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At least 613 records · Page 34Linked to original sources

USGS2007

Evidence of CFC degradation in groundwater under pyrite-oxidizing conditions

A detailed local-scale monitoring network was used to assess CFC distribution in an unconfined sand aquifer in southwestern Ontario where the zone of 1–5-year-old groundwater was known with certainty because of prior use of a bromide tracer. Groundwater ⩽5 years old was confined to an aerobic zone at ⩽5 m depth and had CFC concentrations consistent with modern atmospheric mixing ratios at recharge temperatures of 7–11 °C, as was observed in the 3-m thick vadose zone at the site. At depths below 6 m, the groundwater became progressively more reducing, however, with a denitrifying horizon at 6–7 m depth, and a Mn and Fe reducing zone below 7 m depth. In the anaerobic zone, 3 H/ 3 He ratios indicated that groundwater-age continued to increase uniformly with depth, to a maximum value of 27 years at 13 m depth. CFC concentrations, however, decreased abruptly within the denitrifying zone, leading to substantial age overestimation compared to the 3 H/ 3 He ages. Noble gas data indicated that the apparent CFC mass loss was not likely the result of gas stripping from possible bubble formation; thus, CFC degradation was indicated in the anoxic zone. The field data are consistent with first-order degradation rates of 0.3 yr −1 for CFC-12, 0.7 yr −1 for CFC-11, and 1.6 yr −1 for CFC-113. CFC attenuation at this site coincides with a zone where reduced S (pyrite) is actively oxidized by NO 3 and dissolved oxygen (DO). Similar behavior has been observed at other sites [Tesoriero, A.J., Liebscher, H., Cox, S.E., 2000. Mechanism and rate of denitrification in an agricultural watershed: electron and mass balance along groundwater flow path. Water Resour. Res. 36 (6), 1545–1559; Hinsby, K., Hojberg, A.L., Engesgaard, P., Jensen, K.H., Larsen, F., Plummer, L.N., Busenberg, E., Accepted for publication. Transport and degradation of chlorofluorocarbons (CFCs) in a pyritic aquifer, Rabis Creek, Denmark. Water Resour. Res.], further demonstrating that the use of CFCs for age-dating anaerobic groundwater should be approached with caution, particularly if the sediment contains pyrite.

Journal of Hydrology↗

USGS2008

Inverse geochemical modeling of groundwater evolution with emphasis on arsenic in the Mississippi River Valley alluvial aquifer, Arkansas (USA)

Inverse geochemical modeling (PHREEQC) was used to identify the evolution of groundwater with emphasis on arsenic (As) release under reducing conditions in the shallow (25-30 m) Mississippi River Valley Alluvial aquifer, Arkansas, USA. The modeling was based on flow paths defined by high-precision (??2 cm) water level contour map; X-ray diffraction (XRD), scanning electron microscopic (SEM), and chemical analysis of boring-sediments for minerals; and detailed chemical analysis of groundwater along the flow paths. Potential phases were constrained using general trends in chemical analyses data of groundwater and sediments, and saturation indices data (MINTEQA2) of minerals in groundwater. Modeling results show that calcite, halite, fluorite, Fe oxyhydroxide, organic matter, H2S (gas) were dissolving with mole transfers of 1.40E - 03, 2.13E - 04, 4.15E - 06, 1.25E + 01, 3.11, and 9.34, respectively along the dominant flow line. Along the same flow line, FeS, siderite, and vivianite were precipitating with mole transfers of 9.34, 3.11, and 2.64E - 07, respectively. Cation exchange reactions of Ca2+ (4.93E - 04 mol) for Na+ (2.51E - 04 mol) on exchange sites occurred along the dominant flow line. Gypsum dissolution reactions were dominant over calcite dissolution in some of the flow lines due to the common ion effect. The concentration of As in groundwater ranged from <0.5 to 77 ??g/L. Twenty percent total As was complexed with Fe and Mn oxyhydroxides. The redox environment, chemical data of sediments and groundwater, and the results of inverse geochemical modeling indicate that reductive dissolution of Fe oxyhydroxide is the dominant process of As release in the groundwater. The relative rate of reduction of Fe oxyhydroxide over SO42 - with co-precipitation of As into sulfide is the limiting factor controlling dissolved As in groundwater. ?? 2007 Elsevier B.V. All rights reserved.

