentrations in tributaries were sometimes much higher (up to 7.8 mg/L). The continuous in-situ FDOM measurements indicated sharp rises in DOC concentrations in the mainstem following rainfall events; concentrations were relatively stable during summer base flow. Even though the first autumn storm mobilized appreciable quantities of carbon, higher concentrations of DBPs in finished water were observed 3-weeks later, after the ground was saturated from additional rainfall. The majority of the DOC in the lower Clackamas River appears to originate from the upper basin, suggesting terrestrial carbon was commonly the dominant source. Lower-basin tributaries typically contained the highest concentrations of DOC and DBP precursors and contributed substantially to the overall loads in the mainstem during storms. During low-flow periods, tributaries were not major sources of DOC or DBP precursors to the Clackamas River. Although the dissolved fraction of organic carbon contributed the majority of DBP precursors, at times the particulate fraction (inorganic sediment and organic particles including detritus and algal material) contributed a substantial fraction of DBP precursors. Considering just the main-stem sites, on average, 10 percent of THMFP and 32 percent of HAAFP were attributed to particulate carbon. This finding suggests water-treatment methods that remove particles prior to chlorination would reduce finished-water DBP concentrations to some degree. Overall, concentrations of THM and HAA precursors were closely linked to DOC concentrations; laboratory DBP formation potentials (DBPFPs) clearly showed that THMFP and HAAFP were greatest in the downstream tributaries that contained elevated carbon concentrations. However, carbon-normalized "specific" formation potentials for THMs and HAAs (STHMFP and SHAAFP, respectively) revealed changes in carbon character over time that affected the two types of DBP classes differently. HAA precursors were elevated in waters containing aromatic-rich soil-derived material arising from forested areas. In contrast, THM precursors were associated with carbon having a lower aromatic content; highest STHMFP occurred in autumn 2011 in the mainstem from North Fork Reservoir downstream to LO DWTP. This pattern suggests the potential for a link between THM precursors and algal-derived carbon. The highest STHMFP value was measured within North Fork Reservoir, indicating reservoir derived carbon may be important for this class of DBPs. Weak correlations between STHMFP and SHAAFP emphasize that precursor sources for these types of DBPs may be different. This highlights not only that different locations within the watershed produce carbon with different reactivity (specific DBPFP), but also that different management approaches for each class of DBP precursors could be required for control. Treatability tests conducted on source water during four basin-wide surveys demonstrated that an average of about 40 percent of DOC can be removed by coagulation. While the decrease in THMFP following coagulation was similar to DOC, the decrease in HAAFP was much greater (approximately 70 percent), indicating coagulation is particularly effective at removing HAA precursors'likely because of the aromatic nature of the carbon associated with HAA precursors. Several findings from this study have direct implications for managing drinking-water resources and for providing useful information that may help improve treatment-plant operations. For example, the use of in-situ fluorometers that measure FDOM provided an excellent proxy for DOC concentration in this system and revealed short-term, rapid changes in DOC concentration during storm events. In addition, the strong correlation between FDOM values measured in-situ and HAA5 concentrations in finished water may permit estimation of continuous HAA concentrations, as was done here. As part of this study, multiple in-situ FDOM sensors were deployed continuously and in real-time to characterize the composition of dissolved organic matter. Although the initial results were promising, additional research and engineering developments will be needed to demonstrate the full utility of these sensors for this purpose. In conclusion, although DBPFPs were strongly correlated to DOC concentration, some DBPs formed from particulate carbon, including terrestrial leaf material and algal material such as planktonic species of blue-green algae and sloughed filaments, stalks, and cells of benthic algae. Different precursor sources in the watershed were evident from the data, suggesting specific actions may be available to address some of these sources. In-situ measurements of FDOM proved to be an excellent proxy for DOC concentration as well as HAA formation during treatment, which suggests further development and refinement of these sensors have the potential to provide real-time information about complex watershed processes to operators at the drinking-water treatment plants. Follow-up studies could examine the relative roles that terrestrial and algal sources have on the DBP precursor pool to better understand how watershed-management activities may be affecting the transport of these compounds to Clackamas River drinking-water intakes. Given the low concentrations of algae in the water column during this study, additional surveys during more typical river conditions could provide a more complete understanding of how algae contribute DBP precursors. Further development of FDOM-sensor technology can improve our understanding of carbon dynamics in the river and how concentrations may be trending over time. This study was conducted in collaboration with Clackamas River Water and the City of Lake Oswego water utilities. Other research partners included Oregon Health and Science University in Hillsboro, Oregon, Alexin Laboratory in Tigard, Oregon, U.S. Geological Survey National Research Program Laboratory in Denver, Colorado, and the U.S. Geological Survey Water Science Centers in Portland, Oregon, and Sacramento, California. This project was supported with funding from Clackamas River Water, City of Lake Oswego, the U.S. Geological Survey, and the Water Research Foundation.

