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At least 109 records · Page 6Linked to original sources

Direct comparison of XAFS spectroscopy and sequential extraction for arsenic speciation in coal

The speciation of arsenic in an Ohio bituminous coal and a North Dakota lignite has been examined by the complementary methods of arsenic XAFS spectroscopy and sequential extraction by aqueous solutions of ammonium acetate, HCl, HF, and HNO3. In order to facilitate a more direct comparison of the two methods, the arsenic XAFS spectra were obtained from aliquots of the coal prepared after each stage of the leaching procedure. For the aliquots, approximately linear correlations (r2 > 0.98 for the Ohio coal, > 0.90 for the ND lignite) were observed between the height of the edge-step in the XAFS analysis and the concentration of arsenic measured by instrumental neutron activation analysis. Results from the leaching sequence indicate that there are two major arsenic forms present in both coals; one is removed by leaching with HCl and the other by HNO3. Whereas the XAFS spectral signatures of the arsenic leached by HCl are compatible with arsenate for both coals, the arsenic leached by HNO3 is identified as arsenic associated with pyrite for the Ohio coal and as an As3+ species for the North Dakota lignite. Minor arsenate forms persist in both coals after the final leaching with nitric acid. The arsenate forms extracted in HCl are believed to be oxidation products derived from the other major arsenic forms upon exposure of the pulverized coals to air.

ACS Division of Fuel Chemistry, Preprints

Sediment mineralogy based on visible and near-infrared reflectance spectroscopy

Visible and near-infrared spectroscopy (VNIS) can be used to measure reflectance spectra (wavelength 350-2500 nm) for sediment cores and samples. A local ground-truth calibration of spectral features to mineral percentages is calculated by measuring reflectance spectra for a suite of samples of known mineralogy. This approach has been tested on powders, core plugs and split cores, and we conclude that it works well on all three, unless pore water is present. Initial VNIS studies have concentrated on determination of relative proportions of carbonate, opal, smectite and illite in equatorial Pacific sediments. Shipboard VNIS-based determination of these four components was demonstrated on Ocean Drilling Program Leg 199. ?? The Geological Society of London 2006.

Geological Society Special Publication

1H and 13C resonance designation of antimycin A1 by two-dimensional NMR spectroscopy

Complete 1 H and 13 C resonance assignments of antimycin A 1 were accomplished by two-dimensional NMR techniques, viz. 1 H homonuclear COSY correlation, heteronuclear 13 C- 1 H chemical shift correlation and long-range heteronuclear 13 C- 1 H COLOC correlation. Antimycin A 1 was found to consist of two isomeric components in a 2:1 ratio based on NMR spectroscopic evidence. The structure of the major component was newly assigned as the 8-isopentanoic acid ester. The spectra of the minor component were consistent with the known structure of antimycin A 1 .

Magnetic Resonance in Chemistry

Volcanogenic Sulfur on Earth and Io: Composition and Spectroscopy

The causes of Io's variegated surface, especially the roles of sulfur, and the geochemical history of sulfur compounds on Io are not well understood. Suspecting that minor impurities in sulfur might be important, we have investigated the major and trace element chemistry and spectroscopic reflectance of natural sulfur from a variety of terrestrial volcanic-hydrothermal environments. Evidence suggests that Io may be substantially coated with impure sulfur. On Earth, a few tenths of a percent to a few percent of chalcophile trace elements (e.g., As and Se) comonly occur in sulfur and appear to stabilize material of yellow, brown, orange, and red hues, which may persist even at low temperatures. Percentage levels of chalcophile impurities are reasonably expected to occur on Io in vapor sublimate deposits and flows derived from such deposits. Such impurities join a host of other mechanisms that might explain Io's reds and yellows. Two-tenths to two percent opaque crystalline impurities, particularly pyrite (FeS2), commonly produces green, gray, and black volcanic sulfur on Earth and might explain areas of Io having deposits of these colors. Pyrite produces a broad absorption near 1 ??m that gradually diminishes out to 1.6 ??m - similar but not identical to the spectrum of Io seen in Galileo NIMS data. Percentage amounts of carbonaceous impurities and tens of percent SiO2 (as silicates) also strongly affect the spectral properties of Earth's sulfur. Io's broad absorption between 0.52 and 0.64 ??m remains unexplained by these data but could be due to sodium sulfides, as suggested previously by others, or to As, Se, or other impurities. These impurities and others, such as P and Cl (which could exist on Io's surface in amounts over 1% that of sulfur), greatly alter the molecular structure of molten and solid sulfur. Minor impurities could impact Io's geology, such as the morphology of sulfur lava flows and the ability of sulfur to sustain high relief. We have not found any natural sulfur containing significant Na beyond that attributable to silicate inclusions. In sum, the unique physical-chemical properties of S-rich systems and the strong affinity of certain elements for S may have broad implications for the appearance, spectroscopic interpretation, and geologic processes of Io. Identification of impurities in sulfur may be helpful in tracing the geochemical evolution of surface deposits on Io. Perhaps foretelling of new areas of investigation, Cl has recently been reported in the Io torus (M. Kueppers and N. M. Schneider 1999, Eos Trans.80, 5207), suggesting the presence on Io of either salts, such as halite, or sulfur chlorides. Further evidence of minor iogenic impurities should be sought in Io's neutral cloud and plasma torus as well as in further scrutiny of Io's reflectance spectra. ?? 1999 Academic Press.

