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At least 379 records · Page 21Linked to original sources

USGS2014

Investigating organic matter in Fanno Creek, Oregon, Part 3 of 3: identifying and quantifying sources of organic matter to an urban stream

The sources, transport, and characteristics of organic matter (OM) in Fanno Creek, an urban stream in northwest Oregon, were assessed and quantified using: (1) optical instruments to calculate transported loads of dissolved, particulate, and total organic carbon, (2) fluorescence spectroscopy and stable isotope ratios (δ 13 C, δ 15 N) to elucidate sources and chemical properties of OM throughout the basin, and (3) synoptic sampling to investigate seasonal and hydrologic variations in the characteristics and quantity of OM. Results from this study indicate that of the roughly 324 (±2.9%) metric tons (tonnes, t) of organic carbon exported from the basin during March 2012 to March 2013, most of the OM in Fanno Creek was dissolved (72%) and was present year-round at concentrations exceeding 3–4 milligrams of carbon per liter, whereas particulate carbon typically was mobilized and transported only by higher-flow conditions. The isotopic and fluorescence characteristics of Fanno Creek OM indicate that the carbon originates primarily from terrestrial inputs, most likely riparian vegetative biomass that enters the stream via litterfall and overland transport and then travels through the system episodically as a result of hydrologic processes. The amount of OM exported from the Fanno Creek drainage over the course of a year in this study is consistent with previous estimates of annual riparian litterfall in or near the creek. Although the creek channel is actively eroding, most bank material has too little OM for that to be a dominant source of OM to the stream. Fluorescence data revealed that the OM contains primarily humic and fulvic-like components that become less aromatic as the OM moves downstream. The most significant seasonal variation was associated with OM transported in the first storms of the autumn season (fall flush). That material was characteristically different, with a larger fraction of microbially derived OM that probably resulted from an accumulation of easy-to-mobilize and decomposing material in the streambed during previous months of summertime low-flow conditions. The first fall flush produced the highest concentrations of OM of the entire year, and the resulting load of mobilized and decomposing OM resulted in a significant oxygen demand immediately downstream in the Tualatin River.

Oregon↗

USGS2013

Applying UV cameras for SO 2 detection to distant or optically thick volcanic plumes

Ultraviolet (UV) camera systems represent an exciting new technology for measuring two dimensional sulfur dioxide (SO 2 ) distributions in volcanic plumes. The high frame rate of the cameras allows the retrieval of SO 2 emission rates at time scales of 1 Hz or higher, thus allowing the investigation of high-frequency signals and making integrated and comparative studies with other high-data-rate volcano monitoring techniques possible. One drawback of the technique, however, is the limited spectral information recorded by the imaging systems. Here, a framework for simulating the sensitivity of UV cameras to various SO 2 distributions is introduced. Both the wavelength-dependent transmittance of the optical imaging system and the radiative transfer in the atmosphere are modeled. The framework is then applied to study the behavior of different optical setups and used to simulate the response of these instruments to volcanic plumes containing varying SO 2 and aerosol abundances located at various distances from the sensor. Results show that UV radiative transfer in and around distant and/or optically thick plumes typically leads to a lower sensitivity to SO 2 than expected when assuming a standard Beer–Lambert absorption model. Furthermore, camera response is often non-linear in SO 2 and dependent on distance to the plume and plume aerosol optical thickness and single scatter albedo. The model results are compared with camera measurements made at Kilauea Volcano (Hawaii) and a method for integrating moderate resolution differential optical absorption spectroscopy data with UV imagery to retrieve improved SO 2 column densities is discussed.

Journal of Volcanology and Geothermal Research↗

USGS2015

Quantitative imaging of volcanic plumes — Results, needs, and future trends

Recent technology allows two-dimensional “imaging” of trace gas distributions in plumes. In contrast to older, one-dimensional remote sensing techniques, that are only capable of measuring total column densities, the new imaging methods give insight into details of transport and mixing processes as well as chemical transformation within plumes. We give an overview of gas imaging techniques already being applied at volcanoes (SO 2 cameras, imaging DOAS, FT-IR imaging), present techniques where first field experiments were conducted (LED-LIDAR, tomographic mapping), and describe some techniques where only theoretical studies with application to volcanology exist (e.g. Fabry–Pérot Imaging, Gas Correlation Spectroscopy, bi-static LIDAR). Finally, we discuss current needs and future trends in imaging technology.

