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At least 217 records · Page 12Linked to original sources
USGS2024

Insights on using solid bitumen reflectance as a thermal maturity proxy in the Bakken Formation, Williston Basin, USA

To further refine the use of solid bitumen reflectance (BR o in %) as a measurement of thermal maturity in source-rock reservoirs, we examined its relationship to other thermal proxies in the Bakken Formation. Comparisons included criteria from programmed temperature pyrolysis, gas chromatography (GC), and Fourier transform infrared (FTIR) spectroscopy. Thirty-two organic-rich samples from the lower and upper shale members of the Devonian–Lower Carboniferous Bakken Formation were collected from eight cores across the Williston Basin, USA, at depths (∼7575–11,330 ft) representing immature through post peak oil/early condensate thermal maturity conditions based on proximity to current hydrocarbon production. Unmodified BR o values were correlated to programmed temperature pyrolysis parameters (hydrogen index, production index, and T max ), normal hydrocarbon and isoprenoid analysis of extractable organic matter (pristane/ n -C 17 and phytane/ n -C 18 ) from GC analysis, and peak ratios from FTIR spectroscopy (branching ratio and A -factor). Strong correlations between unmodified BR o values (not corrected to a vitrinite reflectance equivalent, VR e ) and other thermal proxies suggest that BR o can be used as a direct thermal proxy in marine Paleozoic source-rock reservoirs where vitrinite is rare or absent. Moreover, an apparent overestimation of VR e at the lowest thermal maturity investigated herein may argue against the application of BR o conversion to VR e in the Bakken Formation. Solvent extraction caused a consistent decrease in BR o when average post-extraction values from a given well were compared to BR o prior to extraction, although the decrease in mean value was not statistically significant. These results are discussed in the context of advocating for the use of unmodified BR o values as a best practice for thermal maturity determination in Paleozoic marine source-rock reservoirs.

Montana, North Dakota↗
USGS2004

Chemical characterization and sorption capacity measurements of degraded newsprint from a landfill

Newsprint samples collected from 12−16 ft (top layer (TNP)), 20−24 ft (middle layer (MNP)), and 32−36 ft (bottom layer (BNP)) below the surface of the Norman Landfill (NLF) were characterized by infrared (IR) spectroscopy, cross-polarization, magic-angle spinning 13 C nuclear magnetic resonance (CP-MAS 13 C NMR) spectroscopy, and tetramethylammonium hydroxide (TMAH) thermochemolysis gas chromatography/mass spectrometry (GC/MS). The extent of NLF newsprint degradation was evaluated by comparing the chemical composition of NLF newsprint to that of fresh newsprint (FNP) and newsprint degraded in the laboratory under methanogenic conditions (DNP). The O -alkyl/alkyl, cellulose/lignin, and lignin/resin acid ratios showed that BNP was the most degraded, and that all three NLF newsprint samples were more degraded than DNP. 13 C NMR and TMAH thermochemolysis data demonstrated selective enrichment of lignin over cellulose, and TMAH thermochemolysis further exhibited selective enrichment of resin acids over lignin. In addition, the crystallinity of cellulose in NLF newsprint samples was significantly lower relative to that of FNP and DNP as shown by 13 C NMR spectra. The yield of lignin monomers from TMAH thermochemolysis suggested that hydroxyl groups were removed from the propyl side chain of lignin during the anaerobic decomposition of newsprint in the NLF. Moreover, the vanillyl acid/aldehyde ratio, which successfully describes aerobic lignin degradation, was not a good indicator of the anaerobic degradation of lignin on the basis of the TMAH data. The toluene sorption capacity increased as the degree of newsprint degradation increased or as the O -alkyl/alkyl ratio of newsprint decreased. The results of this study further verified that the sorbent O -alkyl/alkyl ratio is useful for predicting sorption capacities of natural organic materials for hydrophobic organic contaminants.

