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Part C: Geochemistry of Soil Samples from 50 Solution-Collapse Features on the Coconino Plateau, Northern Arizona

Soil sampling surveys were conducted during 1984-1986 across 50 solution-collapse features exposed on the Coconino Plateau of northern Arizona in order to determine whether soil geochemistry can be used to distinguish mineralized breccia pipes from unmineralized collapse features. The 50 sampled features represent the variety of collapse features that crop out on plateau surfaces in northwestern Arizonaoodeeplyorooted solution-collapse breccia pipes, near-surface gypsum collapses, and sinkholes. Of the 50 features that were sampled in this study, 3 are confirmed breccia pipes that contain significant uranium and base-metal minerals, I is believed to be a sinkhole with no economic potential, and 4 are stratabound copper deposits whose possible relationship to breccia pipes is yet to be determined. The remaining collapse features are suspected to overlie breccia pipes, although some of these may represent near surface gypsum collapse features. However, no exploratory drilling results or breccia exposures exist to indicate their underlying structure. The low cost and ease of soil sampling suggested that this technique be evaluated for breccia pipe exploration. This report provides the locations and geochemical results for the soil sampling surveys and brief descriptions of the 50 collapse features. The analytical results of almost 2,000 soil samples are provided in tabular hardcopy and dBase III Plus diskcopy format. The analytical data is provided in digital format to allow the reader to choose their own methods for evaluating the effectiveness of soil sampling over known and suspected breccia pipes. A pilot survey conducted over 17 collapse features in 1984 suggested that soil sampling might be useful in distinguishing mineralized breccia pipes from other circular features. Followup detailed surveys in 1985 and 1986 used a radial sampling pattern at each of 50 sites; at least one third of the samples were collected from areas outside of the collapse feature to provide background data. Samples were consistently collected from 3-4 inches depth after the pilot survey showed that metal concentrations were similar in samples from 3-4 inches and 7-8 inches depth. The geochemical analyses of the <80 mesh fractions of the soil samples were performed by the U.S. Geological Survey Analytical Laboratories and Geochemical Services, Inc. The analytical methods applied to these samples by the U.S. Geological Survey laboratories included inductively coupled plasma-atomic emission spectroscopy, X-ray fluorescence spectrometry, neutron activation, atomic absorption, delayed neutron activation, and classical wet chemistry for carbon, fluorine, and sulfur. Geochemical Services, Inc. analyzed the soil samples by inductively coupled plasma emission spectroscopy.

Open-File Report

Part D: Geochemistry of Soil Samples from 50 Solution-Collapse Features on the Coconino Plateau, Northern Arizona

Soil sampling surveys were conducted during 1984-1986 across 50 solution-collapse features exposed on the Coconino Plateau of northern Arizona in order to determine whether soil geochemistry can be used to distinguish mineralized breccia pipes from unmineralized collapse features. The 50 sampled features represent the variety of collapse features that crop out on plateau surfaces in northwestern Arizonaoodeeplyorooted solution-collapse breccia pipes, near-surface gypsum collapses, and sinkholes. Of the 50 features that were sampled in this study, 3 are confirmed breccia pipes that contain significant uranium and base-metal minerals, I is believed to be a sinkhole with no economic potential, and 4 are stratabound copper deposits whose possible relationship to breccia pipes is yet to be determined. The remaining collapse features are suspected to overlie breccia pipes, although some of these may represent near surface gypsum collapse features. However, no exploratory drilling results or breccia exposures exist to indicate their underlying structure. The low cost and ease of soil sampling suggested that this technique be evaluated for breccia pipe exploration. This report provides the locations and geochemical results for the soil sampling surveys and brief descriptions of the 50 collapse features. The analytical results of almost 2,000 soil samples are provided in tabular hardcopy and dBase III Plus diskcopy format. The analytical data is provided in digital format to allow the reader to choose their own methods for evaluating the effectiveness of soil sampling over known and suspected breccia pipes. A pilot survey conducted over 17 collapse features in 1984 suggested that soil sampling might be useful in distinguishing mineralized breccia pipes from other circular features. Followup detailed surveys in 1985 and 1986 used a radial sampling pattern at each of 50 sites; at least one third of the samples were collected from areas outside of the collapse feature to provide background data. Samples were consistently collected from 3-4 inches depth after the pilot survey showed that metal concentrations were similar in samples from 3-4 inches and 7-8 inches depth. The geochemical analyses of the <80 mesh fractions of the soil samples were performed by the U.S. Geological Survey Analytical Laboratories and Geochemical Services, Inc. The analytical methods applied to these samples by the U.S. Geological Survey laboratories included inductively coupled plasma-atomic emission spectroscopy, X-ray fluorescence spectrometry, neutron activation, atomic absorption, delayed neutron activation, and classical wet chemistry for carbon, fluorine, and sulfur. Geochemical Services, Inc. analyzed the soil samples by inductively coupled plasma emission spectroscopy.