Journal of Volcanology and Geothermal Research↗

USGS2017

Olivine-melt relationships and syneruptive redox variations in the 1959 eruption of Kīlauea Volcano as revealed by XANES

The 1959 summit eruption of Kīlauea Volcano exhibited high lava fountains of gas-rich, primitive magma, containing olivine + chromian spinel in highly vesicular brown glass. Microprobe analysis of these samples shows that euhedral rims on olivine phenocrysts, in direct contact with glass, vary significantly in forsterite (Fo) content, at constant major-element melt composition, as do unzoned groundmass olivine crystals. Ferric/total iron (Fe + 3 /Fe T )ratios for matrix and interstitial glasses, plus olivine-hosted glass inclusions in eight 1959 scoria samples have been determined by micro X-ray absorption near-edge structure spectroscopy (μ-XANES). These data show that much of the variation in Fo content reflects variation in oxidation state of iron in the melt, which varies with sulfur concentration in the glass and (locally) with proximity to scoria edges in contact with air. Data for 24 olivine-melt pairs in the better-equilibrated samples from later in the eruption show K D averaging 0.280 ± 0.03 for the exchange of Fe and Mg between olivine and melt, somewhat displaced from the value of 0.30 ± 0.03 given by Roeder and Emslie (1970). This may reflect the low SiO 2 content of the 1959 magmas, which is lower than that in most Kīlauea tholeiites. More broadly, we show the potential of μ-XANES and electron microprobe to revisit and refine the value of K D in natural systems. The observed variations of Fe + 3 /Fe T ratios in the glasses reflect two distinct processes. The main process, sulfur degassing, produces steady decrease of the Fe + 3 /Fe T ratio. Melt inclusions in olivine are high in sulfur (1060–1500 ppm S), with Fe + 3 /Fe T = 0.160–0.175. Matrix glasses are degassed (mostly S < 200 ppm) with generally lower Fe + 3 /Fe T (0.114–0.135). Interstitial glasses within clumps of olivine crystals locally show intermediate levels of sulfur and Fe + 3 /Fe T ratio. The correlation suggests that (1) the 1959 magma was significantly reduced by sulfur degassing during the eruption and (2) the melts originally had Fe + 3 /Fe T ≥ 0.175, consistent with oxygen fugacity ( f O 2 ) at least 0.4 log units above the fayalite-magnetite-quartz (FMQ) buffer at 1 atm and magmatic temperature of 1200 °C. The second process is interaction between the melts and atmospheric oxygen, which results in higher Fe + 3 /Fe T ratios. Detailed μ-XANES traverses show gradients in Fe + 3 /Fe T of 0.145 to 0.628 over distances of 100–150 μm in thin, visibly reddened matrix glass bordering some scoriae, presumably caused by contact with air. This process was extremely rapid, giving insight into how fast the Fe + 3 /Fe T ratio can change in response to changes in external conditions.

Hawaii↗

USGS2025

The ghost plume phenomenon and its impact on zenith-facing remote sensing measurements of volcanic SO2 emission rates