Environmental Science & Technology↗
USGS2007

Spectroscopic evidence for uranium bearing precipitates in vadose zone sediments at the Hanford 300-area site

Uranium (U) solid-state speciation in vadose zone sediments collected beneath the former North Process Pond (NPP) in the 300 Area of the Hanford site (Washington) was investigated using multi-scale techniques. In 30 day batch experiments, only a small fraction of total U (???7.4%) was released to artificial groundwater solutions equilibrated with 1% pCO2. Synchrotron-based micro-X-ray fluorescence spectroscopy analyses showed that U was distributed among at least two types of species: (i) U discrete grains associated with Cu and (ii) areas with intermediate U concentrations on grains and grain coatings. Metatorbernite (Cu[UO2]2[PO 4]2??8H2O) and uranophane (Ca[UO 2]2[SiO3(OH)]2?? 5H 2O) at some U discrete grains, and muscovite at U intermediate concentration areas, were identified in synchrotron-based micro-X-ray diffraction. Scanning electron microscopy/energy dispersive X-ray analyses revealed 8-10 ??m size metatorbernite particles that were embedded in C-, Al-, and Si-rich coatings on quartz and albite grains. In ??- and bulk-X-ray absorption structure (??-XAS and XAS) spectroscopy analyses, the structure of metatorbernite with additional U-C and U-U coordination environments was consistently observed at U discrete grains with high U concentrations. The consistency of the ??- and bulk-XAS analyses suggests that metatorbernite may comprise a significant fraction of the total U in the sample. The entrapped, micrometer-sized metatorbernite particles in C-, Al-, and Si-rich coatings, along with the more soluble precipitated uranyl carbonates and uranophane, likely control the long-term release of U to water associated with the vadose zone sediments. ?? 2007 American Chemical Society.

Environmental Science & Technology↗
USGS2004

Concentrations of arsenic, cadmium, copper, lead, selenium, and zinc in fish from the Mississippi River Basin, 1995

Fish were collected in late 1995 from 34 National Contaminant Biomonitoring Program (NCBP) stations and 12 National Water Quality Assessment Program (NAWQA) stations in the Mississippi River basin (MRB), and in late 1996 from a reference site in West Virginia. The NCBP sites represented key points (dams, tributaries, etc.) in the largest rivers of the MRB. The NAWQA sites were typically on smaller rivers and were selected to represent dominant land uses in their watersheds. The West Virginia site, which is in an Eastern U.S. watershed adjacent to the MRB, was selected to document elemental concentrations in fish used for other aspects of a larger study and to provide additional contemporaneous data on background elemental concentrations. At each site four samples, each comprising (nominally) 10 adult common carp ( Cyprinus carpio , `carp') or black bass ( Micropterus spp., `bass') of the same sex, were collected. The whole fish were composited by station, species, and gender for analysis of arsenic (As), lead (Pb), and selenium (Se) by atomic absorption spectroscopy and for cadmium (Cd), copper (Cu), and zinc (Zn) by inductively-coupled plasma emission spectroscopy. Concentrations of most of the elements examined were lower in both carpand bass from the reference site, a small impoundment located in a rural area, than from the NCBP and NAWQA sites on rivers and larger impoundments. In contrast, there were few overall differences between NCBP sites NAWQA sites. The 1995 results generally confirmed the continued weathering and re-distribution of these elemental contaminants in the MRB; concentrations declined or were unchanged from 1984–1986 to 1995 at most NCBP sites, thus continuing two-decade trends. Exceptions were Se at Station 77 (Arkansas R. at John Martin Reservoir, CO), where concentrations have been elevated historically and increased slightly (to 3.8–4.7 μg g -1 in bass and carp); and Pb, Cd, and Zn at Station 67 (Allegheny R. at Natrona, PA), where levels of these metals were high in the past and increased from 1986 to 1995.

