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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 ( τ ) 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 ( σ′ ) and imaginary ( σ″ ) conductivity, phase ( ϕ ) and apparent formation factor ( F app ). Unlike the control columns, a substantial decrease in σ′ 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 σ′ is opposite to previous studies on hydrocarbon biodegradation. These columns also exhibited increases in ϕ (up to ~ 9 mrad) and σ″ (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 σ″ 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

Combined ESR/U-series chronology of Acheulian hominid-bearing layers at Trinchera Galería site, Atapuerca, Spain

The Sierra de Atapuerca, northern Spain, is known from many prehistoric and palaeontological sites documenting human prehistory in Europe. Three major sites, Gran Dolina, Galería and Sima del Elefante, range in age from the oldest hominin of Western Europe dated to 1.1 to 1.3 Ma (millions of years ago) at Sima del Elefante to c.a. 0.2 Ma on the top of the Galería archaeological sequence. Recently, a chronology based on luminescence methods (Thermoluminescence [TL] and Infrared Stimulated Luminescence [IRSL]) applied to cave sediments was published for the Gran Dolina and Galería sites. The authors proposed for Galería an age of 450 ka (thousands of years ago) for the units lower GIII and GII, suggesting that the human occupation there is younger than the hominid remains of Sima de los Huesos (>530 ka) around 1 km away. In this paper, we present new results obtained by combined Electron Spin Resonance/Uranium-series (ESR/U-series) dating on 20 herbivorous teeth from different levels at the Galería site. They are in agreement with the TL results for the upper part of the stratigraphic sequence (GIV and GIIIb), in the range of between 200 and 250 ka. But for the GIIIa to GIIb levels, the TL ages become abruptly older by 200 ka while ESR ages remain relatively constant. Finally, the TL and ESR data agree in the lowest part of the section (GIIa); both fall in the range of around 350–450 ka. Our results suggest a different interpretation for the GII, GIII and GIV units of Galería and the upper part of Gran Dolina (TD10 and TD11) than obtained by TL. The ESR/U-series results are supported by a Bayesian analysis, which allows a better integration between stratigraphic information and radiometric data.

Atapuerca Mountains

Aquifer-scale controls on the distribution of nitrate and ammonium in ground water near La Pine, Oregon, USA

Geochemical and isotopic tools were applied at aquifer, transect, and subtransect scales to provide a framework for understanding sources, transport, and fate of dissolved inorganic N in a sandy aquifer near La Pine, Oregon. NO3 is a common contaminant in shallow ground water in this area, whereas high concentrations of NH4-N (up to 39 mg/L) are present in deep ground water. N concentrations, N/Cl ratios, tracer-based apparent ground-water ages, N isotope data, and hydraulic gradients indicate that septic tank effluent is the primary source of NO3. N isotope data, N/Cl and N/C relations, 3H data, and hydraulic considerations point to a natural, sedimentary organic matter source for the high concentrations of NH4, and are inconsistent with an origin as septic tank N. Low recharge rates and flow velocities have largely restricted anthropogenic NO3 to isolated plumes within several meters of the water table. A variety of geochemical and isotopic data indicate that denitrification also affects NO3 gradients in the aquifer. Ground water in the La Pine aquifer evolves from oxic to increasingly reduced conditions. Suboxic conditions are achieved after about 15-30 y of transport below the water table. NO3 is denitrified near the oxic/suboxic boundary. Denitrification in the La Pine aquifer is characterized well at the aquifer scale with a redox boundary approach that inherently captures spatial variability in the distribution of electron donors.

Oregon

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

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

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 &minus; 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 &minus; 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 &minus; reduction were correlated and, on an electron milliequivalent basis, denitrification rates tended to exceed O 2 reduction rates. Estimated historical NO 3 &minus; 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

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

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

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

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

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

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

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

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

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

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