Journal of Hydrology↗

USGS2016

Regional oxygen reduction and denitrification rates in groundwater from multi-model residence time distributions, San Joaquin Valley, USA

Rates of oxygen and nitrate reduction are key factors in determining the chemical evolution of groundwater. Little is known about how these rates vary and covary in regional groundwater settings, as few studies have focused on regional datasets with multiple tracers and methods of analysis that account for effects of mixed residence times on apparent reaction rates. This study provides insight into the characteristics of residence times and rates of O 2 reduction and denitrification (NO 3 − reduction) by comparing reaction rates using multi-model analytical residence time distributions (RTDs) applied to a data set of atmospheric tracers of groundwater age and geochemical data from 141 well samples in the Central Eastern San Joaquin Valley, CA. The RTD approach accounts for mixtures of residence times in a single sample to provide estimates of in-situ rates. Tracers included SF 6 , CFCs, 3 H, He from 3 H (tritiogenic He), 14 C, and terrigenic He. Parameter estimation and multi-model averaging were used to establish RTDs with lower error variances than those produced by individual RTD models. The set of multi-model RTDs was used in combination with NO 3 − and dissolved gas data to estimate zero order and first order rates of O 2 reduction and denitrification. Results indicated that O 2 reduction and denitrification rates followed approximately log-normal distributions. Rates of O 2 and NO 3 − reduction were correlated and, on an electron milliequivalent basis, denitrification rates tended to exceed O 2 reduction rates. Estimated historical NO 3 − trends were similar to historical measurements. Results show that the multi-model approach can improve estimation of age distributions, and that relatively easily measured O 2 rates can provide information about trends in denitrification rates, which are more difficult to estimate.

California↗

USGS2025

Advancing broadscale spatial evapotranspiration modelling by incorporating sun-induced chlorophyll fluorescence measurements

Evapotranspiration (ET) describes the sum of water transfer from the ground surface through soil evaporation and water loss from leaf stomata into the atmosphere − critical factors linking the global water and carbon cycles. Myriad ET models based on remote sensing data provide spatially continuous estimates of ET; however, leaf photosynthetic information is critical to ensure accurate ET estimates, which are difficult to measure from space. Remotely sensed sun-induced chlorophyll fluorescence (SIF) provides a proxy of stomatal conductance activity with high performance in predicting plant transpiration, which can account for a large proportion of terrestrial and riverine ET. This study aims to improve estimates of tree water use in semi-arid to arid environments. In this study, a fixed stomatal conductance model and three SIF-driven canopy conductance (g sc ) models were applied to model potential ET (PET). The models estimated PET using the Penman-Monteith equation with: (1) a constant leaf stomatal conductance; (2) a transpiration-driven g sc model; (3) a g sc model based on electron-transfer rate and vapor pressure deficit, and a (4) Ball-Berry stomatal conductance model. A machine learning model was then applied to scale PET to actual ET (AET) using remote sensing and climate data. Accordingly, four AET models were cross-validated with in-situ measured AET at 52 sites, including 21 eddy covariance flux tower sites, and 31 sap-flow measurement sites (semi-arid and plantation area), for various plant functional types in Australia. This study demonstrated that SIF effectively captured seasonal variations of g sc , finding that AET models with SIF-driven g sc models correlated well with in-situ measured AET (R 2 = 0.64). Modelled AET with dynamic variations of g sc generated lower prediction error (0.85 mm day −1 ), while the AET model with fixed stomatal conductance tended to overestimate AET in floodplains and underestimate it in evergreen broadleaf forests, indicating using fixed stomatal conductance results in unstable performance when modelling AET. This study demonstrated that SIF-driven AET models improved broadscale estimation of ET. Our findings provide vital broadscale hydrological data to assist catchment and regional water management, particularly over unmonitored areas at risk of future climate-driven reductions in rainfall.

