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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↗

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↗

USGS2020

Organic petrography of Leonardian (Wolfcamp A) mudrocks and carbonates, Midland Basin, Texas: The fate of oil-prone sedimentary organic matter in the oil window

To better understand evolution of oil-prone sedimentary organic matter to petroleum and expulsion from source rock, we evaluated organic petrographic features of Leonardian Wolfcamp A repetitive siliceous and calcareous mudrock and fine-grained carbonate lithofacies cycles occurring in the R. Ricker #1 core from Reagan County, Midland Basin, Texas. The objectives of the petrographic investigation were to estimate thermal maturity, identify organic matter types and abundances, and identify the presence or absence of migrated hydrocarbons in organic-lean carbonate layers. An integrated analytical program included geochemical screening [total organic carbon (TOC) content by LECO, programmed pyrolysis by hydrocarbon analyzer with kinetics (HAWK) including analysis of solvent-extracted samples], X-ray diffraction mineralogy, organic petrography, scanning electron microscopy with energy dispersive spectroscopy (SEM-EDS) including correlative light and electron microscopy (CLEM), and micro-Fourier transform infrared spectroscopy (μ-FTIR) analyses of solid bitumen. The data indicate all samples are early to middle oil window thermal maturity with solid bitumen reflectance (BR o ) values of 0.55–0.86% and T max of 440–455 °C. Organic matter is predominantly solid bitumen (as identified by optical microscopy) in all lithofacies with minor contributions from inertinite. Solid bitumen abundance decreases from siliceous mudrock (TOC >3.0 wt%) to calcareous mudrock (TOC 1.0 to 3.0 wt%) to fine-grained carbonate (TOC <1.0 wt%) lithofacies. Interpretations of petrographic data suggest siliceous and calcareous mudrocks are source rock lithofacies and contain solid bitumen (with petroleum generation potential) that is residual (what remains) from conversion of an original Type II sedimentary organic matter. In turn, fine-grained carbonates are interpreted as reservoir lithofacies which contained little or no original oil-prone sedimentary organic matter and at present-day contain only a minor component of migrated solid petroleum sourced from adjacent siliceous and calcareous mudrock lithofacies. This work helps to document petroleum generation and migration processes, improve unconventional reservoir characterization and better define areas of oil window thermal maturity in an area critical to United States hydrocarbon production.

Texas↗

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↗

USGS2010

Separation, characterization and initial reaction studies of magnetite particles from Hanford sediments

Magnetic and density separation methods have been applied to composite sediment samples from the Hanford formation from sediment recovered during drilling of an uncontaminated borehole located near the 200 West Area of the Hanford Site in southeastern Washington State. This paper describes the results of using those separation methods and from the characterization and initial reactivity measurements on a highly magnetic fraction isolated from that sediment. X-ray diffraction (XRD) analysis of the highly magnetic sediment fraction indicates that this material contains predominantly magnetite (Fe 3 O 4 ). Particle morphology observed by scanning electron microscopy (SEM) and compositions determined energy dispersive spectroscopy (EDS) are consistent with this identification. Analyses by X-ray photoelectron spectroscopy (XPS) indicates that there is a thin coating on the particles that are likely a type of aluminosilicate. This highly magnetic fraction of material is not reactive with indigo carmine, an organic redox probe molecule that was shown to readily react with synthetic magnetite. Because of the limited amounts of material readily available, initial tests have been conducted that demonstrate the ability to complete U(VI) sorption on individual particles (nominally ∼100 μm in size) of the isolated sediment and to remove and mount these individual particles for analysis of the concentration and chemical state of the sorbed U species using small area XPS.