Icarus

Applications of imaging spectroscopy data: A case study at Summitville, Colorado

From 1985 through 1992, the Summitville open-pit mine produced gold from lowgrade ore using cyanide heap-leach techniques, a method to extract gold whereby the ore pile is sprayed with water containing cyanide, which dissolves the minute gold grains. Environmental problems due to mining activity at Summitville include significant increases in acidic and metal-rich drainage from the site, leakage of cyanide-bearing solutions from the heap-leach pad into an underdrain system, and several surface leaks of cyanide-bearing solutions into the Wightman Fork of the Alamosa River. In general, drainage from the Summitville mine moves downslope into the Wightman Fork, a small tributary of the Alamosa River, which in turn flows east into the Terrace Reservoir before entering the agricultural lands of the San Luis Valley. The increase in the trace-metal burden of the Alamosa River watershed due to the mining activities at Summitville is of concern to farmers and fisherman, as well as Federal and State of Colorado agencies having responsibility for land stewardship. The environment of the Summitville area is a result of 1) its geologic evolution, that culminated in the formation of precious-metal mineral deposits; and 2) previous metal mining activity. Mining accentuates, accelerates, and pertubates natural geochemical processes. The development of underground workings, open pits, mill tailings, and spoil heaps and the extractive processing of ore enhances the likelihood of releasing chemicals and elements to the surrounding areas and at increased rates relative to unmined areas. Both mined and unmined mineralized areas can produce acid drainage from the formation and movement of highly acidic water rich in heavy metals. This acidic water forms principally through the chemical reaction of oxygenated surface water and shallow subsurface water with rocks that contain sulfide minerals, producing sulphuric acid. Heavy metals can be leached by the acid solution that comes in contact with mineralized rocks, a process that may be enhanced by bacterial action. The resulting fluids may be highly toxic and, when mixed with groundwater, surface water, and soil, may have harmful effects on humans, animals, and plants. Thus, understanding the geologic and hydrologic history of this area is a critical piece of the environmental puzzle in the Summitville area. The Summitville mine operators had ceased active mining and begun environmental remediation, including treatment of the heap-leach pile and installation of a water-treatment facility, when it declared bankruptcy in December 1992 and abandoned the mine site. The U.S. Environmental Protection Agency (EPA) immediately took over the Summitville site under EPA Superfund Emergency Response authority. Summitville has focused public attention on the environmental effects of modern mineral-resource development. Soon after the mine was abandoned, Federal, State, and local agencies, along with Alamosa River water users and private companies, began extensive studies at the mine site and surrounding areas. These studies included analysis of water, soil, livestock and vegetation. The role of the U.S. Geological Survey (USGS) was to provide geologic, hydrologic and agricultural information about the mine and surrounding area and to describe and evaluate the environmental condition of the Summitville mine and the downstream effects of the mine on the San Luis Valley (King 1995).