Journal of Hydrology↗

USGS2005

Anatahan, Northern Mariana Islands: Reconnaissance geological observations during and after the volcanic crisis of spring 1990, and monitoring prior to the May 2003 eruption

Anatahan island is 9.5 km east–west by 3.5 km north–south and truncated by an elongate caldera 5 km east–west by 2.5 km north–south. A steep-walled pit crater ∼1 km across and ∼200 m deep occupies the eastern part of the caldera. The island is the summit region of a mostly submarine stratovolcano. The oldest subaerial rocks (stage 1) are exposed low on the outer flanks and in the caldera walls. These include thick (∼10 m) and thin (2–3 m) lava flows, well-indurated tuffs, and scoria units that make up the bulk of the island. Rock compositions range from basaltic andesite to dacite, and most are plagioclase-phyric. On the steep north and south flanks of the volcano, these rocks are cut by numerous east–west-oriented, few-hundred-m-long lineaments of undetermined origin. Indurated breccias unconformably overlie scarps cut into stage 1 units low on the south flank. Intermediate-age eruptive units (stage 2) include caldera-filling lava flows and pyroclastic deposits and, on the outer flanks, vents and valley-filling lava flows. The youngest pre-2003 volcanic unit on Anatahan (stage 3) is a hydromagmatic surge and fall deposit rich in accretionary lapilli. Prior to 2003, this unit was found over almost the entire island, and in many places original depositional surfaces and outcrops could be found in high-energy environments along the coast, indicating a young (but undetermined) age. During reconnaissance visits in 1990, 1992, 1994, and 2001, geothermal activity (fumaroles as well as pits with boiling, sediment-laden pools) was observed in the southern part of the pit crater. In March and April 1990, increased local seismicity, a large regional earthquake, and reported increased fumarolic activity in the pit crater prompted evacuation of Anatahan village, at the west end of the island. Our first field investigation took place in late April 1990 to assess the level of volcanic unrest, conduct reconnaissance geological observations, collect rock and geothermal water samples, and set up a geophysical monitoring network. Results at this time were inconclusive with respect to determining whether the activity was anomalous. Water in some of the geothermal pits within the pit crater was boiling, and pH values as low as 0.7 were recorded in the field. An electronic distance measurement (EDM) network was installed, and over a ∼1-week period, up to 9 cm of extension occurred across some lines but not others. Seismicity was characterized by intermittent local earthquakes but no sustained swarms or tremor. A brief visit in June 1990 revealed that the shallow lake near the boiling pits was gone, but activity in the pits themselves was similar to that of April 1990. Only minor extension had occurred along a single EDM line since the previous visit, and no earthquakes >M2.5 occurred during the visit. Subsequent 1- to 2-day visits occurred in October 1990, May 1992, May 1994, and June 2001. Activity within the geothermal pits was relatively constant during every visit, although during this 11-year period the level of the water in each pit decreased. In June 2001, a ∼50-m-wide region of mud pots and steaming ground in the central part of the geothermal area had developed. No geologic evidence, however, suggested that an eruption would occur < 2 years afterward. Most of the EDM lines showed slight extension between late 1990 and 1992, followed by very gradual contraction from 1992 to 2001. A more extensive seismic-monitoring system was installed on the Northern Mariana Islands during these visits, and it recorded a small seismic swarm at Anatahan from May to July 1993. The telemetry component of the seismic equipment broke prior to 2001 and had not been repaired by the time of the May 2003 eruption, so no precursory seismic data were recorded to indicate pre-eruption unrest.

Northern Mariana Islands↗

USGS2009

An experimental study of hydromagmatic fragmentation through energetic, non-explosive magma-water mixing