Oregon↗

USGS2022

Sources and characteristics of dissolved organic carbon in the McKenzie River, Oregon, related to the formation of disinfection by-products in treated drinking water

Executive Summary This study characterized the concentration and quality of dissolved organic carbon (DOC) in the McKenzie River, a relatively undeveloped watershed in western Oregon, and its link to forming disinfection by-products (DBPs) in treated drinking water. The study aimed to identify the primary source(s) of DOC in source water for the Eugene Water & Electric Board’s (EWEB) conventional treatment plant on the McKenzie River near river mile 11, upstream of Hayden Bridge. The two classes of regulated compounds examined—trihalomethanes (THMs) and haloacetic acids (HAAs)—form when organic carbon in raw source water reacts with chlorine and (or) bromine during water treatment. The objectives of the study were to: characterize the amount and quality of DOC in the McKenzie River and select tributaries during storms; identify the most common types of carbon using UV-vis spectroscopy and other methods; evaluate optical properties for predicting DBP precursors in surface water; and identify land cover classes or vegetation types that may be important sources of organic carbon and DBP precursors in EWEB’s source water. Eleven storms were sampled synoptically in upstream-to-downstream fashion to provide a “snapshot” of water quality conditions at four sites on the McKenzie River from Frissell Bridge (6 miles downstream from Trail Bridge Reservoir) to the EWEB water treatment plant at Hayden Bridge and nine contributing tributaries. Storms included late summer and early autumn “first flush” events and late autumn, winter, and spring storms spanning a range in streamflows from 3,000 to 26,000 cubic feet per second as measured in the main stem McKenzie River at the EWEB water intake. Water samples were analyzed for DOC concentrations and optical properties (fluorescence and ultraviolet absorbance [UVA]) across a range of wavelengths to characterize the quantity and quality of dissolved organic matter (DOM) in the McKenzie River at the drinking water intake and upstream locations. Paired sets of source and finished water samples were collected at the EWEB treatment plant to identify DOC quality parameters in raw source water that might predict DBP concentrations in finished drinking water. DOC concentrations were relatively low in the McKenzie River (0.4–3 milligrams per liter [mg/L]; average 1.5 mg/L) but much higher in the tributaries. The highest DOC concentrations occurred during “first flush” storms in October 2012 and September 2013; the highest value (16 mg/L) was measured at the 52nd Street stormwater outfall. The average DOC concentration in the lower basin-tributaries was 3.8 mg/L; three middle basin tributaries—Quartz, Gate, and Haagen Creeks, which drain private forestland with less coniferous forest compared with other higher elevation tributaries— had slightly lower average DOC concentrations (2.8 mg/L). These middle-basin watersheds may be important sources of DOC and DBP precursors to the McKenzie River, even more so than the lower basin tributaries, depending on their flows (and loads). This is particularly true after the September 2020 Holiday Farm fire, which burned much of this area. DOC concentrations increased 68 percent in the McKenzie River between the uppermost reference site at Frissell Bridge and Vida; this includes drainage from Quartz Creek, Blue River Lake and Cougar Reservoir, which all contributed DOC to the main stem. In contrast, the lowermost tributaries draining most of the agricultural and urban land did not have a large effect on DOC in the McKenzie River despite their higher DOC concentrations because of their