Colorado

Determination of gold, indium, tellurium and thallium in the same sample digest of geological materials by atomic-absorption spectroscopy and two-step solvent extraction

A rock, soil, or stream-sediment sample is decomposed with hydrofluoric acid, aqua regia , and hydrobromic acid-bromine solution. Gold, thallium, indium and tellurium are separated and concentrated from the sample digest by a two-step MIBK extraction at two concentrations of hydrobromic add. Gold and thallium are first extracted from 0.1 M hydrobromic acid medium, then indium and tellurium are extracted from 3 M hydrobromic acid in the presence of ascorbic acid to eliminate iron interference. The elements are then determined by flame atomic-absorption spectrophotometry. The two-step solvent extraction can also be used in conjunction with electrothermal atomic-absorption methods to lower the detection limits for all four metals in geological materials.

Talanta

A rapid method for determining tin and molybdenum in geological samples by flame atomic-absorption spectroscopy

The proposed method uses a lithium metaborate fusion, dissolution of the fusion bead in 15% vv hydrochloric acid, extraction into a 4% solution of trioctylphosphine oxide in methyl isobutyl ketone, and aspiration into a nitrous oxide-acetylene flame. The limits of detection for tin and molybdenum are 1.0 and 0.5 ppm, respectively. Approximately 50 samples can be analysed per day.

Talanta

Studies of a peatified angiosperm log cross section from Indonesia by nuclear magnetic resonance spectroscopy and analytical pyrolysis

Samples from a 10 cm cross-sectional radius of a peatified angiosperm log from Sumatra, Indonesia, were examined by 13 C nuclear magnetic resonance and pyrolysis-gas chromatography in order to understand chemical changes due to the peatification process. NMR results show degradation by selective loss of carbohydrates in all parts of the log section compared with fresh wood; however, the degree of degradation is less near the center of the log section. The degree of ring substitution of aromatic lignin monomeric units, as measured by dipolar dephasing NMR methods, appears to be less at the center of the log section than at the periphery. The methoxyl carbon content of lignin in the log is lower than in unaltered angiospermous lignin but does not appear to change as a function of either radial position or the degree of aromatic ring substitution. Pyrolysis-gas chromatography indicates higher yields of catechols in the outer areas relative to the heartwood. Other than the variations in catechol contents and in the yields of carbohydrate-derived pyrolysis products (e.g. levoglucosan, angelicalactones), the pyrolysis results do not show significant changes related to radial position, indicating that the lignin is not significantly altered across the log section.

Organic Geochemistry

In situ quantitative analysis of individual H2O-CO2 fluid inclusions by laser Raman spectroscopy

Raman spectral parameters for the Raman ??1 (1285??cm- 1) and 2??2 (1388??cm- 1) bands for CO2 and for the O-H stretching vibration band of H2O (3600??cm- 1) were determined in H2O-CO2 fluid inclusions. Synthetic fluid inclusions containing 2.5 to 50??mol% CO2 were analyzed at temperatures equal to or greater than the homogenization temperature. The results were used to develop an empirical relationship between composition and Raman spectral parameters. The linear peak intensity ratio (IR = ICO2/(ICO2 + IH2O)) is related to the CO2 concentration in the inclusion according to the relation:Mole % C O2 = e- 3.959 IR2 + 8.0734 IRwhere ICO2 is the intensity of the 1388 cm- 1 peak and IH2O is the intensity of the 3600 cm- 1 peak. The relationship between linear peak intensity and composition was established at 350????C for compositions ranging from 2.5 to 50??mol% CO2. The CO2-H2O linear peak intensity ratio (IR) varies with temperature and the relationship between composition and IR is strictly valid only if the inclusions are analyzed at 350????C. The peak area ratio is defined as AR = ACO2/(ACO2 + AH2O), where ACO2 is the integrated area under the 1388??cm- 1 peak and AH2O is the integrated area under the 3600??cm- 1 peak. The relationship between peak area ratio (AR) and the CO2 concentration in the inclusions is given as:Mole % C O2 = 312.5 AR. The equation relating peak area ratio and composition is valid up to 25??mol% CO2 and from 300 to 450????C. The relationship between linear peak intensity ratio and composition should be used for inclusions containing ??? 50??mol% CO2 and which can be analyzed at 350????C. The relationship between composition and peak area ratios should be used when analyzing inclusions at temperatures less than or greater than 350????C (300-450) but can only be used for compositions ??? 25??mol% CO2. Note that this latter relationship has a somewhat larger standard deviation compared to the intensity ratio relationship. Calibration relationships employing peak areas for both members of the Fermi diad (??1 at 1285??cm- 1 and 2??2 at 1388??cm- 1) were slightly poorer than those using only the 2??2 (1388??cm- 1) member owing to interference from quartz peak at approximately 1160??cm- 1. The technique has been applied to natural low-salinity H2O-CO2 inclusions from the Butte, Montana, porphyry copper-molybdenum deposit. Carbon dioxide concentrations obtained range from below detection to 4.2??mol% CO2, and are in good agreement with concentrations determined previously based on microthermometric and petrographic observations. ?? 2007 Elsevier B.V. All rights reserved.