A large source of error in SO 2 emission rates derived from mobile Differential Optical Absorption Spectroscopy (DOAS) of volcanic gas plumes is the uncertainty in atmospheric light paths between the sun and the instrument, particularly under non-ideal atmospheric conditions, such as the presence of low clouds. DOAS instruments measure the SO 2 column density along the effective light path, so changes to that pathway directly affect the measured SO 2 signal. Due to complex radiative transfer mechanisms when a cloud is between the DOAS viewing position and a volcanic plume, measured plumes can appear spatially offset from their true location, a phenomenon informally referred to as “ghost plumes.” In addition to the appearance of ghost plumes, DOAS measurements recorded in non-ideal conditions have poorly characterized errors and are often discarded, limiting the data available to characterize volcanic degassing. In this study we simulate the radiative transfer associated with zenith-facing mobile DOAS traverses using the McArtim radiative transfer model for scenarios when there is a cloud layer between the instrument and the volcanic plume. In total, 217 permutations of atmospheric optical conditions are considered with varying cloud opacities (AOD = 0, 1, 2, 4, 8, 20), plume opacities (AOD = 0, 1, 2, 4, 8), solar zenith angles (SZA = 1°, 30°, 60°), and cloud thicknesses (200, 400, 800 m). We first develop objective criteria for selecting SO 2 baseline absorption levels and plume spatial extents. The simulated plume traverses are then integrated to obtain the SO 2 cross-sectional burdens which, after multiplication with the wind speed, yield SO 2 emission rates. We find large modification in the shape of the modeled cross-sectional burdens even under translucent (low AOD) cloud conditions in our modeled scenarios. Despite modification of the plume shape, the presence of a low cloud layer is typically not a large source of error in the SO 2 cross-sectional burden or emission rate obtained from zenith-facing DOAS traverses. We find that all measured cross-sectional burdens simulated using an aerosol-free plume in the above conditions and SZA ≤ 30° are within ±25% of the true value.

Journal of Volcanology and Goethermal Research↗

USGS2025

The crystalline silica respiratory hazard from rhyolitic lava dome eruptions in New Zealand's Taupo Volcanic Zone: A case study from the 1315 CE Kaharoa eruption

The rhyolitic Kaharoa 1315 CE eruption was a complex, long-lived event from Tarawera volcano, New Zealand. Explosive phases were followed by around 5 years of lava dome extrusion and collapse which produced block-and-ash flows (BAF). Lava domes generate crystalline silica in the form of cristobalite, and rhyolitic magmas often contain quartz phenocrysts. Fine-grained ash containing crystalline silica can be formed through dome collapses or explosions, generating a respiratory health hazard for communities affected by ashfall. The aims of this study are to: i) determine whether the Kaharoa eruption dome-forming phase generated substantial quantities of crystalline silica and, therefore, to determine the potential for future dome-forming eruptions of Tarawera to do the same; ii) consider the potential hazard of the crystalline silica by studying the crystal habit and chemistry compared to other lava domes, globally; and iii) assess the particle size and crystalline silica content of the Kaharoa ash, to inform a respiratory hazard assessment. Five co-BAF ash samples and one co-ignimbrite (explosive) ash sample from the Kaharoa pyroclastic deposits were analysed for health-pertinent factors: particle size distribution and crystalline silica content. Eight dome-rock samples were collected from the dome complex and associated BAF deposits and groundmass texture (especially forms of crystalline silica) and quantity of crystalline silica were assessed. Cristobalite was present in the 4 ash samples analysed by X-ray diffraction (XRD; 1.3–3.7 wt%) as was quartz (5.7–12.5 wt%). For the 4 dome samples analysed by XRD, all samples contained quartz (4.1–10.4 wt%) and two contained significant quantities of cristobalite (24.7 and 27.3 wt%). Of the two dome samples with minimal cristobalite (visible as individual vapour-phase crystals by SEM but not quantifiable by XRD), one was from the non-devitrified dome carapace and the other was from the compacted interior but had not undergone devitrification. The two dome samples with substantial cristobalite were from dome interiors and were highly devitrified, with well-developed spherulitic textures. Using energy-dispersive X-ray spectroscopy, cristobalite in all samples contained minor aluminium, as has been seen for volcanic cristobalite from other lava domes, which may ameliorate its toxicity. By laser diffraction, the quantities of ash in the health pertinent size fractions varied, with a range of 1.3–8.1 vol% for particles of <4 μm diameter and 1.7–15.6 vol% for particles of <10 μm diameter, which is lower than measured in ash from large-scale dome collapse events at other volcanoes. The findings suggest a potential for substantial crystalline silica to be formed in future Kaharoa-style eruptions, but that cristobalite generation is site-specific, depending on location within the dome and whether the dome remains sufficiently hot for spherulite formation and glass devitrification. Respiratory hazard will therefore vary depending on the collapse of (or explosions through) individual lobes – although all lava is expected to contain quartz phenocrysts – as well as the size and energy of those collapses, which will influence particle size and quantity of ash generated and dispersed.

