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Ten years of volcanic activity at Mt Etna: High-resolution mapping and accurate quantification of the morphological changes by Pleiades and Lidar data

The topography of Mt. Etna, Italy, is subjected to continuous modifications depending on intensity and magnitude of eruptions that frequently occur at the volcano summit and flanks. In order to make high-resolution maps of morphological changes and accurately calculate the overall volume of the erupted products (e.g., lava flows, tephra fall out, scoriae cones) in ten years, we have compared the altimetry models of Mt. Etna derived from 2005 Airborne Laser Scanning data and 2015 Pleiades stereo satellite imagery. Both models cover a common area of 400 km 2 with spatial resolution of 2 m and comparable vertical accuracy (RMSE < 0.8 m). The results show that the area most affected by the erupted products is the mid-upper portion of the volcano with an altitude ranging from 1300 m to more than 3300 m a.s.l., value reached at the summit of the North East crater. In particular, this portion changes dramatically in the eastern sector due to the birth and growth of the New South-East Crater, the invasion of dozens of lava flows in the Valle del Bove, and the formation of the 2014 scoriae cones and lava field at the base of the North-East Crater. The total volume of products erupted in the investigated period results in 284.3±15.8 x 10 6 m 3 with a yearly average volume of 28.4 x 10 6 m 3 /y comparable with the previous decades. In addition, the products emitted by the 2014 sub-terminal eruption are mapped and quantified including, for the first time, the volume of the 2014 scoriae cones generated on the eastern flank of North-East Crater This study demonstrates how a rigorous comparison between digital elevation models derived from different remote sensing techniques produce high accurate mapping and quantifications of morphological changes applicable for worldwide active volcanoes. This allows to quantify volumes and areas of erupted products reducing the error estimations, a crucial point to provide precise data often used as key parameters for many volcanic hazard studies.

Mt. Etna, Sicily

Complex resistivity signatures of ethanol biodegradation in porous media

Numerous adverse effects are associated with the accidental release of ethanol (EtOH) and its persistence in the subsurface. Geophysical techniques may permit non-invasive, real time monitoring of microbial degradation of hydrocarbon. We performed complex resistivity (CR) measurements in conjunction with geochemical data analysis on three microbial-stimulated and two control columns to investigate changes in electrical properties during EtOH biodegradation processes in porous media. A Debye Decomposition approach was applied to determine the chargeability ( m ), normalized chargeability ( m n ) and time constant ( &tau; ) of the polarization magnitude and relaxation length scale as a function of time. The CR responses showed a clear distinction between the bioaugmented and control columns in terms of real ( &sigma;&prime; ) and imaginary ( &sigma;&Prime; ) conductivity, phase ( ϕ ) and apparent formation factor ( F app ). Unlike the control columns, a substantial decrease in &sigma;&prime; and increase in F app occurred at an early time (within 4 days) of the experiment for all three bioaugmented columns. The observed decrease in &sigma;&prime; is opposite to previous studies on hydrocarbon biodegradation. These columns also exhibited increases in ϕ (up to ~ 9 mrad) and &sigma;&Prime; (up to two order of magnitude higher) 5 weeks after microbial inoculation. Variations in m and m n were consistent with temporal changes in ϕ and &sigma;&Prime; responses, respectively. Temporal geochemical changes and high resolution scanning electron microscopy imaging corroborated the CR findings, thus indicating the sensitivity of CR measurements to EtOH biodegradation processes. Our results offer insight into the potential application of CR measurements for long-term monitoring of biogeochemical and mineralogical changes during intrinsic and induced EtOH biodegradation in the subsurface.