Chemical Geology

The speciation of aqueous zinc(II) bromide solutions to 500 °C and 900 MPa determined using Raman spectroscopy

A Raman spectral study was carried out on 3 solutions of varying concentration and bromide/zinc ratios. Spectra were collected at 11 different temperature-pressure conditions ranging from ambient to 500????C-0.9??GPa. Raman band assignments for zinc(II) bromide species reported in previous studies were used to determine the relative concentrations of ZnBr42-, ZnBr3-, ZnBr2, and ZnBr+ species at various temperatures and pressures. Our results are in close agreement with X-ray absorption spectroscopic (XAS) data, and confirm that the tetrabromo zinc(II) complex, ZnBr42-, is the predominant species up to 500????C in solutions having high Zn concentrations (1??m) and high bromide/zinc molar ratios ([Br]/[Zn] = 8). In agreement with previous solubility and Raman spectroscopic experiments, our measurements indicate that species with a lower number of halide ligands and charge are favored with increasing temperature in dilute solutions, and solutions with low bromide/zinc ratios ([Br]/[Zn] < 2.5). The Raman technique provides an independent experimental means of evaluating the quality of XAS analyses of data obtained from high temperature disordered systems. The combination of these two techniques provides complementary data on speciation and the structure of zinc(II) bromide complexes. The preponderance of the ZnBr42- species in highly saline brines at high temperature is consistent with the predominance of ZnCl42- in chloride-rich brines reported in previous XAS studies. Knowledge of Zn complexing in metal-rich highly saline brines is important for numerical models of ore deposition in high temperature systems such as skarns and porphyry-type deposits. ?? 2008 Elsevier B.V.

Chemical Geology

Multiresidue extraction of current-use pesticides from complex solid matrices using energized dispersive guided extraction with analysis by gas and liquid chromatography tandem mass spectroscopy

The development of sample processing techniques that recover a broad suite of pesticides from solid matrices, while mitigating coextracted matrix interferences, and reducing processing time is beneficial for high throughput analyses. The objective of this study was to evaluate the effectiveness of an automated extraction system for pesticide analyses in solid environmental samples. An Energized Dispersive Guided Extraction (EDGE) system was used to evaluate two different extraction solvents in optimizing the extraction of 210 pesticides and pesticide transformation products. A graphitized carbon cleanup step was implemented, and three elution solvents were evaluated separately for analyte recoveries. Recoveries between 70 and 130% were achieved for 167 compounds in a test soil using acetonitrile as an extraction solvent and carbon cleanup with acetonitrile and dichloromethane elutions. Nine field samples (soil, sediment, and biosolids) were extracted using the newly developed method and were compared with a previously validated pressurized liquid extraction (PLE) method using an Accelerated Solvent Extraction (ASE) system. Concentrations obtained from the two methods were comparable (linear R 2 > 0.999), suggesting similar performance between the EDGE and PLE extractions in complex matrices. The new method provided slightly better sensitivities in comparison to the PLE method, ranging from 0.09 to 2.56 ng g −1 . The method presented here significantly reduces extraction setup and runtimes while also minimizing the volume of carcinogenic solvents ( e.g. , dichloromethane) used in the laboratory and presents a sensitive multiresidue method for a wide range of pesticides in solid matrices.