Taupo Volcanic Zone↗

USGS2011

The characteristics of gas hydrates recovered from the Mount Elbert Gas Hydrate Stratigraphic Test Well, Alaska North Slope

Systematic analyses have been carried out on two gas hydrate-bearing sediment core samples, HYPV4, which was preserved by CH 4 gas pressurization, and HYLN7, which was preserved in liquid-nitrogen, recovered from the BPXA-DOE-USGS Mount Elbert Stratigraphic Test Well. Gas hydrate in the studied core samples was found by observation to have developed in sediment pores, and the distribution of hydrate saturation in the cores imply that gas hydrate had experienced stepwise dissociation before it was stabilized by either liquid nitrogen or pressurizing gas. The gas hydrates were determined to be structure Type I hydrate with hydration numbers of approximately 6.1 by instrumentation methods such as powder X-ray diffraction, Raman spectroscopy and solid state 13 C NMR. The hydrate gas composition was predominantly methane, and isotopic analysis showed that the methane was of thermogenic origin (mean δ 13 C = −48.6‰ and δ D = −248‰ for sample HYLN7). Isotopic analysis of methane from sample HYPV4 revealed secondary hydrate formation from the pressurizing methane gas during storage.

Alaska↗

USGS2014

Grain-scale imaging and compositional characterization of cryo-preserved India NGHP 01 gas-hydrate-bearing cores

We report on grain-scale characteristics and gas analyses of gas-hydrate-bearing samples retrieved by NGHP Expedition 01 as part of a large-scale effort to study gas hydrate occurrences off the eastern-Indian Peninsula and along the Andaman convergent margin. Using cryogenic scanning electron microscopy, X-ray spectroscopy, and gas chromatography, we investigated gas hydrate grain morphology and distribution within sediments, gas hydrate composition, and methane isotopic composition of samples from Krishna–Godavari (KG) basin and Andaman back-arc basin borehole sites from depths ranging 26 to 525 mbsf. Gas hydrate in KG-basin samples commonly occurs as nodules or coarse veins with typical hydrate grain size of 30–80 μm, as small pods or thin veins 50 to several hundred microns in width, or disseminated in sediment. Nodules contain abundant and commonly isolated macropores, in some places suggesting the original presence of a free gas phase. Gas hydrate also occurs as faceted crystals lining the interiors of cavities. While these vug-like structures constitute a relatively minor mode of gas hydrate occurrence, they were observed in near-seafloor KG-basin samples as well as in those of deeper origin (>100 mbsf) and may be original formation features. Other samples exhibit gas hydrate grains rimmed by NaCl-bearing material, presumably produced by salt exclusion during original hydrate formation. Well-preserved microfossil and other biogenic detritus are also found within several samples, most abundantly in Andaman core material where gas hydrate fills microfossil crevices. The range of gas hydrate modes of occurrence observed in the full suite of samples suggests a range of formation processes were involved, as influenced by local in situ conditions. The hydrate-forming gas is predominantly methane with trace quantities of higher molecular weight hydrocarbons of primarily microbial origin. The composition indicates the gas hydrate is Structure I.

Marine and Petroleum Geology↗

USGS2012

Identifying fluorescent pulp mill effluent in the Gulf of Maine and its watershed

Using fluorescence spectroscopy and parallel factor analysis (PARAFAC) we characterized and modeled the fluorescence properties of dissolved organic matter (DOM) in samples from the Penobscot River, Androscoggin River, Penobscot Bay, and the Gulf of Maine (GoM). We analyzed excitation-emission matrices (EEMs) using an existing PARAFAC model ( Cory and McKnight, 2005 ) and created a system-specific model with seven components (GoM PARAFAC). The GoM PARAFAC model contained six components similar to those in other PARAFAC models and one unique component with a spectrum similar to a residual found using the Cory and McKnight (2005) model. The unique component was abundant in samples from the Androscoggin River immediately downstream of a pulp mill effluent release site. The detection of a PARAFAC component associated with an anthropogenic source of DOM, such as pulp mill effluent, demonstrates the importance for rigorously analyzing PARAFAC residuals and developing system-specific models.