In this paper we report the first experimental investigation of non-explosive hydromagmatic fragmentation during energetic mixing with water. We mix magma and water by two methods: (1) pouring a basaltic melt between two converging water sprays; and (2) jetting basaltic melt at high pressure (3??MPa) through a nozzle into a tank of stagnant water. These experiments involved shear at relative velocities of ~ 5-16??m/s and vigorous mixing for less than a second, providing sufficient time for glassy rinds to grow but insufficient time for clot interiors to cool. In resulting fragments, we examined the gross morphology, which reflects fluid deformation during mixing, and surface textures, which reflect the growth and disruption of glassy rinds. We find major differences in both fragment morphology and surface texture between experiments. Water-spray experiments produced Pele's hair, thin bubble shards, melt droplets, and angular, fracture-bound droplet pieces. Melt-jet experiments produced mostly coarse (> 1??mm diameter), wavy fluidal fragments with broken ends. Fluidal surfaces of fragments produced by water-spray experiments were generally shiny under reflected light and, in microscopic examination, smooth down to micron scale, implying no disruption of glassy rinds, except for (a) rare flaking on Pele's hair that was bent prior to solidification; or (b) cracking and alligator-skin textures on segments of melt balls that had expanded before complete cooling. In contrast, textures of fluidal surfaces on fragments produced by melt-jet experiments are dull in reflected light and, in scanning electron images, exhibit ubiquitous discontinuous skins ("rinds") that are flaked, peeled, or smeared away in stripes. Adhering to these surfaces are flakes, blocks, and blobs of detached material microns to tens of microns in diameter. In the water-spray fragments, we interpret the scarcity of disrupted surface rinds to result from lack of bending after surfaces formed. In the melt-jet fragments, the ubiquity of partially detached rinds and rind debris likely reflects repeated bending, scraping, impact, and other disruption through turbulent velocity fluctuations. When extrapolated to jets of Surtseyan scale, where velocity fluctuations reach tens of meters per second and turbulent mixing persists for tens of seconds, rind disintegration could fragment a large fraction of the erupted material.

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↗

USGS2022

Growth of complex volcanic ash aggregates in the Tierra Blanca Joven eruption of Ilopango Caldera, El Salvador

Aggregation processes control both the residence time and dispersal of volcanic ash during eruptions yet remain incompletely understood. The products of aggregation vary from simple ash clusters to large, complexly layered accretionary lapilli. Here we detail the micro-stratigraphy of a single population of accretionary lapilli that grew during the ∼431 CE Tierra Blanca Joven eruption from Ilopango Caldera, El Salvador. The accretionary lapilli were sampled 10 km from the caldera source within a sequence of ash-rich pyroclastic density current deposits and intercalated fall material, known as unit D, which is traceable >40 km from Ilopango. Scanning electron microscopy and image analysis reveal common facies that form distinct layers within the accretionary lapilli. Each facies is distinguished by quantitative and qualitative variations in particle size distribution , porosity, and particle fabric. We infer that these textures resulted from aggregation conditions that differed in terms of liquid water availability, particle concentration and grain size distributions. In our proposed model, a characteristic sequence of facies accreted from core to rim in the accretionary lapilli during passage through ash clouds generated by vent-derived plumes and pyroclastic density currents. The accretionary lapilli are mostly composed of smaller aggregates (ash clusters, ash pellets) and grew predominantly by accretion of already-formed aggregates, rather than by grain-by-grain accretion of individual particles. This finding is consistent with observations of rapid aggregate growth in volcanic plumes, suggesting a common evolutionary pathway for accretionary lapilli formation across diverse eruptions.

Ilopango caldera↗

USGS2010

Shell anomalies observed in a population of Archaias angulatus (Foraminifera) from the Florida Keys (USA) sampled in 1982-83 and 2006-07

Archived specimens of Archaias angulatus collected live at a depth of < 2. m in John Pennekamp Coral Reef State Park, Key Largo, Florida, in June, September and December 1982, and March 1983, were compared to specimens collected live from the same site and months in 2006-07. Shells were examined using light microscopy for anomalous features, which were then documented using scanning electron microscopy. Seven different types of morphological abnormalities and five different surface texture anomalies were observed. Physical abnormalities included profoundly deformed, curled, asymmetrical, and uncoiled shells, irregular suture lines, surface protrusions, and breakage/repair. Textural anomalies observed were surface pits, dissolution features, microborings, microbial biofilms, and the presence of epibionts including bryzoans, cyanobacteria and foraminifers. The same kinds of features were found in this A. angulatus population in both 1982-83 collections and 2006-07 collections. Within-date variability was higher in specimens collected in 1982-83, while between-date variability was higher in 2006-07; overall the range of variability was similar. Given that the site was originally chosen for study because these foraminifers were so abundant, the lack of significant change indicates that the variability of the geochemical habitat is still within the range that A. angulatus can thrive. ?? 2010.