Washington↗

USGS1999

Sulfur-bearing coatings on fly ash from a coal-fired power plant: Composition, origin, and influence on ash alteration

Fly ash samples collected from two locations in the exhaust stream of a coal-fired power plant differ markedly with respect to the abundance of thin (≈0.1 μm) sulfur-rich surface coatings that are observable by scanning electron microscopy. The coatings, tentatively identified as an aluminum-potassium-sulfate phase, probably form upon reaction between condensed sulfuric acid aerosols and glass surfaces, and are preferentially concentrated on ash exposed to exhaust stream gases for longer. The coatings are highly soluble and if sufficiently abundant, can impart an acidic pH to solutions initially in contact with ash. These observations suggest that proposals for ash use and predictions of ash behavior during disposal should consider the transient, acid-generating potential of some ash fractions and the possible effects on initial ash leachability and alteration.

Fuel↗

USGS2002

Trace element abundances in major minerals of Late Permian coals from southwestern Guizhou province, China

Fourteen samples of minerals were separated by handpicking from Late Permian coals in southwestern Guizhou province, China. These 14 minerals were nodular pyrite, massive recrystallized pyrite, pyrite deposited from low-temperature hydrothermal fluid and from ground water; clay minerals; and calcite deposited from low-temperature hydrothermal fluid and from ground water. The mineralogy, elemental composition, and distribution of 33 elements in these samples were studied by optical microscopy, scanning electron microscope equipped with energy-dispersive X-ray spectrometer (SEM-EDX), X-ray diffraction (XRD), cold-vapor atomic absorption spectrometry (CV-AAS), atomic fluorescence spectrometry (AFS), inductively coupled-plasma mass spectrometry (ICP-MS), and ion-selective electrode (ISE). The results show that various minerals in coal contain variable amounts of trace elements. Clay minerals have high concentrations of Ba, Be, Cs, F, Ga, Nb, Rb, Th, U, and Zr. Quartz has little contribution to the concentration of trace elements in bulk coal. Arsenic, Mn, and Sr are in high concentrations in calcite. Pyrite has high concentrations of As, Cd, Hg, Mo, Sb, Se, Tl, and Zn. Different genetic types of calcite in coal can accumulate different trace elements; for example Ba, Co, Cr, Hg, Ni, Rb, Sn, Sr, and Zn are in higher concentrations in calcite deposited from low-temperature hydrothermal fluid than in that deposited from ground water. Furthermore, the concentrations of some trace elements are quite variable in pyrite; different genetic types of pyrites (Py-A, B, C, D) have different concentrations of trace elements, and the concentrations of trace elements are also different in pyrite of low-temperature hydrothermal origin collected from different locations. The study shows that elemental concentration is rather uniform in a pyrite vein. There are many micron and submicron mosaic pyrites in a pyrite vein, which is enriched in some trace elements, such as As and Mo. The content of trace element in pyrite vein depends upon the content of mosaic pyrite and of trace elements in it. Many environmentally sensitive trace elements are mainly contained in the minerals in coal, and hence the physical coal cleaning techniques can remove minerals from coal and decrease the emissions of potentially hazardous trace elements. ?? 2002 Elsevier Science B.V. All rights reserved.

International Journal of Coal Geology↗

USGS2005

Embryonic developmental progression in lake trout ( Salvelinus namaycush ) (Walbaum, 1792) and its relation to lake temperature

Developmental progression of lake trout ( Salvelinus namaycush ) embryos was examined with light and scanning electron microscopy. From this examination, key developmental stages were described in detail. The key developmental stages were then applied to individual lake trout egg lots incubated in constant temperatures of 2, 4, 6, 8, and 10°C. We used Belehradek's, Thermodynamic, and Power models, and also developed the Zero model to determine stage specific developmental rates of lake trout eggs for each background temperature. From the models, hatch dates and staging were predicted for temperature regimes from Lake Superior (1990–91) and Lake Huron (1996–97). Based on the existing lake temperature data and the observed spawning dates, the Zero and the Power models predict that post peak spawning may contribute significantly to overall recruitment success for these years.