Maine↗

USGS2018

Validation of ATR FT-IR to identify polymers of plastic marine debris, including those ingested by marine organisms

Polymer identification of plastic marine debris can help identify its sources, degradation, and fate. We optimized and validated a fast, simple, and accessible technique, attenuated total reflectance Fourier transform infrared spectroscopy (ATR FT-IR), to identify polymers contained in plastic ingested by sea turtles . Spectra of consumer good items with known resin identification codes #1–6 and several #7 plastics were compared to standard and raw manufactured polymers. High temperature size exclusion chromatography measurements confirmed ATR FT-IR could differentiate these polymers. High-density (HDPE) and low-density polyethylene (LDPE) discrimination is challenging but a clear step-by-step guide is provided that identified 78% of ingested PE samples. The optimal cleaning methods consisted of wiping ingested pieces with water or cutting. Of 828 ingested plastics pieces from 50 Pacific sea turtles, 96% were identified by ATR FT-IR as HDPE, LDPE, unknown PE, polypropylene (PP), PE and PP mixtures, polystyrene , polyvinyl chloride , and nylon.

Marine Pollution Bulletin↗

USGS2025

Alteration mapping in granitic gneiss using handheld geophysical and geochemical instruments: Implications for iron oxide-apatite and rare earth elements exploration

The Adirondack Mountains of New York, U.S.A. contain iron oxide-apatite (IOA) mineral deposits with variable concentrations of rare earth elements (REE). The IOA mineral deposits are typically hosted in the Lyon Mountain Granite Gneiss and are spatially correlated with extensive Na metasomatism (albitization) of the surrounding country rocks, although some mineral deposits also occur in metagabbro, paragneiss, and anorthosite hosts. The location of albitization zones is key to finding new IOA mineral deposits and better understanding the mineralization processes associated with their genesis. However, the Na alteration zones are generally not visibly identifiable in outcrop or hand specimens because the color and textural changes are subtle and are thus difficult to map. Here, we discuss the results from testing two spectroscopic techniques (handheld, field gamma-ray spectroscopy, and portable X-ray fluorescence (pXRF)) to characterize albitization zones surrounding IOA mineral deposits. The gamma-ray and pXRF spectrometers successfully distinguished the relative intensity of alteration in the Lyon Mountain Granite Gneiss based on the K abundance. The measured K content decreases towards the IOA mineral deposits, and the magnitude and width of the gradient are similar along the strike of each mineral deposit. Elevated Th and U values are present in host rocks adjacent to REE-bearing IOA mineral deposits. The pXRF and gamma-ray spectrometer K values are remarkably consistent with laboratory-based, whole-rock XRF compositional data and, therefore, useful for semi-quantitative analysis. Notably, albitization aureoles are consistent around REE-rich and REE-poor mineral deposits, suggesting that saline fluids are essential for the petrogenesis of IOA mineral deposits but may not be critical to REE mineralization. Ultimately, this study demonstrates the utility of handheld gamma-ray and pXRF spectrometry for identifying otherwise cryptic albitization gradients associated with IOA mineral deposits in granitic gneiss.

New York↗

USGS2008

Distinguishing solid bitumens formed by thermochemical sulfate reduction and thermal chemical alteration