Marine Micropaleontology↗

USGS2011

Gas hydrate characterization and grain-scale imaging of recovered cores from the Mount Elbert Gas Hydrate Stratigraphic Test Well, Alaska North Slope

Using cryogenic scanning electron microscopy (CSEM), powder X-ray diffraction, and gas chromatography methods, we investigated the physical states, grain characteristics, gas composition, and methane isotopic composition of two gas-hydrate-bearing sections of core recovered from the BPXA–DOE–USGS Mount Elbert Gas Hydrate Stratigraphic Test Well situated on the Alaska North Slope. The well was continuously cored from 606.5 m to 760.1 m depth, and sections investigated here were retrieved from 619.9 m and 661.0 m depth. X-ray analysis and imaging of the sediment phase in both sections shows it consists of a predominantly fine-grained and well-sorted quartz sand with lesser amounts of feldspar, muscovite, and minor clays. Cryogenic SEM shows the gas-hydrate phase forming primarily as a pore-filling material between the sediment grains at approximately 70–75% saturation, and more sporadically as thin veins typically several tens of microns in diameter. Pore throat diameters vary, but commonly range 20–120 microns. Gas chromatography analyses of the hydrate-forming gas show that it is comprised of mainly methane (>99.9%), indicating that the gas hydrate is structure I. Here we report on the distribution and articulation of the gas-hydrate phase within the cores, the grain morphology of the hydrate, the composition of the sediment host, and the composition of the hydrate-forming gas.

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↗

USGS2021

Hydrous pyrolysis of New Albany Shale: A study examining maturation changes and porosity development

The characterization of nanoscale organic structures has improved our understanding of porosity development within source-rock reservoirs, but research linking organic porosity evolution to thermal maturity has generated conflicting results. To better understand this connection, an immature (0.25% solid bitumen reflectance; BR o ) sample of the New Albany Shale was used in four isothermal hydrous pyrolysis (HP) experiment sequences at 300°, 320°, 340°, and 370°C, with residues collected periodically for a maximum of 103 days. The HP residues, along with the original immature sample and two naturally matured (1.49 and 1.56% BR o ) New Albany Shale samples were analyzed for organic petrology, total organic carbon (TOC) content, and organic porosity evaluation using correlative light and electron microscopy (CLEM). All of the HP series increased in thermal maturity with increasing duration of pyrolysis, though reflectance for each series plateaued within 25 days of maturation. Initially, TOC in the HP residues decreases (from 14.24 wt. %) with increasing thermal maturity until ∼1.0% BR o where TOC remains at ∼9–10 wt. % for all remaining residues. Qualitative CLEM observations within the 50–100 day 300° and 340°C HP sequences (0.95–1.70% BR o ), and the naturally matured samples, develop organic porosity in smaller (<5 μm in diameter), void-filling solid bitumen that occurs in spaces between clays and other fine-grained minerals. The 370°C HP residues developed significant organic porosity, relative to the other HP temperature series in all solid bitumen accumulations regardless of size. Overall, the study indicates that temperature and duration of artificial maturation play an important role in the abundance of pores in the HP residues. This work expands on our understanding of the conditions needed for the generation and development of organic porosity in the New Albany Shale and potentially in other marine source-rock petroleum systems.

Illinois, Indiana↗

USGS2022

Diatom influence on the production characteristics of hydrate-bearing sediments: Examples from Ulleung Basin, offshore South Korea

The Ulleung Basin Gas Hydrate field expeditions in 2007 (UBGH1) and 2010 (UBGH2) sought to assess the Basin's gas hydrate resource potential. Coring operations in both expeditions recovered evidence of gas hydrate, primarily as fracture-filling (or vein type) morphologies in mainly silt-sized, fine-grained sediment, but also as pore-occupying hydrate in the coarser-grained layers of interbedded sand and fine-grained systems. A commonality across many of these occurrences is the presence of diatoms in the fine-grained sediment. Here we tested fine-grained sediment (median grain size <12.5 μm) associated with hydrate occurrences at four UBGH2 sites (UBGH2-2-2, UBGH2-3, UBGH2-6 and UBGH2-11) to investigate potential impacts of diatoms on efforts to extract methane from hydrate, or to tap hydrocarbon reservoirs beneath hydrate-bearing sediment. Two key considerations are: the extent to which diatoms control sediment mechanical properties, and the extent to which pore-water freshening, which occurs as gas hydrate breaks down during resource extraction, alters the diatom control on sediment mechanical properties. We conducted experiments to measure sediment index properties, sedimentation behavior and compressibility to address these considerations. We relied on scanning electron microscope (SEM) imagery and X-ray powder diffraction (XRD) to characterize the sediment mineralogy. Our high-level findings are that at the ∼20–45% (by volume) diatom concentrations observed at these UBGH2 sites, sediment compressibility increases with diatom content, but diatoms only appear to increase porosity and permeability at the highest diatom concentration (∼45%). Our measurements suggest in situ compression indices of 0.35–0.55 and permeabilities on the order of 0.01milliDarcies (1 × 10 −17 m 2 ) can be anticipated at these sites. Importantly, these properties are not expected to vary significantly upon pore water freshening that accompanies gas hydrate dissociation during production.