Journal of Contaminant Hydrology

Uptake and distribution of organo-iodine in deep-sea corals

Understanding iodine concentration, transport, and bioavailability is essential in evaluating iodine's impact to the environment and its effectiveness as an environmental biogeotracer. While iodine and its radionuclides have proven to be important tracers in geologic and biologic studies, little is known about transport of this element to the deep sea and subsequent uptake in deep-sea coral habitats. Results presented here on deep-sea black coral iodine speciation and iodine isotope variability provides key information on iodine behavior in natural and anthropogenic environments, and its geochemical pathway in the Gulf of Mexico. Organo-iodine is the dominant iodine species in the black corals, demonstrating that binding of iodine to organic matter plays an important role in the transport and transfer of iodine to the deep-sea corals. The identification of growth bands captured in high-resolution scanning electron images (SEM) with synchronous peaks in iodine variability suggest that riverine delivery of terrestrial-derived organo-iodine is the most plausible explanation to account for annual periodicity in the deep-sea coral geochemistry. Whereas previous studies have suggested the presence of annual growth rings in deep-sea corals, this present study provides a mechanism to explain the formation of annual growth bands. Furthermore, deep-sea coral ages based on iodine peak counts agree well with those ages derived from radiocarbon ( 14 C) measurements. These results hold promise for developing chronologies independent of 14 C dating, which is an essential component in constraining reservoir ages and using radiocarbon as a tracer of ocean circulation. Furthermore, the presence of enriched 129 I/ 127 I ratios during the most recent period of skeleton growth is linked to nuclear weapons testing during the 1960s. The sensitivity of the coral skeleton to record changes in surface water 129 I composition provides further evidence that iodine composition and isotope variability captured in proteinaceous deep-sea corals is a promising geochronometer as well as an emerging tracer for continental material flux.

Journal of Environmental Radioactivity

Habitat used by juvenile lake sturgeon ( Acipenser fulvescens ) in the North Channel of the St. Clair River (Michigan, USA)

Lake sturgeon ( Acipenser fulvescens ) occupy the St. Clair River, part of a channel connecting lakes Huron and Erie in the Laurentian Great Lakes. In the North Channel of the St. Clair River, juvenile lake sturgeon (3–7 years old and 582–793 mm in length) were studied to determine movement patterns and habitat usage. Fourteen juveniles were implanted with ultrasonic transmitters and tracked June–August of 2004, 2005 and 2006. Telemetry data, Geographic Information System software, side-scan sonar, video images of the river bottom, scuba diving, and benthic substrate samples were used to determine the extent and composition of habitats they occupied. Juvenile lake sturgeon habitat selection was strongly related to water depth. No fish were found in <6 m of water and over 97% of the relocations were found at depths greater than 9 m. Available water depths exceeding 18 m only represented 3.5% of the available habitat, however 34.9% of the relocations were found at depths exceeding 18 m. Juvenile lake sturgeon did not use most areas in proportion to their availability. Sturgeon avoided clay ledges and shallow areas with silt or soft clay, which comprised approximately 39% of the benthic habitat in the North Channel. A total of 300 out of 351 documented locations were on sand and gravel habitat types mixed with clay. Lake sturgeon > 700 mm in length selected sand and gravel areas mixed with zebra mussels and areas dominated by zebra mussels, while fish < 700 mm used these habitat types in proportion to their availability.

Michigan

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

The 2003 phreatomagmatic eruptions of Anatahan volcano - Textural and petrologic features of deposits at an emergent island volcano

Stratigraphic and field data are used in conjunction with textural and chemical evidence (including data from scanning electron microscope, electron microprobe, X-ray fluorescence, X-ray diffraction, and instrumental neutron activation analysis) to establish that the 2003 eruption of Anatahan volcano was mainly phreatomagmatic, dominated by explosive interaction of homogeneous composition low-viscosity crystal-poor andesite magma with water. The hydromagmatic mode of eruption contributed to the significant height of initial eruptive columns and to the excavation and eruption of altered rock debris from the sub-volcanic hydrothermal system. Volatile contents of glass inclusions in equilibrium phenocrysts less abundances of these constituents in matrix glass times the estimated mass of juvenile magma indicate minimum emissions of 19 kt SO2 and 13 kt Cl. This petrologic estimate of SO2 emission is an order-of-magnitude less than an estimate from TOMS. Similarly, inferred magma volumes from the petrologic data are an order of magnitude greater than those modeled from deformation data. Both discrepancies indicate additional sources of volatiles, likely derived from a separate fluid phase in the magma. The paucity of near-source volcanic-tectonic earthquakes preceding the eruption, and the dominance of sustained long-period tremor are attributed to the ease of ascent of the hot low-viscosity andesite, followed by a shallow phreatomagmatic mode of eruption. Phreatomagmatic eruptions are probably more common at emergent tropical island volcanoes, where shallow fresh-water lenses occur at near-sea-level vents. These relations suggest that phreatomagmatic explosions contributed to the formation of many of the near-sea-level craters and possibly even to the small calderas at the other Mariana islands.