Open-File Report

Revealing organofluorine contamination in effluents and surface waters with complementary analytical approaches: Fluorine-19 nuclear magnetic resonance spectroscopy (19F-NMR) and liquid chromatography-tandem mass spectrometry (LC-MS/MS)

Fluorinated organic contaminants, including per- and polyfluoroalkyl substances (PFASs) and fluorinated pesticides and pharmaceuticals (FPPs), pose a persistent threat to environmental health. Widely used liquid chromatography-tandem mass spectrometry (LC-MS/MS) methods fail to capture large fractions of total organofluorine in environmental samples, confounding the assessment of fluorinated contamination. Fluorine-19 nuclear magnetic resonance spectroscopy ( 19 F-NMR) is an inclusive method for total and class-based organofluorine analysis. Here, we apply 19 F-NMR to 31 effluent, surface water, and foam samples collected at 13 potential organofluorine point sources or source regions and compare the results to targeted LC-MS/MS for 34 or 64 PFASs. LC-MS/MS detected a median of 11.4% of total organofluorine detected by 19 F-NMR (range: nondetect to 8190 nM F 19 F-NMR; nondetect to 8010 nM F LC-MS/MS). The highest 19 F-NMR total organofluorine concentrations, detected in wastewater treatment plant (WWTP)-associated foam and at a soy oil production facility, arose from resonances characteristic of per- and polyfluorinated alkyl chains. 19 F-NMR resonances from aryl CF 3 moieties were abundant in the WWTP-associated samples, consistent with prior reports of substantial contributions from pharmaceuticals to WWTP effluents. 19 F-NMR enables the quantitative assessment of total organofluorine and qualitative insight into fluorinated structures, providing complementary analysis of organofluorine compounds missed by targeted mass spectrometry-based protocols.

Environmental Science & Technology

Organic petrology and micro-spectroscopy of Tasmanites microfossils: Applications to kerogen transformations in the early oil window

The transformation of kerogen to hydrocarbons in the early stages of oil generation is critical for understanding the resource potential of liquid-rich shale plays. Organic petrology commonly is used for visual evaluation of type, quality, and thermal maturity of organic matter, but the relationship of visual petrographic changes to chemical transformations is not well characterized. To improve understanding of these processes, organic-walled microfossils of the unicellular green alga Tasmanites (composed of algaenan) in Upper Devonian Ohio Shale (Huron Member, Appalachian Basin) were analyzed by micro-spectroscopy techniques including micro-Fourier transform infrared (micro-FTIR), X-ray photoelectron (XPS), electron probe microanalysis (EPMA), and fluorescence. Immature to mid-oil window maturation sequences of core and outcrop samples with solid bitumen reflectance (BR) and vitrinite reflectance (VR) values ranging from 0.45 to 0.80 %Ro were used. Hydrous pyrolysis was applied to low-maturity (BR: 0.25–0.39 %Ro) Huron and time-correlative New Albany shale samples to create similar artificial maturation sequences for comparison. Micro-FTIR spectroscopy revealed a decrease in the CH 2 /CH 3 ratio with increasing maturity, indicating Tasmanites aliphatic chains become shorter and more branched. Oxygenated functional groups decreased relative to aliphatic stretching bands and increased aromaticity was noted at the highest maturities. In samples that were pyrolyzed for 72 h at temperatures of 300–320 °C (BR: 0.56–0.68 %Ro), Tasmanites showed similar trends, whereas at pyrolysis temperatures of 340 °C and higher (BR > 1.0 %Ro), Tasmanites was pseudomorphed by accumulations of solid bitumen, carbonate and sulfide. Replacement of Tasmanites by these phases in hydrous pyrolysis experiments ≥340 °C and its absence at higher maturities (peak oil, VR and BR ≥ 0.9 %Ro) in naturally matured samples, as documented in a previous study, implies that a large fraction of the algaenan component of original organic carbon is converted to petroleum during thermal maturation. XPS analysis indicated the molar proportion of aliphatic carbon increases with increasing thermal maturity, accompanied by decreases in oxygenated functional groups and olefinic carbon. EPMA of Tasmanites showed highest concentrations of S, with concentrations of redox-sensitive trace elements U, Mo, Ni and V generally at or below detection limits. Decrease in organic S with increasing thermal maturity may be related to cleavage of Tasmanites at C S linkages; however, this relationship was inconsistent and presence of adjacent or entrained nanoscale silicate or sulfide phases may impact measured trace element concentrations. Fluorescence microscopy and spectroscopy showed a red shift in spectral maxima and decreased emission intensities with increasing maturity, interpreted as due to non-radiative energy loss possibly because of increased aromaticity. Collectively, these results provide new insights into the in situ chemical transformations that accompany petrographic changes as oil-prone kerogen converts to petroleum with thermal advance from immature conditions into the mid-oil window.