presumed relatively low streamflows and, consequently, DOC loads. Apart from the continuous flow monitors in the McKenzie River and some tributaries (Blue River and South Fork McKenzie River, and streamflow at Hayden Bridge and Vida, Camp Creek and some other locations), streamflow was not assessed during sample collection for this study. This lack of streamflow data precludes a detailed analysis of loads, which is discussed in the future studies section. All DBP concentrations in finished drinking water were less than EPA maximum contaminant levels (MCLs) of 0.080 mg/L for the four trihalomethanes (THM4) and 0.060 mg/L for five haloacetic acids (HAA5). During the 11 storm sampling events the maximum summed concentrations were about 0.040 mg/L for both THM4 and HAA5. Compliance monitoring samples, collected separately by EWEB, yielded some higher concentrations—0.046 mg/L THM4 and 0.047 HAA5—during the December 2012 storm. The corresponding benchmark quotient (BQ) values, which indicate how close a measured DBP concentration is to the MCL, were 0.58 and 0.78, respectively, for THM4 and HAA5. Compared with a similar 2007–08 McKenzie River study that did not target storm events, concentrations of THM4 and HAA5 in finished water were 68 percent and 33 percent higher, respectively, during the current study. Due to the high dilution rates in the McKenzie River main stem, many of the individual fluorescence excitation-emission measurements were low (<0.1 Raman units) and approached analytical detection limits. Parallel factor analysis (PARAFAC) resulted in a five-component model (C1–C5) that represents five unique organic fluorophores. Components C1, C2, and C3 represent DOM associated with soil-derived, humic-like, more degraded organic matter. In contrast, components C4 and C5 represent “fresher” DOM, derived from terrestrial and aquatic plants, including algae and cyanobacteria that are common in the McKenzie River and its tributaries and reservoirs. The fluorescence data and PARAFAC modeling suggest that most of the DOC in the McKenzie River originated from terrestrial sources (primarily components C1 and C2). The largest increases in DOC in the main stem occurred in the reach upstream of Vida, from inflows by Quartz Creek, Blue River, South Fork McKenzie River, and other tributaries. Concentrations of DBPs in EWEB’s finished drinking water were positively correlated with DOC concentrations in raw source water (THM4, p <0.05; HAA5, p <0.01) for paired samples collected 12−24 hours apart. DOC concentrations were significantly positively correlated ( p <0.001) with laboratory-based fluorescent dissolved organic matter (fDOM) measurements, suggesting fDOM as a useful parameter for monitoring and predicting DOC concentration in surface water and DBP concentrations in finished water. Of all the PARAFAC components in surface water, C5 had the highest correlations with DBPs in finished water (rho = 0.77–0.84, p <0.01), followed by components C1 and C2 (rho = 0.75 and 0.71, respectively, p <0.01). This C5 carbon is associated with recently produced DOM, possibly from decomposed terrestrial and aquatic vegetation. Model loadings of these three components were considerably higher in the sampled tributaries relative to the main stem McKenzie River, with most of the observed increases in the main stem apparent at Vida. This points to Quartz Creek or other tributaries in the reach between Frissell Bridge and the sampling site near Vida (South Fork McKenzie and Blue Rivers) as potentially key contributors of DOM source material that leads to the production of DBPs in treated drinking water. A limited load analysis showed that the reservoirs contributed 8–37 percent of the instantaneous DOC loads observed at Vida at the time of sampling, which suggests