Insoluble solid bitumens are organic residues that can form by the thermal chemical alteration (TCA) or thermochemical sulfate reduction (TSR) of migrated petroleum. TCA may actually encompass several low temperature processes, such as biodegradation and asphaltene precipitation, followed by thermal alteration. TSR is an abiotic redox reaction where petroleum is oxidized by sulfate. It is difficult to distinguish solid bitumens associated with TCA of petroleum from those associated with TSR when both processes occur at relatively high temperature. The focus of the present work was to characterize solid bitumen samples associated with TCA or TSR using X-ray photoelectron spectroscopy (XPS). XPS is a surface analysis conducted on either isolated or in situ (>25 ??m diameter) solid bitumen that can provide the relative abundance and chemical speciation of carbon, organic and inorganic heteroatoms (NSO). In this study, naturally occurring solid bitumens from three locations, Nisku Fm. Brazeau River area (TSR-related), LaBarge Field Madison Fm. (TSR-related), and the Alaskan Brooks range (TCA-related), are compared to organic solids generated during laboratory simulation of the TSR and TCA processes. The abundance and chemical nature of organic nitrogen and sulfur in solid bitumens can be understood in terms of the nature of (1) petroleum precursor molecules, (2) the concentration of nitrogen by way of thermal stress and (3) the mode of sulfur incorporation. TCA solid bitumens originate from polar materials that are initially rich in sulfur and nitrogen. Aromaticity and nitrogen increase as thermal stress cleaves aliphatic moieties and condensation reactions take place. Organic sulfur in TCA organic solids remains fairly constant with increasing maturation (<3.4 sulfurs per 100 carbons) due to offsetting preservation and H2S elimination reactions. In contrast, TSR solid bitumens are sulfur rich and nitrogen poor solids. These heteroatom distributions are attributed to the ability of TSR to incorporate copious amounts of inorganic sulfur (>3.5 to ???17 sulfur per 100 carbons) into aromatic structures and to the low levels of nitrogen in their hydrocarbon precursors. Hence, XPS results provide organic chemical composition information that helps to distinguish whether solid bitumen, either in situ or removed and concentrated from the rock matrix, was formed via the TCA or TRS process. ?? 2008 Elsevier Ltd.

Organic Geochemistry↗

USGS2012

Organic geochemistry and petrology of subsurface Paleocene-Eocene Wilcox and Claiborne Group coal beds, Zavala County, Maverick Basin, Texas, USA

Coal samples from a coalbed methane exploration well in northern Zavala County, Maverick Basin, Texas, were characterized through an integrated analytical program. The well was drilled in February, 2006 and shut in after coal core desorption indicated negligible gas content. Cuttings samples from two levels in the Eocene Claiborne Group were evaluated by way of petrographic techniques and Rock–Eval pyrolysis. Core samples from the Paleocene–Eocene Indio Formation (Wilcox Group) were characterized via proximate–ultimate analysis in addition to petrography and pyrolysis. Two Indio Formation coal samples were selected for detailed evaluation via gas chromatography, and Fourier transform infrared (FTIR) and 13 C CPMAS NMR spectroscopy. Samples are subbituminous rank as determined from multiple thermal maturity parameters. Elevated rank (relative to similar age coal beds elsewhere in the Gulf Coast Basin) in the study area is interpreted to be a result of stratigraphic and/or structural thickening related to Laramide compression and construction of the Sierra Madre Oriental to the southwest. Vitrinite reflectance data, along with extant data, suggest the presence of an erosional unconformity or change in regional heat flow between the Cretaceous and Tertiary sections and erosion of up to >5 km over the Cretaceous. The presence of liptinite-rich coals in the Claiborne at the well site may indicate moderately persistent or recurring coal-forming paleoenvironments, interpreted as perennially submerged peat in shallow ephemeral lakes with herbaceous and/or flotant vegetation. However, significant continuity of individual Eocene coal beds in the subsurface is not suggested. Indio Formation coal samples contain abundant telovitrinite interpreted to be preserved from arborescent, above-ground woody vegetation that developed during the middle portion of mire development in forested swamps. Other petrographic criteria suggest enhanced biological, chemical and physical degradation at the beginning and end of Indio mire development. Fluorescence spectra of sporinite and resinite are consistent and distinctly different from each other, attributed to the presence of a greater proportion of complex asphaltene and polar molecules in resinite. Gas chromatography of resinite-rich coal shows sesquiterpenoid and diterpenoid peaks in the C 14–17 range, which are not present in resinite-poor coal. Quantities of extracts suggest bitumen concentration below the threshold for effective source rocks [30–50 mg hydrocarbon/g total organic carbon (HC/g TOC)]. Saturate/aromatic and pristane/phytane (Pr/Ph) ratios are different from values for nearby Tertiary-reservoired crude oil, suggesting that the Indio coals are too immature to source liquid hydrocarbons in the area. However, moderately high HI values (200–400 mg HC/g rock) may suggest some potential for naphthenic–paraffinic oil generation where buried more deeply down stratigraphic/structural dip. Extractable phenols and C 20+ alkanes are suggested as possible intermediates for acetate fermentation in microbial methanogenesis which may, however, be limited by poor nutrient supply related to low rainfall and meteoric recharge rate or high local sulfate concentration.