Northern Mariana Islands

Gas and ash emissions associated with the 2010–present activity of Sinabung Volcano, Indonesia

Sinabung Volcano (Sumatra, Indonesia) awoke from over 1200 years of dormancy with multiple phreatic explosions in 2010. After a period of quiescence, Sinabung activity resumed in 2013, producing frequent explosions, lava dome extrusion, and pyroclastic flows from dome collapses, becoming one of the world's most active volcanoes and displacing over 20,000 citizens. This study presents a compilation of the geochemical datasets collected by the Indonesian Center for Volcanology and Geological Hazard Mitigation (CVGHM) from 2010 - current (2016), which provides insights into the evolution of the eruption. Based on observations of SO2 emissions, ash componentry, leachate chemistry, and bulk ash geochemistry, the eruption can be split into five distinct phases. The initial stage of phreatic summit explosions occurred from August - October 2010, during which background SO2 emissions averaged ~550 ± 180 t/d (1 s.d.). An eruptive pause (phase two) starting in October 2010 abruptly ended in September 2013 with a resumption of conduit-clearing eruptions. This third phase had a relatively modest background SO2 emission rate (avg. ~410 ± 275 t/d) and produced ash consisting entirely of accidental ejecta with high S/Cl leachate ratios (up to 30), suggestive of deep-sourced magma and the incorporation of hydrothermal sulfur-bearing phases. The most intense phase of the eruption (phase four) occurred from December 2013 to February 2014, when juvenile magma first reached the surface. This period included dozens of large eruptions per day, high SO2 emission rates (average: 1,120 ± 1,030 t/d, peak: ~3,800 t/d), the onset of lava dome extrusion, and a dramatic drop in S/Cl ash leachates to ratios < 5, all reflecting increased degassing from shallow magma and the clearing out of sulfurous phases from the old hydrothermal system. From late February 2014 through the time of writing (September 2016), Sinabung settled into a relatively steady state of lower activity (phase five). Ash emissions now consist of dominantly juvenile material, and background SO2 emission rates have been progressively decreasing to an average of ~250 - 300 t/d. Starting August 2016, SO2 emissions started being measured in a continuous manner using a network of permanent scanning DOAS instruments. We find that long-term SO2 emission rates have been gradually declining at Sinabung since early 2014, consistent with an apparent decrease in magma supply. Our degassing model suggests that large explosions and pyroclastic flows could continue in the near-term owing to conduit plugging and dome collapses, remaining a major threat until the magma supply rate decreases further and the eruption ends.

Sumatra

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

Sub-tidal benthic habitats of central San Francisco Bay and offshore Golden Gate area: A review