Environmental Monitoring and Assessment↗
USGS2001

Search for life on Mars in surface samples: Lessons from the 1999 Marsokhod rover field experiment

The Marsokhod 1999 field experiment in the Mojave Desert included a simulation of a rover-based sample selection mission. As part of this mission, a test was made of strategies and analytical techniques for identifying past or present life in environments expected to be present on Mars. A combination of visual clues from high-resolution images and the detection of an important biomolecule (chlorophyll) with visible/near-infrared (NIR) spectroscopy led to the successful identification of a rock with evidence of cryptoendolithic organisms. The sample was identified in high-resolution images (3 times the resolution of the Imager for Mars Pathfinder camera) on the basis of a green tinge and textural information suggesting the presence of a thin, partially missing exfoliating layer revealing the organisms. The presence of chlorophyll bands in similar samples was observed in visible/NIR spectra of samples in the field and later confirmed in the laboratory using the same spectrometer. Raman spectroscopy in the laboratory, simulating a remote measurement technique, also detected evidence of carotenoids in samples from the same area. Laboratory analysis confirmed that the subsurface layer of the rock is inhabited by a community of coccoid Chroococcidioposis cyanobacteria. The identification of minerals in the field, including carbonates and serpentine, that are associated with aqueous processes was also demonstrated using the visible/NIR spectrometer. Other lessons learned that are applicable to future rover missions include the benefits of web-based programs for target selection and for daily mission planning and the need for involvement of the science team in optimizing image compression schemes based on the retention of visual signature characteristics.

California↗
USGS2012

Improving the accuracy of S0 2 column densities and emission rates obtained from upward-looking UV-spectroscopic measurements of volcanic plumes by taking realistic radiative transfer into account

Sulfur dioxide (SO 2 ) is monitored using ultraviolet (UV) absorption spectroscopy at numerous volcanoes around the world due to its importance as a measure of volcanic activity and a tracer for other gaseous species. Recent studies have shown that failure to take realistic radiative transfer into account during the spectral retrieval of the collected data often leads to large errors in the calculated emission rates. Here, the framework for a new evaluation method which couples a radiative transfer model to the spectral retrieval is described. In it, absorption spectra are simulated, and atmospheric parameters are iteratively updated in the model until a best match to the measurement data is achieved. The evaluation algorithm is applied to two example Differential Optical Absorption Spectroscopy (DOAS) measurements conducted at Kilauea volcano (Hawaii). The resulting emission rates were 20 and 90% higher than those obtained with a conventional DOAS retrieval performed between 305 and 315 nm, respectively, depending on the different SO 2 and aerosol loads present in the volcanic plume. The internal consistency of the method was validated by measuring and modeling SO2 absorption features in a separate wavelength region around 375 nm and comparing the results. Although additional information about the measurement geometry and atmospheric conditions is needed in addition to the acquired spectral data, this method for the first time provides a means of taking realistic three-dimensional radiative transfer into account when analyzing UV-spectral absorption measurements of volcanic SO 2 plumes.

Journal of Geophysical Research D: Atmospheres↗
USGS2020

Laboratory electrical conductivity of marine gas hydrate

Methane hydrate was synthesized from pure water ice and flash frozen seawater, with varying amounts of sand or silt added. Electrical conductivity was determined by impedance spectroscopy, using equivalent circuit modeling to separate the effects of electrodes and to gain insight into conduction mechanisms. Silt and sand increase the conductivity of pure hydrate, we infer by contaminant NaCl contributing to conduction in hydrate, to values in agreement with resistivities observed in well logs through hydrate The addition of silt and sand lowers the conductivity of hydrate synthesized from seawater by an amount consistent with Archie's Law. All samples were characterized using cryogenic scanning electron microscopy and energy dispersive spectroscopy, which show good connectivity of salt and brine phases. Electrical conductivity measurements of pure hydrate and hydrate mixed with silt during pressure‐induced dissociation supports previous conclusions that sediment increases dissociation rate.

Geophysical Research Letters↗
USGS2024

Linking dissolved organic matter composition to landscape properties in wetlands across the United States of America