East Sea, Ulleung Basin↗

USGS2007

Manganese-enhanced magnetic resonance microscopy of mineralization

Paramagnetic manganese (II) can be employed as a calcium surrogate to sensitize magnetic resonance microscopy (MRM) to the processing of calcium during bone formation. At high doses, osteoblasts can take up sufficient quantities of manganese, resulting in marked changes in water proton T1, T2 and magnetization transfer ratio values compared to those for untreated cells. Accordingly, inductively coupled plasma mass spectrometry (ICP-MS) results confirm that the manganese content of treated cell pellets was 10-fold higher than that for untreated cell pellets. To establish that manganese is processed like calcium and deposited as bone, calvaria from the skull of embryonic chicks were grown in culture medium supplemented with 1 mM MnCl2 and 3 mM CaCl2. A banding pattern of high and low T2 values, consistent with mineral deposits with high and low levels of manganese, was observed radiating from the calvarial ridge. The results of ICP-MS studies confirm that manganese-treated calvaria take up increasing amounts of manganese with time in culture. Finally, elemental mapping studies with electron probe microanalysis confirmed local variations in the manganese content of bone newly deposited on the calvarial surface. This is the first reported use of manganese-enhanced MRM to study the process whereby calcium is taken up by osteoblasts cells and deposited as bone. ?? 2007 Elsevier Inc. All rights reserved.

Magnetic Resonance Imaging↗

USGS2004

Development of an AMS method to study oceanic circulation characteristics using cosmogenic 39Ar

Initial experiments at the ATLAS facility [Nucl. Instr. and Meth. B 92 (1994) 241] resulted in a clear detection of cosmogenic 39Ar signal at the natural level. The present paper summarizes the recent developments of 39Ar AMS measurements at ATLAS: the use of an electron cyclotron resonance (ECR) positive ion source equipped with a special quartz liner to reduce 39K background, the development of a gas handling system for small volume argon samples, the acceleration of 39Ar8+ ions to 232 MeV, and the final separation of 39Ar from 39K in a gas-filled spectrograph. The first successful AMS measurements of 39Ar in ocean water samples from the Southern Atlantic ventilation experiment (SAVE) are reported. Published by Elsevier B.V.

Conference Paper↗

USGS2020

Apatite trace element geochemistry and cathodoluminescent textures—Acomparison between regional magmatism and the Pea Ridge IOA-REE andBoss IOCG deposits, southeastern Missouri iron metallogenic province, USA