Organic Geochemistry

Multiscale hyperspectral imaging of the Orange Hill Porphyry Copper Deposit, Alaska, USA, with laboratory-, field-, and aircraft-based imaging spectrometers

In the past decade, use of hyperspectral imaging (imaging spectroscopy) for mineral exploration and mining operations has been increasing at different spatial scales. In this paper, we focus on recent trends in applying imaging spectrometer data to: 1) airborne imaging of high latitude deposits, 2) field-based imaging of outcrops, and 3) laboratory-level imaging of geologic samples. Comparing mineral information derived from imaging spectrometer data acquired at these three scales in Alaska in areas of exposed porphyry Cu-Au-Mo deposits, Orange Hill and Bond Creek, we find notable consistency in identifications of spectrally predominant minerals, including white mica, chlorite, clays, and gypsum. Variations in the wavelength position of white mica 2200 nm Al-OH absorption seen at the airborne level are echoed by finerscale field and laboratory imaging, with wavelength positions spanning the 2199 to 2207 nm range. The longerwavelength micas associated with porphyry formation are more phengitic in composition, and thus distinct from mica in plutonic and volcanic arc rocks not affected by magmatic-hydrothermal fluids. The hillside imagery, collected on a cloudy day that would have precluded aircraft survey, gave comparable result to airborne and laboratory data, indicating field-based imaging spectroscopy can be a feasible alternative to airborne survey for accessible targets. Direct spectral observation of molybdenite in rocks collected from the Orange Hill deposit demonstratesthat additional important mineral information can be revealed with laboratory level imaging spectroscopy that is difficult to obtain in coarser scale data, commonly due to low areal extent of target minerals. The spatial association of the clinochlore + white mica and long wavelength white mica spectral classes to multi-element Cu-Mo-Au anomalies from geochemical analyses of rocks and sediments support a causative relationship with magmatic-hydrothermal alteration. Mineral maps from the airborne data were used to guide field sampling that found additional CuMo-Au mineralized areas, which were previously unknown or unreported. The results from this study provide support for utilization of imaging spectroscopy for assisting mineral exploration in other portions of the state of Alaska as well as other areas at high latitudes. Imaging spectroscopy has the potential to provide targeting information for follow-up sampling and investigations, potentially reducing subsequent exploration costs.