Journal of Great Lakes Research↗

USGS1999

Iron reduction in the sediments of a hydrocarbon-contaminated aquifer

Sediments sampled at a hydrocarbon-contaminated, glacial-outwash, sandy aquifer near Bemidji, Minnesota, were analyzed for sediment-associated Fe with several techniques. Extraction with 0.5 M HCl dissolved poorly crystalline Fe oxides and small amounts of Fe in crystalline Fe oxides, and extracted Fe from phyllosilicates. Use of Ti-citrate-EDTA-bicarbonate results in more complete removal of crystalline Fe oxides. The average HCl-extractable Fe(III) concentration in the sediments closest to the crude-oil contamination (16.2 μmol/g) has been reduced by up to 30% from background values (23.8 μmol/g) as a result of Fe(III) reduction in contaminated anoxic groundwater. Iron(II) concentrations are elevated in sediments within an anoxic plume in the aquifer. Iron(II) values under the oil body (19.2 μmol/g) are as much as 4 times those in the background sediments (4.6 μmol/g), indicating incorporation of reduced Fe in the contaminated sediments. A 70% increase in total extractable Fe at the anoxic/oxic transition zone indicates reoxidation and precipitation of Fe mobilized from sediment in the anoxic plume. Scanning electron microscopy detected authigenic ferroan calcite in the anoxic sediments and confirmed abundant Fe(III) oxyhydroxides at the anoxic/oxic boundary. The redox biogeochemistry of Fe in this system is coupled to contaminant degradation and is important in predicting processes of hydrocarbon degradation.

Applied Geochemistry↗

USGS2016

Assessing open-system behavior of 14C in terrestrial gastropod shells

In order to assess open-system behavior of radiocarbon in fossil gastropod shells, we measured the 14 C activity on 10 aliquots of shell material recovered from Illinoian (~190–130 ka) and pre-Illinoian (~800 ka) loess and lacustrine deposits in the Midwestern USA. Eight of the 10 aliquots yielded measurable 14 C activities that ranged from 0.25 to 0.53 percent modern carbon (pMC), corresponding to apparent 14 C ages between 48.2 and 42.1 ka. This small level of open-system behavior is common in many materials that are used for 14 C dating (e.g. charcoal), and typically sets the upper practical limit of the technique. Two aliquots of gastropod shells from the Illinoian-aged Petersburg Silt (Petersburg Section) in central Illinois, USA, however, yielded elevated 14 C activities of 1.26 and 1.71 pMC, which correspond to apparent 14 C ages of 35.1 and 32.7 ka. Together, these results suggest that while many fossil gastropods shells may not suffer from major (>1%) open-system problems, this is not always the case. We then examined the mineralogy, trace element chemistry, and physical characteristics of a suite of fossil and modern gastropod shells to identify the source of contamination in the Petersburg shells and assess the effectiveness of these screening techniques at identifying samples suitable for 14 C dating. Mineralogical (XRD) and trace element analyses were inconclusive, which suggests that these techniques are not suitable for assessing open-system behavior in terrestrial gastropod shells. Analysis with scanning electron microscopy (SEM), however, identified secondary mineralization (calcium carbonate) primarily within the inner whorls of the Petersburg shells. This indicates that SEM examination, or possibly standard microscope examination, of the interior of gastropod shells should be used when selecting fossil gastropod shells for 14 C dating.

Radiocarbon↗

USGS2026

Oil in the Alaska North Slope gas hydrate reservoir: Micro-CT and flow simulation insights into permeability