Chemosphere

Chemical and nanometer-scale structure of kerogen and its change during thermal maturation investigated by advanced solid-state 13 C NMR spectroscopy

We have used advanced and quantitative solid-state nuclear magnetic resonance (NMR) techniques to investigate structural changes in a series of type II kerogen samples from the New Albany Shale across a range of maturity (vitrinite reflectance R 0 from 0.29% to 1.27%). Specific functional groups such as CH 3 , CH 2 , alkyl CH, aromatic CH, aromatic C-O, and other nonprotonated aromatics, as well as "oil prone" and "gas prone" carbons, have been quantified by 13 C NMR; atomic H/C and O/C ratios calculated from the NMR data agree with elemental analysis. Relationships between NMR structural parameters and vitrinite reflectance, a proxy for thermal maturity, were evaluated. The aromatic cluster size is probed in terms of the fraction of aromatic carbons that are protonated (???30%) and the average distance of aromatic C from the nearest protons in long-range H-C dephasing, both of which do not increase much with maturation, in spite of a great increase in aromaticity. The aromatic clusters in the most mature sample consist of ???30 carbons, and of ???20 carbons in the least mature samples. Proof of many links between alkyl chains and aromatic rings is provided by short-range and long-range 1 H- 13 C correlation NMR. The alkyl segments provide most H in the samples; even at a carbon aromaticity of 83%, the fraction of aromatic H is only 38%. While aromaticity increases with thermal maturity, most other NMR structural parameters, including the aromatic C-O fractions, decrease. Aromaticity is confirmed as an excellent NMR structural parameter for assessing thermal maturity. In this series of samples, thermal maturation mostly increases aromaticity by reducing the length of the alkyl chains attached to the aromatic cores, not by pronounced growth of the size of the fused aromatic ring clusters. ?? 2010 Elsevier Ltd. All rights reserved.

Geochimica et Cosmochimica Acta

9969 Braille: Deep Space 1 infrared spectroscopy, geometric albedo, and classification

Spectra of Asteroid 9969 Braille in the 1.25-2.6 ??m region returned by the Deep Space 1 (DS1) Mission show a ???10% absorption band centered at 2 ??m, and a reflectance peak at 1.6 ??m. Analysis of these features suggest that the composition of Braille is roughly equal parts pyroxene and olivine. Its spectrum between 0.4 and 2.5 ??m suggests that it is most closely related to the Q taxonomic type of asteroid. The spectrum also closely matches that of the ordinary chondrites, the most common type of terrestrial meteorite. The geometric albedo of Braille is unusually high (pv = 0.34), which is also consistent with its placement within the rarer classes of stony asteroids, and which suggests it has a relatively fresh, unweathered surface, perhaps due to a recent collision. ?? 2003 Elsevier Inc. All rights reserved.

Icarus

Spectroscopy, morphometry, and photoclinometry of Titan's dunefields from Cassini/VIMS

Fine-resolution (500 m/pixel) Cassini Visual and Infrared Mapping Spectrometer (VIMS) T20 observations of Titan resolve that moon's sand dunes. The spectral variability in some dune regions shows that there are sand-free interdune areas, wherein VIMS spectra reveal the exposed dune substrate. The interdunes from T20 are, variously, materials that correspond to the equatorial bright, 5-??m-bright, and dark blue spectral units. Our observations show that an enigmatic "dark red" spectral unit seen in T5 in fact represents a macroscopic mixture with 5-??m-bright material and dunes as its spectral endmembers. Looking more broadly, similar mixtures of varying amounts of dune and interdune units of varying composition can explain the spectral and albedo variability within the dark brown dune global spectral unit that is associated with dunes. The presence of interdunes indicates that Titan's dunefields are both mature and recently active. The spectrum of the dune endmember reveals the sand to be composed of less water ice than the rest of Titan; various organics are consistent with the dunes' measured reflectivity. We measure a mean dune spacing of 2.1 km, and find that the dunes are oriented on the average in an east-west direction, but angling up to 10?? from parallel to the equator in specific cases. Where no interdunes are present, we determine the height of one set of dunes photoclinometrically to be between 30 and 70 m. These results pave the way for future exploration and interpretation of Titan's sand dunes. ?? 2007 Elsevier Inc. All rights reserved.