Deep-water potential estuarine and marine benthic habitat types were defined from a variety of new and interpreted data sets in central San Francisco Bay and offshore Golden Gate area including multibeam echosounder (MBES), side-scan sonar and bottom grab samples. Potential estuarine benthic habitats identified for the first time range from hard bedrock outcrops on island and mainland flanks and some Bay floor regions, to soft, very dynamic bedforms consisting of sediment waves and ripples. Soft sediment ranges from mud and sand to bimodal (two or more grain sizes) sediment of gravel, pebbles, and cobbles. In addition, considerable anthropogenic features (i.e., pipelines, bridge abutments, dredged channels, dump sites) were distinguished. Of the 52 potential benthic habitat types mapped (compressed to 14 types for this paper), 24 were of un-consolidated sediment with five of these comprised of dynamic bedforms or sediment waves and dunes, five of mixed (soft over hard) substrate type, six of hard substrate or rock outcrop, 13 of anthropogenically disturbed areas and four hard anthropogenic features. Rock outcrops and rubble are considered the primary habitat type for rockfish ( Sebastes spp. ), lingcod ( Ophiodon elongatus ) and in shallow water for herring ( Clupea pallasii ) spawning. Dynamic bedforms such as sand waves are considered potential foraging habitat for juvenile lingcod, may be sub-tidal habitat for the Pacific sand lance ( Ammodytes hexapterus ) forage fish, and possibly resting habitat for migratory fishes such as sturgeon ( Acipenser medirostris ). The potential marine benthic habitats identified in San Francisco Bay are not unlike those found in other estuaries around the world and this study should contribute significant information that will be of interest to scientists, managers and fishers investigating and utilizing bay and estuarine resources. As described in the many papers of this special issue, the understanding of the interrelationship of geology and ecology is critical to the identification of essential habitats and the sustainability of a healthy ecosystem.

California

Refining the link between the Holocene development of the Mississippi River Delta and the geologic evolution of Cat Island, MS: implications for delta-associated barrier islands

The geologic evolution of barrier islands is profoundly influenced by the nature of the deposits underlying them. Many researchers have speculated on the origin and evolution of Cat Island in Mississippi, but uncertainty remains about whether or not the island is underlain completely or in part by deposits associated with the past growth of the Mississippi River delta. In part, this is due to a lack of comprehensive geological information offshore of the island that could augment previous stratigraphic interpretations based on terrestrial borings. An extensive survey of Cat Island and its surrounding waters was conducted, including shallow-water geophysics (e.g., high-resolution chirp seismic, side-scan sonar, and swath and single-beam bathymetry) and both terrestrial and marine vibracoring. High-resolution seismic data and vibracores from south and east of the island show two horizontally laminated silt units; marine radiocarbon dates indicate that they are St. Bernard delta complex (SBDC) deposits. Furthermore, seismic data reveal that the SBDC deposits taper off toward the southern shoreline of Cat Island and to the west, morphology consistent with the distal edge of a delta complex. The sedimentology and extent of each unit suggest that the lower unit may have been deposited during an earlier period of continuous river flow while the upper unit may represent reduced or sporadic river flow. OSL dates from the island platform (beneath beach ridge complexes) indicate three stages of terrestrial evolution: island emergence resulting from relative sea-level rise (~ 5400 ybp) island aggradation via littoral transport (~ 2500–4000 ybp) and island degradation due to delta-mediated changes in wave direction (present– ~ 3600 ybp). Finally, the combination of terrestrial and marine data shows that portions of Cat Island that are lower in elevation than the central part of the island are younger and are likely underlain by a thin layer of deltaic sediments. This underscores the potential for increased future vulnerability of barrier islands that develop adjacent to major river delta complexes.

Mississippi

Tracking diagenetic alteration of magnetic susceptibility in thrust ridge and slope basin sediments of the Cascadia margin (ODP Sites 1249 and 1252; IODP Site U1325)