Gas hydrate-bearing sands on the Alaska North Slope (ANS) host minor volumes of crude oil whose impact on formation permeability has never been quantified relative to a gas hydrate reservoir system. Here, we combine in situ pressure-core microcomputed-tomography (μ-CT), thermogravimetric analysis (TGA), gas-chromatography–mass-spectrometry (GC–MS), scanning-electron microscopy coupled with energy-dispersive spectroscopy (SEM-EDS), and Stokes-flow simulation to (i) quantify oil saturation, (ii) infer its source, and (iii) evaluate its influence on permeability after gas-hydrate dissociation. μ-CT and SEM-EDS imaging identify the host sediment as silty, with some grain-coating clay present. Eight representative 300 3 -voxel subvolumes extracted from a preserved pressure core (Core 15P-3c, from the B1 sand (unit B), HYDRATE 02 Geo Data Well (GDW), 886.96–887.29 m measured depth, MD) exhibit porosities of 0.34–0.37 and an average oil saturation of 0.09 ± 0.03, in comparison to an independent TGA-based estimate of 0.16. GC-MS fingerprints obtained from an adjacent depressurized core (Core 17P-1, 891.37–891.44 m MD), together with oil pore habit revealed by μ-CT, suggest that the oil is partly native but also includes contributions from mineral oil-based drilling fluid contamination. Further analysis of oil–porewater interactions and flushing tests confirms that native oil saturation in the analyzed samples ranges from 0.04 to 0.08 with an average of approximately 0.06, and the oil is highly immobile. Flow simulations demonstrate that the native oil saturation of ≈0.06 reduces permeability by approximately 50% due to both pore blockage and increased flow-path tortuosity. These findings reveal the potential presence of native oil within the ANS gas hydrate reservoir and suggest that future simulation models may need to account for its impact on permeability to improve long-term performance predictions of gas and water production.

Alaska↗

USGS2002

An unusual occurrence of arsenic-bearing pyrite in the Upper Freeport coal bed, West-Central Pennsylvania

Scanning electron microscopy and electron microprobe analysis were used to identify a rare type of As-bearing pyrite in selected specific gravity separates from the Pennsylvanian age Upper Freeport coal bed, west-central Pennsylvania. Arsenic was detected mainly in cell-wall replacement pyrite where concentrations ranged from nondetectable to 1.9 wt %. Although the majority of arsenic-bearing pyrite in the Upper Freeport coal bed is concentrated in massive and late diagenetic pyrite morphologies, the rarer As-bearing cell-replacement pyrite was observed in both light and heavy gravity separates from the three coal facies examined. Arsenic was occasionally detected in cell-filling replacement pyrite, but this As appears to be an artifact produced by signals from underlying and/or adjacent As-bearing cell-wall replacement pyrite. It is postulated that some plants of the Upper Freeport paleoswamp may have biomethylated As, which later could have been converted to dimethylarsine or other volatile organoarsenic compounds by either biologically or chemically driven processes. Once liberated, the arsenic may have been incorporated into pyrite during pyritization of the cell walls. The As incorporation occurred early, before significant compaction of the peat, because the pyritized cell walls are not compacted.

Pennsylvania↗

USGS2013

A USANS/SANS study of the accessibility of pores in the Barnett Shale to methane and water

Shale is an increasingly important source of natural gas in the United States. The gas is held in fine pores that need to be accessed by horizontal drilling and hydrofracturing techniques. Understanding the nature of the pores may provide clues to making gas extraction more efficient. We have investigated two Mississippian Barnett Shale samples, combining small-angle neutron scattering (SANS) and ultrasmall-angle neutron scattering (USANS) to determine the pore size distribution of the shale over the size range 10 nm to 10 μm. By adding deuterated methane (CD 4 ) and, separately, deuterated water (D 2 O) to the shale, we have identified the fraction of pores that are accessible to these compounds over this size range. The total pore size distribution is essentially identical for the two samples. At pore sizes >250 nm, >85% of the pores in both samples are accessible to both CD 4 and D 2 O. However, differences in accessibility to CD 4 are observed in the smaller pore sizes (~25 nm). In one sample, CD 4 penetrated the smallest pores as effectively as it did the larger ones. In the other sample, less than 70% of the smallest pores (<25 nm) were accessible to CD 4 , but they were still largely penetrable by water, suggesting that small-scale heterogeneities in methane accessibility occur in the shale samples even though the total porosity does not differ. An additional study investigating the dependence of scattered intensity with pressure of CD 4 allows for an accurate estimation of the pressure at which the scattered intensity is at a minimum. This study provides information about the composition of the material immediately surrounding the pores. Most of the accessible (open) pores in the 25 nm size range can be associated with either mineral matter or high reflectance organic material. However, a complementary scanning electron microscopy investigation shows that most of the pores in these shale samples are contained in the organic components. The neutron scattering results indicate that the pores are not equally proportioned in the different constituents within the shale. There is some indication from the SANS results that the composition of the pore-containing material varies with pore size; the pore size distribution associated with mineral matter is different from that associated with organic phases.