Alaska

Biogeochemical transformation of Fe minerals in a petroleum-contaminated aquifer

The Bemidji aquifer in Minnesota, USA is a well-studied site of subsurface petroleum contamination. The site contains an anoxic groundwater plume where soluble petroleum constituents serve as an energy source for a region of methanogenesis near the source and bacterial Fe(III) reduction further down gradient. Methanogenesis apparently begins when bioavailable Fe(III) is exhausted within the sediment. Past studies indicate that Geobacter species and Geothrix fermentens -like organisms are the primary dissimilatory Fe-reducing bacteria at this site. The Fe mineralogy of the pristine aquifer sediments and samples from the methanogenic (source) and Fe(III) reducing zones were characterized in this study to identify microbiologic changes to Fe valence and mineral distribution, and to identify whether new biogenic mineral phases had formed. Methods applied included X-ray diffraction; X-ray fluorescence (XRF); and chemical extraction; optical, transmission, and scanning electron microscopy; and Mössbauer spectroscopy. All of the sediments were low in total Fe content (≈ 1%) and exhibited complex Fe-mineralogy. The bulk pristine sediment and its sand, silt, and clay-sized fractions were studied in detail. The pristine sediments contained Fe(II) and Fe(III) mineral phases. Ferrous iron represented approximately 50% of Fe TOT . The relative Fe(II) concentration increased in the sand fraction, and its primary mineralogic residence was clinochlore with minor concentrations found as a ferroan calcite grain cement in carbonate lithic fragments. Fe(III) existed in silicates (epidote, clinochlore, muscovite) and Fe(III) oxides of detrital and authigenic origin. The detrital Fe(III) oxides included hematite and goethite in the form of mm-sized nodular concretions and smaller-sized dispersed crystallites, and euhedral magnetite grains. Authigenic Fe(III) oxides increased in concentration with decreasing particle size through the silt and clay fraction. Chemical extraction and Mössbauer analysis indicated that this was a ferrihydrite like-phase. Quantitative mineralogic and Fe(II/III) ratio comparisons between the pristine and contaminated sediments were not possible because of textural differences. However, comparisons between the texturally-similar source (where bioavailable Fe(III) had been exhausted) and Fe(III) reducing zone sediments (where bioavailable Fe(III) remained) indicated that dispersed detrital, crystalline Fe(III) oxides and a portion of the authigenic, poorly crystalline Fe(III) oxide fraction had been depleted from the source zone sediment by microbiologic activity. Little or no effect of microbiologic activity was observed on silicate Fe(III). The presence of residual “ferrihydrite” in the most bioreduced, anoxic plume sediment (source) implied that a portion of the authigenic Fe(III) oxides were biologically inaccessible in weathered, lithic fragment interiors. Little evidence was found for the modern biogenesis of authigenic ferrous-containing mineral phases, perhaps with the exception of thin siderite or ferroan calcite surface precipitates on carbonate lithic fragments within source zone sediments.

Geochimica et Cosmochimica Acta

Evaluating the potential for remote bathymetric mapping of a turbid, sand-bed river: 2. application to hyperspectral image data from the Platte River

This study examined the possibility of mapping depth from optical image data in turbid, sediment-laden channels. Analysis of hyperspectral images from the Platte River indicated that depth retrieval in these environments is feasible, but might not be highly accurate. Four methods of calibrating image-derived depth estimates were evaluated. The first involved extracting image spectra at survey point locations throughout the reach. These paired observations of depth and reflectance were subjected to optimal band ratio analysis (OBRA) to relate ( R 2 = 0.596) a spectrally based quantity to flow depth. Two other methods were based on OBRA of data from individual cross sections. A fourth strategy used ground-based reflectance measurements to derive an OBRA relation ( R 2 = 0.944) that was then applied to the image. Depth retrieval accuracy was assessed by visually inspecting cross sections and calculating various error metrics. Calibration via field spectroscopy resulted in a shallow bias but provided relative accuracies similar to image-based methods. Reach-aggregated OBRA was marginally superior to calibrations based on individual cross sections, and depth retrieval accuracy varied considerably along each reach. Errors were lower and observed versus predicted regression R 2 values higher for a relatively simple, deeper site than a shallower, braided reach; errors were 1/3 and 1/2 the mean depth for the two reaches. Bathymetric maps were coherent and hydraulically reasonable, however, and might be more reliable than implied by numerical metrics. As an example application, linear discriminant analysis was used to produce a series of depth threshold maps for characterizing shallow-water habitat for roosting cranes.

Platte River

Thermal infrared and ultraviolet remote sensing of sulfur dioxide gas emitted during the 2018 lower East Rift Zone eruption of Kilauea, Hawaiʻi