other sources such as Quartz Creek and other streams in the reach between Frissell Bridge and Vida are more important. Random forest analyses identified PARAFAC components C1 and C5 and fluorescence peaks A, C, M, T and N as the best predictors for HAA5 concentrations in finished drinking water, explaining 62.5 percent of the variation. The best predictors for THM4 were C1, C4 + C5, and peaks T, A, and N, which explained 33 percent of the variation. Several land cover and vegetation classes were correlated with DOC concentration and other optical measurements. The percentage of evergreen forest in each of the subwatersheds sampled was negatively correlated ( p <0.001) with DOC concentration and many optical indicators of DOM quantity: UVA 254 , fDOM, and all of the fluorescence peaks. In contrast, mixed (deciduous) forest was positively correlated ( p <0.001) with DOC, fDOM, UVA 254 , and several fluorescence peaks, demonstrating the importance of deciduous leaf fall in generating DOC and DBP precursors. The high level of human activities in the middle and lower portion of the basin—including timber harvesting and road construction on private forestland, agricultural, rural, industrial, and urban development—have resulted in the greatest loss in native coniferous and mixed deciduous forests in the basin. DOC loading from these tributaries and reservoir releases, which contain DOC from terrestrial and aquatic productivity, both enrich the McKenzie River. Concentrations of DOC increased an average of 71 percent (range 30–120 percent) in the McKenzie River between Frissell Bridge, the upstream reference site, and Vida. PARAFAC components C1, C2, and C5—which were correlated with DBPs in finished water—increased, on average, 109–136 percent (range 20–250 percent) in this same Frissell-to-Vida reach. These increases occur from input of tributaries in the middle basin such as Quartz Creek and others, as noted above. Future monitoring, field, and lab studies can improve our understanding of seasonal and spatial sources of organic carbon contributing DBP precursors to the McKenzie River and allow detection of long-term trends resulting from the recent Holiday Farm Fire, which burned 173,393 acres of forestland, including riparian areas along the main stem, and numerous structures, homes, and outbuildings in September 2020. Future studies could examine DOC fluxes and flushing of carbon from the watershed, investigate the role of precipitation amount and intensity in mobilizing carbon and sediment, and evaluate impacts to aquatic communities and human health as part of a post-fire assessment. Other areas ripe for study include evaluating the impacts of potential temperature increases on carbon sequestration and decomposition in the burned and unburned forests and identifying practices that foster sequestration of carbon in forest soils. The use of fluorescence sensors such as fDOM to monitor the concentration and composition of raw water supplies may be improved for detection of specific DBP precursors, to provide continuous and real-time information to treatment plant operators. Future studies that monitor DOM amount and quality, and DBP Formation Potential (FP), particularly during storm events, paired with streamflow measurements, as suggested above, could help identify areas that contribute high DOC loads and thus help managers identify the key areas to focus restoration activities. Other studies could examine treatment options for currently regulated DBPs and potentially unregulated compounds, including advanced biological treatments for their removal. This study was a collaboration between the U.S. Geological Survey (USGS) and EWEB in Eugene, Oregon, with additional funding provided from USGS Cooperative Matching Funds Program.