Texas↗

USGS2015

Using chromate to investigate the impact of natural organics on the surface reactivity of nanoparticulate magnetite

Chromate was used as a chemical probe to investigate the size-dependent influence of organics on nanoparticle surface reactivity. Magnetite–chromate sorption experiments were conducted with ∼90 and ∼6 nm magnetite nanoparticles in the presence and absence of fulvic acid (FA), natural organic matter (NOM), and isolated landfill leachate (LL). Results indicated that low concentrations (1 mg/L) of organics had no noticeable impact on chromate sorption, whereas concentrations of 50 mg/L or more resulted in decreased amounts of chromate sorption. The adsorption of organics onto the magnetite surfaces interfered equally with the ability of the 6 and 90 nm particles to sorb chromate from solution, despite the greater surface area of the smaller particles. Results indicate the presence of organics did not impact the redox chemistry of the magnetite–chromate system over the duration of the experiments (8 h), nor did the organics interact with the chromate in solution. Brunauer–Emmett–Teller (BET) and scanning electron microscopy (SEM) results indicate that the organics blocked the surface reactivity by occupying surface sites on the particles. The similarity of results with FA and NOM suggests that coverage of the reactive mineral surface is the main factor behind the inhibition of surface reactivity in the presence of organics.

Environmental Science & Technology↗

USGS1996

Limestone characterization to model damage from acidic precipitation: Effect of pore structure on mass transfer

The pore structure of Salem limestone is investigated, and conclusions regarding the effect of the pore geometry on modeling moisture and contaminant transport are discussed based on thin section petrography, scanning electron microscopy, mercury intrusion porosimetry, and nitrogen adsorption analyses. These investigations are compared to and shown to compliment permeability and capillary pressure measurements for this common building stone. Salem limestone exhibits a bimodal pore size distribution in which the larger pores provide routes for convective mass transfer of contaminants into the material and the smaller pores lead to high surface area adsorption and reaction sites. Relative permeability and capillary pressure measurements of the air/water system indicate that Salem limestone exhibits high capillarity end low effective permeability to water. Based on stone characterization, aqueous diffusion and convection are believed to be the primary transport mechanisms for pollutants in this stone. The extent of contaminant accumulation in the stone depends on the mechanism of partitioning between the aqueous and solid phases. The described characterization techniques and modeling approach can be applied to many systems of interest such as acidic damage to limestone, mass transfer of contaminants in concrete and other porous building materials, and modeling pollutant transport in subsurface moisture zones.

Environmental Science & Technology↗

USGS2003

CO2 hydrate: Synthesis, composition, structure, dissociation behavior, and a comparison to structure I CH4 hydrate