Wetlands are integral to the global carbon cycle, serving as both a source and a sink for organic carbon. Their potential for carbon storage will likely change in the coming decades in response to higher temperatures and variable precipitation patterns. We characterized the dissolved organic carbon (DOC) and dissolved organic matter (DOM) composition from 12 different wetland sites across the USA spanning gradients in climate, landcover, sampling depth, and hydroperiod for comparison to DOM in other inland waters. Using absorption spectroscopy, parallel factor analysis modeling, and ultra-high resolution mass spectroscopy, we identified differences in DOM sourcing and processing by geographic site. Wetland DOM composition was driven primarily by differences in landcover where forested sites contained greater aromatic and oxygenated DOM content compared to grassland/herbaceous sites which were more aliphatic and enriched in N and S molecular formulae. Furthermore, surface and porewater DOM was also influenced by properties such as soil type, organic matter content, and precipitation. Surface water DOM was relatively enriched in oxygenated higher molecular weight formulae representing HUP High O/C compounds than porewaters, whose DOM composition suggests abiotic sulfurization from dissolved inorganic sulfide. Finally, we identified a group of persistent molecular formulae (3,489) present across all sites and sampling depths (i.e., the signature of wetland DOM) that are likely important for riverine-to-coastal DOM transport. As anthropogenic disturbances continue to impact temperate wetlands, this study highlights drivers of DOM composition fundamental for understanding how wetland organic carbon will change, and thus its role in biogeochemical cycling.

Global Biogeochemical Cycles↗
USGS2017

Nanoscale geochemical and geomechanical characterization of dispersed organic matter in shale by infrared nanoscopy

Solid organic matter (OM) plays an essential role in the generation, migration, storage, and production of hydrocarbons from economically important shale rock formations. Electron microscopy images have documented spatial heterogeneity in the porosity of OM at nanoscale, and bulk spectroscopy measurements have documented large variation in the chemical composition of OM during petroleum generation. However, information regarding the heterogeneity of OM chemical composition at the nanoscale has been lacking. Here we demonstrate the first application of atomic force microscopy-based infrared spectroscopy (AFM-IR) to measure the chemical and mechanical heterogeneity of OM in shale at the nanoscale, orders of magnitude finer than achievable by traditional chemical imaging tools such as infrared microscopy. We present a combination of optical microscopy and AFM-IR imaging to characterize OM heterogeneity in an artificially matured series of New Albany Shales. The results document the evolution of individual organic macerals with maturation, providing a microscopic picture of the heterogeneous process of petroleum generation.

Nature Communications↗
USGS2023

Supervised discretization for decluttering classification models

Presented here is the first demonstration of supervised discretization to ‘declutter’ multivariate classification data in chemical sensor applications. The performance of multivariate classification models is often limited by the non-informative chemical variance within each target class; decluttering methods seek to reduce within-class variance while retaining between-class variance. Supervised discretization is shown to declutter classes in a manner that is superior to the state-of-the-art External Parameter Orthogonalization (EPO) by constructing a more parsimonious model with fewer parameters to optimize and is, consequently, less susceptible to overfitting and information loss. The comparison of supervised discretization and EPO is performed on three classification applications: X-ray fluorescence spectra of pine ash where the pine was grown in three distinct soil types, laser induced breakdown spectroscopy of colored artisanal glasses, and laser induced breakdown spectroscopy of exotic hardwood species.

Analyst↗
USGS2018

Spatial spectroscopic models for remote exploration

Ancient hydrothermal systems are a high-priority target for a future Mars sample return mission because they contain energy sources for microbes and can preserve organic materials (Farmer, 2000 ; MEPAG Next Decade Science Analysis Group, 2008 ; McLennan et al., 2012 ; Michalski et al., 2017 ). Characterizing these large, heterogeneous systems with a remote explorer is difficult due to communications bandwidth and latency; such a mission will require significant advances in spacecraft autonomy. Science autonomy uses intelligent sensor platforms that analyze data in real-time, setting measurement and downlink priorities to provide the best information toward investigation goals. Such automation must relate abstract science hypotheses to the measurable quantities available to the robot. This study captures these relationships by formalizing traditional “science traceability matrices” into probabilistic models. This permits experimental design techniques to optimize future measurements and maximize information value toward the investigation objectives, directing remote explorers that respond appropriately to new data. Such models are a rich new language for commanding informed robotic decision making in physically grounded terms. We apply these models to quantify the information content of different rover traverses providing profiling spectroscopy of Cuprite Hills, Nevada. We also develop two methods of representing spatial correlations using human-defined maps and remote sensing data. Model unit classifications are broadly consistent with prior maps of the site's alteration mineralogy, indicating that the model has successfully represented critical spatial and mineralogical relationships at Cuprite. Key Words: Autonomous science—Imaging spectroscopy—Alteration mineralogy—Field geology—Cuprite—AVIRIS-NG—Robotic exploration. Astrobiology 18, 934–954.