Oregon↗

USGS1983

Preliminary plasma spectrometric analyses for selected elements in some geothermal waters from Cerro Prieto, Mexico

As part of a cooperative study with Dr. Alfred Truesdell, water samples collected from geothermal power production wells at Cerro Prieto, Mexico, were analyzed for selected elements by d.c. argon plasma emission spectroscopy. Spectral interferences due to the presence of high concentrations of Ca, Si, Na and K in these water affected the apparent concentration values obtained. These effects were evaluated and correction techniques were developed and applied to the analytical values. Precipitates present in the samples at the time of analysis adversely affected the accuracy, precision and interpretability of the data. (USGS)

Water-Resources Investigations Report↗

USGS1994

Characterization of the hydrogeology and water quality at the Management Systems Evaluation Area near Princeton, Minnesota, 1991-92

The Management Systems Evaluation Area (MSEA) program is part of a multi-scale, inter-agency initiative to evaluate the effects of agricultural management systems on water quality in the midwest corn belt. The Minnesota MSEA project is one of five projects selected to represent the principal hydrogeologic settings and geographic diversity of prevailing management systems in the midwest corn belt. The Minnesota MSEA research area is located in the Anoka Sand Plain about 5 kilometers southwest of Princeton, Minnesota. The water-quality monitoring network within the 65-hectare research area consists of 29 observation wells and 22 multiport wells. Thirteen observation wells also are located outside the research area. Glacial deposits beneath the research area generally consist of fine to medium sand in the unsaturated zone and coarse to very coarse sand and gravel in the saturated zone. The average depth to the water table is about 3.6 meters below land surface. Ground-water recharge during 1992 was lower (4.9-13.2 centimeters) than during 1991 (11.7-25.7 centimeters) because of reduced precipitation (58.5 centimeters during 1992 and 94.5 centimeters during 1991). Estimates of saturated horizontal hydraulic conductivity for the surficial aquifer were made using five methods. Results were within about two orders of magnitude and also agree favorably with estimates from a previous study of the Anoka Sand Plain. The smallest hydraulic conductivities were obtained using laboratory analyses (0.0052 centimeters per second) and the largest estimate was obtained from results of an aquifer test (0.2820 centimeters per second). The estimate of hydraulic conductivity based on the time of travel of chloride (0.0655 centimeters per second) is considered most accurate and representative of the surficial aquifer in the research area. Anthropogenic effects of previous land use were detected in water samples collected during April 1991, prior to implementation of the MSEA farming systems. Concentrations of nitrate-nitrogen (nitrate-N) in the surficial aquifer equaled or exceeded the U.S. Environmental Protection Agency's recommended maximum contaminant level of 10 milligrams per liter (mg/L) in 4 of the 7 wells in the research area. The maximum concentration of nitrate-N in ground water from these wells was 23 mg/L with a median of 10 mg/L. The median concentration of nitrate-N for these wells exceeded the median in wells located upgradient from the research area (2.1 mg/L). Similarly, the median concentration of chloride from wells in the research area (11 mg/L) exceeded the median in upgradient wells (3.8 mg/L). On-site sources of the elevated nitrate-N include decomposition of alfalfa, grown on-site during 1981-89, and application of nitrogen fertilizer to corn during 1990. A likely on-site source of the elevated chloride is application of potassium-chloride fertilizer to crops prior to 1991. Atrazine was detected by gas chromatography mass spectroscopy in 2 of the 7 wells in the research area at concentrations of 0.04 and 0.17 micrograms per liter (ug/L), well below the U.S. Environmental Protection Agency's recommended maximum contaminant level of 3 ug/L. The median concentration in these Wells was less than the qualitative detection limit of 0.01 ug/L. Atrazine metabolite de-ethylatrazine was the most frequently detected herbicide or herbicide metabolite. De-ethylatrazine was detected in 5 of the 7 wells in the research area at concentrations ranging from 0.12 to 0.32 ug/L with a median concentration of 0.14 ug/L. Atrazine metabolite de-isopropylatrazine was not detected above the qualitative detection limit of 0.06 ug/L. The most likely sources of atrazine are applications to the research area during 1990 or from precipitation.

Minnesota↗

USGS2009

A proposed origin for fossilized Pennsylvanian plant cuticles by pyrite oxidation (Sydney Coalfield, Nova Scotia, Canada)