Texas↗

USGS2012

Structural stability of coprecipitated natural organic matter and ferric iron under reducing conditions

The objective was to assess the interaction of Fe coprecipitated with dissolved organic matter (DOM) and its effect on Fe (hydr)oxide crystallinity and DOM retention under abiotic reducing conditions. A Fe-based coagulant was reacted with DOM from an agricultural drain and the resulting precipitate (floc) was exposed to S(-II) and Fe(II). Solution concentrations of Fe(II/III) and DOM were monitored, floc crystallinity was determined using X-ray diffraction, and the composition and distribution of functional groups were assessed using scanning transmission X-ray microscopy (STXM) and near edge X-ray absorption fine structure (NEXAFS) spectroscopy. Results indicate coprecipitation of Fe(III) with DOM forms a non-crystalline floc that withstands crystallization regardless of change in pH, Fe:DOM ratio and type of reductant added. There was no evidence that exposure to reducing conditions led to release of DOM from the floc, indicating that coprecipitation with complex natural DOM in aquatic environments may stabilize Fe (hydr)oxides against crystallization upon reaction with reduced species and lead to long term sequestration of the DOM. STXM analysis identified spatially distinct regions with remarkable functional group purity, contrary to the model of DOM as a relatively uniform complex polymer lacking identifiable organic compounds. Polysaccharide-like OM was strongly and directly correlated with the presence of Fe but showed different Fe binding strength depending on the presence of carboxylic acid functional groups, whereas amide and aromatic functional groups were inversely correlated with Fe content.

Organic Geochemistry↗

USGS2013

Multivariate analysis of ATR-FTIR spectra for assessment of oil shale organic geochemical properties

In this study, attenuated total reflectance (ATR) Fourier transform infrared spectroscopy (FTIR) was coupled with partial least squares regression (PLSR) analysis to relate spectral data to parameters from total organic carbon (TOC) analysis and programmed pyrolysis to assess the feasibility of developing predictive models to estimate important organic geochemical parameters. The advantage of ATR-FTIR over traditional analytical methods is that source rocks can be analyzed in the laboratory or field in seconds, facilitating more rapid and thorough screening than would be possible using other tools. ATR-FTIR spectra, TOC concentrations and Rock–Eval parameters were measured for a set of oil shales from deposits around the world and several pyrolyzed oil shale samples. PLSR models were developed to predict the measured geochemical parameters from infrared spectra. Application of the resulting models to a set of test spectra excluded from the training set generated accurate predictions of TOC and most Rock–Eval parameters. The critical region of the infrared spectrum for assessing S1, S2, Hydrogen Index and TOC consisted of aliphatic organic moieties (2800–3000 cm −1 ) and the models generated a better correlation with measured values of TOC and S2 than did integrated aliphatic peak areas. The results suggest that combining ATR-FTIR with PLSR is a reliable approach for estimating useful geochemical parameters of oil shales that is faster and requires less sample preparation than current screening methods.

Organic Geochemistry↗

USGS2019

Hydrous heating experiments at 130°C yield insights into the occurrence of hydrogen sulfide and light alkanes in natural gas reservoirs

Improved understanding of the origin of produced volatiles from conventional reservoirs and unconventional source rocks is critical for petroleum exploration and production. A series of hydrous heating experiments using two immature Type II siliciclastic source rocks, Pennsylvanian Turner Mine shale (TMS) and Devonian New Albany Shale (NAS), at 130 °C over one to two years were conducted to assess gas generation at low temperature. Elemental sulfur (ES) was added to the NAS samples to evaluate the role of sulfur on thermochemical sulfate reduction (TSR). The produced volatile composition was investigated in situ using Raman spectroscopy at the end of the heating experiments. Results show that the two source rocks yield different types and concentrations of volatiles. Only CH 4 and CO 2 were detected following hydrous heating of the TMS source rock in contrast to CH 4 , C 2 H 6 , C 3 H 8 , and CO 2 which were observed in experiments using NAS. Variations in the produced volatiles are likely the result of compositional differences within the respective source rock organic matter. Experiments involving ES show strong H 2 S signals that are likely due to the formation of H 2 S from the reaction of ES with water at 130 °C. H 2 S signals correlate with a greater relative concentration of CH 4 and CO 2 compared to experiments where ES was not added, on a time-normalized basis. The correlation between the presence of H 2 S and an increase in CH 4 and CO 2 concentration could indicate the occurrence of TSR. Here we propose that H 2 S in siliciclastic shale can be generated in the presence of ES at low temperatures via both disproportionation of ES into H 2 S and SO 4 2– , and TSR. Our findings from this study provide experimental evidence that may aid efforts to interpret the origin of H 2 S in low-temperature sedimentary basins.