The southeast Missouri iron metallogenic province contains a remarkable wealth of historically important Fe, Cu, Au, and rare earth element (REE) deposits including the Pea Ridge iron oxide-apatite-rare earth element (IOA-REE) deposit and the Boss iron oxide-copper-gold (IOCG) deposit. These deposits are coeval with silicic and intermediate composition magmatism in the St. Francois Mountains terrane. Magmatism, iron-oxide (±Cu, Au, Co) and apatite formation, and REE mineralization overlapped in space and time, but the specific role of regional magmatism in the metallogenesis of these deposits remains unclear and basic petrogenetic models are still debated. We report results from high-spatial resolution textural and geochemical analyses of apatite from regional igneous and ore rocks to elucidate their petrogenetic histories and evaluate deposit models. Backscattered electron and spectral cathodoluminescence imaging of apatite reveal no primary igneous zoning, but show different domains with intricate rims and dissolution/reprecipitation textures, each with distinctive REE patterns in many samples. Apatite from all samples are nearly endmember fluorapatite containing up to ~1.3 wt% Cl and F/Cl ratios span nearly three orders of magnitude. Fresh igneous fluorapatite contain low Na2O (0.15 wt%) while most Pea Ridge ore samples contain higher Na2O (up to ~0.45 wt%), and concentrations of sulfur in fluorapatite of all types are generally moderate to low (0.3 wt% SO3). Significant amounts of Fe (60,000 ppm), Mg (30,000 ppm), Mn (7,000 ppm), and Sr (12,000 ppm) are contained in fluorapatite of all sample types, and they also have moderate amounts of As (4,000 ppm), Ba (2,000 ppm), Th (400 ppm), and U (80 ppm). Fluorapatite show an extraordinarily large range of REE (~0.1-2.0 wt%) and Y (~100-7000 ppm) concentrations. While fresh igneous fluorapatite share many geochemical features with metasomatized igneous fluorapatite and ore-stage fluorapatite from the Pea Ridge IOA and Boss IOCG ore zones, they also have distinct geochemical signatures that are indicative of unique trace element partitioning and substitution mechanisms. These distinguishing textural and geochemical signatures preclude ore-zone fluorapatite genesis directly from a magma (i.e., crystallization directly from a silicate melt) but are permissive of ore-zone fluorapatite formation by magmatic-hydrothermal fluids derived from the regional magmas. Basinal brines may play an important role in the formation of fluorapatite, especially from the Pea Ridge hematite and Boss magnetite-rich zones. Fluorapatite from different ore zones likely formed by crystallization during pulses of hydrothermal fluids with varying Cl-, Na-, and F-contents, which fundamentally controlled the carrying capacity and solubility of REE+Y and generated geochemically distinctive generations of fluorapatite. Exploration geologists using fluorapatite trace element geochemistry to identify IOA and IOCG deposits should proceed with caution, as more high-quality data from these deposits are needed to improve multivariate discrimination analysis. Fluorapatite from IOA/IOCG deposits can be reasonably discriminated from that of other mineral deposit types (e.g., porphyry/epithermal, skarn, orogenic), but no criteria successfully discriminate yet between IOA and IOCG deposits.

Missouri↗

USGS2022

Indicator mineral analyses of stream-sediment samples using automated mineralogy and mineral chemistry: Applicability to exploration in covered terranes in eastern Alaska, USA

In the past two decades, significant research efforts have been devoted to porphyry copper indicator mineral (PCIM) identification and mineral chemistry to assist exploration. Such studies are important in the Yukon-Tanana upland region of eastern Alaska because well-established geochemical exploration techniques, such as the geochemistry of stream-sediment samples, are less effective in the search for mineral resources owing to cover materials that subdue geochemical signatures. The unglaciated Yukon-Tanana upland region is well-endowed with mineral resources, including porphyry Cu-Mo-Au deposits at Taurus, Bluff, Dennison, and Oreo. Using automated scanning electron microscope (SEM) techniques, numerous PCIMs have been identified in rocks and stream-sediment samples that would likely not have been observed using visual binocular microscope methods. Sulfide minerals such as chalcopyrite, chalcocite, covellite, bornite, molybdenite, and pyrrhotite were identified in rock samples, and more than half of the stream-sediment samples from drainages containing known porphyry mineral occurrences contain chalcopyrite with or without bornite. Many drainages without known occurrences also contain these minerals, which suggests potential for additional occurrences. Svanbergite, an aluminum phosphate sulfate (APS) mineral [SrAl 3 (PO 4 )(SO 4 )(OH) 6 ], was identified in some of the altered or mineralized rock samples from Taurus, and in stream drainages containing porphyry occurrences and may represent the best indicator mineral for Taurus-like porphyry deposits. Apatite chemistry has great potential as a tool for assessing the presence of porphyry mineralization. Grains from rock and stream-sediment samples that contain high Cl (>∼0.4 wt%), Fe (>0.4 wt%), and Mn (>2000 ppm) clearly distinguish apatite from other sources (metamorphic, unmineralized igneous rocks). This study is one of the first to document new streamlined indicator mineral sample collection and processing methods and to combine automated SEM techniques and chemistry of minerals derived from both bedrock and surficial (stream) sediments as they apply to porphyry exploration.

Alaska↗

USGS2017

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

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

Organic Geochemistry↗