Fossilized cuticles, though rare in the roof rocks of coal seam in the younger part of the Pennsylvanian Sydney Coalfield, Nova Scotia, represent nearly all of the major plant groups. Selected for investigation, by methods of Fourier transform infrared spectroscopy (FTIR) and elemental analysis, are fossilized cuticles (FCs) and cuticles extracted from compressions by Schulze's process (CCs) of Alethopteris ambigua. These investigations are supplemented by FTIR analysis of FCs and CCs of Cordaites principalis, and a cuticle-fossilized medullosalean(?) axis. The purpose of this study is threefold: (1) to try to determine biochemical discriminators between FCs and CCs of the same species using semi-quantitative FTIR techniques; (2) to assess the effects chemical treatments have, particularly Schulze's process, on functional groups; and most importantly (3) to study the primary origin of FCs. Results are equivocal in respect to (1); (2) after Schulze's treatment aliphatic moieties tend to be reduced relative to oxygenated groups, and some aliphatic chains may be shortened; and (3) a primary chemical model is proposed. The model is based on a variety of geological observations, including stratal distribution, clay and pyrite mineralogies associated with FCs and compressions, and regional geological structure. The model presupposes compression-cuticle fossilization under anoxic conditions for late authigenic deposition of sub-micron-sized pyrite on the compressions. Rock joints subsequently provided conduits for oxygen-enriched ground-water circulation to initiate in situ pyritic oxidation that produced sulfuric acid for macerating compressions, with resultant loss of vitrinite, but with preservation of cuticles as FCs. The timing of the process remains undetermined, though it is assumed to be late to post-diagenetic. Although FCs represent a pathway of organic matter transformation (pomd) distinct from other plant-fossilization processes, global applicability of the chemical models remains to be tested. CCs and FCs are inferred endpoints on a spectrum of pomd which complicates assessing origin of in-between transformations (partially macerated cuticles). FCs index highly acidic levels that existed locally in the roof rocks.

Bulletin of Geosciences↗

USGS2020

Mineralogy and lithology of the Upper Cretaceous Niobrara Formation determined by hyperspectral core imaging

Sections of the Upper Cretaceous (Coniacian to Campanian) Niobrara Formation in two cores from Kansas and Colorado, the Amoco Rebecca Bounds and USGS Portland 1, respectively, were examined by hyperspectral core imaging and analysis. A spectral imaging system combining high-resolution photography (50 μm), 3D laser profiling (20 μm), and near-visible + short-wave infrared reflectance spectroscopy (wavelengths from 450 to 2500 nm, 500 μm pixel size) was applied to these cores to provide spectral and textural data facilitating creation of continuous mineral and lithology class maps. In addition, compositing of pixel-based results to group pixels to create mineralogical and lithological logs (0.5 ft resolution) was performed to facilitate comparisons to other geochemical datasets. The results show general correspondence in trends identified by previous geochemistry studies, with some exceptions due to instrumental limitations related to low reflectance of some rock intervals and the limited range of infrared wavelengths examined. This study provides a cursory overview of an extensive dataset meant to demonstrate the utility of hyperspectral core scanning to studies of mudrocks in petroleum systems as well as the kinds of information this technique can provide for detailed examination of stratigraphic features in sedimentary systems more generally.

Mountain Geologist↗

USGS2022

Geochemical studies of the Green River Formation in the Piceance Basin, Colorado: I. Major, minor, and trace elements