Ultraviolet (UV) remote sensing is widely used to detect volcanic sulfur dioxide (SO₂) due to its high sensitivity and favorable spatial and temporal resolution. However, significant discrepancies have been reported between ground-based and satellite-based UV observations of dense volcanic plumes. A notable example is the 2018 lower East Rift Zone eruption of Kīlauea, where SO₂ emission rates derived from ground-based Differential Optical Absorption Spectroscopy (DOAS) measurements differed substantially from those obtained by the spaceborne Tropospheric Monitoring Instrument (TROPOMI). In this study, we investigate these differences by applying thermal infrared (TIR) satellite retrievals using a modified version of the SO₂-ALTA algorithm to Moderate Resolution Imaging Spectroradiometer (MODIS) observations. The resulting TIR-derived SO₂ fluxes are compared with ground-based DOAS data, satellite UV observations, and petrological estimates of gas emissions. Our results show strong agreement between TIR-derived fluxes, ground-based DOAS measurements, and petrological estimates, particularly during the peak and plateau phases of the eruption. In contrast, satellite UV-derived SO₂ emissions are systematically lower. We find that TIR observations are more effective in quantifying high-concentration SO₂ plumes in the near-vent region, while UV measurements are more sensitive under lower-concentration conditions but more affected by scattering in optically dense plumes. These findings highlight the complementary strengths of UV and TIR remote sensing techniques and emphasize the importance of accounting for plume density and observation geometry when interpreting satellite SO₂ retrievals.

Hawaii

Advances in spectroscopic methods for quantifying soil carbon

The current gold standard for soil carbon (C) determination is elemental C analysis using dry combustion. However, this method requires expensive consumables, is limited by the number of samples that can be processed (~100/d), and is restricted to the determination of total carbon. With increased interest in soil C sequestration, faster methods of analysis are needed, and there is growing interest in methods based on diffuse reflectance spectroscopy in the visible, near-infrared or mid-infrared spectral ranges. These spectral methods can decrease analytical requirements and speed sample processing, be applied to large landscape areas using remote sensing imagery, and be used to predict multiple analytes simultaneously. However, the methods require localized calibrations to establish the relationship between spectral data and reference analytical data, and also have additional, specific problems. For example, remote sensing is capable of scanning entire watersheds for soil carbon content but is limited to the surface layer of tilled soils and may require difficult and extensive field sampling to obtain proper localized calibration reference values. The objective of this chapter is to discuss the present state of spectroscopic methods for determination of soil carbon.

Book chapter

Python Hyperspectral Analysis Tool (PyHAT) user guide

This report is a user guide for the 0.1.2 release of the Python Hyperspectral Analysis Tool (PyHAT) and its graphical user interface (GUI). The GUI is intended to provide an intuitive front end to allow users to apply sophisticated preprocessing and analysis methods to spectroscopic data. Though the PyHAT package has been developed with a particular focus on laser-induced breakdown spectroscopy (LIBS), the package uses a simple comma separated values (CSV)-based data format and is readily applicable in other spectroscopy applications. This guide provides background information about the package and its capabilities. It also provides practical guidance on usage and example workflows for a wide variety of datasets.

Open-File Report

Mineralogical basis for the interpretation of multi-element (ICP-AES), oxalic acid, and aqua regia partial digestions of stream sediments for reconnaissance exploration geochemistry

We have applied partial digestion procedures, primarily oxalic acid and aqua regia leaches, to several regional geochemical reconnaissance studies carried out using Inductively Coupled Plasma-Atomic Emission Spectroscopy (ICP-AES) analytical methods. We have chosen to use these two acids because the oxalic acid primarily attacks those compounds formed during secondary geochemical processes, whereas aqua regia will digest the primary sulfide phases as well as secondary phases. Application of the partial digestion technique has proven superior to total digestion because the concentration of metals in hydromorphic compounds and the sulfides is enhanced relative to the metals bound in the unattacked silicate phases. The aqua regia digestion attacks and leaches metals from the mafic chain silicates and the phyllosilicates (coordination number of VI or more), yielding a characteristic geochemical signature, but does not leach appreciable metal from many other silicates. In order to interpret the results from these leach studies, we have initiated an investigation of a large suite of hand-picked mineral separates. The study includes analyses of about two hundred minerals representing the common rock-forming minerals as well as end-member compositions of various silicates, oxides, sulfides, carbonates, sulfates, and some vanadates, molybdates, tungstates, and phosphates. The objective of this study is to evaluate the effect of leaching by acids of particular lattice sites in specific mineral structures.

Journal of Geochemical Exploration

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

BOREHOLE NEUTRON ACTIVATION: THE RARE EARTHS.