We investigated sediment core records from the Cascadia Margin (Ocean Drilling Program Sites 1249 and 1252 at Hydrate Ridge; Integrated Ocean Drilling Program Site U1325 offshore Vancouver Island) using a Zr/Rb heavy mineral proxy from X-ray fluorescence (XRF) core scanning to identify intervals of primary detrital magnetic susceptibility (κ) and predict intervals where diagenesis caused magnetite dissolution by hydrogen sulfide. We also measured total sulfur (TS) content, grain size distributions, total organic carbon (TOC) content, and the magnetic mineral assemblage to further constrain the role of diagenesis on κ. Understanding how κ can be used to better characterize the varied effects of detrital and diagenetic signals in marine settings is important for understanding biogeochemical cycling and records of paleoenvironmental change. The upper 100 m of slope basin Site 1252 contains multiple intervals (> 90 m total) of decreased κ correlated with elevated TS content, consistent with dissolution of magnetite and precipitation of pyrite, iron monosulfides, and/or elemental sulfur. Similarly at the other slope basin site, Site U1325, κ is lower and TS is elevated in the interval between 24 and 51 mbsf, due to sulfide formation. At both slope basin sites, these low κ intervals correspond with high TOC, suggesting the possibility that organoclastic sulfate reduction (OSR) is likely a major driver of diagenetic alteration of κ at these sites. High TS:TOC ratios at Site U1325 suggests anaerobic oxidation of methane (AOM) during sulfate-methane transition zone (SMTZ) migration may have contributed to alteration of κ. In contrast, within the upper 90 m of Site 1249, a methane seep site at the summit of Hydrate Ridge, κ is almost entirely altered by diagenetic processes, with much of the low κ explained by a high degree of iron sulfide formation, while some intervals are affected by precipitation of magnetic iron sulfides that maintain or even increase κ. The presence of abundant methane seepage and gas hydrate as well as chemosynthetic seafloor fauna at this site, suggests that sulfide is released to the water column and AOM, rather than OSR, drives diagenetic alteration of κ at this site. Overall, the slope basin sites show episodic variation of κ that is influenced by TOC content, likely driven by changes in marine primary productivity and sedimentation rate, while the seep site shows consistently altered κ with lower TS content and no correlation with TOC. Methane seep environments likely experience loss of hydrogen sulfide to the water column and oxidation of hydrogen sulfide by seafloor seep fauna, which limits the amount of solid phase sulfur (pyrite, iron monosulfides, elemental sulfur) that can be precipitated within the sediments. In contrast, the migration of a buried SMTZ at slope basin sites results in enhanced sulfur precipitation within the sediments. This integrated magnetic and geochemical approach reveals the diagenetic production pathway and residence time of sulfide with the sediment column ultimately controls the style and degree of diagenetic loss of κ in marine sediments. This approach works best in environments with unaltered reference intervals/sites, consistent magnetic mineralogy, and clay-to-silt grain sizes.

Cascadia margin, Pacific Ocean

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

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

Examination of core samples from the Mount Elbert Gas Hydrate Stratigraphic Test Well, Alaska North Slope: Effects of retrieval and preservation

Collecting and preserving undamaged core samples containing gas hydrates from depth is difficult because of the pressure and temperature changes encountered upon retrieval. Hydrate-bearing core samples were collected at the BPXA-DOE-USGS Mount Elbert Gas Hydrate Stratigraphic Test Well in February 2007. Coring was performed while using a custom oil-based drilling mud, and the cores were retrieved by a wireline. The samples were characterized and subsampled at the surface under ambient winter arctic conditions. Samples thought to be hydrate bearing were preserved either by immersion in liquid nitrogen (LN), or by storage under methane pressure at ambient arctic conditions, and later depressurized and immersed in LN. Eleven core samples from hydrate-bearing zones were scanned using x-ray computed tomography to examine core structure and homogeneity. Features observed include radial fractures, spalling-type fractures, and reduced density near the periphery. These features were induced during sample collection, handling, and preservation. Isotopic analysis of the methane from hydrate in an initially LN-preserved core and a pressure-preserved core indicate that secondary hydrate formation occurred throughout the pressurized core, whereas none occurred in the LN-preserved core, however no hydrate was found near the periphery of the LN-preserved core. To replicate some aspects of the preservation methods, natural and laboratory-made saturated porous media samples were frozen in a variety of ways, with radial fractures observed in some LN-frozen sands, and needle-like ice crystals forming in slowly frozen clay-rich sediments. Suggestions for hydrate-bearing core preservation are presented.

Alaska

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&ndash;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&ndash;80 &mu;m, 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

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

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

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