The Eocene Green River Formation contains the largest oil shale deposits in the world and is a welldocumented example of a lacustrine depositional system. In addition, mineral resources associated with oil shale in the Piceance Basin nahcolite [NaHCO3] and dawsonite [NaAl(CO3)(OH)2)] are of current and potential economic value, respectively. Detailed geochemical analysis across the basin can aid in the understanding of the depositional environment, sedimentary processes, and water-chemistry evolution in this system. Quantitative geochemical data for Green River oil shale from the Piceance Basin of Colorado were collected by inductively coupled plasma optical emission spectroscopy and mass spectrometry as part of this study. The basin margin is represented by samples from exposures at Douglas Pass (Garfield County) and the basin center area is characterized by core samples from two drilled wells: the Shell 23X-2 and John Savage 24-1 (Rio Blanco County). Major elements and groups of elements are used as proxies for clastic influx (Si, Al, K, Ti), carbonate deposition (Ca, Mg), salinity (Na), paleo-productivity (P), and redox state (Fe, S), respectively. Minor and trace elements reinforce observations based on major elements, including Rb, Zr, Nb for clastic influx and Mn, Sr for carbonate. Trace elements are used to characterize redox conditions (As, Mo, U, V, Co, Ni, Cu, Zn) and salinity (Rb/K, B/Ga). Chemical distinctions between the basin margin and the basin center, in terms of these components and total organic carbon concentrations, support the model of a permanently stratified lake through most of the depositional interval. A primary purpose of the study was to conduct more extensive sampling to confirm conclusions of a previous reconnaissance study. Geochemical data from this study indicates elevated Na around the basin margin occurring earlier than in the deeper basin. Early in the history of Lake Uinta, the salinity may have been elevated first in the shallower marginal waters, due to increased evaporation, which then led to elevated salinity in the basin center through transport of saline density currents. Other indicators of salinity (Rb/K, B/Ga) do not track Na content in intervals where clay minerals are absent due to diagenetic alteration under hypersaline conditions but may be used to indicate the salinities at which authigenic Na-bearing minerals begin to form. Most Na-rich samples show high proportions of clastic constituents (Si, Al, K, Ti) compared to conventional carbonate constituents (Ca, Mg). Redox-sensitive period IV transition metal elements (V, Co, Ni, Cu, Zn) show only local occurrence of significant enrichment relative to average shale abundances. Analysis of Fe/Al ratios for this dataset suggests that the depletion of these elements may be related to source rocks depleted in mafic constituents, with apparent redox-related enrichments subdued by this effect. The basin margin samples reflect generally oxic bottom waters, with some intervals deposited under more reducing, possibly dysoxic to anoxic conditions. The basin center results indicate more reducing conditions, with Mo and U enrichment factors suggesting operation of a particulate shuttle mechanism that scavenged Mo on Fe/Mn-oxyhydroxides that redissolved at depth, with Mo precipitating along with sulfides and/or organic matter at or near the sediment/water interface.

Colorado↗

USGS2022

Geochemical studies of the Green River Formation in the Piceance Basin, Colorado: II. Chemofacies from hierarchical cluster analysis

Hierarchical cluster analysis (HCA) was applied to a geochemical dataset representing the Eocene Green River Formation in the Piceance Basin of Colorado to identify chemofacies in core and outcrop samples from the basin margin and the basin center. The input dataset consisted of inductively coupled plasma optical emission spectroscopy and mass spectrometry and total organic carbon (TOC) content analyses of 186 basin margin outcrop samples and 190 basin center core samples discussed in Part 1 of this study (this volume). TOC values and twenty-five major and trace elements were used as variables to define statistical clusters of samples for the overall dataset, for the two basin center cores, and for each separate core or outcrop dataset by HCA applying Euclidean distance and Ward’s method algorithms. For each dataset, five cluster-defined chemofacies were identified. The chemofacies for each dataset show chemical affinities with five informally defined rock types– mudstone, marlstone, carbonate-rich mudstone, siliciclastic-rich mudstone/siltstone/sandstone, and Na-rich (saline) mudstone, with each showing variations in TOC content and abundance of redox sensitive minor and trace elements. A close relationship between enrichment of redox sensitive elements, particularly As and Mo, and TOC is identified in the basin center. Whereas enrichment factors (relative to average shale) are relatively low for many Period IV (PIV) transition metals, as discussed in Part 1 of this study, their consistent coherence in enrichment or depletion in HCA-defined chemofacies demonstrates the expected relationship between redox state and organic richness. Enrichment in PIV transition metals also shows a correlation to enrichment in elements with affinity for siliciclastic sediment. Enrichment/depletion among several groups of redox indicators is not everywhere consistent, with some chemofacies showing, for example, enrichment of PIV transition metals and depletion of sulfur and arsenic. Early timing of saline conditions in the basin margin is clearly displayed in the chemofacies log display, consistent with observations based on geochemical interpretations of concentrations and elemental ratios discussed in Part 1. Overall, the chemofacies are consistent with major mineralogical units and lake history stages defined in previous work, but provide more detail on the fluctuations in lake chemistry that occurred during deposition of Green River oil shale in the Piceance Basin.

Colorado↗