Neutron-induced borehole gamma-ray spectroscopy has been widely used as a geophysical exploration technique by the petroleum industry, but its use for mineral exploration is not as common. Nuclear methods can be applied to mineral exploration, for determining stratigraphy and bed correlations, for mapping ore deposits, and for studying mineral concentration gradients. High-resolution detectors are essential for mineral exploration, and by using them an analysis of the major element concentrations in a borehole can usually be made. A number of economically important elements can be detected at typical ore-grade concentrations using this method. Because of the application of the rare-earth elements to high-temperature superconductors, these elements are examined in detail as an example of how nuclear techniques can be applied to mineral exploration.

IEEE Transactions on Nuclear Science

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

Geographic determination of Pinus ponderosa using DART TOFMS, ICP-MS, and LIBS handheld analyzer

Due to legal requirements on international imports, it is important for law enforcement and regulatory agencies to identify the geographical provenance of timber. Current methods for geographic identification utilize data generated by direct analysis in real time time-of-flight mass spectrometry (DART TOFMS), genetics, and isotope-ratio mass spectrometry (IRMS), but identification methods based on genetics and IRMS data require months to years to create usable databases. This study used machine learning algorithms to compare the results of DART TOFMS, inductively coupled plasma mass spectrometry (ICP-MS), and a handheld laser-induced breakdown spectroscopy (LIBS) analyzer for use in geographic identification of five populations of Pinus ponderosa spaced between 14 to 72 km apart. The results of the study showed comparable performances from machine learning algorithms applied to the ICP-MS and LIBS data with accuracy and kappa values over 90% while the DART TOFMS had an accuracy of 76% and a kappa value of 70%. This study demonstrated that data from the LIBS handheld analyzer is a viable and intriguing alternative to ICP-MS and DART TOFMS analyses in generating training databases and further indicates that trace elemental analysis via ICP-MS is a promising method for generating databases used to identify the origin of timber.

California, Oregon

A preliminary assessment of hyperspectral remote sensing technology for mapping submerged aquatic vegetation in the Upper Delaware River National Parks

Hyperspectral remote sensing of submerged aquatic vegetation is a complex and difficult process that is affected by unique constraints on the energy flow profile near and below the water surface. In addition, shallow, winding, lotic systems, such as the Upper Delaware River, present additional remote sensing problems in the form of specular reflectance, variable depth and constituents in the water column and sometimes extremely weak signal strength due to absorption and scattering in the water column that can be statistically overwhelmed by the reflectance from upland vegetation in any individual image scene. Here we test hyperspectral imagery from the Civil Air Patrol’s (CAP), Airborne Real-time Cueing Hyperspectral Enhanced Recon (ARCHER) system in the scenic waters of two National Parks on the Upper Delaware River. A number of unique image processing problems were encountered, including specular reflectance from winding lotic systems, variable depth and flow dynamics of the riverine environment, and disproportionate signal strength from surface reflectance in this riverine environment. This were solved by applying a specular reflectance removal algorithm, applying field data collections to classification results and masking upland vegetation so as to not statistically overwhelm the weak reflectance signal from surface and near-surface water. Much was learned about conducting imaging spectroscopy in such difficult conditions. Significant results include successful mapping of SAV presenece/absence, advantages of upland masking of the reflectance signal, and a numkber of processing approaches that are unique to this environment. In this paper we summarize our results and identify unique issues that must be addressed in this environment

New Jersey, New York, Pennsylvania

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

Examination of inertinite within immature Eagle Ford Shale at the nanometer-scale using atomic force microscopy-based infrared spectroscopy

The nanoscale molecular composition of sedimentary organic matter is challenging to characterize in situ given the limited tools available that can adequately interrogate its complex chemical structure. This is a particularly relevant issue in source rocks, as kerogen composition will strongly impact its reactivity and so is critical to understanding petroleum generation processes during catagenesis. The recent advent of tip-enhanced analytical methods, such as atomic force microscopy-based infrared spectroscopy (AFM-IR), has allowed for the major compositional features of kerogen and other types of in situ organic matter to be elucidated at spatial resolutions at or below 50 nm. Here AFM-IR was applied to examine inertinite, an important organic matter type, present in a thermally immature Eagle Ford calcareous mudstone. The data show that the nanoscale molecular composition of the examined inertinite is (i) less heterogeneous than solid bitumen in more thermally mature Eagle Ford samples and (ii) more hydrogen- and oxygen-rich than inertinite examined in the New Albany Shale.

Texas