Astrobiology↗
USGS2024

Depths in a day - A new era of rapid-response Raman-based barometry using fluid inclusions

Rapid-response petrological monitoring is a major advance for volcano observatories, allowing them to build and validate models of plumbing systems that supply eruptions in near-real-time. The depth of magma storage has recently been identified as high-priority information for volcanic observatories, yet this information is not currently obtainable via petrological monitoring methods on timescales relevant to eruption response. Fluid inclusion barometry (using micro-thermometry or Raman spectroscopy) is a well-established petrological method to estimate magma storage depths and has been proposed to have potential as a rapid-response monitoring tool, although this has not been formally demonstrated. To address this deficiency, we performed a near-real-time rapid-response simulation for the September 2023 eruption of Kīlauea, Hawaiʻi. We show that Raman-based fluid inclusion barometry can robustly determine reservoir depths within a day of receiving samples — a transformative timescale that has not previously been achieved by petrological methods. Fluid inclusion barometry using micro-thermometric techniques has typically been limited to systems with relatively deep magma storage (>0.4 g/cm 3 or >7 km) where measurements of CO 2 density are easy and accurate because the CO 2 fluid homogenizes into the liquid phase. Improvements of the accuracy of Raman spectroscopy measurements of fluids with low CO 2 density over the past couple of decades has enabled measurements of fluid inclusions from shallower magmatic systems. However, one caveat of examining shallower systems is that the fraction of H 2 O in the fluid may be too high to reliably convert CO 2 density to pressure. To test the global applicability of rapid response fluid inclusion barometry, we compiled a global melt inclusion dataset (>4000 samples) and calculate the fluid composition at the point of vapor saturation (⁠X H 2 O⁠ ). We show that fluid inclusions in crystal-hosts from mafic compositions (<57 wt. % SiO 2 ) — likely representative of magmas recharging many volcanic systems worldwide — trap fluids with X H 2 O low enough to make fluid inclusion barometry useful at many of the world’s most active and hazardous mafic volcanic systems (e.g., Iceland, Hawaiʻi, Galápagos Islands, East African Rift, Réunion, Canary Islands, Azores, Cabo Verde).

Hawaii↗
USGS2016

Coesite in suevites from the Chesapeake Bay impact structure

The occurrence of coesite in suevites from the Chesapeake Bay impact structure is confirmed within a variety of textural domains in situ by Raman spectroscopy for the first time and in mechanically separated grains by X-ray diffraction. Microtextures of coesite identified in situ investigated under transmitted light and by scanning electron microscope reveal coesite as micrometer-sized grains (1–3 μm) within amorphous silica of impact-melt clasts and as submicrometer-sized grains and polycrystalline aggregates within shocked quartz grains. Coesite-bearing quartz grains are present both idiomorphically with original grain margins intact and as highly strained grains that underwent shock-produced plastic deformation. Coesite commonly occurs in plastically deformed quartz grains within domains that appear brown (toasted) in transmitted light and rarely within quartz of spheroidal texture. The coesite likely developed by a mechanism of solid-state transformation from precursor quartz. Raman spectroscopy also showed a series of unidentified peaks associated with shocked quartz grains that likely represent unidentified silica phases, possibly including a moganite-like phase that has not previously been associated with coesite.

Chesapeake Bay↗
USGS2002

A compact high-resolution 3-D imaging spectrometer for discovering Oases on Mars

A new design for a very lightweight, very high throughput reflectance sectrometer enabled by two new technologies being developed is presented. These new technologies include integral field unit optics to enable simultaneous imaging and spectroscopy at high spatial resolution with an infrared (IR) array, and silicon grisms to enable compact and high-resolution spectroscopy.