Icarus

Characterizing canopy biochemistry from imaging spectroscopy and its application to ecosystem studies

For two decades, remotely sensed data from imaging spectrometers have been used to estimate non-pigment biochemical constituents of vegetation, including water, nitrogen, cellulose, and lignin. This interest has been motivated by the important role that these substances play in physiological processes such as photosynthesis, their relationships with ecosystem processes such as litter decomposition and nutrient cycling, and their use in identifying key plant species and functional groups. This paper reviews three areas of research to improve the application of imaging spectrometers to quantify non-pigment biochemical constituents of plants. First, we examine recent empirical and modeling studies that have advanced our understanding of leaf and canopy reflectance spectra in relation to plant biochemistry. Next, we present recent examples of how spectroscopic remote sensing methods are applied to characterize vegetation canopies, communities and ecosystems. Third, we highlight the latest developments in using imaging spectrometer data to quantify net primary production (NPP) over large geographic areas. Finally, we discuss the major challenges in quantifying non-pigment biochemical constituents of plant canopies from remotely sensed spectra.

Remote Sensing of Environment

Mapping changing distributions of dominant species in oil-contaminated salt marshes of Louisiana using imaging spectroscopy

The April 2010 Deepwater Horizon (DWH) oil spill was the largest coastal spill in U.S. history. Monitoring subsequent change in marsh plant community distributions is critical to assess ecosystem impacts and to establish future coastal management priorities. Strategically deployed airborne imaging spectrometers, like the Airborne Visible/Infrared Imaging Spectrometer (AVIRIS), offer the spectral and spatial resolution needed to differentiate plant species. However, obtaining satisfactory and consistent classification accuracies over time is a major challenge, particularly in dynamic intertidal landscapes. Here, we develop and evaluate an image classification system for a time series of AVIRIS data for mapping dominant species in a heavily oiled salt marsh ecosystem. Using field-referenced image endmembers and canonical discriminant analysis (CDA), we classified 21 AVIRIS images acquired during the fall of 2010, 2011 and 2012. Classification results were evaluated using ground surveys that were conducted contemporaneously to AVIRIS collection dates. We analyzed changes in dominant species cover from 2010 to 2012 for oiled and non-oiled shorelines. CDA discriminated dominant species with a high level of accuracy (overall accuracy = 82%, kappa = 0.78) and consistency over three imaging dates (overall 2010 = 82%, overall 2011 = 82%, overall 2012 = 88%). Marshes dominated by Spartina alterniflora were the most spatially abundant in shoreline zones (≤ 28 m from shore) for all three dates (2010 = 79%, 2011 = 61%, 2012 = 63%), followed by Juncus roemerianus (2010 = 11%, 2011 = 19%, 2012 = 17%) and Distichlis spicata (2010 = 4%, 2011 = 10%, 2012 = 7%). Marshes that were heavily contaminated with oil exhibited variable responses from 2010 to 2012. Marsh vegetation classes converted to a subtidal, open water class along oiled and non-oiled shorelines that were similarly situated in the landscape. However, marsh loss along oil-contaminated shorelines doubled that of non-oiled shorelines. Only S. alterniflora dominated marshes were extensively degraded, losing 15% (354,604 m 2 ) cover in oiled shoreline zones, suggesting that S. alterniflora marshes may be more vulnerable to shoreline erosion following hydrocarbon stress, due to their landscape position.

Louisiana

Quantifying uncertainty for remote spectroscopy of surface composition

Remote surface measurements by imaging spectrometers play an important role in planetary and Earth science. To make these measurements, investigators calibrate instrument data to absolute units, invert physical models to estimate atmospheric effects, and then determine surface properties from the spectral reflectance. This study quantifies the uncertainty in this process. Global missions demand predictive uncertainty models that can estimate future errors for varied environments and observing conditions. Here we validate uncertainty predictions with remote surface composition retrievals and in situ measurements in a field analogue of Earth and planetary exploration. We consider rover transects at Cuprite, Nevada, and remote observations by NASA's Next- Generation Airborne Visible Infrared Imaging Spectrometer (AVIRIS-NG). We show that accounting for input uncertainties can benefit mineral detection methods such as constrained spectrum fitting. This suggests that operational uncertainty estimates could improve future NASA missions like the Earth Mineral dust source InvesTigation (EMIT) and the Lunar Trailblazer mission, as well as NASA's Decadal Surface Biology and Geology (SBG) Investigation.

Remote Sensing of Environment