Structure I (sI) carbon dioxide (CO 2 ) hydrate exhibits markedly different dissociation behavior from sI methane (CH 4 ) hydrate in experiments in which equilibrated samples at 0.1 MPa are heated isobarically at 13 K/h from 210 K through the H 2 O melting point (273.15 K). The CO 2 hydrate samples release only about 3% of their gas content up to temperatures of 240 K, which is 22 K above the hydrate phase boundary. Up to 20% is released by 270 K, and the remaining CO 2 is released at 271.0 plusmn; 0.5 K, where the sample temperature is buffered until hydrate dissociation ceases. This reproducible buffering temperature for the dissociation reaction CO 2 ·nH 2 O = CO 2 (g) + nH 2 O(1 to s) is measurably distinct from the pure H 2 O melting point at 273.15 K, which is reached as gas evolution ceases. In contrast, when si CH 4 hydrate is heated at the same rate at 0.1 MPa, >95% of the gas is released within 25 K of the equilibrium temperature (193 K at 0.1 MPa). In conjunction with the dissociation study, a method for efficient and reproducible synthesis of pure polycrystalline CO 2 hydrate with suitable characteristics for material properties testing was developed, and the material was characterized. CO 2 hydrate was synthesized from CO 2 liquid and H 2 O solid and liquid reactants at pressures between 5 and 25 MPa and temperatures between 250 and 281 K. Scanning electron microscopy (SEM) examination indicates that the samples consist of dense crystalline hydrate and 50-300 μm diameter pores that are lined with euhedral cubic hydrate crystals. Deuterated hydrate samples made by this same procedure were analyzed by neutron diffraction at temperatures between 4 and 215 K; results confirm that complete conversion of water to hydrate has occurred and that the measured unit cell parameter and thermal expansion are consistent with previously reported values. On the basis of measured weight gain after synthesis and gas yields from the dissociation experiments, approximately all cages in the hydrate structure are filled such that n ≈ 5.75.

Journal of Physical Chemistry B↗

USGS2008

Diffuse flow hydrothermal manganese mineralization along the active Mariana and southern Izu-Bonin arc system, western Pacific

Abundant ferromanganese oxides were collected along 1200 km of the active Izu-Bonin-Mariana arc system. Chemical compositions and mineralogy show that samples were collected from two deposit types: Fe-Mn crusts of mixed hydrogenetic/hydrothermal origin and hydrothermal Mn oxide deposits; this paper addresses only the second type. Mn oxides cement volcaniclastic and biogenic sandstone and breccia layers (Mn sandstone) and form discrete dense stratabound layers along bedding planes and within beds (stratabound Mn). The Mn oxide was deposited within coarse-grained sediments from diffuse flow systems where precipitation occurred below the seafloor. Deposits were exposed at the seabed by faulting, mass wasting, and erosion. Scanning electron microscopy and microprobe analyses indicate the presence of both amorphous and crystalline 10 ?? and 7 ?? manganate minerals, the fundamental chemical difference being high water contents in the amorphous Mn oxides. Alternation of amorphous and crystalline laminae occurs in many samples, which likely resulted from initial rapid precipitation of amorphous Mn oxides from waxing pulses of hydrothermal fluids followed by precipitation of slow forming crystallites during waning stages. The chemical composition is characteristic of a hydrothermal origin including strong fractionation between Fe (mean 0.9 wt %) and Mn (mean 48 wt %) for the stratabound Mn, generally low trace metal contents, and very low rare earth element and platinum group element contents. However, Mo, Cd, Zn, Cu, Ni, and Co occur in high concentrations in some samples and may be good indicator elements for proximity to the heat source or to massive sulfide deposits. For the Mn sandstones, Fe (mean-8.4%) and Mn (12.4%) are not significantly fractionated because of high Fe contents in the volcaniclastic material. However, the proportion of hydrothermal Fe (nondetrital Fe) to total Fe is remarkably constant (49-58%) for all the sample groups, regardless of the degree of Mn mineralization. Factor analyses indicate various mixtures of two dominant components: hydrothermal Mn oxide for the stratabound Mn and detrital aluminosilicate for the Mn-cemented sandstone; and two minor components, hydrothermal Fe oxyhydroxide and biocarbonate/biosilica. Our conceptual model shows that Mn mineralization was produced by hydrothermal convection cells within arc volcanoes and sedimentary prisms that occur along, the flanks and within calderas. The main source of hydrothermal fluid was seawater that penetrated through fractures, faults, and permeable volcanic edifices. The fluids were heated by magma, enriched in metals by leaching of basement rocks and sediments, and mixed with magmatic fluids and gases. Dikes and sills may have been another source of heat that drove small-scale circulation within sedimentary prisms. Copyright 2008 by the American Geophysical Union.

Journal of Geophysical Research B: Solid Earth↗