Conference Paper↗
USGS2007

Formation of tellurium nanocrystals during anaerobic growth of bacteria that use Te oxyanions as respiratory electron acceptors

Certain toxic elements support the metabolism of diverse prokaryotes by serving as respiratory electron acceptors for growth. Here, we demonstrate that two anaerobes previously shown to be capable of respiring oxyanions of selenium also achieve growth by reduction of either tellurate [Te(VI)] or tellurite [Te(IV)] to elemental tellurium [Te(0)]. This reduction achieves a sizeable stable-Te-isotopic fractionation (isotopic enrichment factor [ε] = −0.4 to −1.0 per ml per atomic mass unit) and results in the formation of unique crystalline Te(0) nanoarchitectures as end products. The Te(0) crystals occur internally within but mainly externally from the cells, and each microorganism forms a distinctly different structure. Those formed by Bacillus selenitireducens initially are nanorods (∼10-nm diameter by 200-nm length), which cluster together, forming larger (∼1,000-nm) rosettes composed of numerous individual shards (∼100-nm width by 1,000-nm length). In contrast, Sulfurospirillum barnesii forms extremely small, irregularly shaped nanospheres (diameter < 50 nm) that coalesce into larger composite aggregates. Energy-dispersive X-ray spectroscopy and selected area electron diffraction indicate that both biominerals are composed entirely of Te and are crystalline, while Raman spectroscopy confirms that they are in the elemental state. These Te biominerals have specific spectral signatures (UV-visible light, Raman) that also provide clues to their internal structures. The use of microorganisms to generate Te nanomaterials may be an alternative for bench-scale syntheses. Additionally, they may also generate products with unique properties unattainable by conventional physical/chemical methods.

Applied and Environmental Microbiology↗
USGS2017

Graphite in the Bishop Tuff and its effect on postcaldera oxygen fugacity

Several cubic kilometers of Paleozoic graphite-bearing argillitic country rocks are present as lithic fragments in Bishop Tuff ignimbrite and fallout. The lithics were entrained by the 650 km 3 of rhyolite magma that vented during the 5- to 6-day-long, caldera-forming eruption at Long Valley, California. The caldera is floored by a 350 km 2 roof plate that collapsed during the eruption and consists in large part of the Paleozoic strata that provided the abundant hornfelsed metapelitic lithic clasts in the tuff. Graphite has been identified by Raman spectroscopy, electron-dispersive spectroscopy, and X-ray diffraction as an irregularly dispersed component in the small fraction of Bishop Tuff pumice that is dark-colored. Carbon concentration has been determined in pumice, lithics, and wall rocks. Values of δ 13 C range from –21‰ to –29‰ Vienna Peedee Belemnite (VPDB) for pumice, lithics, and argillitic wall rocks, reflecting the biogenic origin of the reduced carbon in oxygen-limited black Paleozoic marine mudrocks. Carbonate contents, measured separately, are negligible in fresh pumice and lithics. Microprobe analyses of titanomagnetite-ilmenite pairs show that oxygen-fugacity values of numerous batches of postcaldera Early Rhyolite (750–640 ka; ~100 km 3 ) are up to one log unit more reduced than those of the temperature–oxygen fugacity (T-fO 2 ) array of the Bishop Tuff (767 ka), despite similar major-element compositions and Fe-Ti–oxide temperature ranges. All of the many batches of Early Rhyolite, which erupted episodically over an interval of ~125,000 years, yield the reduced fO 2 values, indicating that reaction with graphite lowered magmatic fO 2 after the caldera-forming eruption but before the first eruption of Early Rhyolite. It is inferred that reaction of postcaldera rhyolite magma with the reduced carbon in a great mass of subsided roof rocks lowered its fO 2 . It is suggested that comparable effects could have attended caldera collapse of other magma chambers hosted in continental sedimentary rocks.