Pennsylvania↗

USGS2025

Nanometer-scale relationships between sedimentary organic matter molecular composition, fluorescence, cathodoluminescence, and reflectance: The importance of oxygen content at low thermal maturities

Molecular characterization of sedimentary organic matter (SOM), termed macerals, is a common goal when seeking to understand petroleum generation as well as other geologic processes in deep time. However, unambiguous measurement of discrete macerals is challenging due to the small size of organic particles in sedimentary rocks, the proximity of different organic matter types to one another, mineral-organic matter interactions, and maceral mixing that occurs during SOM isolation prior to ex situ analysis. The recent advent of infrared spectrometers capable of nanometer-scale resolution and the application of these technologies to geologic samples has enabled advances in rapid, in situ molecular characterization of SOM allowing for insights into paleoenvironmental processes, such as organic matter productivity and preservation, among others. Here we employ one such technology, optical photothermal infrared (OPTIR) spectroscopy, to map SOM functional group distributions at 500-nm resolution in a sample from the Lower Cretaceous Sunniland Limestone of the South Florida Basin. Examined fields of view include occurrences of amorphous organic matter (AOM), inertinite, micrinite, solid bitumen, telalginite, and vitrinite. OPTIR data from these macerals are compared against traditional organic petrographic data from the same organic grains including fluorescence intensity and white light reflectance as well as against cathodoluminescence response, an emerging organic petrographic approach. Maceral oxygen content (using carbonyl functional group abundance as a proxy) is observed to vary widely between maceral types but correlates strongly with fluorescence and cathodoluminescence intensity as well as against reflectance. These findings highlight the important role that oxygen content plays in determining the optical properties of SOM and further demonstrate the ability of OPTIR to discriminate subtle molecular differences between SOM types.

Organic Geochemistry↗

USGS2026

Evidence for a biological origin of uranium-rich carbon masses within the Ediacaran Salt Range Formation of Pakistan

Thucholites are unique organic structures found in igneous and sedimentary rocks composed of a U-C-rich interior enclosed by an organic outer shell. Their formation and occurrence have perplexed scientists for over 100 years. Typically, thucholites are sparse in sedimentary rocks but where found in abundance, they may be the result of rapid paleoecological disruptions, e.g., volcanic ashfall. Here, we evaluated thucholites from the Ediacaran Salt Range Formation of the Indus Basin in Pakistan using field emission scanning electron microscopy (FESEM) and nanoscale secondary ion mass spectroscopy (NanoSIMS) to propose a two-stage mechanism for thucholite development. NanoSIMS results suggest organic matter in thucholite cores formed by biological fractionation (represented by the presence of lighter 13 C/ 12 C and 34 S/ 32 S) while the outer organic mantle formed via radiolysis-induced polymerization. FESEM elemental analysis confirms compositional differences between the two thucholite components (core and mantle), further implying their contrasting origins. Dimensional comparison of thucholite cores and their U-bearing mineral morphologies to ancient and modern U-biomineralized microbes suggests that the thucholite cores formed from metal-biological interactions. The presence of volcanogenic biotite, alkali feldspar, and clay spherules (interpreted as devitrified volcanic glass) with thucholite suggests that the thucholite cores in the Salt Range Formation are biological responses to rapid paleoenvironmental change from volcanic eruption which preserved the fossilized morphologies of Proterozoic microorganisms.

Salt Range↗