Long Valley caldera↗
USGS2016

Nitrosation and nitration of fulvic acid, peat and coal with nitric acid

Nitrohumic acids, produced from base extraction of coals and peats oxidized with nitric acid, have received considerable attention as soil ammendments in agriculture. The nitration chemistry however is incompletely understood. Moreover, there is a need to understand the reaction of nitric acid with natural organic matter (NOM) in general, in the context of a variety of environmental and biogeochemical processes. Suwannee River NOM, Suwannee River fulvic acid, and Pahokee Peat fulvic acid were treated with 15 N-labeled nitric acid at concentrations ranging from 15% to 22% and analyzed by liquid and solid state 15 N NMR spectroscopy. Bulk Pahokee peat and Illinois #6 coal were also treated with nitric acid, at 29% and 40% respectively, and analyzed by solid state 15 N NMR spectroscopy. In addition to nitro groups from nitration of aromatic carbon, the 15 N NMR spectra of all five samples exhibited peaks attributable to nitrosation reactions. These include nitrosophenol peaks in the peat fulvic acid and Suwannee River samples, from nitrosation of phenolic rings, and N-nitroso groups in the peat samples, from nitrosation of secondary amides or amines, the latter consistent with the peat samples having the highest naturally abundant nitrogen contents. Peaks attributable to Beckmann and secondary reactions of the initially formed oximes were present in all spectra, including primary amide, secondary amide, lactam, and nitrile nitrogens. The degree of secondary reaction product formation resulting from nitrosation reactions appeared to correlate inversely with the 13 C aromaticities of the samples. The nitrosation reactions are most plausibly effected by nitrous acid formed from the reduction of nitric acid by oxidizable substrates in the NOM and coal samples.

PLoS ONE↗
USGS2017

Analysis of artificially matured shales with confocal laser scanning raman microscopy: Applications to organic matter characterization

Raman spectroscopy has been suggested as a method for characterizing the thermal maturity of rocks. The literature contains many empirical correlations between thermal maturity proxies, such as vitrinite reflectance (V Ro ) and pyrolysis-T max , with spectral metrics such as Raman peak-widths, peak-center positions, peak-areas and all manner of differences and ratios of these parameters. However, while these correlations may be convincing for small data sets from limited sample series, broader application of these metrics to disparate and heterogeneous samples proves difficult and there remains no consensus. In this extended abstract, Raman spectroscopy is introduced and the history of Raman analysis of carbonaceous material is briefly outlined, highlighting some of the latent difficulties and potential sources of bias. We suggest the organization of a community working group to establish terminology, guidelines, procedures and standards necessary for the successful development of this technique to characterize organic matter in an accessible, unbiased, and reproducible manner. For the present multi-phase study, immature shale samples from the Bakken and Duvernay formations were subjected to hydrous pyrolysis for 72 hours at temperatures from 280°C to 360°C. Rock residues were mounted and polished for analysis via confocal laser-scanning Raman microscopy and reflectance. The maturation series from the Bakken was randomized for the Phase-I single-blind study to be presented at this conference. For the Phase-II study, solid bitumen reflectance (B Ro ) values for the Duvernay series will be known. Multiple hyperspectral maps were collected from each Bakken sample, with each map consisting of a single diffraction-limited spot-size spectrum per 1 µm 2 in rectangular areas several hundred micrometers on a side. Initial attempts at using basic spectral metrics on small numbers of hand-selected spectra to sort the blind series produced inconclusive results: any number of possible correlations could be found. In an improved approach, the statistics of the full spectral datasets were leveraged to: 1) objectively identify organic carbon types (OCTs) in a given map based on Raman and fluorescence spectral characteristics, 2) identify those OCTs in other maps from the same sample and determine if the heterogeneity of the sample has been adequately characterized, and 3) identify the same OCTs in maps from other samples in the maturation series. In ongoing work, our goals are to: 1) use these analyses of the blind series to develop a hypothesis for a correlation to maturation, 2) test the hypothesis by applying the same analyses to the known Duvernay series (in Phase-II), 3) if necessary refine the hypothesis based on observations from the Duvernay analysis, and 4) finally reveal the true order of the Bakken series to verify if the hypothesized correlation accurately predicts the maturity order of the samples. In this document, we share progress to date. The analysis of one area of interest is detailed showing the differentiation of two OCTs based on Raman and fluorescence spectral features, including the use of 2-factor histograms, Principle Components Analysis (PCA), and Nonlinear Iterative Peak Fitting (NIPF).

Conference Paper↗